JP3810838B2 - Herbicidal isoxazoline derivatives - Google Patents

Herbicidal isoxazoline derivatives Download PDF

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JP3810838B2
JP3810838B2 JP31818395A JP31818395A JP3810838B2 JP 3810838 B2 JP3810838 B2 JP 3810838B2 JP 31818395 A JP31818395 A JP 31818395A JP 31818395 A JP31818395 A JP 31818395A JP 3810838 B2 JP3810838 B2 JP 3810838B2
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isoxazoline
chloromethyl
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JPH08225548A (en
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隆実 米田
宗治 水貝
直人 塚口
淳二 門谷
豊邦 本間
正 天笠
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三共アグロ株式会社
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【０００１】
【発明の属する技術分野】
本発明は、優れた除草活性を有する新規なイソオキサゾリン誘導体及びそれを有効成分として含有する除草剤に関する。
【０００２】
【従来の技術】
これまで、除草活性を有する２−イソオキサゾリン骨格を有する化合物は、ＥＰ３３４１２０Ａ１及びＥＰ５１４９８７Ａ１に記載されている。
【０００３】
しかし、ＥＰ３３４１２０Ａ１に記載の化合物は、２−イソオキサゾリン環３位に、アルキル、シクロアルキル、置換フェニル、５員及び６員ヘテロ環が直結した化合物であり、２−イソオキサゾリン環３位が（置換）メチレンスルフィド、（置換）メチレンスルホキシド、（置換）メチレンスルホンである本願化合物とは、構造が全く異なる。また、ＥＰ５１４９８７Ａ１に記載の化合物は、２−イソオキサゾリン環３位に置換フェニル基が直結した化合物のみであり、やはり本願化合物とは、構造が全く異なる。
【０００４】
さらに、２−イソオキサゾリン環を有する化合物が、特開平５−１０５６７２号公報に記載されているが、これら化合物はすべてイソオキサゾリン環５位にシアノ基が直結した化合物であり、この点本願化合物と構造上全く異なる。さらに、当該特開平５−１０５６７２号公報には、除草活性については何ら記載されていない。
【０００５】
【発明が解決しようとする課題】
本発明者等は、２−イソオキサゾリン環を有する誘導体の合成とその生物活性について永年に亘り鋭意研究を行なった結果、既知の化合物とは構造を異にした、新規な２−イソオキサゾリン誘導体が、優れた除草活性を有することを見出し、本発明を完成した。
【０００６】
本発明の化合物は、水田においては、特に水田の強害雑草であるタイヌビエに対して低薬量で優れた除草活性を示し、かつ水稲に対する薬害が極めて少なく、また、コナギ、アゼナ、アブノメ、キカシグサ等の広葉雑草や、ホタルイ、ミズガヤツリ等のカヤツリグサ科雑草に対しても強い殺草作用を有する。
【０００７】
更には、畑地においても、メヒシバ、イヌビエ、エノコログサ等のイネ科雑草に対して低薬量で優れた除草活性を示し、かつトウモロコシ、ビート、ダイズ、ワタに対する薬害が極めて少なく、また、イヌビユ、アカザ、カラシナ、アオゲイトウ等の広葉雑草に対しても強い殺草作用を有する。
【０００８】
【発明の構成】
【０００９】
【課題を解決するための手段】
本発明は、下記一般式（Ｉ）
【００１０】
【化６】

Figure 0003810838
【００１１】
［式中、Ｒ1 は、同一又は異なった１乃至３個のハロゲン原子により置換された低級アルキル基を示し、Ｒ2 は、低級アルキル基を示し、Ｒ3 及びＲ4 は同一又は異なって、水素原子又は低級アルキル基を示し、Ｒ5 は、ハロゲン原子、低級アルキル基（当該低級アルキル基は、置換基群ａから選ばれる同一又は異なった１乃至３個の置換基により置換されていても良い）又は低級アルコキシ基（当該低級アルコキシ基は、置換基群ａから選ばれる同一又は異なった１乃至３個の置換基により置換されていても良く、また、近接する当該低級アルコキシ基が２個結合して低級アルキレンジオキシ基を形成しても良く、当該低級アルキレンジオキシ基は同一又は異なった１乃至４個のハロゲン原子により置換されていても良い）を示すか、又は、Ｒ4 とＲ5 が一緒になって低級アルキレン基又は低級アルキレンオキシ基を形成しても良く（ｍが２以上の場合、Ｒ5 は同一又は異なっていても良い）、ｍは０、１、２、３、４又は５を示し、ｎは０、１又は２を示す。
【００１２】
（置換基群ａ）
ハロゲン原子、低級アルコキシ基（当該低級アルコキシ基は同一又は異なった１乃至３個のハロゲン原子により置換されていても良く、また、近接する当該低級アルコキシ基が２個結合して低級アルキレンジオキシ基を形成しても良い）］
好適には、
［式中、Ｒ1 は、同一又は異なった１乃至３個のハロゲン原子により置換された炭素数１個又は２個のアルキル基を示し、Ｒ2 は、炭素数１個又は２個のアルキル基を示し、Ｒ3 及びＲ4 は同一又は異なって、水素原子又は炭素数１個乃至３個のアルキル基を示し、Ｒ5 は、ハロゲン原子、炭素数１個乃至３個のアルキル基又は炭素数１個乃至３個アルコキシ基（近接する当該アルコキシ基が２個結合して炭素数１又は２個のアルキレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは０、１又は２を示し、ｎは０又は２を示す。］
より好適には、
［式中、Ｒ1 は、１個乃至３個の塩素原子により置換された炭素数１個又は２個のアルキル基を示し、Ｒ2 は、メチル基を示し、Ｒ3 及びＲ4 は同一又は異なって、水素原子又はメチル基を示し、Ｒ5 は、弗素原子、塩素原子、臭素原子、メチル基、エチル基、イソプロピル基、メトキシ基、エトキシ基、イソプロピルオキシ基（近接する当該メトキシ基、エトキシ基が２個結合してメチレンジオキシ基、エチレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは０、１又は２を示し、ｎは０又は２を示す。］更に好適には、
［式中、Ｒ1 は、クロロメチル基を示し、Ｒ2 は、メチル基を示し、Ｒ3 及びＲ4 は、水素原子を示し、Ｒ5 は、弗素原子、塩素原子、メチル基、エチル基、メトキシ基、エトキシ基（近接する当該メトキシ基、エトキシ基が２個結合してメチレンジオキシ基、エチレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは１又は２を示し、ｎは２を示す。］
より更に好適には、
［式中、Ｒ1 は、クロロメチル基を示し、Ｒ2 は、メチル基を示し、Ｒ3 及びＲ4 は、水素原子を示し、Ｒ5 は、塩素原子、エチル基、メトキシ基（近接する当該メトキシ基が２個結合してメチレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは１又は２を示し、ｎは２を示す。］
で表わされる化合物である。
【００１３】
本願において、「ハロゲン原子」とは、弗素原子、塩素原子、臭素原子、沃素原子である。Ｒ1 において、好適には弗素原子、塩素原子であり、更に好適には塩素原子である。
【００１４】
Ｒ5 において、好適には弗素原子、塩素原子、臭素原子であり、更に好適には弗素原子、塩素原子であり、
Ｒ5 が低級アルキレンジオキシ基を形成する場合には、好適には弗素原子である。置換基群ａにおいて、好適には弗素原子であり、置換基群ａが低級アルコキシ基の場合には、好適には弗素原子である。
【００１５】
本願において、「低級アルキル基」とは、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、s-ブチル、t-ブチル、n-ペンチル、イソペンチル、2-メチルブチル、ネオペンチル、1-エチルプロピル、n-ヘキシル、4-メチルペンチル、3-メチルペンチル、2-メチルペンチル、1-メチルペンチル、3,3-ジメチルブチル、2,2-ジメチルブチル、1,1-ジメチルブチル、1,2-ジメチルブチル、1,3-ジメチルブチル、2,3-ジメチルブチル、2-エチルブチルのような炭素数１乃至６個の直鎖又は分枝鎖アルキル基である。Ｒ1 及びＲ2 において、好適にはメチル、エチルであり、更に好適にはメチルである。Ｒ3 及びＲ4 において、好適には炭素数１乃至３個の直鎖又は分枝鎖アルキル基であり、更に好適にはメチルである。Ｒ5 において、好適にはメチル、エチル、イソプロピルであり、最も好適にはメチル、エチルである。
【００１６】
本願において、「低級アルコキシ基」とは、例えばメトキシ、エトキシ、n-プロポキシ、イソプロポキシ、n-ブトキシ、イソブトキシ、s-ブトキシ、t-ブトキシ、n-ペンチルオキシ、イソペンチルオキシ、2-メチルブトキシ、ネオペンチルオキシ、1-エチルプロポキシ、n-ヘキシルオキシ、4-メチルペンチルオキシ、3-メチルペンチルオキシ、2-メチルペンチルオキシ、1-メチルペンチルオキシ、3,3-ジメチルブトキシ、2,2-ジメチルブトキシ、1,1-ジメチルブトキシ、1,2-ジメチルブトキシ、1,3-ジメチルブトキシ、2,3-ジメチルブトキシ、2-エチルブトキシのような炭素数１乃至６個の直鎖又は分枝鎖アルコキシ基である。Ｒ5 において、好適には炭素数１乃至４個の直鎖又は分枝鎖アルコキシ基であり、最も好適にはメトキシ、エトキシである。置換基群ａにおいて、好適にはメトキシ、エトキシであり、更に好適にはエトキシである。
【００１７】
本願において、「低級アルキレン基」とは、例えばメチレン、エチレン、プロピレン、テトラメチレン、ペンタメチレン、ヘキサメチレン、メチルメチレン、エチルメチレン、ジメチルメチレン、n-プロピルメチレン、イソプロピルメチレン、メチルエチルメチレン、n-ブチルメチレン、イソブチルメチレン、s-ブチルメチレン、メチルn-プロピルメチレン、メチルイソプロピルメチレン、ジエチルメチレン、n-ペンチルメチレン、イソペンチルメチレン、2-メチルブチルメチレン、ネオペンチルメチレン、1-エチルプロピルメチレン、メチルn-ブチルメチレン、メチルイソブチルメチレン、メチルs-ブチルメチレン、メチルt-ブチルメチレン、エチルn-プロピルメチレン、エチルイソプロピルメチレンのような炭素数１乃至６個の直鎖又は分枝鎖アルキレン基である。Ｒ4 とＲ5 が一緒になった場合、好適には炭素数２乃至３個の直鎖又は分枝鎖アルキレン基である。
【００１８】
本願において、「低級アルキレンオキシ基」とは、例えばメチレンオキシ、エチレンオキシ、プロピレンオキシ、テトラメチレンオキシ、ペンタメチレンオキシ、ヘキサメチレンオキシ、メチルメチレンオキシ、エチルメチレンオキシ、ジメチルメチレンオキシ、n-プロピルメチレンオキシ、イソプロピルメチレンオキシ、メチルエチルメチレンオキシ、n-ブチルメチレンオキシ、イソブチルメチレンオキシ、s-ブチルメチレンオキシ、メチルn-プロピルメチレンオキシ、メチルイソプロピルメチレンオキシ、ジエチルメチレンオキシ、n-ペンチルメチレンオキシ、イソペンチルメチレンオキシ、2-メチルブチルメチレンオキシ、ネオペンチルメチレンオキシ、1-エチルプロピルメチレンオキシ、メチルn-ブチルメチレンオキシ、メチルイソブチルメチレンオキシ、メチルs-ブチルメチレンオキシ、メチルt-ブチルメチレンオキシ、エチルn-プロピルメチレンオキシ、エチルイソプロピルメチレンオキシのような炭素数１乃至６個の直鎖又は分枝鎖アルキレンオキシ基である。Ｒ4 とＲ5 が一緒になった場合、好適には炭素数２乃至３個の直鎖又は分枝鎖アルキレンオキシ基であり、更に好適にはエチレンオキシである。
【００１９】
本願において、「低級アルキレンジオキシ基」とは、例えばメチレンジオキシ、エチレンジオキシ、プロピレンジオキシ、テトラメチレンジオキシ、ペンタメチレンジオキシ、ヘキサメチレンジオキシ、メチルメチレンジオキシ、エチルメチレンジオキシ、ジメチルメチレンジオキシ、n-プロピルメチレンジオキシ、イソプロピルメチレンジオキシ、メチルエチルメチレンジオキシ、n-ブチルメチレンジオキシ、イソブチルメチレンジオキシ、s-ブチルメチレンジオキシ、メチルn-プロピルメチレンジオキシ、メチルイソプロピルメチレンジオキシ、ジエチルメチレンジオキシ、n-ペンチルメチレンジオキシ、イソペンチルメチレンジオキシ、2-メチルブチルメチレンジオキシ、ネオペンチルメチレンジオキシ、1-エチルプロピルメチレンジオキシ、メチルn-ブチルメチレンジオキシ、メチルイソブチルメチレンジオキシ、メチルs-ブチルメチレンジオキシ、メチルt-ブチルメチレンジオキシ、エチルn-プロピルメチレンジオキシ、エチルイソプロピルメチレンジオキシのような炭素数１乃至６個の直鎖又は分枝鎖アルキレンジオキシ基である。Ｒ5 及び置換基群ａにおいて、好適には炭素数１乃至３個の直鎖又は分枝鎖アルキレンジオキシ基であり、更に好適にはメチレンジオキシ、エチレンジオキシである。
【００２０】
Ｒ1 において、「同一又は異なった１乃至３個のハロゲン原子により置換された低級アルキル基」とは、例えばクロルメチル、2-クロルエチル、ジクロルメチル、トリクロルメチル、ブロモメチル、2-ブロモエチル、ジブロモメチル、フルオロメチル、2-フルオロエチル、ジフルオロメチル、トリフルオロメチル、2,2,2-トリフルオロエチル、パーフルオロエチル、パーフルオロプロピルのようなハロゲン原子置換低級アルキル基であり、好適には、クロルメチル、ジフルオロメチルであり、更に好適には、クロルメチルである。
【００２１】
Ｒ5 において、「同一又は異なった１乃至４個のハロゲン原子により置換された低級アルキレンジオキシ基」とは、例えばフルオロメチレンジオキシ、ジフルオロメチレンジオキシのような基である。
【００２２】
置換基群ａにおいて、「同一又は異なった１乃至３個のハロゲン原子により置換された低級アルコキシ基」とは、例えばジフルオロメトキシ、トリフルオロメトキシのような基である。
【００２３】
一般式（Ｉ）において、Ｒ1 は、好適には、同一又は異なった１個乃至３個のハロゲン原子により置換された炭素数１個又は２個のアルキル基であり、更に好適には、１個乃至３個の塩素原子により置換された炭素数１個又は２個のアルキル基であり、最も好適には、クロロメチル基である。
【００２４】
一般式（Ｉ）において、Ｒ2 は、好適には、炭素数１個又は２個のアルキル基であり、最も好適には、メチル基である。
【００２５】
一般式（Ｉ）において、Ｒ3 は、好適には、水素原子又は炭素数１個乃至３個の直鎖又は分枝鎖アルキル基であり、更に好適には、水素原子又はメチル基であり、最も好適には、水素原子である。
【００２６】
一般式（Ｉ）において、Ｒ4 は、好適には、水素原子又は炭素数１個乃至３個の直鎖又は分枝鎖アルキル基であり、更に好適には、水素原子又はメチル基であり、最も好適には、水素原子である。
【００２７】
一般式（Ｉ）において、Ｒ5 は、好適には、ハロゲン原子、炭素数１乃至３個のアルキル基、炭素数１乃至３個のアルコキシ基であり、ｍが２以上のとき、隣接するＲ5 が一緒になって、炭素数１乃至２個のアルキレンジオキシ基であってもよく、更に好適には、弗素原子、塩素原子、臭素原子、メチル基、エチル基、イソプロピル基、メトキシ基、エトキシ基、イソプロピルオキシ基であり、ｍが２以上のとき、隣接するＲ5 が一緒になって、メチレンジオキシ基、エチレンジオキシ基であってもよく、より好適には、弗素原子、塩素原子、メチル基、エチル基、メトキシ基、エトキシ基であり、ｍが２以上のとき、隣接するＲ5 が一緒になって、メチレンジオキシ基、エチレンジオキシ基であってもよく、より更に好適には、塩素原子、エチル基、メトキシ基であり、ｍが２以上のとき、隣接するＲ5 が一緒になって、メチレンジオキシ基であってもよい。
【００２８】
一般式（Ｉ）において、ｍは、好適には、０、１又は２であり、最も好適には、１又は２である。
【００２９】
一般式（Ｉ）において、ｎは、好適には、０又は２であり、最も好適には、２である。
【００３０】
置換基群ａは、好適には、ハロゲン原子又は炭素数１個又は２個のアルコキシ基であり、更に好適には、弗素原子、メトキシ基、エトキシ基であり、最も好適には、弗素原子である。
【００３１】
本発明の代表化合物を下記表１に例示するが、本発明はこれらの化合物に限定されるものではない。
【００３２】
表中、「No. 」は、化合物番号を示し、Ｍｅはメチル基を、Ｅｔはエチル基を、ｎＰｒはｎ−プロピル基を、ｉＰｒはイソプロピル基を、ｎＢｕはｎ−ブチル基を、ｉＢｕはイソブチル基を、ｓＢｕはｓｅｃ−ブチル基を、ｔＢｕはｔｅｒｔ−ブチル基を、ｎＰｅｎはｎ−ペンチル基を、Ｐｈはフェニル基を、Ｂｎはベンジル基を、Ａｃはアセチル基をそれぞれ示す。
【００３３】
（Ｒ5 ）m の欄において、置換基の前の数字は、その置換基のフェニル基における置換位置を示し、置換基の後の下付きの数字はその置換基の置換数を示す。例えば、2-CF3 は２位に置換したトリフルオロメチル基、2,4-Cl2 は２，４−ジクロロ基、3,4-OCH2CH2O- は、３，４−エチレンジオキシ基である。
【００３４】
【化７】
Figure 0003810838
【００３５】
【表１】
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
上記の例示化合物中、好適なものとしては、2001,2002,2003,2005,2006,2007,2008,2009,2010,2011,2012,2020,2035,2040,2051,2053,2054,2055,2056,2057,2058,2059,2060,2061,2064,2068,2070,2071,2072,2077,2078,2080,2082,2083,2088,2089,2092,2095,2097,2098,2099,2101,2102,2104,2105,2107,2111,2113,2114,2120,2121,2125,2126,2127,2143,2145,2151,2152,2161,2166 の化合物を挙げることができる。
【００３６】
更に好適なものとしては、2002,2005,2008,2012,2054,2071,2077,2088,2099,2102,2125,2127,2166の化合物を挙げることができる。
【００３７】
最も好適なものとしては、2012,2102,2125の化合物を挙げることができる。
【００３８】
【発明の実施の形態】
本発明の一般式（Ｉ）を有するイソオキサゾリン誘導体は、以下に記載する方法によって製造することができる。
【００３９】
Ａ工程
【００４０】
【化８】
Figure 0003810838
【００４１】
上記工程中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 及びｍは前記と同意義を示し、Ｘ1 はハロゲン原子を示す。Ｘ1 は、好適には塩素原子である。
【００４２】
Ａ工程は一般式（Ｉ）においてｎが０である化合物（Ｉａ）を製造する方法である。
【００４３】
Ａ−１工程は、イソオキサゾリン環３位にハロゲン原子が置換した一般式（ＩＩ）を有する化合物を製造する工程で、一般式（ＩＩＩ）を有する化合物を、不活性溶剤中、塩基存在下に、一般式（ＩＶ）を有する化合物と反応させることにより、達成される。
【００４４】
なお、化合物（ＩＩＩ）は、例えば、テトラヘドロン、４９巻、第４１１７ページ、１９９３年（Tetrahedron 49, 4117 (1993) ）記載の化合物であり、市販のものを用いるか、又はウィッティッヒ(Wittig)反応等の公知の方法により製造される。また、化合物（ＩＶ）は、例えば、リービッヒ・アンナーレン・ケミー、第９８５ページ、１９８９年（Liebigs Annalen der Chemie 985 (1989) ）記載の化合物であり、市販のものを用いるか、又は当該文献記載の方法に準じて製造される。
【００４５】
Ａ−１工程に使用される塩基としては、化合物（ＩＶ）からニトリルオキシドを発生させる強さの塩基であれば特に限定はないが、好適には、炭酸水素ナトリウム、炭酸水素カリウムのようなアルカリ金属炭酸水素塩；水酸化ナトリウム、水酸化カリウムのようなアルカリ金属水酸化物；水酸化カルシウム、水酸化マグネシウムのようなアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウムのようなアルカリ金属炭酸塩；酢酸ナトリウム、酢酸カリウムのようなアルカリ金属酢酸塩；フッ化ナトリウム、フッ化カリウムのようなアルカリ金属フッ素化塩；トリエチルアミン、エチルジイソプロピルアミン、トリブチルアミンのような三級低級アルキルアミン；１、８−ジアザビシクロ［５．４．０］ウンデカン−７−エン（ＤＢＵ）、１、４−ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）のような三級脂環式アミン類を挙げることができる。
【００４６】
使用される溶剤としては、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はないが、好適には、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチルエーテル、ジオキサン、テトラヒドロフランのようなエーテル類；塩化メチレン、クロロホルム、四塩化炭素、ジクロロエタンのようなハロゲン化炭化水素類；ベンゼン、トルエンのような芳香族炭化水素類、酢酸エチル、酢酸ブチルのような酢酸エステル類；アセトニトリルのようなニトリル類；上記有機溶剤と水との混合溶剤；水を挙げることができる。
【００４７】
反応温度および反応時間は、原料化合物、溶剤並びに塩基の種類により異なるが、反応温度は、通常０℃乃至１５０℃、好適には１５℃乃至８０℃であり、反応時間は、通常１５分乃至２４時間、好適には３０分乃至８時間である。
【００４８】
Ａ−２工程は、一般式（Ｉａ）を有する化合物を製造する工程で、不活性溶剤中、塩基を用いて、一般式（Ｖ）を有するメルカプタン化合物を、Ａ−１工程により製造した一般式（ＩＩ）を有する化合物と反応させることにより、達成される。
【００４９】
なお、化合物（Ｖ）は、例えば、シンセティック・コミュニーケーションズ、１６巻、第１１７３ページ、１９８６年（Synthetic Communications 16, 1173 (1986)）記載の方法で合成できるハロゲン化化合物を原料として、例えば、ジャーナル・オブ・アメリカン・ケミカル・ソサエティー、６２巻、第２６７４ページ、１９４０年（Journal of American Chemical Society 62, 2674 (1940)）記載の方法を用いて得られる化合物である。
【００５０】
使用される塩基としては、優先的にチオール類のプロトンを脱離させる強さの塩基であれば特に限定はないが、好適には、水素化ナトリウム、水素化カリウム、水素化リチウムのようなアルカリ金属水素化物；ナトリウムメトキシド、ナトリウムエトキシド、カリウムｔ−ブトキシドのようなアルカリ金属アルコキシド；ナトリウムアミド、リチウムイソプロピルアミドのようなアルカリ金属アミド；トリエチルアミン、エチルジイソプロピルアミン、トリブチルアミンのような三級低級アルキルアミン；１、８−ジアザビシクロ［５．４．０］ウンデカン−７−エン（ＤＢＵ）；１、４−ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）のような三級脂環式アミン類を挙げることができる。
【００５１】
使用される溶剤としては、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はないが、好適には、ジオキサン、テトラヒドロフランのようなエーテル類；塩化メチレン、クロロホルム、四塩化炭素、ジクロロエタンのようなハロゲン化炭化水素類；ベンゼン、トルエンのような芳香族炭化水素類；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリジノンのようなアミド類；メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ｔ−ブタノールのようなアルコール類；アセトン、２−ブタノンのようなケトン類；アセトニトリルのようなニトリル類；ジメチルスルホキシドのようなスルホキシド類：及びこれらの溶剤の混合溶剤を挙げることができる。
【００５２】
反応温度および反応時間は、原料化合物、溶剤並びに塩基の種類により異なるが、反応温度は、通常０℃乃至１５０℃、好適には０℃乃至８０℃であり、反応時間は通常１５分乃至２４時間、好適には３０分乃至８時間である。
【００５３】
Ｃ工程
【００５４】
【化９】
Figure 0003810838
【００５５】
上記工程中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 及びｍは前記と同意義を示す。
【００５６】
Ｃ工程は、一般式（Ｉ）において、ｎが１である化合物（Ｉｃ２）、及び、一般式（Ｉ）において、ｎが２である化合物（Ｉｃ３）を製造する方法である。
【００５７】
Ｃ−１工程及びＣ−２工程は、一般式（Ｉｃ２）を有する化合物、及び、一般式（Ｉｃ３）を有する化合物を製造する工程で、不活性溶剤中、酸化剤を用いて、一般式（Ｉ）においてｎが０である化合物（Ｉｃ１）の酸化反応を行うことにより、達成される。
【００５８】
化合物（Ｉｃ１）は、上記Ａ工程、下記Ｅ工程及びＩ工程により製造される。使用される酸化剤としては、スルフィド類及びスルホキシド類を酸化できる強さの酸化剤であれば特に限定はないが、好適には、ｍ−クロロ過安息香酸、過ギ酸、過酢酸のような有機過酸化物；過酸化水素、過マンガン酸カリウム、過ヨウ素酸ナトリウムのような無機過酸化物を挙げることができる。
【００５９】
酸化剤はＣ−１、Ｃ−２工程共、基質に対し１．０乃至１．１当量使用されるが、スルホキシド類（Ｉｃ２）を単離することなくスルホン類（Ｉｃ３）を直接得るには、化合物（Ｉｃ１）に対し、酸化剤を２．０乃至３．０当量使用することにより達成される。
【００６０】
使用される溶剤としては、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はないが、好適には、塩化メチレン、クロロホルム、四塩化炭素、ジクロロエタンのようなハロゲン化炭化水素類；テトラヒドロフラン、ジオキサン、ジエチルエーテルのようなエーテル類；アセトン、２−ブタノンのようなケトン類；メタノール、エタノール、ｔ−ブタノールのようなアルコール類；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリジノンのようなアミド類；アセトニトリルのようなニトリル類；酢酸；水；水と上記有機溶剤との混合溶剤を挙げることができる。
【００６１】
反応温度および反応時間は、原料化合物、溶剤、酸化剤及び目的化合物の種類により異なるが、目的物が化合物（Ｉｃ２）の場合、反応温度は、通常−２０℃乃至５０℃、好適には−５℃乃至１０℃であり、反応時間は通常１０分乃至５時間、好適には、３０分乃至２時間であり、目的物が化合物（Ｉｃ３）の場合、反応温度は、通常０℃乃至１００℃、好適には１０℃乃至６０℃であり、反応時間は通常１５分乃至２日間、好適には３０分乃至１日間である。
【００６２】
Ｅ工程
【００６３】
【化１０】
Figure 0003810838
【００６４】
上記工程中、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、ｍ及びｎは前記と同意義を示し、ｐは１乃至６を示し、Ｘ4 はハロゲン原子を示す。
【００６５】
Ｅ工程は、一般式（Ｉ）において、Ｒ1 がハロゲン原子１個により置換された低級アルキル基である化合物（Ｉｅ）を製造する方法である。
【００６６】
Ｅ−１工程は、一般式（Ｉｅ）を有する化合物を製造する工程で、不活性溶剤中、ハロゲン化剤を用いて、化合物（ＶＩ）をハロゲン化反応させることにより、達成される。
【００６７】
化合物（ＶＩ）は、上記Ａ工程及びＣ工程に準じて製造される。
【００６８】
使用されるハロゲン化剤としては、アルキルアルコール類をハロゲン化させるものであれば特に限定はないが、好適には、臭素、Ｎ−ブロモスクシンイミド（ＮＢＳ）、五臭化リン、塩素、Ｎ−クロロスクシンイミド（ＮＣＳ）、五塩化リン、スルフリルクロリド、チオニルクロリド、四塩化炭素−トリフェニルホスフィンを挙げることができる。
【００６９】
反応は，塩基存在下促進される。使用される塩基としては、トリエチルアミン、エチルジイソプロピルアミン、トリブチルアミンのような三級低級アルキルアミン；１、８−ジアザビシクロ［５．４．０］ウンデカン−７−エン（ＤＢＵ）；１、４−ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）のような三級脂環式アミン類；Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリンのような三級アニリン類を挙げることができる。
【００７０】
使用される溶剤としては、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はないが、好適には、ベンゼン、トルエンのような芳香族炭化水素類；塩化メチレン、クロロホルム、四塩化炭素、ジクロロエタンのようなハロゲン化炭化水素類；テトラヒドロフラン、ｉ−プロピルエーテル、ジオキサン、エチルエーテルのようなエーテル類；ピリジンのような塩基類；及びこれらの溶剤の混合溶剤を挙げることができる。
【００７１】
反応温度および反応時間は、原料化合物、溶剤並びにハロゲン化剤の種類により異なるが、反応温度は、通常−２０℃乃至１５０℃、好適には０℃乃至８０℃であり、反応時間は、通常５分乃至２４時間、好適には１０分乃至４時間である。
【００７２】
Ｈ工程
【００７３】
【化１１】
Figure 0003810838
【００７４】
上記工程中、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、ｍ及びｎは前記と同意義を示す。
【００７５】
Ｈ工程は、イソオキサゾリン環５位にホルミル基を有する化合物（ＶＩＩＩ）を製造する方法である。
【００７６】
Ｈ−１工程は、一般式（ＶＩＩＩ）を有する化合物を製造する工程で、不活性溶剤中、酸化剤を用いて、イソオキサゾリン環５位にヒドロキシメチル基を有する化合物（ＶＩＩ）を酸化することにより、達成される。
【００７７】
化合物（ＶＩＩ）は、上記Ａ工程及びＣ工程に準じて製造される。
【００７８】
使用される酸化剤としては、比較的温和な酸化剤であれば特に限定はないが、好適には、Ｎ，Ｎ−ジメチルスルホキシドに対し、ジシクロヘキシルアミド、オキザリルクロリド、ホスゲン、クロロ蟻酸エステル、無水酢酸、五酸化リン、ピリジン−無水硫酸との錯体、メチルスルフィドとＮ−クロロスクシンイミドあるいは塩素などの塩素化剤とから生じるスルホニウム塩（ＤＭＳＯ酸化）；クロム酸のようなクロム酸塩；プラチナのような金属触媒存在下の酸素；過マンガン酸カリウムのような過マンガン酸塩；次亜塩素酸ナトリウム、ｔ−ブチルハイポクロライトのような次亜塩素酸化合物；オキソンのようなパーオキシサルフェート；四酸化ルテニウム及び反応系中でそれを発生させ得るルテニウム塩類；次亜塩素酸ナトリウムと２，２，６，６−テトラメチル−１−ピペリジニルオキシフリーラジカルの組み合わせからなるオキソアンモニウム塩を挙げることができる。
【００７９】
酸化剤の当量は用いる条件によって大きく変わるが、ＤＭＳＯ酸化であれば、基質に対し、オキザリルクロリド１乃至５当量、Ｎ，Ｎ−ジメチルスルホキシド１乃至１０当量とすることができる。
【００８０】
使用される溶剤としては、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はないが、好適には、ジオキサン、テトラヒドロフラン、エーテル、ジメトキシエタンのようなエーテル類；塩化メチレン、クロロホルム、ジクロロエタンのようなハロゲン化炭化水素類；ベンゼン、トルエン、キシレンのような芳香族炭化水素類；アセトン、２−ブタノンのようなケトン類；アセトニトリルのようなニトリル類；酢酸エチル、酢酸ブチルのようなエステル類；及びこれらの溶剤の混合溶剤を挙げることができる。
【００８１】
反応温度および反応時間は、原料化合物、溶剤及び酸化剤の種類により異なるが、反応温度は、通常−８０℃乃至２００℃、好適には−７０℃乃至１５０℃であり、反応時間は、通常１０分乃至３日間、好適には３０分乃至２４時間である。
【００８２】
Ｉ工程
【００８３】
【化１２】
Figure 0003810838
【００８４】
上記工程中、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、ｍ及びｎは前記と同意義を示し、Ｒ8 は水素原子または炭素数１乃至５個の低級アルキル基を示す。
【００８５】
Ｉ工程は、一般式（Ｉ）において、Ｒ1 が２個の弗素素原子で置換された低級アルキル基である化合物（Ｉｉ）を製造する方法である。
【００８６】
Ｉ−１工程は、一般式（Ｉｉ）を有する化合物を製造する工程で、不活性溶剤中、弗素化剤を用いて、一般式（ＩＸ）を有するアルデヒド類またはケトン類を弗素化反応させることにより、達成される。
【００８７】
化合物（ＩＸ）は、上記Ａ工程、Ｃ工程及びＨ工程に準じて製造される。
【００８８】
使用される弗素化剤としては、カルボニル酸素を弗素原子で置き換えるものであれば特に限定はないが、好適には、ジエチルアミノサルファートリフルオリド（ＤＡＳＴ）、ジメチルアミノサルファートリフルオリドのようなジアルキルアミノサルファートリフルオリド類；四弗化硫黄を挙げることができる。
【００８９】
使用される溶剤としては、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はないが、好適には、ジオキサン、テトラヒドロフランのようなエーテル類；トリクロロフルオロメタン、塩化メチレン、クロロホルム、四塩化炭素、ジクロロエタンのようなハロゲン化炭化水素類；ベンゼン、トルエンのような芳香族炭化水素類；イソオクタンのような炭化水素類；及びこれらの溶剤の混合溶剤を挙げることができる。
【００９０】
反応温度および反応時間は、原料化合物、溶剤及び弗素化剤の種類により異なるが、反応温度は、通常−７８℃乃至２００℃、好適には−６０℃乃至８０℃であり、反応時間は、通常５分乃至７日間、好適には１０分乃至１０時間である。
【００９１】
上記各反応工程終了後、各工程の目的化合物は常法に従って反応混合物から採取することができる。例えば、反応混合物を適宜中和し、又、不純物が存在する場合には濾過により除去した後、水と混和しない有機溶媒を加え、水洗後、溶剤を留去することによって得られる。得られた目的化合物は必要ならば、常法、例えば再結晶、再沈殿又はクロマトグラフィー等によって更に精製できる。
【００９２】
本発明の化合物は、担体及び必要に応じて他の補助剤と混合して、除草剤として通常用いられる製剤形態、例えば粉剤、粗粉剤、粒剤、顆粒剤、水和剤、水溶剤、乳剤、液剤等に調製して使用される。ここでいう担体とは、有効成分化合物の植物への到達性を助け又は有効成分の貯蔵、輸送若しくは取り扱いを容易にするために除草剤中に混合される、合成又は天然の無機又は有機物質を意味する。
【００９３】
適当な固体担体としては、例えば、カオリナイト群、モンモリロナイト群、アタパルジャイト群等で代表されるクレー類、タルク、雲母、葉ロウ石、軽石、バーミキュライト、石膏、ドロマイト、けいそう土、マグネシウム石灰、燐石灰、ゼオライト、無水ケイ酸、合成ケイ酸カルシウム、カオリン、ベントナイト、炭酸カルシウム等の無機物質、大豆粉、タバコ粉、クルミ粉、小麦粉、木粉、澱粉、結晶セルロース等の植物性有機物質、クマロン樹脂、石油樹脂、アルキド樹脂、ポリ塩化ビニル、ポリアルキレングリコール、ケトン樹脂、エステルガム、コーパルガム、ダンマルガム等の合成又は天然の高分子化合物、カルナバロウ、パラフィンロウ、蜜ロウ等のワックス類或は尿素等を挙げることができる。
【００９４】
適当な液体担体としては、例えば、ケロシン、鉱油、スピンドル油、ホワイトオイル等のパラフィン系若しくはナフテン系炭化水素、ベンゼン、トルエン、キシレン、エチルベンゼン、クメン、メチルナフタレン等の芳香族炭化水素、四塩化炭素、クロロホルム、トリクロルエチレン、モノクロルベンゼン、クロルトルエン等の塩素化炭化水素、ジオキサン、テトラヒドロフラン等のエーテル類、アセトン、メチルエチルケトン、ジイソブチルケトン、シクロヘキサノン、アセトフェノン、イソホロン等のケトン類、酢酸エチル、酢酸アミル、エチレングリコールアセテート、ジエチレングリコールアセテート、マレイン酸ジブチル、コハク酸ジエチル等のエステル類、メタノール、n-ヘキサノール、エチレングリコール、ジエチレングリコール、シクロヘキサノール、ベンジルアルコール等のアルコール類、エチレングリコールエチルエーテル、エチレングリコールフェニルエーテル、ジエチレングリコールエチルエーテル、ジエチレングリコールブチルエーテル等のエーテルアルコール類、ジメチルホルムアミド、ジメチルスルホキシド等の極性溶媒或は水等を挙げることができる。
【００９５】
乳化、分散、湿潤、拡展、結合、崩壊性調節、有効成分安定化、流動性改良、防錆、植物への吸収促進等の目的で使用される界面活性剤は、イオン性でも非イオン性でもよい。
【００９６】
適当な非イオン性界面活性剤としては、例えば、脂肪酸の蔗糖エステル、ラウリルアルコール、ステアリルアルコール、オレイルアルコール等の高級脂肪族アルコールの酸化エチレン重合付加物、イソオクチルフェノール、ノニルフェノール等のアルキルフェノールの酸化エチレン重合付加物、ブチルナフトール、オクチルナフトール等のアルキルナフトールの酸化エチレン重合付加物、パルミチン酸、ステアリン酸、オレイン酸等の高級脂肪酸の酸化エチレン重合付加物、ステアリル燐酸ジラウリル燐酸等のモノ若しくはジアルキル燐酸の酸化エチレン重合付加物、ドデシルアミン、ステアリン酸アミド等の高級脂肪族アミンの酸化エチレン重合付加物、ソルビタン等の多価アルコールの高級脂肪酸エステル及びその酸化エチレン重合付加物並びに酸化エチレンと酸化プロピレンの共重合体等を挙げることができる。
【００９７】
適当な陰イオン性界面活性剤としては、例えば、ラウリル硫酸ナトリウム、オレイルアルコール硫酸エステルアミン塩等のアルキル硫酸エステル塩、スルホコハク酸ジオクチルエステルナトリウム、オレイン酸ナトリウム、ステアリン酸ナトリウム等の脂肪酸塩類、イソプロピルナフタレンスルホン酸ナトリウム、メチレンビスナフタレンスルホン酸ナトリウム、リグニンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等のアルキルアリールスルホン酸塩等を挙げることができる。
【００９８】
適当な陽イオン性界面活性剤としては、例えば、高級脂肪族アミン、第４級アンモニウム塩類、アルキルピリジニウム塩類等を挙げることができる。
【００９９】
さらに、本発明の除草剤には、製剤の性状を改善し生物効果を高める目的で、他の成分として、例えば、ゼラチン、アラビアゴム、カゼイン、アルブミン、ニカワ、アルギン酸ソーダ、ポリビニルアルコール、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース等の高分子化合物、ポリリン酸ナトリウム、ベントナイト等のチキソトロピー剤及びその他の補助剤を含有することもある。
【０１００】
上記の担体及び種々の補助剤は製剤の剤型適用場面を考慮して、目的に応じてそれぞれ単独に或は組み合わされて適宜使用される。
【０１０１】
粉剤は有効成分化合物を通常２乃至１０重量部含有し、残部は固体担体である。
【０１０２】
水和剤は有効成分を通常１０乃至８０重量部含有し、残部は固体担体、分散湿潤剤であって、必要に応じて保護コロイド剤、チキソトロピー剤、消泡剤等が加えられる。
【０１０３】
粒剤は有効成分化合物を通常０．１乃至１０重量部含有し、残部は大部分が固体担体である。有効成分化合物は固体担体と均一に混合されているか或は固体担体の表面に均一に固着若しくは吸着されており、粒の径は約０．２乃至１．５ｍｍ程度である。
【０１０４】
乳剤は有効成分を通常１乃至５０重量部含有しており、これに約５乃至２０重量部の乳剤が含まれ、残部は液体担体であり、必要に応じて防錆剤が加えられる。
【０１０５】
このようにして種々の剤型に調製された本発明の化合物を、例えば、水田において雑草の発芽前又は発芽後に土壌処理するときは、１０ａあたり有効成分として１乃至１０００ｇ好ましくは１０乃至３００ｇを処理することにより、有効に雑草を駆除することができる。
【０１０６】
更に、畑地において雑草の発芽前に土壌処理、又は発芽後に茎葉処理するときは、１０ａあたり有効成分として１乃至１０００ｇ好ましくは１０乃至３００ｇを処理することにより、有効に雑草を駆除することができる。
【０１０７】
本発明の除草剤に対して、殺草スペクトラムを広げるために他の除草剤が配合されることは好ましく、場合によっては相乗効果を期待することもできる。
【０１０８】
本発明の除草剤は、もちろん他の植物成長調節剤、殺菌剤、殺虫剤、殺ダニ剤、殺線虫剤又は肥料等と混合して使用することができる。
【０１０９】
以下に本発明除草剤の実施例及び製剤例を示し具体的に説明するが、本発明はこれらに限られるものではない。
【０１１０】
【実施例】
【０１１１】
【実施例１】
３−ベンジルチオ−５−クロロメチル−５−メチル−２−イソオキサゾリン（化合物番号１）（Ａ工程）
（１） ３−クロロ−５−クロロメチル−５−メチル−２−イソオキサゾリン（Ａ−１工程）
２−ヒドロキシイミノ酢酸４３．２ｇとＮ−クロロスクシンイミド１２９．６ｇをジメトキシエタン４００ｍｌに溶解し、油浴中８０℃に加熱、撹拌した。３分後、油浴を取り除き、室温まで放冷した。この溶液に、メタリルクロリド４８ｍｌ、炭酸水素カリウム１９４．４ｇ、水８ｍｌを順に加え、室温で８時間撹拌した。反応溶液にヘキサンを加えた後、セライトを用いて吸引濾過した。濾液の有機溶媒を留去した後、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３０：１）により精製し、標記化合物５１．６ｇ（６４％）を油状物として得た。
【０１１２】
1H-NMR(CDCl3) δ: 1.59(3H,s), 3.14(2H,ABq,J=17.5, Δν=76.4Hz), 3.57(2H,ABq,J=11.4Δν=16.0Hz)ppm
（２） ３−ベンジルチオ−５−クロロメチル−５−メチル−２−イソオキサゾリン（Ａ−２工程）
（１）で得られた３−クロロ−５−クロロメチル−５−メチル−２−イソオキサゾリン１７６．１ｍｇとベンジルメルカプタン０．３５ｍｌをテトラヒドロフラン：Ｎ，Ｎ−ジメチルホルムアミド＝８：１の混合溶媒９ｍｌに溶解し、室温で６０％水素化ナトリウム１２５ｍｇを少しずつ加えた。室温で３時間撹拌した後、反応溶液に水を加え、酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。濾過し、溶媒を留去後、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２０：１）により精製し、油状の目的物１８２．８ｍｇ（６８％）を得た。
【０１１３】
1H-NMR(CDCl3) δ: 1.57(3H,s), 3.00(2H,ABq,J=16.8, Δν=75.3Hz), 3.52(2H,d,J=2.2Hz), 4.27(2H,s), 7.29-7.40(5H,m)ppm
実施例１の方法に準じて製造した化合物を、以下に示す。
【０１１４】
なお、以下、化合物名の後の括弧内の前の数字は前記表１における化合物番号を示し、その後ろに「mp」として融点（℃）を示すか、「oil 」として油状物であることを示か、又は「Amorphous 」としてアモルファスであることを示す。
【０１１５】
3-(2-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(2,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.40(3H,s), 3.01(2H,ABq,J=16.6, Δν=74.7Hz), 3.54(2H,d,J=3.1Hz), 4.29(2H,s), 7.16-7.20(3H,m), 7.30-7.34(1H,m)ppm
3-(3-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(3,mp40-43)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.35(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.3Hz), 3.53(2H,ABq,J=11.2, Δν=7.2Hz), 4.23(2H,s), 7.08-7.31(4H,m)ppm
3-(4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(4,mp53-54)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.34(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.1Hz), 3.53(2H,ABq,J=11.2, Δν=7.3Hz), 4.24(2H,s), 7.11-7.29(4H,m)ppm
3-(2,3-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(5,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.29(6H,br), 3.02(2H,ABq,J=16.6,Δν=74.5Hz), 3.55(2H,ABq,J=11.2, Δν=9.3Hz), 4.32(2H,s), 7.06-7.21(3H,m)ppm
3-(2,4-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(6,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.31(3H,s), 2.36(3H,s), 3.01(2H,ABq,J=16.9, Δν=74.5Hz), 3.54(2H,ABq,J=11.1, Δν=9.0Hz), 4.26(2H,s), 6.95-7.23(3H,m)ppm
3-(2,5-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(7,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.30(3H,s), 2.35(3H,s), 3.02(2H,ABq,J=16.7, Δν=74.5Hz), 3.55(2H,ABq,J=11.3, Δν=9.1Hz), 4.26(2H,s), 7.02-7.14(3H,m)ppm
3-(2,6-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(8,mp72-73)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 2.42(6H,s), 3.05(2H,ABq,J=16.8, Δν=73.4Hz), 3.58(2H,ABq,J=11.2, Δν=11.2Hz), 4.36(2H,s), 7.01-7.15(3H,m)ppm
3-(3,4-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(9,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.23(6H,s), 3.00(2H,ABq,J=16.7, Δν=74.9Hz), 3.52(2H,ABq,J=11.2, Δν=7.4Hz), 4.21(2H,s), 7.09(2H,s), 7.13(1H,s)ppm
3-(3,5-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(10,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.30(6H,s), 3.01(2H,ABq,J=16.7, Δν=75.3Hz), 3.53(2H,d,J=2.2Hz), 4.20(2H,s), 6.92(1H,br), 6.98(2H,br)ppm
3-(2,4,6-トリメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(11,mp90-92)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 2.26(3H,s), 2.38(6H,s), 3.04(2H,ABq,J=16.7, Δν=73.1Hz), 3.57(2H,ABq,J=11.1, Δν=10.9Hz), 4.33(2H,s), 6.87(2H,s)ppm
3-(2-エチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(12,oil)
1H-NMR(200MHz,CDCl3)δ: 1.26(3H,t,J=7.5Hz), 1.56(3H,s), 2.74(2H,q,J=7.5Hz), 3.02(2H,ABq,J=16.8, Δν=74.5Hz), 3.55(2H,ABq,J=11.3, Δν=9.3Hz), 4.32(2H,s), 7.15-7.36(4H,m)ppm
3-(4-エチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(14,oil)
1H-NMR(200MHz,CDCl3)δ: 1.22(3H,t,J=7.5Hz), 1.54(3H,s), 2.64(2H,q,J=7.5Hz), 3.00(2H,ABq,J=16.7, Δν=74.9Hz), 3.52(2H,d,J=2.0Hz), 4.24(2H,s), 7.16(2H,d,J=8.0Hz), 7.28(2H,d,J=8.0Hz)ppm
3-(2,6-ジエチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(15,mp40-42)
1H-NMR(200MHz,CDCl3)δ: 1.27(6H,t,J=7.5Hz), 1.59(3H,s), 2.76(4H,q,J=7.5Hz), 3.04(2H,ABq,J=16.7, Δν=72.7Hz), 3.58(2H,ABq,J=11.2, Δν=11.6Hz), 4.39(2H,s), 7.06-7.26(3H,m)ppm
3-(4-n-プロピルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(19,mp34-36)
1H-NMR(200MHz,CDCl3)δ: 0.93(3H,t,J=7.3Hz), 1.55(3H,s), 1.57-1.72(2H,m), 2.57(2H,t,J=7.2Hz), 3.00(2H,ABq,J=16.6,Δν=74.9Hz), 3.52(2H,ABq,J=11.1, ν=7.0Hz), 4.24(2H,s), 7.14(2H,d,J=8.0Hz), 7.28(2H,d,J=8.0Hz)ppm
3-(4-tert-ブチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(31,oil)
1H-NMR(200MHz,CDCl3)δ: 1.30(9H,s), 1.54(3H,s), 3.00(2H,ABq,J=16.6, Δν=74.6Hz), 3.52(2H,d,J=1.7Hz), 4.24(2H,s), 7.31-7.40(4H,m)ppm
3-(2-(5,6,7,8-テトラヒドロナフチル)チオ)-5-クロロメチル-5-メチル-2-イソオキサゾリン(33,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 1.75-1.81(4H,m), 2.71-2.77(4H,m), 3.00(2H,ABq, J=16.8,Δν=74.9Hz), 3.53(2H,ABq,J=11.2, Δν=7.7Hz), 4.20(2H,s), 6.99-7.11(3H,m)ppm
3-(2-クロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(34,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.2Hz), 3.52(2H,ABq,J=11.3, Δν=7.2Hz), 4.22(2H,s), 7.26(3H,m), 7.37(1H,m)ppm
3-(3-クロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(35,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.9, Δν=76.9Hz), 3.53(2H,ABq,J=14.6, Δν=8.0Hz), 4.22(2H,s), 7.27(3H,s), 7.37(1H,s)ppm
3-(4-クロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(36,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=17.0, Δν=77.0Hz), 3.51(2H,s), 4.21(2H,s), 7.30(4H,s)ppm
3-(2,3-ジクロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(37,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.99(2H,ABq,J=16.9, Δν=76.6Hz), 3.52(2H,ABq,J=11.6, Δν=6.3Hz), 4.38(2H,s), 7.12-7.16(1H,m), 7.38-7.46(2H,m)ppm
3-(2,4-ジクロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(38,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=74.2Hz), 3.52(2H,d,J=1.9Hz), 4.32(2H,s), 7.21(1H,dd,J=8.4,1.9Hz), 7.41(1H,d,J=1.9), 7.47(1H,d,J=8.4Hz)ppm
3-(2,5-ジクロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(39,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.00(2H,ABq,J=16.5, Δν=73.9Hz), 3.53(2H,d,J=2.3Hz), 4.32(2H,s), 7.21(1H,dd,J=8.5,2.3Hz), 7.32(1H,d,J=8.5Hz), 7.52(1H,d,J=2.3Hz)ppm
3-(2,6-ジクロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(40,mp80-81)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 3.06(2H,ABq,J=16.6, Δν=73.9Hz), 3.57(2H,ABq,J=11.2, Δν=11.4Hz), 4.63(2H,s), 7.14-7.35(3H,m)ppm
3-(3,4-ジクロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(41,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.99(2H,ABq,J=16.6, Δν=75.4Hz), 3.52(2H,d,J=2.0Hz), 4.19(2H,s), 7.23(1H,dd,J=8.0,1.7Hz), 7.39(1H,d,J=8.0Hz), 7.48(1H,d,J=1.7Hz)ppm
3-(3,5-ジクロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(42,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=17.2, Δν=74.9Hz), 3.53(2H,ABq,J=11.2, Δν=7.3Hz), 4.18(2H,s), 7.25(1H,s), 7.27(2H,s)ppm
3-(2,4,6-トリクロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(44,Amorphous)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 3.05(2H,ABq,J=16.7, Δν=74.5Hz), 3.57(2H,ABq,J=11.3, Δν=10.8Hz), 4.59(2H,s), 7.36(2H,s)ppm
3-(3-クロロ-4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(45,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.36(3H,s), 2.99(2H,ABq,J=16.7, Δν=75.2Hz), 3.52(2H,ABq,J=11.2, Δν=7.2Hz), 4.19(2H,s), 7.11-7.36(3H,m)ppm
3-(2,4-ジクロロ-3-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(48,oil)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 2.49(3H,s), 2.99(2H,ABq,J=16.7, Δν=74.0Hz), 3.52(2H,d,J=1.9Hz), 4.34(2H,s), 7.21-7.34(2H,m)ppm
3-(2,5-ジクロロ-4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(49,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.33(3H,s), 3.00(2H,ABq,J=16.8, Δν=73.8Hz), 3.53(2H,ABq,J=11.2, Δν=7.8Hz), 4.30(2H,s), 7.27(1H,s), 7.49(1H,s)ppm
3-(2-ブロモベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(50,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.9, Δν=75.2Hz), 3.53(2H,d,J=2.1Hz), 4.38(2H,s), 7.14-7.18(1H,m), 7.24-7.31(1H,m), 7.50-7.59(2H,m)ppm
3-(3-ブロモベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(51,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.6, Δν=75.1Hz), 3.53(2H,d,J=2.1Hz), 4.21(2H,s), 7.15-7.34(2H,m), 7.38-7.53(2H,m)ppm
3-(4-ブロモベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(52,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.98(2H,ABq,J=16.7, Δν=75.6Hz), 3.52(2H,d,J=1.8Hz), 4.20(2H,s), 7.23-7.28(2H,m), 7.42-7.47(2H,m)ppm
3-(2-フルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(53,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.01(2H,ABq,J=16.8, Δν=74.5Hz), 3.53(2H,d,J=2.1Hz), 4.29(2H,s), 7.01-7.14(2H,m), 7.23-7.31(1H,m), 7.44(1H,t,J=7.7Hz)ppm
3-(3-フルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(54,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.4Hz), 3.52(2H,d,J=2.1Hz), 4.24(2H,s), 6.97-7.32(4H,m)ppm
3-(4-フルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(55,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=75.1Hz), 3.52(2H,ABq,J=11.1, Δν=6.8Hz), 4.23(2H,s), 6.96-7.05(2H,m), 7.31-7.38(2H,m)ppm
3-(2,3-ジフルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(56,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=74.7Hz), 3.53(2H,ABq,J=11.2, Δν=7.4Hz), 4.31(2H,d,J=1.4Hz), 7.02-7.22(3H,m)ppm
3-(2,4-ジフルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(57,oil)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 2.99(2H,ABq,J=16.7, Δν=74.1Hz), 3.51(2H,ABq,J=11.2, Δν=7.2Hz), 4.24(2H,s), 6.75-6.88(2H,m), 7.37-7.49(1H,m)ppm
3-(2,5-ジフルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(58,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.18(2H,ABq,J=16.7, Δν=74.6Hz), 3.53(2H,ABq,J=11.2, Δν=7.5Hz), 4.25(2H,s), 6.92-7.05(2H,m), 7.14-7.23(1H,m)ppm
3-(2,6-ジフルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(59,mp58-61)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.03(2H,ABq,J=16.7, Δν=75.2Hz), 3.55(2H,ABq,J=11.2, Δν=9.8Hz), 4.35(2H,s), 6.87-6.96(2H,m), 7.19-7.31(1H,m)ppm
3-(3,4-ジフルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(60,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.6, Δν=75.3Hz), 3.52(2H,ABq,J=11.3, Δν=6.9Hz), 4.19(2H,s), 7.06-7.23(3H,m)ppm
3-(3,5-ジフルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(61,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.19(2H,ABq,J=16.7, Δν=75.4Hz), 3.52(2H,ABq,J=11.3, Δν=7.3Hz), 4.21(2H,s), 6.66-6.95(3H,m)ppm
3-(2-フルオロ-3-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(64,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.28(3H,d,J=2.1Hz), 3.00(2H,ABq,J=16.8, Δν=74.5Hz), 3.52(2H,ABq,J=11.2, Δν=7.5Hz), 4.28(2H,s), 6.98(1H,t,J=7.57Hz), 7.08-7.12(1H,m), 7.21-7.28(1H,m)ppm
3-(3-フルオロ-4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(65,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.25(3H,d,J=1.9Hz), 3.00(2H,ABq,J=16.7, Δν=75.2Hz), 3.52(2H,ABq,J=11.2, Δν=7.2Hz), 4.21(2H,s), 7.01-7.17(3H,m)ppm
3-(2,3,5,6-テトラフルオロ-4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(66,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.24(3H,dt,J=12.8,2.0Hz), 2.85(1H,dd,J=16.8,5.2Hz), 3.18(1H,dd,J=16.8,5.9Hz), 3.53(2H,ABq,J=3.5,Δν=3.0Hz),
4.35(2H,d,J=22.4Hz)ppm
3-(2-フルオロ-3-クロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(67,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=74.1Hz), 3.52(2H,ABq,J=11.3, Δν=7.1Hz), 4.29(2H,s), 7.04(1H,t,J=7.9Hz), 7.28-7.40(2H,m)ppm
3-(2-クロロ-4-フルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(68,oil)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 2.99(2H,ABq,J=16.8, Δν=73.8Hz), 3.52(2H,ABq,J=11.2, Δν=7.1Hz), 4.33(2H,s), 6.95(1H,td,J=8.4,2.6Hz), 7.14(1H,dd,J=8.4,2.6Hz), 7.50(1H,dd,J=8.4,6.1Hz)ppm
3-(2-クロロ-6-フルオロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(70,oil)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.04(2H,ABq,J=16.7, Δν=76.4Hz), 3.55(2H,ABq,J=11.2, Δν=10.5Hz), 4.47(2H,d,J=1.6Hz), 6.97-7.26(3H,m)ppm
3-(2-トリフルオロメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(71,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.00(2H,ABq,J=16.7, Δν=73.5Hz), 3.54(2H,ABq,J=11.2, Δν=8.8Hz), 4.46(2H,s), 7.35-7.43(1H,m), 7.49-7.56(1H,m), 7.64-7.71(2H,m)ppm
3-(3-トリフルオロメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(72,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.4Hz), 3.51(2H,d,J=2.0Hz), 4.30(2H,s), 7.44-7.64(4H,m)ppm
3-(4-トリフルオロメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(73,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.8, Δν=75.7Hz), 3.52(2H,d,J=1.9Hz), 4.29(2H,s), 7.53(2H,d,J=8.4Hz), 7.57(2H,d,J=8.4Hz)ppm 3-(2,4-ビストリフルオロメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(74,Amorphous)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.01(2H,ABq,J=16.7, Δν=74.4Hz), 3.55(2H,ABq,J=11.8, Δν=8.9Hz), 4.49(2H,s), 7.78(1H,d,J=7.9Hz), 7.90(2H,d,J=7.9Hz)ppm
3-(3.5-ビストリフルオロメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(75,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.01(2H,ABq,J=17.0, Δν=75.6Hz), 3.52(2H,ABq,J=11.2, Δν=6.8Hz), 4.34(2H,s), 7.79(1H,br), 7.86(2H,br)ppm
3-(2-フルオロ-4-トリフルオロメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(76,mp46-48)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.16(2H,ABq,J=16.8, Δν=74.8Hz), 3.52(2H,ABq,J=11.3, Δν=6.9Hz), 4.31(2H,s), 7.33(1H,d,J=9.3Hz), 7.38(1H,d,J=9.3Hz), 7.62(1H,t,J=7.3Hz)ppm
3-(2-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(77,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.00(2H,ABq,J=16.8, Δν=74.3Hz), 3.51(2H,ABq,J=18.3, Δν=8.6Hz), 3.87(3H,s), 4.29(2H,s), 6.86-6.95(2H,m), 7.23-7.39(2H,m)ppm
3-(3-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(78,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.00(2H,ABq,J=16.8, Δν=75.3Hz), 3.53(2H,ABq,J=11.2, Δν=7.7Hz), 3.81(3H,s), 4.24(2H,s), 6.80-6.97(3H,m), 7.21-7.28(1H,m)ppm
3-(4-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(79,mp32-33)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.7, Δν=74.9Hz), 3.52(2H,d,J=2.1Hz), 3.80(3H,s), 4.22(2H,s), 6.85(2H,d,J=8.6Hz), 7.30(2H,d,J=8.6Hz)ppm
3-(2,3-ジメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(80,oil)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 3.06(2H,ABq,J=17.0, Δν=77.0Hz), 3.53(2H,d,J=2.3Hz), 3.86(3H,s), 3.89(3H,s), 4.31(2H,s), 6.83-6.91(1H,m), 6.97-7.05(2H,m)ppm
3-(2,4-ジメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(81,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.99(2H,ABq,J=16.6, Δν=73.8Hz), 3.52(2H,ABq,J=11.3, Δν=7.7Hz), 3.80(3H,s), 3.84(3H,s), 4.24(2H,s), 6.41-6.45(2H,m), 7.25-7.30(1H,m)ppm
3-(2,5-ジメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(82,mp50-53)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.6, Δν=73.9Hz), 3.52(2H,ABq,J=11.3, Δν=7.9Hz), 3.77(3H,s), 3.83(3H,s), 4.26(2H,s), 6.78-6.80(2H,m), 6.97(1H,d,J=1.6Hz)ppm
3-(2,6-ジメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(83,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.06(2H,ABq,J=16.6, Δν=75.5Hz), 3.55(2H,ABq,J=11.2, Δν=10.9Hz), 3.85(6H,s), 4.40(2H,s), 6.55(2H,d,J=8.4Hz), 7.22(1H,t,J=8.4Hz)ppm
3-(3,4-ジメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(84,mp95-97)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=77.5Hz), 3.53(2H,d,J=2.3Hz), 3.87(3H,s), 3.89(3H,s), 4.20(2H,s), 6.79-6.94(3H,m)ppm
3-(3,5-ジメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(85,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3h,s), 3.01(2H,ABq,J=16.7, Δν=75.4Hz), 3.53(2H,d,J=2.7Hz), 3.79(6H,s), 4.21(2H,s), 6.38(1H,t,J=2.3Hz), 6.53(2H,d,J=2.2Hz)ppm
3-(3,4,5-トリメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(87,Amorphous)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.01(2H,ABq,J=16.7, Δν=75.9Hz), 3.53(2H,d,J=2.5Hz), 3.84(3H,s), 3.86(6H,s), 4.22(2H,s), 6.61(2H,s)ppm
3-(2-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(88,oil)
1H-NMR(200MHz,CDCl3)δ: 1.44(3H,t,J=7.0Hz), 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=73.8Hz), 3.52(2H,ABq,J=11.2, Δν=7.2Hz), 4.09(2H,q,J=7.0Hz), 4.31(2H,s), 6.84-6.93(2H,m), 7.20-7.29(1H,m), 7.35-7.40(1H,m)ppm
3-(3-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(89,oil)
1H-NMR(200MHz,CDCl3)δ: 1.41(3H,t,J=7.0Hz), 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.1Hz), 3.53(2H,ABq,J=11.2, Δν=7.5Hz), 4.03(2H,q,J=7.0Hz), 4.23(2H,s), 6.78-6.95(3H,m), 7.21(1H,d,J=7.3Hz)ppm
3-(4-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(90,mp64)
1H-NMR(200MHz,CDCl3)δ: 1.41(3H,t,J=7.0Hz), 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=75.1Hz), 3.52(2H,d,J=2.2Hz), 4.02(2H,q,J=7.0Hz), 4.22(2H,s), 6.84(2H,d,J=8.6Hz), 7.28(2H,d,J=7.6Hz)ppm
3-(2-イソプロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(92,oil)
1H-NMR(200MHz,CDCl3)δ: 1.36(6H,d,J=6.1Hz), 1.54(3H,s), 2.99(2H,ABq,J=16.9, Δν=73.4Hz), 3.52(2H,ABq,J=11.2, Δν=7.7Hz), 4.28(2H,s), 4.61(1H,quintet,J=6.3Hz), 6.83-6.91(2H,m), 7.18-7.26(1H,m), 7.27-7.40(1H,m)ppm
3-(3-イソプロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(93,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.2Hz), 3.53(2H,ABq,J=11.2, Δν=7.6Hz), 4.23(2H,s), 4.55(1H,quintet,J=6.1Hz), 6.77-7.18(3H,m), 7.24(1H,d,J=8.1Hz)ppm
3-(4-イソプロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(94,mp34-36)
1H-NMR(200MHz,CDCl3)δ: 1.33(3H,d,J=6.2Hz), 1.54(3H,s), 3.00(2H,ABq,J=16.6, Δν=74.8Hz), 3.52(2H,d,J=2.2Hz), 4.22(2H,s), 4.53(1H,septet,J=6.2Hz), 6.83(2H,d,J=8.7Hz), 7.27(2H,d,J=8.7Hz)ppm
3-(2-メトキシ-3-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(95,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2,22-2.27(1H,m), 2.31(3H,s), 3.01(2H,ABq, J=16.8, Δν=74.5Hz), 3.54(2H,ABq,J=11.2, Δν=8.8Hz), 3.80(3H,s), 4.32(2H,s), 6.95-7.02(1H,m), 7.13(1H,d,J=6.0Hz)ppm
3-(3-メチル-4-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(97,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.31(3H,s), 3.02(2H,ABq,J=16.8, Δν=74.4Hz), 3.54(2H,ABq,J=11.1, Δν=9.0Hz), 3.81(3H,s), 4.32(2H,s), 6.95-7.27(3H,m)ppm
3-(3-メトキシ-4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(98,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.19(3H,s), 3.01(2H,ABq,J=16.8, Δν=75.6Hz), 3.53(2H,ABq,J=11.2, Δν=7.7Hz), 3.83(3H,s), 4.24(2H,s), 6.86(2H,d,J=5.6Hz), 7.08(1H,d,J=7.7Hz)ppm
3-(2-エトキシ-3-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(99,oil)
1H-NMR(200MHz,CDCl3)δ: 1.44(3H,t,J=7.2Hz), 1.55(3H,s), 2.30(3H,s), 3.01(2H,ABq,J=16.9, Δν=73.9Hz), 3.54(2H,d,J=3.0Hz), 3.93(2H,q,J=7.2Hz), 4.32(2H,s), 6.98-7.02(1H,m), 7.12(1H,d,J=6.1Hz), 7.23-7.26(1H,m)ppm
3-(2-イソプロピルオキシ-3-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(100,oil)
1H-NMR(200MHz,CDCl3)δ: 1.32(6H,d,J=6.2Hz), 1.58(3H,s), 2.29(3H,s), 3.01(2H,ABq,J=16.7, Δν=73.6Hz), 3.53(2H,ABq,J=5.9,Δν=6.2Hz), 4.24-4.38(1H,m), 4.34(2H,s)ppm
3-(3-クロロ-2-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(101,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.01(2H,ABq,J=16.9, Δν=74.4Hz), 3.53(2H,ABq,J=11.1, Δν=8.6Hz), 3.94(3H,s), 4.31(2H,s), 6.98-7.05(1H,m), 7.29-7.37(2H,m)ppm
3-(4-クロロ-2-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(102,mp63-64)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.98(2H,ABq,J=16.7, Δν=74.5Hz), 3.52(2H,ABq,J=11.0, Δν=7.1Hz), 3.86(3H,s), 4.23(2H,s), 6.85-6.92(2H,m), 7.31(1H,d,J=7.7Hz)ppm
3-(2-クロロ-5-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(103,mp50-54)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=72.9Hz), 3.53(2H,ABq,J=11.2, Δν=8.0Hz), 3.78(3H,s), 4.33(2H,s), 6.78(1H,dd,J=8.8,3.0Hz), 7.06(1H,d,J=3.0Hz), 7.26(1H,d,J=8.8Hz)ppm
3-(5-クロロ-2-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(104,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.99(2H,ABq,J=16.7, Δν=74.3Hz), 3.53(2H,ABq, J=11.1,Δν=7.6Hz), 3.85(3H,s), 4.23(2H,s), 6.79(1H,d,J=8.8Hz), 7.22(1H,dd,J=8.8,2.7Hz), 7.36(1H,d,J=2.7Hz)ppm
3-(4-クロロ-3-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(105,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.8, Δν=75.7Hz), 3.43(2H,ABq,J=11.3, Δν=7.3Hz), 3.91(3H,s), 4.22(2H,s), 6.88-6.98(2H,m), 7.30(1H,d,J=8.1Hz)ppm
3-(3,5-ジクロロ-2-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(106,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.01(2H,ABq,J=16.8, Δν=74.5Hz), 3.54(2H,ABq,J=11.3, Δν=8.7Hz), 3.91(3H,s), 4.26(2H,s), 7.31-7.35(2H,m)ppm
3-(2,6-ジメトキシ-3-クロロベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(107,oil)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.05(2H,ABq,J=16.6, Δν=75.3Hz), 3.56(2H,ABq,J=11.2, Δν=11.6Hz), 3.85(3H,s), 3.92(3H,s), 4.39(2H,s), 6.63(1H,d,J=8.9Hz), 7.28(1H,d,J=8.9Hz)ppm
3-(2-クロロ-3,4-ジメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(108,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.6, Δν=72.7Hz), 3.53(2H,d,J=2.6Hz), 3.87(6H,s), 4.33(2H,s), 6.79(1H,d,J=8.5Hz), 7.23(1H,d,J=8.5Hz)ppm
3-(3,5-ジクロロ-4-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(109,mp41-47)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.00(2H,ABq,J=16.8, Δν=74.5Hz), 3.53(2H,ABq,J=11.3, Δν=7.7Hz), 3.89(3H,s), 4.15(2H,s), 7.32(2H,s)ppm
3-(3-クロロ-2-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(110,oil)
1H-NMR(200MHz,CDCl3)δ: 1.46(3H,t,J=7.0Hz), 3.00(3H,s), (2H,ABq,J=16.8, Δν=74.1Hz),3.52(2H,d,J=2.2Hz), 4.11(2H,q,J=7.0Hz), 4.32(2H,s), 7.00(1H,t,J=7.8Hz), 7.32(2H,t,J=2.4Hz)ppm
3-(4-クロロ-2-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(111,oil)
1H-NMR(200MHz,CDCl3)δ: 1.44(3H,t,J=7.0Hz), 1.53(3H,s), 2.98(2H,ABq,J=16.7, Δν=73.9Hz), 3.51(2H,d,J=1.8Hz), 4.06(2H,q,J=7.0Hz), 4.23(2H,s), 6.83-6.89(2H,m), 7.31(1H,d,J=7.9Hz)ppm
3-(2-クロロ-5-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(112,oil)
1H-NMR(200MHz,CDCl3)δ: 1.40(3H,t,J=7.0Hz), 1.54(3H,s), 2.99(2H,ABq,J=16.7, Δν=73.0Hz), 3.53(2H,ABq,J=11.3, Δν=7.8Hz), 4.00(2H,q,J=7.0Hz), 4.33(2H,s), 6.77(1H,dd,J=8.8,3.0Hz), 7.05(1H,d,J=3.0Hz), 7.25(1H,d,J=8.8Hz)ppm
3-(5-クロロ-2-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(113,oil)
1H-NMR(200MHz,CDCl3)δ: 1.43(3H,t,J=7.0Hz), 1.54(3H,s), 2.99(2H,ABq,J=16.7, Δν=73.8Hz), 3.53(2H,ABq,J=11.3, Δν=7.4Hz), 4.05(2H,q,J=7.0Hz), 4.24(2H,s), 6.77(1H,d,J=8.7Hz), 7.18(1H,dd,J=8.7,2.7Hz), 7.36(1H,d,J=2.7Hz)ppm
3-(4-クロロ-3-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(114,oil)
1H-NMR(200MHz,CDCl3)δ: 1.47(3H,t,J=7.0Hz), 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=75.7Hz), 3.52(2H,ABq,J=11.2, Δν=7.9Hz), 4.11(2H,q,J=7.0Hz), 4.20(2H,s), 6.88(1H,dd,J=8.1,2.0Hz), 6.96(1H,d,J=2.0Hz), 7.29(1H,d,J=8.1Hz)ppm
3-(3,5-ジクロロ-2-エトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(115,oil)
1H-NMR(200MHz,CDCl3)δ: 1.46(3H,t,J=7.0Hz), 1.55(3H,s), 3.00(2H,ABq,J=16.8, Δν=74.1Hz), 3.53(2H,d,J=2.2Hz), 4.12(2H,q,J=7.0Hz), 4.32(2H,s), 7.28(1H,d,J=1.8Hz)ppm
3-(4-クロロ-2-イソプロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(116,oil)
1H-NMR(200MHz,CDCl3)δ: 1.36(6H,d,J=6.0Hz), 1.53(3H,s), 2.97(2H,ABq,J=16.7, Δν=73.4Hz), 3.52(2H,d,J=2.0Hz), 4.21(2H,s), 4.57(1H,quintet,J=6.0Hz), 6.82-6.87(2H,m), 7.30(1H,d,J=8.7Hz)ppm
3-(2-クロロ-5-イソプロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(117,oil)
1H-NMR(200MHz,CDCl3)δ: 1.32(6H,d,J=6.1Hz), 1.54(3H,s), 2.99(2H,ABq,J=16.3, Δν=73.6Hz), 3.52(2H,d,J=2.4Hz), 4.32(2H,s), 4.51(1H,quintet,J=6.0Hz), 6.75(1H,dd,J=8.6,3.0Hz), 7.05(1H,d,J=3.0Hz), 7.24(1H,d,J=8.6Hz)ppm
3-(5-クロロ-2-イソプロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(118,oil)
1H-NMR(200MHz,CDCl3)δ: 1.35(6H,d,J=6.1Hz), 1.55(3H,s), 2.99(2H,ABq,J=16.6, Δν=73.6Hz), 3.53(2H,ABq,J=11.2, Δν=7.8Hz), 4.22(2H,s), 4.55(1H,quintet,J=5.9Hz), 6.78(1H,d,J=8.8Hz), 7.18(1H,dd,J=8.8,2.7Hz), 7.35(1H,d,J=2.7Hz)ppm
3-(4-クロロ-3-イソプロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(119,oil)
1H-NMR(200MHz,CDCl3)δ: 1.38(6H,d,J=6.0Hz), 1.53(3H,s), 2.99(2H,ABq,J=16.8, Δν=76.0Hz), 3.52(2H,ABq,J=11.3, Δν=7.0Hz), 4.20(2H,s), 4.56(1H,quintet,J=6.0Hz), 6.87(1H,dd,J=8.1,2.0Hz), 6.99(1H,d,J=2.0Hz), 7.29(1H,d,J=8.1Hz)ppm
3-(2-フルオロ-6-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(120,mp56-59)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.04(2H,ABq,J=16.8, Δν=75.2Hz), 3.40(2H,ABq,J=11.2, Δν=10.4Hz), 3.88(3H,s), 4.36(2H,d,J=1.2Hz), 6.67-6.75(2H,m), 7.17-7.29(1H,m)ppm
3-(2-エトキシ-3-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(121,oil)
1H-NMR(200MHz,CDCl3)δ: 1.39(3H,t,J=7.1Hz), 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=73.6Hz), 3.53(2H,ABq,J=11.2, Δν=8.6Hz), 4.19(2H,q,J=7.1Hz), 4.31(2H,s), 6.82-6.87(1H,m), 7.00(2H,d,J=4.6Hz)ppm
3-(2-エトキシ-6-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(122,oil)
1H-NMR(200MHz,CDCl3)δ: 1.42(3H,t,J=7.0Hz), 1.56(3H,s), 3.06(2H,ABq,J=16.8, Δν=74.4Hz), 3.55(2H,ABq,J=11.0, Δν=10.7Hz), 3.85(3H,s), 4.07(2H,q,J=7.0Hz), 4.40(2H,s), 6.53(2H,d,J=8.2Hz), 7.20(1H,t,J=8.2Hz)ppm
3-(3-メトキシ-2-プロピルオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(123,oil)
1H-NMR(200MHz,CDCl3)δ: 1.04(3H,t,J=7.45), 1.54(3H,s), 1.81(2H,septet,J=7.1Hz), 3.00(2H,ABq,J=16.7, Δν=74.0Hz), 3.53(2H,ABq,J=11.2, Δν=8.2Hz), 3.84(3H,s), 3.99(2H,t,J=6.9Hz), 4.31(2H,s), 6.99(2H,d,J=5.5Hz)ppm
3-(2-イソプロピルオキシ-3-メトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(124,oil)
1H-NMR(200MHz,CDCl3)δ: 1.29(6H,d,J=6.2Hz), 1.55(3H,s), 3.00(2H,ABq,J=16.7, Δν=72.1Hz), 3.53(2H,ABq,J=11.2, Δν=9.0Hz), 3.83(3H,s), 4.34(2H,s), 4.59(1H,quintet,J=6.1Hz), 6.81-6.85(1H,m), 6.94-7.03(2H,m)ppm
3-(2,3-メチレンジオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(125,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.02(2H,ABq,J=16.8, Δν=76.4Hz), 3.52(2H,ABq,J=11.1, Δν=7.3Hz), 4.28(2H,s), 5.99(2H,s), 6.73-6.90(3H,m)ppm
3-(3,4-メチレンジオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(126,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.6, Δν=74.9Hz), 3.53(2H,d,J=2.4Hz), 4.19(2H,s), 5.95(2H,s), 6.72-6.86(3H,m)ppm
3-(2,3-エチレンジオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(127,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=74.9Hz), 3.53(2H,ABq,J=11.2, Δν=8.0Hz), 4.24-4.34(6H,m), 6.74-6.84(2H,m), 6.94(1H,dd,J=6.1,3.2Hz)ppm
3-(2-メチル-3,4-エチレンジオキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(131,mp83-85) 1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.22(3H,s), 3.01(2H,ABq,J=16.9, Δν=74.2Hz), 3.54(2H,ABq,J=11.1, Δν=9.2Hz), 4.20-4.31(6H,m), 6.68(1H,d,J=8.4Hz), 6.83(1H,d,J=8.3Hz)ppm
3-(4-トリフルオロメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(142,oil)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.3Hz), 3.52(2H,ABq,J=11.3, Δν=6.9Hz), 4.24(2H,s), 7.16(2H,d,J=8.7Hz), 7.41(2H,d,J=8.7Hz)ppm
3-(2-ジフルオロメトキシ-3-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(143,oil)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 2.33(3H,s), 3.14(2H,ABq,J=17.5, Δν=76.6Hz), 4.15(2H,ABq,J=11.4, Δν=15.6Hz), 4.33(2H,s), 6.43(1H,t,J=74.0Hz), 7.13-7.17(2H,m), 7.37(1H,dd,J=6.3,2.3Hz)ppm
3-(2-ジフルオロメトキシ-4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(144,oil)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 2.34(3H,s), 2.99(2H,ABq,J=16.7, Δν=73.5Hz), 3.52(2H,d,J=2.1Hz), 4.27(2H,s), 6.53(1H,t,J=74.0Hz), 6.94-7.01(2H,m), 7.37(1H,d,J=7.8Hz)ppm
3-(2-ジフルオロメトキシ-5-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(145,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.32(3H,s), 3.00(2H,ABq,J=16.7, Δν=73.1Hz), 3.52(2H,ABq,J=11.2, Δν=7.6Hz), 4.27(2H,s), 6.51(1H,t,J=73.9Hz), 7.04-7.12(2H,m), 7.28(1H,d,J=1.6Hz)ppm
3-(3-ジフルオロメトキシ-4-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(146,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.27(3H,s), 2.99(2H,ABq,J=16.6, Δν=75.1Hz), 3.52(2H,ABq,J=11.3, Δν=7.2Hz), 4.22(2H,s), 6.50(1H,t,J=74.1Hz), 7.10-7.20(3H,m)ppm
3-(3-クロロ-2-ジフルオロメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(147,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.8, Δν=73.4Hz), 3.52(2H,ABq,J=11.2, Δν=7.4Hz), 4.36(2H,s), 6.06(1H,t,J=74.4Hz), 7.18(1H,t,J=7.9Hz), 7.04(1H,dd,J=7.9,1.7Hz), 7.50(1H,dd,J=1.8,1.7Hz)ppm
3-(2-クロロ-5-ジフルオロメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(148,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=74.0Hz), 3.52(2H,ABq,J=11.3, Δν=7.3Hz), 4.34(2H,s), 6.49(1H,t,J=73.4Hz), 7.02(1H,dd,J=8.8,2.9Hz), 7.33(1H,d,J=2.9Hz), 7.37(1H,d,J=8.8Hz)ppm
3-(5-クロロ-2-ジフルオロメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(149,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=73.6Hz), 3.52(2H,d,J=2.3Hz), 4.25(2H,s), 6.53(1H,t,J=73.3Hz), 7.08(1H,d,J=8.8Hz), 7.26(1H,dd,J=8.8,2.5Hz), 7.50(1H,d,J=2.5Hz)ppm
3-(4-クロロ-3-ジフルオロメトキシベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(150,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=75.5Hz), 3.52(2H,ABq,J=10.4, Δν=6.9Hz), 4.21(2H,s), 6.54(1H,t,J=73.4Hz), 7.08-7.41(3H,m)ppm
3-(2-メトキシメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(151,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.01(2H,ABq,J=16.5, Δν=74.3Hz), 3.41(3H,s), 3.54(2H,ABq,J=11.2, Δν=8.5Hz), 4.37(2H,s), 4.56(2H,s), 7.26-7.45(4H,m)ppm
3-(2-エトキシメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(152,oil)
1H-NMR(200MHz,CDCl3)δ: 1.26(3H,t,J=7.0Hz), 1.55(3H,s), 3.00(2H,ABq,J=16.9, Δν=74.3Hz), 3.52-3.62(4H,m), 4.38(2H,s), 4.60(2H,s), 7.25-7.45(4H,m)ppm
3-(2-(2,2,2-トリフルオロエトキシメチル)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(153,oil)1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.00(2H,ABq,J=17.8, Δν=82.4Hz), 3.53(2H,d,J=2.4Hz), 3.86(2H,q,J=8.8Hz), 4.35(2H,s), 4.80(2H,s), 7.3-7.5(4H,m)ppm
3-(3-(2,2,2-トリフルオロエトキシメチル)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(154,oil)1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.8, Δν=75.4Hz), 3.52(2H,d,J=2.0Hz), 3.84(2H,q,J=8.6Hz), 4.27(2H,s), 4.67(2H,s), 7.29-7.36(4H,m)ppm
3-(2-(2-メトキシエトキシ)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(155,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=73.6Hz), 3.52(2H,ABq,J=9.5,Δν=6.5Hz), 3.78(2H,t,J=4.8Hz), 4.18(2H,t,J=4.8Hz), 4.31(2H,s), 6.86-6.96(2H,m), 7.21-7.40(2H,m)ppm
3-(3-(2-メトキシエトキシ)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(156,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.7, Δν=75.1Hz), 3.52(2H,ABq,J=12.0, Δν=7.5Hz), 3.45(3H,s), 3.75(2H,t,J=4.7Hz), 4.12(2H,t,J=4.7Hz), 4.23(2H,s), 6.82-6.98(3H,m), 7.23(1H,t,J=7.4Hz)ppm
3-(2-(2,2-ジメトキシエトキシ)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(157,oil)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 2.98(2H,ABq,J=17.1, Δν=73.8Hz), 3.47(6H,s), 3.52(2H,s), 4.23(2H,d,J=5.7Hz), 4.30(2H,s), 4.75(1H,t,J=5.9Hz), 6.89-6.93(2H,m), 7.21-7.41(2H,m)ppm
3-(3-(2,2-ジメトキシエトキシ)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(158,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.00(2H,ABq,J=16.8, Δν=75.1Hz), 3.46(6H,s), 3.52(2H,d,J=2.4Hz), 4.00(2H,d,J=5.2Hz), 4.23(2H,s), 4.72(1H,t,J=5.2Hz), 6.82-6.87(1H,m), 6.96-7.20(2H,m), 7.23-7.28(1H,m)ppm
3-(2-(2,2-エチレンジオキシエトキシ)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(159,mp79-80.5)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 2.99(2H,ABq,J=16.7, Δν=73.1Hz), 3.52(2H,ABq,J=11.1, Δν=7.4Hz), 3.93-4.08(4H,m), 4.09(2H,d,J=3.6Hz), 4.31(2H,s), 5.33(1H,t,J=3.7Hz), 6.86-6.96(2H,m), 7.20-7.29(1H,m), 7.38(1H,dd,J=7.5,0.8Hz)ppm
3-(3-(2,2-エチレンジオキシエトキシ)ベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(160,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.99(2H,ABq,J=16.8, Δν=74.9Hz), 3.52(2H,ABq,J=11.2, Δν=7.7Hz), 3.92-4.10(6H,m), 4.23(2H,s), 5.29(1H,t,J=4.0Hz), 6.82-6.99(3H,m), 7.19-7.27(1H,m)ppm
3-(α-メチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(161,oil)
1H-NMR(200MHz,CDCl3)δ: 1.49(s),1.51(s)(3H), 1.75(d,J=7.0Hz),1.76(d,J=7.0Hz)(3H), 2.92(ABq,J=16.7,Δν=74.5Hz),2.95(ABq,J=16.7, Δν=74.1Hz)(2H), 3.46(2H,s), 4.79(q,J=7.0Hz),4.79(q,J=7.0Hz)(1H), 7.23-7.42(5H,m)ppm
3-(α，α-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(162,oil)
1H-NMR(200MHz,CDCl3)δ: 1.37(3H,s), 1.91(6H,s), 2.61(2H,ABq,J=17.1, Δν=77.3Hz), 3.30(2H,ABq,J=11.2, Δν=11.9Hz), 7.25-7.39(3H,m), 7.56-7.60(2H,m)ppm
3-(α-イソプロピルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(165,oil)
1H-NMR(200MHz,CDCl3)δ: 0.89(d,J=6.7Hz)+0.89(d,J=6.7Hz)(3H), 1.09(d,J=6.7Hz)+1.10(d,J=6.7Hz)(3H), 1.43(3H,s), 2.16-2.24(1H,m), 2.69(1H,dd,J=17.1,12.1Hz), 3.07(1H,dd,J=16.7,14.4Hz), 3.36(2H,ABq,J=13.4,Δν=7.0Hz), 4.44(d,J=7.9Hz)+4.46(d,J=7.7Hz)(1H), 7.22-7.32(5H,m)ppm
3-( α,2-ジメチルベンジル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(166,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(s)+1.56(s)(3H), 1.76(d,J=6.9Hz)+1.78(d,J=6.9Hz)(3H), 2.42(3H,s), 2.96(ABq,J=16.6,Δν=73.0Hz)+2.96(ABq,J=16.8, Δν=71.3Hz)(2H), 3.49(2H,d,J=2.7Hz), 5.01(1H,q,J=6.9Hz), 7.16-7.23(3H,m), 7.40-7.44(1H,m)ppm
3-(4-クロマニル)チオ-5-クロロメチル-5-メチル-2-イソオキサゾリン(167,mp83-84)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 2.38-2.48(2H,m), 2.84(d,J=16.9Hz)+2.92(d,J=16.8Hz)(1H), 3.14(d,J=16.7Hz)+3.21(d,J=16.7Hz)(1H), 3.50-3.64(2H,m), 4.31-4.37(2H,m), 5.00(1H,t,J=6.4Hz), 6.79-6.93(2H,m), 7.13-7.21(1H,m), 7.28-7.33(1H,m)ppm
3-(1-(1,2,3,4-テロラヒドロナフチル)チオ)-5-クロロメチル-5-メチル-2-イソオキサゾリン(169,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 1.89-2.32(4H,m), 2.74-3.65(6H,m), 5.08(1H,brs), 7.08-7.21(3H,m), 7.38-7.42(1H,m)ppm
3-ベンジルチオ-5-トリフルオロメチル-5-メチル-2-イソオキサゾリン(179,mp56-59)
1H-NMR(200MHz,CDCl3)δ: 1.60(3H,d,J=1.9Hz), 2.97(1H,dd,J=7.1,0.8Hz), 3.34(1H,d,J=17.2Hz), 4.28(3H,s), 7.30-7.38(5H,m)ppm
【０１１６】
【実施例２】
３−ベンジルスルフィニル−５−クロロメチル−５−メチル−２−イソオキサゾリン（化合物番号１００１）及び３−ベンジルスルホニル−５−クロロメチル−５−メチル−２−イソオキサゾリン（化合物番号２００１）（Ｃ工程）
（１） ３−ベンジルスルフィニル−５−クロロメチル−５−メチル−２−イソオキサゾリン（Ｃ−１工程）
実施例１の方法で製造した３−ベンジルチオ−５−クロロメチル−５−メチル−２−イソオキサゾリン（化合物番号１）９２６．７ｍｇを１，２−ジクロロエタン２０ｍｌに溶解し、攪拌しながらｍ−クロロ過安息香酸８９２．４ｍｇを室温で加えた。更に室温で４５分間攪拌した後、反応液に飽和亜硫酸ナトリウム水溶液を加え、塩化メチレンで抽出し、有機層を炭酸水素ナトリウム水溶液、食塩水で順に洗浄した。無水硫酸ナトリウムで乾燥した後、濾過し、溶媒を留去後、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝４：１）により精製し、融点６０−６５℃を有する目的物７１０．９ｍｇ（７２％）を得た。
【０１１７】
1H-NMR(200MHz,CDCl3)δ: 1.54(s)+1.56(s)(3H), 2.85(2H,ABq,J=17.9,Δν=201.3Hz), 3.43-3.57(2H,m), 4.16-4.36(2H,m), 7.30-7.42(5H,m)ppm
（２） ３−ベンジルスルホニル−５−クロロメチル−５−メチル−２−イソオキサゾリン（Ｃ−１，Ｃ−２工程）
実施例１の方法で製造した３−ベンジルチオ−５−クロロメチル−５−メチル−２−イソオキサゾリン（化合物番号１）１３３．１ｍｇを塩化メチレン５ｍｌに溶解し、撹拌しながらｍ−クロロ過安息香酸３８５ｍｇの塩化メチレン溶液５ｍｌを室温で滴下した。更に室温で２時間撹拌した後、反応液に飽和亜硫酸ナトリウム水溶液を加え、塩化メチレンで抽出し、有機層を炭酸水素ナトリウム水溶液、食塩水で順に洗浄した。無水硫酸ナトリウムで乾燥した後、濾過し、溶媒を留去後、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１０：１）により精製し、融点８７−８８℃を有する目的物８６．２ｍｇ（５８％）を得た。
【０１１８】
1H-NMR(200MHz,CDCl3)δ: 1.50(3H,s), 2.98(2H,ABq,J=17.9, Δν=86.1Hz), 3.49(2H,s), 4.60(2H,s), 7.43(5H,m)ppm
実施例２（１）の方法及び実施例２（２）の方法に準じて製造した化合物を、以下に示す。
【０１１９】
3-(2-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2002,oil)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 2.46(3H,s), 3.03(2H,ABq,J=17.7, Δν=88.4Hz), 3.52(2H,s), 4.69(2H,s), 7.23-7.40(4H,m)ppm
3-(3-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2003,mp51-54)
1H-NMR(200MHz,CDCl3)δ: 1.50(3H,s), 2.37(3H,s), 2.97(2H,ABq,J=17.8, Δν=84.9Hz), 3.48(2H,s), 4.56(2H,s), 7.20-7.30(4H,m)ppm
3-(4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2004,mp99-101)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H.s), 2.37(3H,s), 2.97(2H,ABq,J=17.9, Δν=78.5Hz), 3.49(2H,s), 4.56(2H,s), 7.22(2H,d,J=8.1Hz), 7.31(2H,d,J=8.1Hz)ppm
3-(2,3-ジメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2005,Amorphous)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 2.33(3H,s), 2.34(3H,s), 3.01(2H,ABq,J=17.5, Δν=88.3Hz), 3.52(2H,br), 4.72(2H,s), 7.09-7.24(3H,m)ppm
3-(2,4-ジメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2006,oil)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 2.33(3H,s), 2.41(3H,s), 3.02(2H,ABq,J=17.8, Δν=80.6Hz), 3.51(2H,s), 4.64(2H,s), 7.03-7.13(2H,m), 7.24-7.27(1H,m)ppm
3-(2,5-ジメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2007,oil)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 2.33(3H,s), 2.41(3H,s), 3.03(2H,ABq,J=17.9, Δν=88.7Hz), 3.52(2H,s), 4.64(2H,s), 7.14-7.17(3H,m)ppm
3-(2,6-ジメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2008,Amorphous)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 2.48(6H,s), 3.17(2H,ABq,J=17.8, Δν=85.7Hz), 3.58(2H,d,J=1.8Hz), 4.85(2H,s), 7.08-7.26(3H,m)ppm
3-(3,4-ジメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2009,mp87-88)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 2.28(6H,s), 2.96(2H,ABq,J=17.8, Δν=75.5Hz), 3.47(2H,s), 4.53(2H,s), 7.16(3H,s)ppm
3-(3,5-ジメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2010,mp73-75)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 2.33(6H,s), 2.97(2H,ABq,J=17.9, Δν=84.4Hz), 3.48(2H,s), 4.52(2H,s), 7.03(3H,br)ppm
3-(2,4,6-トリメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2011,mp121-123)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 2.29(3H,s), 2.43(6H,s), 3.14(2H,ABq,J=17.7, Δν=78.6Hz), 3.56(2H,s), 4.80(2H,s), 6.94(2H,s)ppm
3-(2-エチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2012,oil)
1H-NMR(200MHz,CDCl3)δ: 1.24(3H,t,J=7.5Hz), 1.53(3H,s), 2.81(2H,q,J=7.5Hz), 3.02(2H,ABq,J=17.9, Δν=88.7Hz), 3.52(2H,s), 4.71(2H,s), 7.20-7.41(4H,m)ppm
3-(4-エチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2014,mp112-113)
1H-NMR(200MHz,CDCl3)δ: 1.24(3H,t,J=7.7Hz), 1.50(3H,s), 2.67(2H,q,J=7.7Hz), 2.96(2H,ABq,J=18.0, Δν=80.8Hz), 3.47(2H,s), 4.57(2H,s), 7.24(2H,d,J=8.1Hz), 7.34(2H,d,J=8.1Hz)ppm
3-(2,6-ジエチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2015,mp58-61)
1H-NMR(200MHz,CDCl3)δ: 1.24(6H,t,J=7.5Hz), 1.57(3H,s), 2.85(4H,q,J=7.5Hz), 3.13(2H,ABq,J=17.7, Δν=86.3Hz), 3.56(2H,s), 4.89(2H,s), 7.17(2H,d,J=7.7Hz), 7.26-7.36(1H,m)ppm
3-(4-nプロピルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2019,mp101-103)
1H-NMR(200MHz,CDCl3)δ: 0.94(3H,t,J=7.3Hz), 1.49(3H,s), 1.64(2H,sextet,J=7.3Hz), 2.61(2H,t,J=7.3Hz), 2.95(2H,ABq,J=17.9,Δν=84.5Hz), 3.48(2H,s), 4.56(2H,s), 7.22(2H,d,J=8.3Hz), 7.34(2H,d,J=8.3Hz)ppm
3-(2-イソプロピルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2020,mp76-78)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.08(2H,ABq,J=17.9, Δν=90.9Hz), 3.23-3.36(1H,m), 3.54(2H,ABq,J=11.7,Δν=5.8Hz), 4.75(2H,s), 7.18-1.42(4H,m)ppm
3-(4-tert-ブチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2031,mp108-110)
1H-NMR(200MHz,CDCl3)δ: 1.32(9H,s), 1.49(3H,s), 2.94(2H,ABq,J=17.8, Δν=81.2Hz), 3.46(2H,d,J=1.3Hz), 4.57(2H,s), 7.35(2H,d,J=8.6Hz), 7.44(2H,d,J=8.6Hz)ppm
3-(2-(5,6,7,8-テトラヒドロナフチル)スルホニル)-5-クロロメチル-5-メチル-2-イソオキサゾリン(2033,mp69-73)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 1.76-1.82(4H,m), 2.74-2.77(4H,m), 2.98(2H,ABq,J=18.0, Δν=73.0Hz), 3.47(2H,s), 4.52(2H,s), 7.09-7.18(3H,m)ppm
3-(2-クロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2034,mp92-94)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.08(2H,ABq,J=17.9, Δν=83.2Hz), 3.54(2H,ABq,J=11.8, Δν=7.9Hz), 4.58(2H,s), 7.33-7.42(4H,m)ppm
3-(3-クロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2035,mp95-97)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.08(2H,ABq,J=17.8, Δν=83.6Hz), 3.54(2H,d,J=1.4Hz), 4.57(2H,s), 7.32-7.43(4H,m)ppm
3-(4-クロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2036,mp89-90)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.10(2H,ABq,J=17.8, Δν=82.4Hz), 3.54(2H,d,J=2.4Hz), 4.58(2H,s), 7.38(4H,s)ppm
3-(2,3-ジクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2037,mp71-73)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.17(2H,ABq,J=17.7, Δν=81.4Hz), 3.57(2H,ABq,J=11.8, Δν=10.1Hz), 4.90(2H,s), 7.27(1H,t,J=7.9Hz), 7.46-7.57(2H,m)ppm
3-(2,4-ジクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2038,mp111-113)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.21(2H,ABq,J=17.7, Δν=80.7Hz), 3.69(2H,ABq,J=11.8, Δν=10.7Hz), 4.82(2H,s), 7.33(1H,dd,J=8.4,2.0Hz), 7.49-7.53(2H,m)ppm
3-(2,5-ジクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2039,mp135-136)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.20(2H,ABq,J=17.7, Δν=81.7Hz), 3.59(2H,ABq,J=11.7, Δν=11.5Hz), 4.81(2H,s), 7.33(1H,dd,J=8.6,2.2Hz), 7.42(1H,d,J=8.6Hz), 7.56(1H,d,J=2.2Hz)ppm
3-(2,6-ジクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2040,mp147-148)
1H-NMR(200MHz,CDCl3)δ: 1.63(3H,s), 3.29(2H,ABq,J=17.8, Δν=83.0Hz), 3.62(2H,d,J=4.7Hz), 5.15(2H,s), 7.29-7.45(3H,m)ppm
3-(3,4-ジクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2041,mp88-90)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.17(2H,ABq,J=17.8, Δν=80.5Hz), 3.56(2H,ABq,J=11.8, Δν=10.7Hz), 4.56(2H,s), 7.29(1H,dd,J=8.3,2.0Hz), 7.50(1H,d,J=8.4Hz), 7.54(1H,d,J=2.0Hz)ppm
3-(3,5-ジクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2042,mp96-98)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.16(2H,ABq,J=18.0, Δν=81.6Hz), 3.57(2H,ABq,J=11.9, Δν=11.5Hz), 4.55(2H,s), 7.34(2H,d,J=1.8Hz), 7.42(1H,t,J=1.8Hz)ppm
3-(2,3,5-トリクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2043,mp124-127)
1H-NMR(200MHz,CDCl3)δ: 1.60(3H,s), 3.21(2H,ABq,J=17.9, Δν=81.6Hz), 3.59(2H,ABq,J=11.7, Δν=11.5Hz), 4.81(2H,s), 7.31-7.56(2H,m)ppm
3-(2,4,6-トリクロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2044,mp137-139)
1H-NMR(200MHz,CDCl3)δ: 1.64(3H,s), 3.32(2H,ABq,J=17.8, Δν=83.4Hz), 3.63(2H,ABq,J=11.7, Δν=12.2Hz), 5.11(2H,s), 7.45(2H,s)ppm
3-(3-クロロ-4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2045,mp79-83)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.39(3H,s), 3.09(2H,ABq,J=17.8, Δν=81.7Hz), 3.53(2H,ABq,J=9.6,Δν=6.0Hz), 4.54(2H,s), 7.17-7.40(3H,m)ppm 3-(3-メチル-4-クロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2046,mp88-90)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.39(3H,s), 3.09(2H,ABq,J=17.8, Δν=81.3Hz), 3.53(2H,ABq,J=11.7, Δν=6.5Hz), 4.55(2H,s), 7.17-7.40(3H,m)ppm
3-(3,4-ジクロロ-2-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2047,mp86-90)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 2.54(3H,s), 3.20(2H,ABq,J=17.9, Δν=82.7Hz), 3.59(2H,ABq,J=11.7, Δν=11.5Hz), 4.72(2H,s), 7.25(1H,d,J=8.0Hz), 7.37(1H,d,J=8.4Hz)ppm
3-(2,4-ジクロロ-3-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2048,mp110-112)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 2.52(3H,s), 3.18(2H,ABq,J=17.9, Δν=77.8Hz), 3.57(2H,ABq,J=11.6, Δν=9.2Hz), 4.86(2H,s), 7.35(2H,s)ppm
3-(2,5-ジクロロ-4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2049,mp116-118)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 2.37(3H,s), 3.19(2H,ABq,J=18.0, Δν=78.5Hz), 3.58(2H,ABq,J=11.8, Δν=9.7Hz), 4.77(2H,s), 7.35(1H,s), 7.53(1H,s)ppm
3-(2-ブロモベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2050,mp73-75)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.12(2H,ABq,J=17.9, Δν=81.5Hz), 3.56(2H,ABq,J=11.5, Δν=9.5Hz), 4.89(2H,s), 7.28-7.38(2H,m), 7.57-7.68(2H,m)ppm
3-(3-ブロモベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2051,mp90)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.09(2H,ABq,J=17.6, Δν=83.5Hz), 3.54(2H,d,J=2.4Hz), 4.57(2H,s), 7.29-7.42(2H,m), 7.56(2H,d,J=7.8Hz)ppm
3-(4-ブロモベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2052,mp114-115)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.10(2H,ABq,J=17.6, Δν=81.8Hz), 3.54(2H,d,J=2.4Hz), 4.57(2H,s), 7.31(2H,d,J=8.3Hz), 7.56(2H,d,J=8.3Hz)ppm
3-(2-フルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2053,mp82-84)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.95(2H,ABq,J=17.7, Δν=81.9Hz), 3.56(2H,ABq,J=11.6, Δν=8.2Hz), 4.68(2H,s), 7.14-7.25(2H,m), 7.37-7.51(2H,m)ppm
3-(3-フルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2054,mp95-97)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 3.09(2H,ABq,J=17.7, Δν=83.3Hz), 3.53(2H,ABq,J=11.7, Δν=7.6Hz), 4.60(2H,s), 7.12-7.23(3H,m), 7.34-7.41(1H,m)ppm
3-(4-フルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2055,mp75-76)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 3.10(2H,ABq,J=17.8, Δν=83.4Hz), 3.53(2H,ABq,J=11.7, Δν=7.5Hz), 4.58(2H,s), 7.06-7.15(2H,m), 7.38-7.45(2H,m)ppm
3-(2,3-ジフルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2056,mp83-85)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.22(2H,ABq,J=17.9, Δν=81.2Hz), 3.59(2H,ABq,J=11.8, Δν=10.6Hz), 4.70(2H,s), 7.13-7.26(3H,m)ppm
3-(2,4-ジフルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2057,mp81)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 3.21(2H,ABq,J=17.7, Δν=80.6Hz), 3.58(2H,ABq,J=11.7, Δν=10.6Hz), 4.64(2H,s), 6.86-7.01(2H,m,7.43-7.55(1H,m)ppm
3-(2,5-ジフルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2058,mp127-129)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.22(2H,ABq,J=17.7, Δν=80.8Hz), 3.58(2H,ABq,J=11.7, Δν=10.5Hz), 4.65(2H,s), 7.08-7.25(3H,m)ppm
3-(2,6-ジフルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2059,mp92-93)
1H-NMR(200MHz,CDCl3)δ: 1.62(3H,s), 3.27(2H,ABq,J=17.7, Δν=82.3Hz), 3.61(2H,ABq,J=11.6, Δν=10.6Hz), 4.37(2H,s), 6.97-7.05(2H,m), 7.37-7.46(1H,m)ppm
3-(3,4-ジフルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2060,mp104)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.17(2H,ABq,J=17.8, Δν=80.8Hz), 3.56(2H,ABq,J=11.7, Δν=10.9Hz), 4.57(2H,s), 7.12-7.34(3H,m)ppm
3-(3,5-ジフルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2061,mp108-110)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.17(2H,ABq,J=17.8, Δν=81.3Hz), 3.57(2H,ABq,J=11.9, Δν=11.1Hz), 4.59(2H,s), 6.88-7.02(3H,m)ppm
3-(2-フルオロ-3-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2064,mp96-97)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.31(3H,d,J=2.0Hz), 3.14(2H,ABq,J=17.8, Δν=84.1Hz), 3.55(2H,ABq,J=11.7, Δν=6.2Hz), 4.66(2H,s), 7.09(1H,t,J=7.7Hz), 7.28(2H,q,J=7.3Hz)ppm
3-(3-フルオロ-4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2065,mp88-89)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.29(3H,d,J=1.9Hz), 3.07(2H,ABq,J=17.9, Δν=78.2Hz), 3.52(2H,s), 4.56(2H,s), 7.08-7.27(3H,br)ppm
3-(2,3,5,6-テトラフルオロ-4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2066,mp115-117)
1H-NMR(200MHz,CDCl3)δ: 1.62(3H,d,J=7.1Hz), 2.29(3H,dt,J=13.1,2.2Hz), 3.09(1H,dd,J=17.8,11.7Hz), 3.41-3.69(3H,m), 4.70(2H,d,J=20.5Hz)ppm
3-(2-フルオロ-3-クロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2067,mp90-92)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.38(2H,ABq,J=17.8, Δν=81.1Hz), 3.58(2H,ABq,J=11.7, Δν=10.4Hz), 4.69(2H,s), 7.12-7.20(1H,m), 7.37-7.52(2H,m)ppm
3-(2-クロロ-4-フルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2068,mp80-82)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.20(2H,ABq,J=17.9, Δν=81.4Hz), 3.59(2H,ABq,J=11.7, Δν=11.0Hz), 4.81(2H,s), 7.07(1H,td,J=8.6,2.7Hz), 7.12-7.25(1H,m), 7.56(1H,dd,J=8.6,5.9Hz)ppm
3-(2-クロロ-6-フルオロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2070,mp118)
1H-NMR(200MHz,CDCl3)δ: 1.63(3H,s), 3.27(2H,ABq,J=17.8, Δν=82.8Hz), 3.62(2H,ABq,J=11.7, Δν=11.1Hz), 4.91(2H,d,J=1.6Hz), 7.12-7.39(3H,m)ppm
3-(2-トリフルオロメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2071,mp78)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.21(2H,ABq,J=17.8, Δν=80.3Hz), 3.58(2H,ABq,J=11.7, Δν=9.8Hz), 4.87(2H,s), 7.55-7.64(2H,m), 7.77(2H,d,J=7.4Hz)ppm
3-(3-トリフルオロメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2072,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.14(2H,ABq,J=17.8, Δν=84.6Hz), 3.54(2H,d,J=2.6Hz), 4.67(2H,s), 7.59-7.70(4H,m)ppm
3-(4-トリフルオロメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2073,mp107-109)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.14(2H,ABq,J=18.0, Δν=81.2Hz), 3.55(2H,ABq,J=11.8, Δν=9.4Hz), 4.68(2H,s), 7.58(2H,d,J=8.3Hz), 7.69(2H,d,J=8.3Hz)ppm
3-(2,4-ビストリフルオロメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2074,mp84-85)
1H-NMR(200MHz,CDCl3)δ: 1.62(3H,s), 3.30(2H,ABq,J=17.6, Δν=78.9Hz), 3.62(2H,ABq,J=11.8, Δν=13.4Hz), 4.93(2H,s), 7.91(2H,br.d,J=2.6Hz), 8.02(1H,br)ppm
3-(3,5-ビストリフルオロメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2075,mp105-106)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 3.23(2H,ABq,J=17.7, Δν=82.3Hz), 3.58(2H,ABq,J=11.9, Δν=12.7Hz), 4.75(2H,s), 7.92(3H,br)ppm
3-(2-フルオロ-4-トリフルオロメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2076,mp93-94)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.25(2H,ABq,J=17.6, Δν=79.7Hz), 3.59(2H,ABq,J=11.8, Δν=11.9Hz), 4.74(2H,s), 7.41-7.51(2H,m), 7.67(1H,t,J=7.0Hz)ppm
3-(2-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2077,mp85-87)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.05(2H,ABq,J=17.8, Δν=85.5Hz), 3.49(2H,s), 3.87(3H,s), 4.71(2H,s), 6.93-7.00(2H,m), 7.39-7.45(2H,m)ppm
3-(3-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2078,oil)
1H-NMR(200MHz,CDCl3)δ: 1.50(3H,s), 2.96(2H,ABq,J=17.9, Δν=82.1Hz), 3.49(2H,s), 3.82(3H,s), 4.56(2H,s), 6.92-7.01(3H,m), 7.27-7.34(1H,m)ppm
3-(4-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2079,mp84-85)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 3.00(2H,ABq,J=17.6, Δν=81.2Hz), 3.50(2H,s), 3.82(3H,s), 4.54(2H,s), 6.93(2H,d,J=8.7Hz), 7.34(2H,d,J=8.7Hz)ppm
3-(2,3-ジメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2080,mp94-95)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.11(2H,ABq,J=17.8, Δν=71.4Hz), 3.56(2H,ABq,J=11.4, Δν=13.8Hz), 3.86(3H,s), 3.93(3H,s), 4.69(2H,s), 6.95-7.13(3H,m)ppm
3-(2,4-ジメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2081,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.06(2H,ABq,J=17.8, Δν=82.3Hz), 3.50(2H,s), 3.83(3H,s), 3.85(3H,s), 6.49-6.56(2H,m), 4.63(2H,s), 7.34(1H,d,J=8.3Hz) ppm
3-(2,5-ジメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2082,mp92-94)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 3.06(2H,ABq,J=17.9, Δν=83.1Hz), 3.50(2H,s), 3.78(3H,s), 3.83(3H,s), 4.67(2H,s), 6.89-7.00(3H,m)ppm
3-(2,6-ジメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2083,mp128-130)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.13(2H,Abq,J=17.7, Δν=87.9Hz), 3.53(2H,s), 3.87(6H,s), 4.80(2H,s), 6.60(2H,d,J=8.4Hz), 7.33(1H,t,J=7.3Hz)ppm
3-(3,4-ジメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2084,mp117-118)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 3.01(2H,ABq,J=17.8, Δν=83.0Hz), 3.51(2H,s), 3.90(6H,s), 4.55(2H,s), 6.86-6.99(3H,m)ppm
3-(3,5-ジメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2085,mp128-128.5)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 2.97(2H,ABq,J=17.9, Δν=79.1Hz), 3.50(2H,s), 3.80(6H,s), 4.52(2H,s), 6.49(1H,t,J=2.2Hz), 6.55(2H,d,J=2.2Hz)ppm
3-(3,4,5-トリメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2087,mp105-106)
1H-NMR(200MHz,CDCl3)δ: 1.52(3H,s), 3.04(2H,ABq,J=17.9, Δν=88.3Hz), 3.52(2H,d,J=1.8Hz), 3.86(3H,s), 3.87(6H,s), 4.54(2H,s), 6.63(2H,s)ppm
3-(2-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2088,mp97-99)
1H-NMR(200MHz,CDCl3)δ: 1.45(3H,t,J=7.0Hz), 1.51(3H,s), 2.99(2H,ABq,J=17.8, Δν=87.0Hz), 3.48(2H,s), 4.09(2H,q,J=7.0Hz), 4.73(2H,s), 6.91-7.03(2H,m), 7.33-7.46(2H,m)ppm
3-(3-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2089,mp86-88)
1H-NMR(200MHz,CDCl3)δ: 1.42(3H,t,J=7.0Hz), 1.55(3H,s), 2.96(2H,ABq,J=17.9, Δν=81.9Hz), 3.49(2H,s), 4.04(2H,q,J=7.0Hz), 4.55(2H,s), 6.92-6.99(3H,m), 7.27-7.31(1H,m)ppm
3-(4-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2090,mp104-105)
1H-NMR(200MHz,CDCl3)δ: 1.42(3H,t,J=7.0Hz), 1.51(3H,s), 2.99(2H,ABq,J=18.0, Δν=82.3Hz), 3.50(2H,s), 4.04(2H,d,J=7.0Hz), 4.53(2H,s), 6.91(2H,d,J=8.6Hz), 7.32(2H,d,J=8.4Hz)ppm
3-(2,6-ジエトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2091, mp81-82)
1H-NMR(200MHz,CDCl3)δ: 1.43(6H,t,J=7.0Hz), 1.55(3H,s), 3.02(2H,ABq,J=17.8, Δν=89.8Hz), 3.50(2H,s), 4.08(4H,q,J=7.0Hz), 4.85(2H,s), 6.55(2H,d,J=8.3Hz), 7.27(1H,t,J=8.3Hz)ppm
3-(2-イソプロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2092,mp89-92)
1H-NMR(200MHz,CDCl3)δ: 1.37(6H,d,J=6.0Hz), 1.51(3H,s), 2.98(2H,ABq,J=17.7, Δν=83.7Hz), 3.48(2H,s), 4.61(1H,quintet,J=6.1Hz), 4.71(2H,s), 6.91-6.99(2H,m), 7.30-7.46(2H,m)ppm
3-(3-イソプロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2093,mp66-68)
1H-NMR(200MHz,CDCl3)δ: 1.50(3H,s), 2.68(6H,d,J=6.1Hz), 2.96(2H,ABq,J=17.8, Δν=83.4Hz), 3.48(2H,s), 4.53-4.59(3H,m), 6.90-6.98(3H,m), 7.30-7.34(1H,m)ppm
3-(4-イソプロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2094,mp76-78)
1H-NMR(200MHz,CDCl3)δ: 1.35(3H,d,J=6.2Hz), 1.51(3H,s), 3.00(2H,ABq,J=17.8, Δν=82.5Hz), 3.50(2H,s), 4.53(2H,s), 4.53(1H,septet,J=6.2Hz), 6.90(2H,d,J=8.6Hz), 7.31(2H,d,J=8.6Hz)ppm
3-(2-メトキシ-3-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2095,mp110-113)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.34(3H,s), 3.08(3H,s), 3.11(2H,ABq,J=17.5, Δν=77.9Hz), 3.55(2H,ABq,J=12.1, Δν=11.1Hz), 4.67(2H,s), 7.04-7.12(1H,m), 7.23-7.35(2H,m)ppm
3-(3-メチル-4-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2097,mp110-111)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.34(3H,s), 3.10(2H,ABq,J=17.6, Δν=77.5Hz), 3.54(2H,ABq,J=11.4, Δν=10.8Hz), 3.80(3H,s), 4.67(2H,s), 7.04-7.12(1H,m), 7.23-7.34(2H,m)ppm
3-(3-メトキシ-4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2098,mp86-88)
1H-NMR(200MHz,CDCl3)δ: 1.50(3H,s), 2.22(3H,s), 2.96(2H,ABq,J=17.8, Δν=83.2Hz), 3.48(2H,s), 3.85(3H,s), 4.56(2H,s), 6.87-6.92(2H,m), 7.15(1H,d,J=7.4Hz)ppm
3-(2-エトキシ-3-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2099,oil)
1H-NMR(200MHz,CDCl3)δ: 1.41(3H,t,J=7.1Hz), 1.56(3H,s), 2.31(3H,s), 3.08(2H,ABq,J=17.8, Δν=75.0Hz), 3.55(2H,ABq,J=11.5, Δν=12.0Hz), 3.93(2H,q,J=7.1Hz), 4.65(2H,s), 7.07(1H,t,J=7.5Hz), 7.25(1H,m), 7.34(1H,d,J=7.5Hz)ppm
3-(2-イソプロピルオキシ-3-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2100,mp105-106)
1H-NMR(200MHz,CDCl3)δ: 1.30(6H,d,J=6.2Hz), 1.56(3H,s), 2.30(3H,s), 2.96(2H,ABq,J=17.7, Δν=70.0Hz), 3.51(2H,ABq,J=11.4, Δν=6.7Hz), 4.22(1H,quintet,J=6.1Hz), 4.64(2H,s), 7.07(1H,t,J=7.8Hz), 7.24(1H,d,J=7.6Hz), 7.36(1H,d,J=7.8Hz)ppm
3-(3-クロロ-2-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2101,mp83-85)
1H-NMR(200MHz,CDCl3)δ: 1.59(3H,s), 3.18(2H,ABq,J=17.7, Δν=81.7Hz), 3.59(2H,ABq,J=11.6, Δν=14.3Hz), 3.97(3H,s), 4.70(2H,s), 7.07-7.15(1H,m), 7.39-7.46(2H,m)ppm
3-(4-クロロ-2-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2102,mp110-112)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.14(2H,ABq,J=17.8, Δν=83.2Hz), 3.54(2H,s), 3.88(3H,s), 4.68(2H,s), 6.94-7.02(2H,m), 7.36(1H,d,J=8.1Hz)ppm
3-(2-クロロ-5-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2103,mp101-103)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.12(2H,ABq,J=17.9, Δν=80.8Hz), 3.56(2H,ABq,J=11.6, Δν=8.8Hz), 3.82(3H,s), 4.79(2H,s), 6.91(1H,dd,J=8.9,3.0Hz), 7.10(1H,d,J=3.1Hz), 7.35(1H,d,J=8.9Hz)ppm
3-(5-クロロ-2-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2104,mp109-111)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.14(2H,ABq,J=17.9, Δν=83.4Hz), 3.55(2H,ABq,J=11.7, Δν=5.7Hz), 3.87(3H,s), 4.68(2H,s), 6.89(1H,d,J=8.8Hz), 7.34(1H, dd, J=8.8,2.5Hz), 7.41(1H,d,J=2.5Hz)ppm
3-(4-クロロ-3-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2105,mp91-93)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.10(2H,ABq,J=17.7, Δν=85.0Hz), 3.54(2H,ABq,J=11.7, Δν=14.6Hz), 3.93(3H,s), 4.58(2H,s), 6.93-7.00(2H,m), 7.40(1H,d,J=8.0Hz)ppm
3-(3,5-ジクロロ-2-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2106,mp85-87)1H-NMR(200MHz,CDCl3)δ: 1.61(3H,s), 3.24(2H,ABq,J=17.9, Δν=81.9Hz), 3.61(2H,ABq,J=11.6, Δν=15.2Hz), 3.96(3H,s), 4.68(2H,s), 7.39(1H,d,J=2.6Hz), 7.44(1H,d,J=2.6Hz)ppm
3-(2,6-ジメトキシ-3-クロロベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2107,mp85-88)
1H-NMR(200MHz,CDCl3)δ: 1.61(3H,s), 3.20(2H,ABq,J=17.6, Δν=84.4Hz), 3.61(2H,ABq,J=11.4, Δν=15.5Hz), 3.87(3H,s), 3.96(3H,s), 4.78(2H,s), 6.70(1H,d,J=8.9Hz), 7.37(1H,d,J=8.9Hz)ppm
3-(2-クロロ-3,4-ジメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2108,oil)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 3.17(2H,ABq,J=17.8, Δν=81.0Hz), 3.57(2H,ABq,J=11.6, Δν=8.1Hz), 3.88(3H,s), 3.90(3H,s), 4.78(2H,s), 6.89(1H,d,J=8.9Hz), 7.29(1H,d,J=8.9Hz)ppm
3-(3,5-ジクロロ-4-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2109,mp126-127)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 3.38(2H,ABq,J=17.8, Δν=77.9Hz), 3.58(2H,ABq,J=11.8, Δν=11.5Hz), 3.92(3H,s), 4.51(2H,s), 7.83(2H,s)ppm
3-(3-クロロ-2-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2110,oil)
1H-NMR(200MHz,CDCl3)δ: 1.46(3H,t,J=7.0Hz), 1.59(3H,s), 3.15(2H,ABq,J=17.8, Δν=79.8Hz), 3.58(2H,ABq,J=11.6, Δν=14.5Hz), 4.12(2H,q,J=7.2Hz), 4.68(2H,s), 7.17(1H,t,J=8.0Hz), 7.41(1H,q,J=1.6Hz), 7.45(1H,q,J=1.8Hz)ppm
3-(4-クロロ-2-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2111,mp118)
1H-NMR(200MHz,CDCl3)δ: 1.45(3H,t,J=6.9Hz), 1.54(3H,s), 3.09(2H,ABq,J=17.6, Δν=84.2Hz), 3.53(2H,s), 4.08(2H,q,J=6.9Hz), 4.69(2H,s), 6.92-7.00(2H,m), 7.36(1H, d,J=8.1Hz)ppm
3-(2-クロロ-5-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2112,mp113-114)
1H-NMR(200MHz,CDCl3)δ: 1.42(3H,t,J=7.0Hz), 1.54(3H,s), 3.10(2H,ABq,J=17.8, Δν=80.6Hz), 3.55(2H,d,J=3.3Hz), 4.03(2H,q,J=7.0Hz), 4.77(2H,s), 6.89(1H,dd,J=8.8, 3.1Hz), 7.08(1H,d,J=3.1Hz), 7.34(1H,d,J=8.8Hz)ppm
3-(5-クロロ-2-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2113,mp75-77)
1H-NMR(200MHz,CDCl3)δ: 1.44(3H,t,J=7.0Hz), 1.55(3H,s), 3.09(2H,ABq,J=17.8, Δν=84.2Hz), 3.55(2H,s), 4.07(2H,q,J=7.0Hz), 4.69(2H,s), 6.86(1H,d,J=8.8Hz), 7.31(1H,dd,J=8.8,2.6Hz), 7.40(1H,d,J=2.6Hz)ppm
3-(4-クロロ-3-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2114,mp85-88)
1H-NMR(200MHz,CDCl3)δ: 1.48(3H,t,J=7.0Hz), 1.53(3H,s), 3.08(2H,ABq,J=17.8, Δν=85.3Hz), 3.53(2H,ABq,J=11.7, Δν=8.2Hz), 4.13(2H,q,J=7.0Hz), 4.56(2H,s), 6.92(1H,dd,J=8.0,2.0Hz), 6.98(1H,d,J=2.0Hz), 7.38(1H,d,J=8.0Hz)ppm
3-(3,5-ジクロロ-2-エトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2115,mp78-80)
1H-NMR(200MHz,CDCl3)δ: 1.45(3H,t,J=6.8Hz), 1.61(3H,s), 3.21(2H,ABq,J=17.8, Δν=80.5Hz), 3.60(2H,ABq,J=11.4, Δν=15.2Hz), 4.15(2H,q,J=6.8Hz), 4.66(2H,s), 7.40(1H,d,J=2.4Hz), 7.44(1H,d,J=2.6Hz)ppm
3-(4-クロロ-2-イソプロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2116,mp92-95)
1H-NMR(200MHz,CDCl3)δ: 1.38(6H,d,J=6.0Hz), 1.54(3H,s), 3.09(2H,ABq,J=17.7, Δν=82.3Hz), 3.53(2H,d,J=1.4Hz), 4.58(1H,m), 4.68(2H,s), 6.92(1H,m), 6.97(1H,d,J=1.9Hz), 7.35(1H,d,J=7.9Hz)ppm
3-(2-クロロ-5-イソプロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2117,mp53-57)
1H-NMR(200MHz,CDCl3)δ: 1.33(6H,d,J=6.0Hz), 1.56(3H,s), 3.10(2H,ABq,J=17.8, Δν=80.5Hz), 3.55(2H,ABq,J=11.6, Δν=7.9Hz), 4.53(1H,quintet,J=6.1Hz), 4.77(2H,s), 6.87(1H,dd,J=8.9,3.0Hz), 7.07(1H,d,J=3.0Hz), 7.33(1H,d,J=8.9Hz)ppm
3-(5-クロロ-2-イソプロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2118,mp64-66)
1H-NMR(200MHz,CDCl3)δ: 1.36(6H,d,J=6.1Hz), 1.55(3H,s), 3.10(2H,ABq,J=17.8, Δν=82.4Hz), 3.54(2H,ABq,J=11.6, Δν=7.0Hz), 4.57(1H,quintet,J=6.0Hz), 4.68(2H,s), 6.86(1H,d,J=8.8Hz), 7.30(1H,dd,J=8.8,2.6Hz), 7.40(1H,d,J=2.6Hz)ppm
3-(4-クロロ-3-イソプロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2119,mp94-95)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 3.09(2H,ABq,J=17.8, Δν=85.8Hz), 3.54(2H,ABq,J=11.7, Δν=7.5Hz), 4.56(2H,s), 4.59(1H,quintet,J=6.3Hz), 6.91(1H,dd,J=8.1,1.9Hz), 7.01(1H,d,J=1.9Hz), 7.38(1H,d,J=8.1Hz)ppm
3-(2-フルオロ-6-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2120,mp105-107)
1H-NMR(200MHz,CDCl3)δ: 1.60(3H,s), 3.20(2H,ABq,J=17.8, Δν=84.3Hz), 3.58(2H,ABq,J=11.5, Δν=7.2Hz), 3.91(3H,s), 4.76(2H,d,J=1.2Hz), 6.74-6.82(2H,m), 7.30-7.41(1H,m)ppm
3-(2-エトキシ-3-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2121,oil)
1H-NMR(200MHz,CDCl3)δ: 1.38(3H,t,J=7.0Hz), 1.56(3H,s), 3.07(2H,ABq,J=17.8, Δν=67.1Hz), 3.55(2H,ABq,J=11.4, Δν=15.5Hz), 3.85(2H,s), 4.15(2H,q,J=7.0Hz), 4.68(2H,d,J=1.5Hz), 6.93-6.98(1H,m), 7.05-7.09(2H,m)ppm
3-(2-エトキシ-6-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2122,mp105-108)
1H-NMR(200MHz,CDCl3)δ: 1.43(3H,t,J=7.0Hz), 1.50(3H,s), 3.08(2H,ABq,J=17.7, Δν=88.6Hz), 3.52(2H,s), 3.86(3H,s), 4.09(2H,q,J=7.0Hz), 4.82(2H,s), 6.57(2H,d,J=8.4Hz), 7.30(1H,t,J=8.4Hz)ppm
3-(3-メトキシ-2-プロピルオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2123,oil)
1H-NMR(200MHz,CDCl3)δ: 1.02(3H,t,J=7.4Hz), 1.54(3H,s), 1.79(2H,septet,J=7.2Hz), 3.03(2H,ABq,J=17.6,Δν=63.6Hz), 3.54(2H,ABq,J=11.5, Δν=14.6Hz), 3.85(3H,s), 4.02(2H,t,J=6.7Hz), 4.67(2H,q,J=13.8Hz), 6.92-6.99(1H,m), 7.03-7.08(2H,m)ppm
3-(2-イソプロピルオキシ-3-メトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2124,mp95-98)
1H-NMR(200MHz,CDCl3)δ: 1.27(6H,dd,J=6.1,2.7Hz), 1.53(3H,s), 3.07(2H,ABq,J=17.7,Δν=50.6Hz), 3.53(2H,ABq,J=11.3, Δν=15.6Hz), 3.84(3H,s), 4.64(1H,septet,J=6.3Hz), 4.64(2H,ABq,J=13.8,Δν=16.4Hz), 6.92-6.97(1H,m), 7.07-7.10(2H,m)ppm
3-(2,3-メチレンジオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2125,mp121-122)1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.13(2H,ABq,J=17.8, Δν=85.2Hz), 3.54(2H,ABq,J=11.7, Δν=6.2Hz), 4.60(2H,s), 6.02(2H,s), 6.85-6.95(3H,m)ppm
3-(3,4-メチレンジオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2126,mp81-83)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.07(2H,ABq,J=17.4, Δν=76.7Hz), 3.52(2H,s), 4.51(2H,s), 6.00(2H,s), 6.80-6.90(3H,m)ppm
3-(2,3-エチレンジオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2127,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.08(2H,ABq,J=17.8, Δν=88.8Hz), 3.52(2H,s), 4.25-4.34(4H,m), 4.67(2H,s), 6.82-7.01(3H,m)ppm
3-(3,4-エチレンジオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2128,mp74-76)
1H-NMR(200MHz,CDCl3)δ: 1.52(3H,s), 2.99(2H,ABq,J=18.0, Δν=71.3Hz), 3.50(2H,s), 4.25(4H,s), 4.46(2H,s), 6.88(2H,s), 6.91(1H,s)ppm
3-(2-メチル-3,4-エチレンジオキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2131,mp110-112)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.26(3H,s), 3.03(2H,ABq,J=18.0, Δν=75.9Hz), 3.52(2H,s), 4.24-4.28(4H,m), 4.61(2H,s), 6.76(1H,d,J=8.4Hz), 6.87(1H,d,J=8.5Hz)ppm
3-(4-トリフルオロメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2142,mp106-107)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 3.12(2H,ABq,J=17.6, Δν=85.0Hz), 3.54(2H,ABq,J=11.8, Δν=8.8Hz), 4.62(2H,s), 7.27(2H,d,J=8.4Hz), 7.49(2H,d,J=8.4Hz)ppm
3-(2-ジフルオロメトキシ-3-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2143,oil)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 2.35(3H,s), 3.20(2H,ABq,J=17.7, Δν=77.8Hz), 3.58(2H,ABq,J=11.7, Δν=8.9Hz), 4.73(1H,s), 6.47(1H,t,J=73.3Hz),7.26-7.34(2H,m), 7.43(1H,dd,J=7.0,1.8Hz)ppm
3-(2-ジフルオロメトキシ-4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2144,oil)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 2.39(3H,s), 3.19(2H,ABq,J=17.8, Δν=77.3Hz), 3.57(2H,ABq,J=11.6, Δν=9.0Hz), 4.70(2H,s), 6.52(1H,t,J=73.7Hz), 7.04-7.11(2H,m), 7.40(1H,d,J=7.7Hz)ppm
3-(2-ジフルオロメトキシ-5-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2145,mp64)
1H-NMR(200MHz,CDCl3)δ: 1.58(3H,s), 2.36(3H,s), 3.20(2H,ABq,J=17.8, Δν=80.0Hz), 3.57(2H,ABq,J=11.7, Δν=9.8Hz), 4.68(2H,s), 6.51(1H,t,J=73.8Hz), 7.18(2H,dd,J=1.8,8.3Hz), 7.26(1H,d,J=1.8Hz)ppm
3-(3-ジフルオロメトキシ-4-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2146,mp63-65)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 2.31(3H,s), 3.10(2H,ABq,J=17.8, Δν=78.8Hz), 3.53(2H,d,J=1.4Hz), 4.58(2H,s), 6.54(1H,t,J=73.6Hz), 7.16-7.21(3H,m)ppm
3-(3-クロロ-2-ジフルオロメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2147,oil)
1H-NMR(200MHz,CDCl3)δ: 1.60(3H,s), 3.24(2H,ABq,J=17.8, Δν=78.7Hz), 3.58(2H,ABq,J=11.7, Δν=11.2Hz), 4.76(2H,s), 6.60(1H,t,J=73.6Hz), 7.30-7.34(1H,m), 7.52-7.56(2H,m)ppm
3-(2-クロロ-5-ジフルオロメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2148,mp85-86)
1H-NMR(200MHz,CDCl3)δ: 1.60(3H,s), 3.21(2H,ABq,J=17.8, Δν=80.6Hz), 3.58(2H,ABq,J=11.7, Δν=10.7Hz), 4.83(2H,s), 6.53(1H,t,J=72.8Hz), 7.16(1H,dd,J=8.8,2.8Hz), 7.36(1H,d,J=2.8Hz), 7.47(1H,d,J=8.8Hz)ppm
3-(5-クロロ-2-ジフルオロメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2149,oil)
1H-NMR(200MHz,CDCl3)δ: 1.60(3H,s), 3.24(2H,ABq,J=17.8, Δν=80.6Hz), 3.59(2H,ABq,J=11.7, Δν=12.4Hz), 4.71(2H,s), 6.52(1H,t,J=73.2Hz), 7.20(1H,d,J=8.8Hz), 7.41(1H,dd,J=8.8,2.6Hz), 7.52(1H,d,J=2.6Hz)ppm
3-(4-クロロ-3-ジフルオロメトキシベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2150,oil)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.18(2H,ABq,J=17.8, Δν=80.8Hz), 3.56(2H,ABq,J=11.9, Δν=10.3Hz), 4.59(2H,s), 6.57(1H,t,J=72.9Hz), 7.26(1H,dd,J=8.2,2.0Hz), 7.34(1H,br), 7.50(1H,d,J=8.2Hz)ppm
3-(2-メトキシメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2151,oil)
1H-NMR(200MHz,CDCl3)δ: 1.54(3H,s), 3.04(2H,ABq,J=18.0, Δν=81.8Hz), 3.41(3H,s), 3.54(2H,ABq,J=12.7, Δν=5.7Hz), 4.61(2H,s), 4.83(2H,s), 7.36-7.49(4H,m)ppm
3-(2-エトキシメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2152,oil)
1H-NMR(200MHz,CDCl3)δ: 1.25(3H,t,J=7.0Hz), 1.54(3H,s), 3.04(2H,ABq,J=17.8, Δν=81.3Hz), 3.47-4.14(4H,m), 4.66(2H,s), 4.86(2H,s), 7.33-7.48(4H,m)ppm
3-(2-(2,2,2-トリフルオロエトキシメチル)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2153,mp<40)
1H-NMR(200MHz,CDCl3)δ: 1.56(3H,s), 3.13(2H,ABq,J=17.8, Δν=83.7Hz), 3.56(2H,d,J=3.2Hz), 3.86(2H,q,J=8.8Hz), 4.83(2H,s), 4.87(2H,s), 7.4-7.5(4H,m)ppm
3-(3-(2,2,2-トリフルオロエトキシメチル)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2154,mp<40)
1H-NMR(200MHz,CDCl3)δ: 1.53(3H,s), 3.07(2H,ABq,J=17.6, Δν=80.5Hz), 3.51(2H,d,J=1.6Hz) 3.86(2H,q,J=8.8Hz), 4.62(2H,s), 4.70(2H,s), 7.41-7.43(4H,m)ppm
3-(2-(2-メトキシエトキシ)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2155,oil)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 3.03(2H,ABq,J=17.8, Δν=78.1Hz), 3.45(3H,s), 3.50(2H,d,J=1.5Hz), 3.77(2H,t,J=4.8Hz), 4.17(2H,t,J=4.8Hz), 4.73(2H,s), 6.94-7.05(2H,m), 7.32-7.46(2H,m)ppm
3-(3-(2-メトキシエトキシ)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2156,oil)
1H-NMR(200MHz,CDCl3)δ: 1.50(3H,s), 2.96(2H,ABq, J=17.7,Δν=82.3Hz), 3.46(3H,s), 3.49(2H,s), 3.76(2H,t,J=4.6Hz), 4.13(2H,t,J=4.6Hz), 4.56(2H,s), 6.99(3H, d, J=3.5Hz), 7.27-7.36(1H,m)ppm
3-(2-(2,2-ジメトキシエトキシ)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2157,oil)
1H-NMR(200MHz,CDCl3)δ: 1.52(3H,s), 3.03(2H,ABq,J=17.8, Δν=80.2Hz), 3.48(6H,s), 3.51(2H,d,J=1.5Hz), 4.04(2H,d,J=5.3Hz), 4.74(3H,t), 6.93-7.06(2H,m), 7.33-7.46(2H,m)ppm
3-(3-(2,2-ジメトキシエトキシ)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2158,mp55-58)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 2.98(2H,ABq,J=17.9, Δν=81.4Hz), 3.47(6H,s), 3.50(2H,s), 4.02(2H,d,J=5.2Hz), 4.56(2H,s), 4.72(1H,t,J=5.2Hz), 6.96-7.03(3H,m), 7.26-7.34(1H,m)ppm
3-(2-(2,2-エチレンジオキシエトキシ)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2159,oil)
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 3.04(2H,ABq,J=17.7, Δν=76.1Hz), 3.50(2H,ABq,J=11.6, Δν=5.7Hz), 3.92-4.07(4H,m), 4.09(2H,d,J=3.8Hz), 4.73(2H,s), 5.30(1H,t,J=3.7Hz), 6.94-7.07(2H,m), 7.33-7.48(2H,m)ppm
3-(3-(2,2-エチレンジオキシエトキシ)ベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2160,mp74-76)
1H-NMR(200MHz,CDCl3)δ: 1.50(3H,s), 2.97(2H,ABq,J=17.9, Δν=81.6Hz), 3.49(2H,s), 3.96-4.11(6H,m), 4.55(2H,s), 5.29(1H,t,J=3.8Hz), 6.97-7.03(3H,m), 7.26-7.32(1H,m)ppm
3-(α-メチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2161,mp62-64)
1H-NMR(200MHz,CDCl3)δ: 1.36(s)+1.47(s)(3H), 1.88(3H,d,J=7.2Hz), 2.69(ABq,J=17.9, Δν=179.4Hz)+2.70(s)(2H), 3.31(ABq,J=11.5, Δν=17.7Hz)+3.45(s)(2H), 4.58(q,J=7.2Hz)+4.59(q,J=7.2Hz)(1H), 7.39-7.45(5H,m)ppm
3-(α，α-ジメチルベンジルスルホニル)-5-クロロメチル-5-メチル-2-イソオキサゾリン(2162,mp102-105)
1H-NMR(200MHz,CDCl3)δ: 1.32(3H,s), 1.95(6H,s), 2.26(2H,ABq,J=18.0, Δν=88.6Hz), 3.31(2H,ABq,J=11.5, Δν=10.0Hz), 7.41-7.47(3H,m), 7.60-7.65(2H,m)ppm
3-(α-イソプロピルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2165,mp75-80)
1H-NMR(200MHz,CDCl3)δ: 0.92(3H,d,J=6.7Hz), 1.31(d,J=6.6Hz)+1.33(d,J=6.6Hz)(3H), 1.19(s)+1.40(s)(3H), 1.82-3.38(5H,m), 4.18(d,J=8.7Hz)+4.20(d,J=8.2Hz)(1H), 7.42(5H,s)ppm
3-( α,2-ジメチルベンジル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2166,oil)
1H-NMR(200MHz,CDCl3)δ: 1.31(s)+1.55(s)(3H), 1.83(3H,d,J=7.0Hz), 2.41(3H,d,J=1.9Hz), 2.71(ABq,J=18.0, Δν=202.4Hz)+2.73(ABq,J=16.9,Δν=25.8Hz)(2H), 3.25(ABq,J=11.5,Δν=29.5Hz)+3.48(d,J=2.1Hz)(2H), 7.21-7.34(3H,m), 7.56-7.61(1H,m)ppm
3-(4-クロマニル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2167,oil)
1H-NMR(200MHz,CDCl3)δ: 1.55(3H,s), 2.39-2.47(1H,m), 2.72-2.96(1H,m), 2.99(d,J=4.8Hz)+3.02(ABq,J=17.9,Δν=143.2Hz)(2H), 3.45(s)+3.57(ABq,J=11.8, Δν=15.2Hz)(2H), 4.22-4.30(1H,m), 4.46-4.60(1H,m), 4.66-4.72(1H,m), 6.91-7.01(2H,m), 7.30-7.34(1H,m), 7.47-7.51(1H,m)ppm
3-(1-インダニル)スルホニル-5-クロロメチル-5-メチル-2-イソオキサゾリン(2168,oil)
1H-NMR(200MHz,CDCl3)δ: 1.38(s)+1.52(s)(3H), 2.35-3.59(8H,m), 4.92(1H,dt,J=8.9,3.3Hz), 7.28-7.37(3H,m), 7.64(1H,d,J=7.3Hz)ppm
3-(1-(1,2,3,4-テロラヒドロナフチル)スルホニル)-5-クロロメチル-5-メチル-2-イソオキサゾリン(2169,oil)
1H-NMR(200MHz,CDCl3)δ: 1.38(s)+1.50(s)(3H), 2.18-2.29(2H,m), 2.61-2.85(4H,m), 2.79(2H,ABq,J=17.9, Δν=176.0Hz), 3.36(d,J=4.3Hz)+3.51(d,J=3.2Hz)(2H), 4.67-4.72(1H,m), 7.17-7.35(3H,m), 7.54-7.60(1H,m)ppm
3-ベンジルスルホニル-5-(2-クロロエチル)-5-メチル-2-イソオキサゾリン(2170,mp74-75)
1H-NMR(200MHz,CDCl3)δ: 1.39(3H,s), 2.13(2H,t,J=7.3Hz), 2.86(2H,ABq,J=17.6, Δν=32.9Hz), 3.49(2H,t,J=7.3Hz), 4.61(2H,s), 7.43(5H,s)ppm
3-ベンジルスルホニル-5-ジフルオロメチル-5-メチル-2-イソオキサゾリン(2178,mp78-80)
1H-NMR(200MHz,CDCl3)δ: 1.47(3H,s), 3.02(2H,ABq,J=18.1, Δν=95.4Hz), 4.61(2H,s), 5.65(1H,t,J=55.5Hz), 7.35-7.46(5H,br)ppm
3-ベンジルスルホニル-5-トリフルオロメチル-5-メチル-2-イソオキサゾリン(2179,mp106-107)
1H-NMR(200MHz,CDCl3)δ: 1.57(3H,s), 3.11(2H,ABq,J=18.3, Δν=79.9Hz), 4.62(2H,s), 7.43(5H,s)ppm
3-ベンジルスルホニル-5-クロロメチル-5-エチル-2-イソオキサゾリン(2181,oil)
1H-NMR(200MHz,CDCl3)δ: 0.92(3H,t,J=7.4Hz), 1.81(2H,q,J=7.4Hz), 3.00(2H,ABq,J=18.0,Δν=51.0Hz), 3.51(2H,ABq,J=11.8, Δν=7.0Hz), 4.60(2H,s), 7.42(5H,s)ppm
【０１２０】
【実施例３】
３−ベンジルチオ−５−クロロメチル−５−エチル−２−イソオキサゾリン（化合物番号１８１）（Ｅ工程）
実施例１の方法に準じて製造した３−ベンジルチオ−５−ヒドロキシメチル−５−エチル−２−イソオキサゾリン３．０３ｇとトリフェニルホスフィン３．３８ｇを四塩化炭素３０ｍｌに溶かし、一晩還流した。室温に冷却後、反応溶液を濾過し、溶媒を留去後、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝４０：１）により精製し、油状の目的物１．１３ｇ（２８％）を得た。
【０１２１】
1H-NMR(200MHz,CDCl3)δ: 0.98(3H,t,j=7.4Hz), 1.85(2H,q,J=7.4Hz), 2.98(2H,ABq,J=16.9, Δν=50.9Hz), 3,55(2H,ABq,J=11.3, Δν=17.5Hz), 4.26(2H,s), 7.28-7.41(5H,m)ppm
【０１２２】
【実施例４】
３−ベンジルチオ−５−ジフルオロメチル−５−メチル−２−イソオキサゾリン（化合物番号１７８）（Ｈ、Ｉ工程）
（１）３−ベンジルチオ−５−ホルミル−５−メチル−２−イソオキサゾリン（Ｈ工程）
オキザリルクロリド０．１１ｍｌを塩化メチレン３ｍｌに溶解し、−６０℃に冷却した後、Ｎ，Ｎ−ジメチルスルホキシド０．１５ｍｌと塩化メチレン１．９ｍｌの混合溶液を滴下した。−６０℃で２０分間撹拌した後、実施例１の方法に準じて製造した３−ベンジルチオ−５−ヒドロキシメチル−５−メチル−２−イソオキサゾリン２４４．３ｍｇの塩化メチレン溶液２ｍｌを滴下し、−６０℃で２０分間撹拌した。更に反応溶液にトリエチルアミン０．４３ｍｌを加え、−６０℃で３０分間、室温に昇温しながら１時間４０分撹拌した。反応溶液に水を加え、塩化メチレンで抽出し、有機層を水、１Ｎ−塩酸及び飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。濾過し、溶媒を留去後、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）により精製し、油状の目的物２３８．１ｍｇ（９８％）を得た。
【０１２３】
1H-NMR(200MHz,CDCl3)δ: 1.51(3H,s), 3.09(2H,ABq,J=16.5, Δν=103.9Hz), 4.26(2H,d,J=1.2Hz), 7.28-7.40(5H,m), 9.62(1H,s)ppm
（２）３−ベンジルチオ−５−ジフルオロメチル−５−メチル−２−イソオキサゾリン（化合物番号１７８）（Ｉ工程）
（１）の方法で製造した３−ベンジルチオ−５−ホルミル−５−メチル−２−イソオキサゾリン２２０．８ｍｇを塩化メチレン４．４ｍｌに溶解し、氷水浴中、ジエチルアミノサルファトリフルオライド（ＤＡＳＴ）０．５ｍｌを加えた。２時間攪拌した後、氷水浴を取り除き、室温まで昇温した。更に１２時間攪拌した後、反応溶液に氷を加え、塩化メチレンで抽出し、有機層を水、飽和食塩水で順に洗浄し、無水硫酸ナトリウムで乾燥した。濾過し、溶媒を留去後、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝５０：１）により精製し、油状の目的物１１６．４ｍｇ（４８％）を得た。
【０１２４】
1H-NMR(200MHz,CDCl3)δ: 1.49(3H,s), 3.04(2H,ABq,J=16.9, Δν=80.6Hz), 4.27(2H,s), 5.68(1H,t,J=56.0Hz), 7.23-7.42(5H,m)ppm
【０１２５】
【製剤例】
【０１２６】
【製剤例１】
（水和剤）
化合物番号２１６１番の化合物２５％、ドデシルベンゼンスルホン酸ナトリウム塩２．５％、リグニンスルホン酸カルシウム塩２．５％及び珪藻土７０％をよく粉砕混合して水和剤を得た。
【０１２７】
【製剤例２】
（乳剤）
化合物番号２番の化合物３０％、ドデシルベンゼンスルホン酸カルシウム塩２．６８％、ポリエオキシエチレンアルキルエーテル４．９２％、ポリオキシエチレンノニルフェニルエーテルリン酸カルシウム塩０．４％及びキシレン６２％をよく混合して乳剤を得た。
【０１２８】
【製剤例３】
（粒剤）
化合物番号２０１１番の化合物５％、ホワイトカーボン１％、リグニンスルホン酸カルシウム塩５％、ベントナイト２０％及びクレー６９％をよく粉砕混合し、水を加えてよく練り合せた後、造粒乾燥して粒剤を得た。
【０１２９】
【製剤例４】
（水和顆粒）
化合物番号１６２番の化合物８０％、特殊ポリカルボン酸重合物ナトリウム塩１．２５％、水３．７５％、ドデシルベンゼンスルホン酸ナトリウム塩３％、デキストリン７％及び酸化チタン５％を混合し、次いでエアーミルで粉砕し、回転ミキサー又は流動床ミキサー中に加え、水を噴霧して顆粒化させた。大部分が１．０−０．１５ｍｍになったら顆粒を取り出し、乾燥後、篩にかけた。オーバーサイズの物質を粉砕し、１．０−０．１５ｍｍの顆粒を得た。
【０１３０】
【製剤例５】
（水性懸濁液）
化合物番号２１７０番の化合物２５部、ナトリウムジオクチルスルホサクシネート０．７部、プロピレングリコール０．１５部、リグニンスルホン酸カルシウム塩１０部、水４４．１５部及びプロピレングリコール１０部を固形粒子が５ミクロン以下の直径に減少されるまで、ボールミル、サンドミル又はローラーミル中で一緒に粉砕した。この粉砕スラリー９０部に、０．０５％（Ｗ／Ｗ）キサンタンガム水溶液１０部を加えて混合し、水性懸濁液を得た。
【０１３１】
【発明の効果】
本発明の化合物（Ｉ）は、殺草作用を有しており、除草剤として使用することができる。その作用は一般に双子葉植物に対するよりも単子葉植物に対する方が強い。例えば、水田においては、雑草の発芽前又は発芽後に湛水土壌処理することにより、水田の強雑草であるタイヌビエ、ヒメタイヌビエ、ケイヌビエ等のイネ科雑草を特に強力に駆除し、また従来の除草剤では防除が困難なマツバイ、ホタルイ、クログワイ、ミズガヤツリ等のカヤツリグサ科多年生雑草及びウリカワ、オモダカ等のオモダカ科多年生雑草も駆除することができ、更に、アゼナ等のゴマノハグサ科雑草、キカシグサ、ヒメミソハギ、ミズマツバ等のミソハギ科雑草、コナギ、ミズアオイ等のミズアオイ科雑草の広葉雑草をも有効に駆除することができる。
【０１３２】
一方、水稲に対しては、選択性が大きく、移植水稲は薬害を受けることはなく、処理適用幅が大きいという利点がある。
【０１３３】
また、畑地においては、雑草の発芽前に土壌処理することにより、又は発芽後に茎葉処理することにより、畑地の強雑草であるアカザ、シロザ、コアカザ等のアカザ科雑草、カラシナ等のアブラナ科雑草、イヌビユ、アオゲイトウ、イノコズチ等のヒユ科雑草、イヌホウズキ等のナス科雑草等を有効に駆除することができるが、中でもイヌビユ、メヒシバ、コメヒシバ、エノコログサ、アキノエノコログサ、セイバンモロコシ、オオクサキビ等のイネ科雑草及び黄ハマスゲ等のカヤツリグサ科雑草を極めて強力に駆除することができ、一方、トウモロコシ、ビート、ワタ、ダイズ等の作物は薬害を受けることがない。
【０１３４】
次に、生物試験例を挙げて、具体的にその効果を示す。
【０１３５】
【試験例】
【０１３６】
【試験例１】
水田雑草発芽前処理
１００ｃｍ2 ポットに水田土壌を充填し、休眠覚醒したタイヌビエ、ホタルイの種子を表層１ｃｍに混和した。また、２葉期の水稲の苗を移植して湛水状態とし、温室で生育させた。３日後に、製剤例１に準じて調製した水和剤を用いて所定の薬量を湛水土壌処理し、２１日後に次に示す判定基準に従って調査を行なった。その結果を表２に示した。
（判定基準）
０： 生育抑制率 ０− １０％
１： 生育抑制率 １１− ３０％
２： 生育抑制率 ３１− ５０％
３： 生育抑制率 ５１− ７０％
４： 生育抑制率 ７１− ９０％
５： 生育抑制率 ９１−１００％
【０１３７】
【試験例２】
タイヌビエ１．５葉期処理
試験例１と同じ方法で、タイヌビエの１．５葉期に、製剤例１に準じて調製した水和剤を用いて所定の薬量を湛水土壌処理し、２１日後に調査を行なった。その結果を表２に示した（判定基準は試験例１と同じ）。
【０１３８】
なお、表２において、比較１、比較２、比較３とあるのは、それぞれ比較化合物１、比較化合物２、比較化合物３のことである。
【０１３９】
比較化合物１は、（５−クロロメチル−３−フェニルスルホニル−２−イソオキサゾリン）であり、ヘテロサイクルズ、第２２巻、第１０号、第２１８７ページ（１９８４年）記載の化合物である。
【０１４０】
比較化合物２は、（５−シアノ−５−メチル−３−ベンジルチオ−２−イソオキサゾリン）であり、特開平５−１０５６７２号公報記載の化合物である。
【０１４１】
比較化合物３は、（５−シアノ−５−メチル−３−（３−トリフルオロメチルベンジル）スルホニル−２−イソオキサゾリン）であり、特開平５−１０５６７２号公報記載の化合物である。
【０１４２】
これら比較化合物が除草活性を有するということは、上記文献中には何ら記載されていない。
【０１４３】
【表２】
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
【０１４４】
【試験例３】
畑作雑草発芽前処理
６０ｃｍ3 、深さ４ｃｍの角型ポットにクレハ園芸培土を充填し、各種供試雑草及び作物の種子をそれぞれ播種し、約１ｃｍ覆土した。これらのポットに製剤例２に準じて調製した乳剤を用いて所定の薬量を均一に散布処理した。処理後、これらのポットを温室内において植物を生育した。処理後２１日目に、各雑草に対する除草効果及び作物に対する薬害を、次に示す判定基準に従って調査を行なった。その結果を表３に示した。
【０１４５】
なお、表中ＢＧはイヌビエ（ｂａｒｎｙａｒｄｇｒａｓｓ）、ＣＲはメヒシバ（ｃｒａｂｇｒａｓｓ）、ＦＯはエノコログサ（ｆｏｘｔａｉｌ）、ＪＯはセイバンモロコシ（ｊｏｈｎｓｏｎｇｒａｓｓ）、ＰＡはオオクサキビ（ｐａｎｉｃｕｍ）、ＮＵは黄ハマスゲ（ｙｅｌｌｏｗ ｎｕｔｓｅｄｇｅ）、ＬＡはシロザ（ｌａｍｂｓｑｕａｒｔｅｒｓ）、ＭＵはカラシナ（ｍｕｓｔａｒｄ）、ＰＩはアオゲイトウ（ｐｉｇｗｅｅｄ）を、それぞれ示す。
【０１４６】
（判定基準）
０： 生育抑制率 ０− ９％
１： 生育抑制率 １０−１９％
２： 生育抑制率 ２０−２９％
３： 生育抑制率 ３０−３９％
４： 生育抑制率 ４０−４９％
５： 生育抑制率 ５０−５９％
６： 生育抑制率 ６０−６９％
７： 生育抑制率 ７０−７９％
８： 生育抑制率 ８０−８９％
９： 生育抑制率 ９０−９９％
１０： 生育抑制率 １００％
【０１４７】
【表３】
Figure 0003810838
【０１４８】
【試験例４】
畑作茎葉処理
６０ｃｍ3 、深さ４ｃｍの角型ポットにクレハ園芸培土を充填し、各種供試雑草及び作物の種子をそれぞれ播種し、約１ｃｍ覆土した。これらのポットを温室内において植物を生育した。各植物が２〜３葉期に達した時（播種後約１０日）、これらのポットに、製剤例２に準じて調整した乳剤を用いて所定の薬量を茎葉部に均一に散布処理した。処理後１４日目に、各雑草に対する除草効果及び作物に対する薬害の調査を行なった。その結果を表４に示した（判定基準と及び略号は試験例３と同じ）。
【０１４９】
【表４】
Figure 0003810838
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel isoxazoline derivative having excellent herbicidal activity and a herbicide containing it as an active ingredient.
[0002]
[Prior art]
So far, compounds having a 2-isoxazoline skeleton having herbicidal activity are described in EP334120A1 and EP514987A1.
[0003]
However, the compound described in EP334120A1 is a compound in which an alkyl, cycloalkyl, substituted phenyl, 5-membered and 6-membered heterocycle is directly linked to the 3-isoxazoline ring 3-position, and the 3-isoxazoline ring 3-position is (substituted) The structure is completely different from the compound of the present invention, which is methylene sulfide, (substituted) methylene sulfoxide, and (substituted) methylene sulfone. Further, the compound described in EP 514987A1 is only a compound in which a substituted phenyl group is directly linked to the 3-position of the 2-isoxazoline ring, and the structure is completely different from the compound of the present application.
[0004]
Furthermore, although compounds having a 2-isoxazoline ring are described in JP-A-5-105672, all of these compounds are compounds in which a cyano group is directly connected to the 5-position of the isoxazoline ring. The structure is completely different. Further, JP-A-5-105672 does not describe any herbicidal activity.
[0005]
[Problems to be solved by the invention]
As a result of intensive studies on the synthesis of a derivative having a 2-isoxazoline ring and its biological activity over many years, the present inventors have found a novel 2-isoxazoline derivative having a structure different from that of a known compound. The present invention was completed by finding that it has excellent herbicidal activity.
[0006]
The compound of the present invention shows excellent herbicidal activity at a low dose against Tainubie, which is a particularly harmful weed of paddy fields, and has very little phytotoxicity to paddy rice in paddy fields, and also has the following effects: kogi, azena, absome, kikasugusa. It has a strong herbicidal action against broad-leaved weeds such as firefly and cyperaceae weeds such as firefly and sedge.
[0007]
Furthermore, even in upland fields, it exhibits excellent herbicidal activity at low doses against grass weeds such as barnyard grass, barnyard grass and sorghum, and has very little phytotoxicity against corn, beet, soybean and cotton. In addition, it has strong herbicidal action against broad-leaved weeds such as mustard and mustard.
[0008]
[Structure of the invention]
[0009]
[Means for Solving the Problems]
The present invention relates to the following general formula (I)
[0010]
[Chemical 6]
Figure 0003810838
[0011]
[Wherein R1 Represents a lower alkyl group substituted with 1 to 3 halogen atoms, the same or different, and R2 Represents a lower alkyl group and RThree And RFour Are the same or different and each represents a hydrogen atom or a lower alkyl group, and RFive Is a halogen atom, a lower alkyl group (the lower alkyl group may be substituted with the same or different 1 to 3 substituents selected from the substituent group a) or a lower alkoxy group (the lower alkoxy group May be substituted with the same or different 1 to 3 substituents selected from the substituent group a, and two adjacent lower alkoxy groups may be bonded to form a lower alkylenedioxy group. The lower alkylenedioxy group may be substituted with 1 to 4 halogen atoms which may be the same or different, or RFour And RFive Together may form a lower alkylene group or a lower alkyleneoxy group (when m is 2 or more, RFive May be the same or different), m represents 0, 1, 2, 3, 4 or 5, and n represents 0, 1 or 2.
[0012]
(Substituent group a)
A halogen atom, a lower alkoxy group (the lower alkoxy group may be substituted by the same or different 1 to 3 halogen atoms, and two adjacent lower alkoxy groups are bonded to form a lower alkylenedioxy group; May be formed)]
Preferably,
[Wherein R1 Represents an alkyl group having 1 or 2 carbon atoms substituted with 1 to 3 halogen atoms which are the same or different, and R2 Represents an alkyl group having 1 or 2 carbon atoms, and RThree And RFour Are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;Five Is a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms (two adjacent alkoxy groups are bonded to form an alkylenedioxy group having 1 or 2 carbon atoms) (If m is 2, RFive May be the same or different), m represents 0, 1 or 2, and n represents 0 or 2. ]
More preferably,
[Wherein R1 Represents an alkyl group having 1 or 2 carbon atoms substituted by 1 to 3 chlorine atoms, and R2 Represents a methyl group and RThree And RFour Are the same or different and each represents a hydrogen atom or a methyl group;Five Is a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, an isopropyloxy group (two adjacent methoxy groups and ethoxy groups are bonded to form a methylenedioxy group, ethylene Dioxy group may be formed) (when m is 2, RFive May be the same or different), m represents 0, 1 or 2, and n represents 0 or 2. More preferably,
[Wherein R1 Represents a chloromethyl group and R2 Represents a methyl group and RThree And RFour Represents a hydrogen atom and RFive Is a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group (two adjacent methoxy groups or ethoxy groups may combine to form a methylenedioxy group or an ethylenedioxy group) (When m is 2, RFive May be the same or different), m represents 1 or 2, and n represents 2. ]
Even more preferably,
[Wherein R1 Represents a chloromethyl group and R2 Represents a methyl group and RThree And RFour Represents a hydrogen atom and RFive Represents a chlorine atom, an ethyl group, or a methoxy group (two adjacent methoxy groups may be bonded to form a methylenedioxy group).Five May be the same or different), m represents 1 or 2, and n represents 2. ]
It is a compound represented by these.
[0013]
In the present application, the “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R1 Are preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.
[0014]
RFive Are preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom or a chlorine atom,
RFive Is preferably a fluorine atom when it forms a lower alkylenedioxy group. In the substituent group a, it is preferably a fluorine atom, and when the substituent group a is a lower alkoxy group, it is preferably a fluorine atom.
[0015]
In the present application, “lower alkyl group” means, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, 1- Ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1, A straight-chain or branched alkyl group having 1 to 6 carbon atoms such as 2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl and 2-ethylbutyl. R1 And R2 Are preferably methyl or ethyl, and more preferably methyl. RThree And RFour Are preferably a straight-chain or branched alkyl group having 1 to 3 carbon atoms, and more preferably methyl. RFive Are preferably methyl, ethyl and isopropyl, and most preferably methyl and ethyl.
[0016]
In the present application, the “lower alkoxy group” means, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentyloxy, isopentyloxy, 2-methylbutoxy , Neopentyloxy, 1-ethylpropoxy, n-hexyloxy, 4-methylpentyloxy, 3-methylpentyloxy, 2-methylpentyloxy, 1-methylpentyloxy, 3,3-dimethylbutoxy, 2,2- Linear or branched having 1 to 6 carbon atoms such as dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 2-ethylbutoxy It is a chain alkoxy group. RFive Are preferably straight-chain or branched alkoxy groups having 1 to 4 carbon atoms, and most preferably methoxy or ethoxy. In the substituent group a, methoxy and ethoxy are preferable, and ethoxy is more preferable.
[0017]
In the present application, the “lower alkylene group” means, for example, methylene, ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, methylmethylene, ethylmethylene, dimethylmethylene, n-propylmethylene, isopropylmethylene, methylethylmethylene, n- Butylmethylene, isobutylmethylene, s-butylmethylene, methyl n-propylmethylene, methylisopropylmethylene, diethylmethylene, n-pentylmethylene, isopentylmethylene, 2-methylbutylmethylene, neopentylmethylene, 1-ethylpropylmethylene, methyl 1- to 6-carbon straight or branched chain polymers such as n-butylmethylene, methylisobutylmethylene, methyls-butylmethylene, methyl t-butylmethylene, ethyl n-propylmethylene, ethylisopropylmethylene It is a ruxylene group. RFour And RFive Are preferably a straight-chain or branched alkylene group having 2 to 3 carbon atoms.
[0018]
In the present application, the “lower alkyleneoxy group” means, for example, methyleneoxy, ethyleneoxy, propyleneoxy, tetramethyleneoxy, pentamethyleneoxy, hexamethyleneoxy, methylmethyleneoxy, ethylmethyleneoxy, dimethylmethyleneoxy, n-propylmethylene Oxy, isopropylmethyleneoxy, methylethylmethyleneoxy, n-butylmethyleneoxy, isobutylmethyleneoxy, s-butylmethyleneoxy, methyl n-propylmethyleneoxy, methylisopropylmethyleneoxy, diethylmethyleneoxy, n-pentylmethyleneoxy, iso Pentylmethyleneoxy, 2-methylbutylmethyleneoxy, neopentylmethyleneoxy, 1-ethylpropylmethyleneoxy, methyl n-butylmethyleneoxy, methylisobutyl A straight-chain or branched alkyleneoxy group having 1 to 6 carbon atoms such as methyleneoxy, methyl s-butylmethyleneoxy, methyl t-butylmethyleneoxy, ethyl n-propylmethyleneoxy, ethylisopropylmethyleneoxy. RFour And RFive Are preferably a straight-chain or branched alkyleneoxy group having 2 to 3 carbon atoms, more preferably ethyleneoxy.
[0019]
In the present application, the “lower alkylenedioxy group” means, for example, methylenedioxy, ethylenedioxy, propylenedioxy, tetramethylenedioxy, pentamethylenedioxy, hexamethylenedioxy, methylmethylenedioxy, ethylmethylenedioxy , Dimethylmethylenedioxy, n-propylmethylenedioxy, isopropylmethylenedioxy, methylethylmethylenedioxy, n-butylmethylenedioxy, isobutylmethylenedioxy, s-butylmethylenedioxy, methyln-propylmethylenedioxy , Methylisopropylmethylenedioxy, diethylmethylenedioxy, n-pentylmethylenedioxy, isopentylmethylenedioxy, 2-methylbutylmethylenedioxy, neopentylmethylenedioxy, 1-ethylpropylmethylenedioxy 1 carbon number such as methyl n-butylmethylenedioxy, methylisobutylmethylenedioxy, methyl s-butylmethylenedioxy, methyl t-butylmethylenedioxy, ethyl n-propylmethylenedioxy, ethylisopropylmethylenedioxy To 6 straight or branched alkylenedioxy groups. RFive In the substituent group a, a linear or branched alkylenedioxy group having 1 to 3 carbon atoms is preferable, and methylenedioxy and ethylenedioxy are more preferable.
[0020]
R1 The lower alkyl group substituted by the same or different 1 to 3 halogen atoms is, for example, chloromethyl, 2-chloroethyl, dichloromethyl, trichloromethyl, bromomethyl, 2-bromoethyl, dibromomethyl, fluoromethyl, 2 -A halogen-substituted lower alkyl group such as fluoroethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, and perfluoropropyl, preferably chloromethyl and difluoromethyl. More preferred is chloromethyl.
[0021]
RFive The “lower alkylenedioxy group substituted by the same or different 1 to 4 halogen atoms” is, for example, a group such as fluoromethylenedioxy and difluoromethylenedioxy.
[0022]
In the substituent group a, the “lower alkoxy group substituted with 1 to 3 halogen atoms which are the same or different” is, for example, a group such as difluoromethoxy and trifluoromethoxy.
[0023]
In general formula (I), R1 Is preferably an alkyl group having 1 or 2 carbon atoms substituted with 1 to 3 halogen atoms which are the same or different, and more preferably substituted with 1 to 3 chlorine atoms. Or an alkyl group having 1 or 2 carbon atoms, and most preferably a chloromethyl group.
[0024]
In general formula (I), R2 Is preferably an alkyl group having 1 or 2 carbon atoms, and most preferably a methyl group.
[0025]
In general formula (I), RThree Is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. .
[0026]
In general formula (I), RFour Is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. .
[0027]
In general formula (I), RFive Is preferably a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and when m is 2 or more, adjacent RFive Together may be an alkylenedioxy group having 1 to 2 carbon atoms, more preferably a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group. An isopropyloxy group, and when m is 2 or more, adjacent RFive May be a methylenedioxy group or an ethylenedioxy group, more preferably a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and m is 2 or more. The adjacent RFive May be a methylenedioxy group or an ethylenedioxy group, more preferably a chlorine atom, an ethyl group, or a methoxy group, and when m is 2 or more, adjacent RFive Together may be a methylenedioxy group.
[0028]
In the general formula (I), m is preferably 0, 1 or 2, and most preferably 1 or 2.
[0029]
In the general formula (I), n is preferably 0 or 2, and most preferably 2.
[0030]
Substituent group a is preferably a halogen atom or an alkoxy group having 1 or 2 carbon atoms, more preferably a fluorine atom, a methoxy group, or an ethoxy group, and most preferably a fluorine atom. is there.
[0031]
Representative compounds of the present invention are exemplified in the following Table 1, but the present invention is not limited to these compounds.
[0032]
In the table, “No.” indicates a compound number, Me represents a methyl group, Et represents an ethyl group, nPr represents an n-propyl group, iPr represents an isopropyl group, nBu represents an n-butyl group, and iBu represents An isobutyl group, sBu represents a sec-butyl group, tBu represents a tert-butyl group, nPen represents an n-pentyl group, Ph represents a phenyl group, Bn represents a benzyl group, and Ac represents an acetyl group.
[0033]
(RFive )m In the column, the number before the substituent indicates the substitution position of the substituent in the phenyl group, and the subscript after the substituent indicates the number of substitutions of the substituent. For example, 2-CFThree Is the trifluoromethyl group substituted at the 2-position, 2,4-Cl2 Is 2,4-dichloro group, 3,4-OCH2CH2O- is a 3,4-ethylenedioxy group.
[0034]
[Chemical 7]
Figure 0003810838
[0035]
[Table 1]
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Among the above exemplified compounds, preferred examples are 2001, 2002, 2003, 2005, 2006, 2007, 2008, 2009, 2010, 2011, 2012, 2020, 2035, 2040, 2051, 2053, 2054, 2055, 2056, 2057,2058,2059,2060,2061,2064,2068,2070,2071,2072,2077,2078,2080,2082,2083,2088,2089,2092,2095,2097,2098,2099,2101,2102,2104, 2105, 2107, 2111, 2113, 2114, 2120, 2121, 2125, 2126, 2127, 2143, 2145, 2151, 2152, 2161, 2166.
[0036]
More preferable examples include compounds of 2002, 2005, 2008, 2012, 2054, 2071, 2077, 2088, 2099, 2102, 2125, 2127, 2166.
[0037]
Most preferred are compounds of 2012, 2102, 2125.
[0038]
DETAILED DESCRIPTION OF THE INVENTION
The isoxazoline derivative having the general formula (I) of the present invention can be produced by the method described below.
[0039]
Process A
[0040]
[Chemical 8]
Figure 0003810838
[0041]
During the above process, R1 , R2 , RThree , RFour , RFive And m are as defined above, and X1 Represents a halogen atom. X1 Is preferably a chlorine atom.
[0042]
Step A is a method for producing compound (Ia) in which n is 0 in general formula (I).
[0043]
Step A-1 is a step of producing a compound having the general formula (II) in which a halogen atom is substituted at the 3-position of the isoxazoline ring. The compound having the general formula (III) is removed in the presence of a base in an inert solvent. This is achieved by reacting with a compound having the general formula (IV).
[0044]
Compound (III) is, for example, tetrahedron, vol. 49, page 4117, 1993 (Tetrahedron49, 4117 (1993)), which is commercially available, or produced by a known method such as a Wittig reaction. Compound (IV) is a compound described in, for example, Liebig Annalen der Chemie 985 (1989), commercially available, or described in the literature. Manufactured according to the method.
[0045]
The base used in step A-1 is not particularly limited as long as it is a strong base capable of generating nitrile oxide from compound (IV), but preferably an alkali such as sodium hydrogen carbonate or potassium hydrogen carbonate. Metal bicarbonates; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate Salts; alkali metal acetates such as sodium acetate and potassium acetate; alkali metal fluorinated salts such as sodium fluoride and potassium fluoride; tertiary lower alkyl amines such as triethylamine, ethyldiisopropylamine and tributylamine; 8-diazabicyclo [5.4.0] undecan-7-ene (DBU), 4- diazabicyclo [2.2.2] tertiary alicyclic amines such as octane (DABCO) can be exemplified.
[0046]
The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but is preferably ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethyl ether, dioxane, tetrahydrofuran or the like. Ethers; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane; aromatic hydrocarbons such as benzene and toluene; acetates such as ethyl acetate and butyl acetate; Nitriles, mixed solvents of the above organic solvents and water, and water.
[0047]
The reaction temperature and reaction time vary depending on the types of the raw material compound, solvent and base, but the reaction temperature is usually 0 ° C. to 150 ° C., preferably 15 ° C. to 80 ° C., and the reaction time is usually 15 minutes to 24 ° C. Time, preferably 30 minutes to 8 hours.
[0048]
Step A-2 is a step for producing a compound having the general formula (Ia). The general formula for producing a mercaptan compound having the general formula (V) in the inert solvent using a base in the step A-1. This is achieved by reacting with a compound having (II).
[0049]
Compound (V) is, for example, Synthetic Communications, Vol. 16, page 1173, 1986 (Synthetic Communications16, 1173 (1986)) as a raw material, for example, Journal of American Chemical Society, Vol. 62, p. 2674, 1940 (Journal of American Chemical Society)62, 2674 (1940)).
[0050]
The base to be used is not particularly limited as long as it is a base having a strength capable of preferentially releasing protons of thiols, but preferably an alkali such as sodium hydride, potassium hydride, or lithium hydride. Metal hydrides; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal amides such as sodium amide and lithium isopropylamide; tertiary lower groups such as triethylamine, ethyldiisopropylamine and tributylamine Tertiary cycloaliphatic amines such as alkylamines; 1,8-diazabicyclo [5.4.0] undecan-7-ene (DBU); 1,4-diazabicyclo [2.2.2] octane (DABCO) Can be mentioned.
[0051]
The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but preferably ethers such as dioxane and tetrahydrofuran; methylene chloride, chloroform, carbon tetrachloride Halogenated hydrocarbons such as dichloroethane; aromatic hydrocarbons such as benzene and toluene; amides such as N, N-dimethylacetamide, N, N-dimethylformamide and N-methyl-2-pyrrolidinone; Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and t-butanol; ketones such as acetone and 2-butanone; nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide: and these List solvent mixtures of other solvents It can be.
[0052]
The reaction temperature and reaction time vary depending on the types of raw material compound, solvent and base, but the reaction temperature is usually 0 ° C. to 150 ° C., preferably 0 ° C. to 80 ° C., and the reaction time is usually 15 minutes to 24 hours. It is preferably 30 minutes to 8 hours.
[0053]
Process C
[0054]
[Chemical 9]
Figure 0003810838
[0055]
During the above process, R1 , R2 , RThree , RFour , RFive And m are as defined above.
[0056]
Step C is a method for producing compound (Ic2) in which n is 1 in general formula (I) and compound (Ic3) in which n is 2 in general formula (I).
[0057]
Steps C-1 and C-2 are steps for producing a compound having the general formula (Ic2) and a compound having the general formula (Ic3), and using an oxidant in an inert solvent, the general formula ( This is achieved by carrying out an oxidation reaction of the compound (Ic1) in which n is 0 in I).
[0058]
Compound (Ic1) is produced by the above-mentioned Step A, Step E and Step I below. The oxidizing agent to be used is not particularly limited as long as it is an oxidizing agent having a strength capable of oxidizing sulfides and sulfoxides, and preferably an organic material such as m-chloroperbenzoic acid, performic acid, and peracetic acid. Examples of peroxides include inorganic peroxides such as hydrogen peroxide, potassium permanganate, and sodium periodate.
[0059]
The oxidizing agent is used in 1.0 to 1.1 equivalents with respect to the substrate in both the C-1 and C-2 steps. To obtain the sulfones (Ic3) directly without isolating the sulfoxides (Ic2). This is achieved by using 2.0 to 3.0 equivalents of an oxidizing agent relative to compound (Ic1).
[0060]
The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but is preferably a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane. Ethers such as tetrahydrofuran, dioxane and diethyl ether; ketones such as acetone and 2-butanone; alcohols such as methanol, ethanol and t-butanol; N, N-dimethylacetamide and N, N-dimethyl Examples thereof include amides such as formamide and N-methyl-2-pyrrolidinone; nitriles such as acetonitrile; acetic acid; water; a mixed solvent of water and the above organic solvent.
[0061]
The reaction temperature and reaction time vary depending on the raw material compound, the solvent, the oxidizing agent and the type of the target compound, but when the target product is the compound (Ic2), the reaction temperature is usually −20 ° C. to 50 ° C., preferably −5 The reaction time is usually 10 minutes to 5 hours, preferably 30 minutes to 2 hours. When the target compound is Compound (Ic3), the reaction temperature is usually 0 ° C. to 100 ° C. The reaction time is preferably 10 ° C. to 60 ° C., and the reaction time is usually 15 minutes to 2 days, preferably 30 minutes to 1 day.
[0062]
E process
[0063]
Embedded image
Figure 0003810838
[0064]
During the above process, R2 , RThree , RFour , RFive , M and n are as defined above, p is 1 to 6, XFour Represents a halogen atom.
[0065]
The E step is represented by R in general formula (I).1 Is a method for producing a compound (Ie) in which is a lower alkyl group substituted by one halogen atom.
[0066]
Step E-1 is a step for producing a compound having the general formula (Ie), and is achieved by subjecting compound (VI) to a halogenation reaction in an inert solvent using a halogenating agent.
[0067]
Compound (VI) is manufactured according to the said A process and C process.
[0068]
The halogenating agent used is not particularly limited as long as it can halogenate alkyl alcohols, but is preferably bromine, N-bromosuccinimide (NBS), phosphorus pentabromide, chlorine, N-chloro. Mention may be made of succinimide (NCS), phosphorus pentachloride, sulfuryl chloride, thionyl chloride, carbon tetrachloride-triphenylphosphine.
[0069]
The reaction is promoted in the presence of a base. Bases used include tertiary lower alkyl amines such as triethylamine, ethyldiisopropylamine, tributylamine; 1,8-diazabicyclo [5.4.0] undecan-7-ene (DBU); 1,4-diazabicyclo [2.2.2] Tertiary alicyclic amines such as octane (DABCO); tertiary anilines such as N, N-dimethylaniline and N, N-diethylaniline.
[0070]
The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but is preferably an aromatic hydrocarbon such as benzene and toluene; methylene chloride, chloroform, And halogenated hydrocarbons such as carbon tetrachloride and dichloroethane; ethers such as tetrahydrofuran, i-propyl ether, dioxane and ethyl ether; bases such as pyridine; and a mixed solvent of these solvents. .
[0071]
The reaction temperature and reaction time vary depending on the types of the raw material compound, solvent and halogenating agent, but the reaction temperature is usually -20 ° C to 150 ° C, preferably 0 ° C to 80 ° C, and the reaction time is usually 5 ° C. Minutes to 24 hours, preferably 10 minutes to 4 hours.
[0072]
H process
[0073]
Embedded image
Figure 0003810838
[0074]
During the above process, R2 , RThree , RFour , RFive , M and n are as defined above.
[0075]
Step H is a method for producing a compound (VIII) having a formyl group at the 5-position of the isoxazoline ring.
[0076]
Step H-1 is a step of producing a compound having the general formula (VIII), and oxidizing the compound (VII) having a hydroxymethyl group at the 5-position of the isoxazoline ring using an oxidizing agent in an inert solvent. Is achieved.
[0077]
Compound (VII) is manufactured according to the said A process and C process.
[0078]
The oxidizing agent to be used is not particularly limited as long as it is a relatively mild oxidizing agent, but preferably N, N-dimethylsulfoxide is dicyclohexylamide, oxalyl chloride, phosgene, chloroformate, anhydrous Sulfonium salts (DMSO oxidation) formed from acetic acid, phosphorus pentoxide, pyridine-sulfuric anhydride complexes, methyl sulfide and chlorinating agents such as N-chlorosuccinimide or chlorine; chromates such as chromic acid; Oxygen in the presence of various metal catalysts; permanganates such as potassium permanganate; hypochlorite compounds such as sodium hypochlorite and t-butyl hypochlorite; peroxysulfates such as oxone; Ruthenium oxide and ruthenium salts capable of generating it in the reaction system; sodium hypochlorite and 2, , It can be exemplified oxoammonium salt comprising a combination of 6,6-tetramethyl-1-piperidinyloxy free radical.
[0079]
The equivalent of the oxidizing agent varies greatly depending on the conditions used, but in the case of DMSO oxidation, it can be 1 to 5 equivalents of oxalyl chloride and 1 to 10 equivalents of N, N-dimethyl sulfoxide with respect to the substrate.
[0080]
The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Preferably, ethers such as dioxane, tetrahydrofuran, ether, dimethoxyethane; methylene chloride, Halogenated hydrocarbons such as chloroform and dichloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and 2-butanone; nitriles such as acetonitrile; ethyl acetate and butyl acetate Such esters; and mixed solvents of these solvents.
[0081]
The reaction temperature and reaction time vary depending on the types of the raw material compound, the solvent and the oxidizing agent, but the reaction temperature is usually from -80 ° C to 200 ° C, preferably from -70 ° C to 150 ° C, and the reaction time is usually 10 ° C. Minutes to 3 days, preferably 30 minutes to 24 hours.
[0082]
I process
[0083]
Embedded image
Figure 0003810838
[0084]
During the above process, R2 , RThree , RFour , RFive , M and n are as defined above, and R8 Represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.
[0085]
The step I is represented by R in general formula (I).1 Is a method for producing a compound (Ii) in which is a lower alkyl group substituted with two fluorine atoms.
[0086]
Step I-1 is a step of producing a compound having the general formula (Ii), and fluorinating an aldehyde or ketone having the general formula (IX) using a fluorinating agent in an inert solvent. Is achieved.
[0087]
Compound (IX) is manufactured according to the said A process, C process, and H process.
[0088]
The fluorinating agent to be used is not particularly limited as long as it replaces carbonyl oxygen with a fluorine atom, but preferably a dialkylaminosulfur trifluoride such as diethylaminosulfur trifluoride (DAST) or dimethylaminosulfur trifluoride. Lido; sulfur tetrafluoride can be mentioned.
[0089]
The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but preferably ethers such as dioxane and tetrahydrofuran; trichlorofluoromethane, methylene chloride, chloroform , Halogenated hydrocarbons such as carbon tetrachloride and dichloroethane; aromatic hydrocarbons such as benzene and toluene; hydrocarbons such as isooctane; and a mixed solvent of these solvents.
[0090]
The reaction temperature and reaction time vary depending on the types of the raw material compound, the solvent and the fluorinating agent, but the reaction temperature is usually -78 ° C to 200 ° C, preferably -60 ° C to 80 ° C, and the reaction time is usually 5 minutes to 7 days, preferably 10 minutes to 10 hours.
[0091]
After completion of each reaction step, the target compound in each step can be collected from the reaction mixture according to a conventional method. For example, it can be obtained by neutralizing the reaction mixture as appropriate, removing impurities by filtration, adding an organic solvent immiscible with water, washing with water, and distilling off the solvent. If necessary, the obtained target compound can be further purified by a conventional method such as recrystallization, reprecipitation or chromatography.
[0092]
The compound of the present invention is mixed with a carrier and other auxiliary agents as necessary, and is usually used as a herbicide, for example, powder, coarse powder, granule, granule, wettable powder, water solvent, emulsion It is prepared and used as a liquid agent. As used herein, a carrier refers to a synthetic or natural inorganic or organic substance mixed in a herbicide to help reach the plant of an active ingredient compound or to facilitate storage, transportation or handling of the active ingredient. means.
[0093]
Suitable solid carriers include, for example, clays represented by the kaolinite group, montmorillonite group, attapulgite group, talc, mica, phyllite, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium lime, phosphorus Inorganic substances such as lime, zeolite, anhydrous silicic acid, synthetic calcium silicate, kaolin, bentonite, calcium carbonate, vegetable organic substances such as soybean powder, tobacco powder, walnut powder, wheat flour, wood flour, starch, crystalline cellulose, coumarone Synthetic or natural polymer compounds such as resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal gum, dammar gum, waxes such as carnauba wax, paraffin wax, beeswax, urea, etc. Can be mentioned.
[0094]
Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene, carbon tetrachloride, etc. Chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene and chlorotoluene, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone and isophorone, ethyl acetate, amyl acetate, ethylene Esters such as glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate, methanol, n-hexanol, ethylene glycol, diethylene glycol Alcohols such as ethylene, cyclohexanol and benzyl alcohol, ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether, polar solvents such as dimethylformamide and dimethyl sulfoxide, or water Can do.
[0095]
Surfactants used for emulsification, dispersion, wetting, spreading, bonding, disintegration control, active ingredient stabilization, fluidity improvement, rust prevention, plant absorption promotion, etc. are ionic or nonionic But you can.
[0096]
Suitable nonionic surfactants include, for example, fatty acid sucrose esters, lauryl alcohol, stearyl alcohol, ethylene oxide polymerization adducts of higher aliphatic alcohols such as oleyl alcohol, and ethylene oxide polymerization of alkylphenols such as isooctylphenol and nonylphenol. Oxidized ethylene polymerized adducts of adducts, alkyl naphthols such as butyl naphthol and octyl naphthol, ethylene polymerized adducts of higher fatty acids such as palmitic acid, stearic acid and oleic acid, oxidation of mono- or dialkyl phosphoric acids such as stearyl phosphate dilauryl phosphate Ethylene polymerized adducts, ethylene oxide polymerized adducts of higher aliphatic amines such as dodecylamine and stearamide, higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide polymerized adducts thereof And it can be exemplified copolymers of ethylene oxide and propylene oxide.
[0097]
Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt, fatty acid salts such as sodium dioctyl sulfosuccinate, sodium oleate and sodium stearate, isopropyl naphthalene, and the like. Examples thereof include alkylaryl sulfonates such as sodium sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.
[0098]
Examples of suitable cationic surfactants include higher aliphatic amines, quaternary ammonium salts, alkylpyridinium salts, and the like.
[0099]
Furthermore, the herbicide of the present invention has other components such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, carboxymethylcellulose, for the purpose of improving the properties of the preparation and enhancing the biological effect. It may contain polymer compounds such as methylcellulose and hydroxymethylcellulose, thixotropic agents such as sodium polyphosphate and bentonite, and other adjuvants.
[0100]
The above carriers and various adjuvants are appropriately used alone or in combination depending on the purpose in consideration of the application form of the preparation.
[0101]
The powder usually contains 2 to 10 parts by weight of the active ingredient compound, and the balance is a solid carrier.
[0102]
The wettable powder usually contains 10 to 80 parts by weight of the active ingredient, and the balance is a solid carrier and a dispersion wetting agent, and a protective colloid agent, thixotropic agent, antifoaming agent and the like are added as necessary.
[0103]
Granules usually contain 0.1 to 10 parts by weight of the active ingredient compound, and the balance is mostly a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm.
[0104]
Emulsions usually contain 1 to 50 parts by weight of the active ingredient, including about 5 to 20 parts by weight of the emulsion, the remainder being a liquid carrier, and a rust inhibitor is added if necessary.
[0105]
When the compound of the present invention thus prepared in various dosage forms is treated with soil before or after germination of weeds in paddy fields, for example, 1 to 1000 g, preferably 10 to 300 g as an active ingredient is treated per 10a. By doing so, weeds can be controlled effectively.
[0106]
Furthermore, when soil treatment before weed germination or foliage treatment after germination in a field, weeds can be effectively controlled by treating 1 to 1000 g, preferably 10 to 300 g as an active ingredient per 10a.
[0107]
It is preferable that other herbicides are added to the herbicide of the present invention in order to broaden the herbicidal spectrum, and in some cases, a synergistic effect can be expected.
[0108]
The herbicide of the present invention can of course be used by mixing with other plant growth regulators, fungicides, insecticides, acaricides, nematicides or fertilizers.
[0109]
Examples and formulation examples of the herbicide of the present invention will be shown and described in detail below, but the present invention is not limited thereto.
[0110]
【Example】
[0111]
[Example 1]
3-Benzylthio-5-chloromethyl-5-methyl-2-isoxazoline(Compound No. 1) (Step A)
(1) 3-chloro-5-chloromethyl-5-methyl-2-isoxazoline (step A-1)
43.2 g of 2-hydroxyiminoacetic acid and 129.6 g of N-chlorosuccinimide were dissolved in 400 ml of dimethoxyethane, and heated and stirred at 80 ° C. in an oil bath. After 3 minutes, the oil bath was removed and allowed to cool to room temperature. To this solution, 48 ml of methallyl chloride, 194.4 g of potassium hydrogen carbonate, and 8 ml of water were sequentially added, and the mixture was stirred at room temperature for 8 hours. Hexane was added to the reaction solution, followed by suction filtration using Celite. After evaporating the organic solvent of the filtrate, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 30: 1) to obtain 51.6 g (64%) of the title compound as an oil.
[0112]
1H-NMR (CDClThree) δ: 1.59 (3H, s), 3.14 (2H, ABq, J = 17.5, Δν = 76.4Hz), 3.57 (2H, ABq, J = 11.4Δν = 16.0Hz) ppm
(2) 3-Benzylthio-5-chloromethyl-5-methyl-2-isoxazoline (step A-2)
17 ml of 3-chloro-5-chloromethyl-5-methyl-2-isoxazoline obtained in (1) and 0.35 ml of benzyl mercaptan were mixed with 9 ml of a mixed solvent of tetrahydrofuran: N, N-dimethylformamide = 8: 1. And 60% sodium hydride 125 mg was added little by little at room temperature. After stirring at room temperature for 3 hours, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration and evaporation of the solvent, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1) to obtain 182.8 mg (68%) of the oily desired product.
[0113]
1H-NMR (CDClThree) δ: 1.57 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 75.3Hz), 3.52 (2H, d, J = 2.2Hz), 4.27 (2H, s), 7.29-7.40 (5H , m) ppm
The compound produced according to the method of Example 1 is shown below.
[0114]
In the following, the number in parentheses after the compound name indicates the compound number in Table 1, followed by “mp” indicating a melting point (° C.), or “oil” indicating an oily substance. Or “Amorphous” indicates amorphous.
[0115]
3- (2-Methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (2, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.40 (3H, s), 3.01 (2H, ABq, J = 16.6, Δν = 74.7Hz), 3.54 (2H, d, J = 3.1Hz), 4.29 (2H, s ), 7.16-7.20 (3H, m), 7.30-7.34 (1H, m) ppm
3- (3-Methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (3, mp40-43)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.35 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.3Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.2Hz), 4.23 (2H, s), 7.08-7.31 (4H, m) ppm
3- (4-Methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (4, mp53-54)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.34 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.1Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.3Hz), 4.24 (2H, s), 7.11-7.29 (4H, m) ppm
3- (2,3-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (5, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.29 (6H, br), 3.02 (2H, ABq, J = 16.6, Δν = 74.5Hz), 3.55 (2H, ABq, J = 11.2, Δν = 9.3Hz), 4.32 (2H, s), 7.06-7.21 (3H, m) ppm
3- (2,4-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (6, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.31 (3H, s), 2.36 (3H, s), 3.01 (2H, ABq, J = 16.9, Δν = 74.5Hz), 3.54 (2H, ABq, J = 11.1, Δν = 9.0Hz), 4.26 (2H, s), 6.95-7.23 (3H, m) ppm
3- (2,5-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (7, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.30 (3H, s), 2.35 (3H, s), 3.02 (2H, ABq, J = 16.7, Δν = 74.5Hz), 3.55 (2H, ABq, J = 11.3, (Δν = 9.1Hz), 4.26 (2H, s), 7.02-7.14 (3H, m) ppm
3- (2,6-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (8, mp72-73)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 2.42 (6H, s), 3.05 (2H, ABq, J = 16.8, Δν = 73.4Hz), 3.58 (2H, ABq, J = 11.2, Δν = 11.2Hz), 4.36 (2H, s), 7.01-7.15 (3H, m) ppm
3- (3,4-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (9, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.23 (6H, s), 3.00 (2H, ABq, J = 16.7, Δν = 74.9Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.4Hz), 4.21 (2H, s), 7.09 (2H, s), 7.13 (1H, s) ppm
3- (3,5-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (10, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.30 (6H, s), 3.01 (2H, ABq, J = 16.7, Δν = 75.3Hz), 3.53 (2H, d, J = 2.2Hz), 4.20 (2H, s ), 6.92 (1H, br), 6.98 (2H, br) ppm
3- (2,4,6-trimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (11, mp90-92)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 2.26 (3H, s), 2.38 (6H, s), 3.04 (2H, ABq, J = 16.7, Δν = 73.1Hz), 3.57 (2H, ABq, J = 11.1, Δν = 10.9Hz), 4.33 (2H, s), 6.87 (2H, s) ppm
3- (2-Ethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (12, oil)
1H-NMR (200MHz, CDClThree) δ: 1.26 (3H, t, J = 7.5Hz), 1.56 (3H, s), 2.74 (2H, q, J = 7.5Hz), 3.02 (2H, ABq, J = 16.8, Δν = 74.5Hz), 3.55 (2H, ABq, J = 11.3, Δν = 9.3Hz), 4.32 (2H, s), 7.15-7.36 (4H, m) ppm
3- (4-Ethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (14, oil)
1H-NMR (200MHz, CDClThree) δ: 1.22 (3H, t, J = 7.5Hz), 1.54 (3H, s), 2.64 (2H, q, J = 7.5Hz), 3.00 (2H, ABq, J = 16.7, Δν = 74.9Hz), 3.52 (2H, d, J = 2.0Hz), 4.24 (2H, s), 7.16 (2H, d, J = 8.0Hz), 7.28 (2H, d, J = 8.0Hz) ppm
3- (2,6-Diethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (15, mp40-42)
1H-NMR (200MHz, CDClThree) δ: 1.27 (6H, t, J = 7.5Hz), 1.59 (3H, s), 2.76 (4H, q, J = 7.5Hz), 3.04 (2H, ABq, J = 16.7, Δν = 72.7Hz), 3.58 (2H, ABq, J = 11.2, Δν = 11.6Hz), 4.39 (2H, s), 7.06-7.26 (3H, m) ppm
3- (4-n-propylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (19, mp34-36)
1H-NMR (200MHz, CDClThree) δ: 0.93 (3H, t, J = 7.3Hz), 1.55 (3H, s), 1.57-1.72 (2H, m), 2.57 (2H, t, J = 7.2Hz), 3.00 (2H, ABq, J = 16.6, Δν = 74.9Hz), 3.52 (2H, ABq, J = 11.1, ν = 7.0Hz), 4.24 (2H, s), 7.14 (2H, d, J = 8.0Hz), 7.28 (2H, d, J = 8.0Hz) ppm
3- (4-tert-Butylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (31, oil)
1H-NMR (200MHz, CDClThree) δ: 1.30 (9H, s), 1.54 (3H, s), 3.00 (2H, ABq, J = 16.6, Δν = 74.6Hz), 3.52 (2H, d, J = 1.7Hz), 4.24 (2H, s ), 7.31-7.40 (4H, m) ppm
3- (2- (5,6,7,8-tetrahydronaphthyl) thio) -5-chloromethyl-5-methyl-2-isoxazoline (33, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 1.75-1.81 (4H, m), 2.71-2.77 (4H, m), 3.00 (2H, ABq, J = 16.8, Δν = 74.9Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.7Hz), 4.20 (2H, s), 6.99-7.11 (3H, m) ppm
3- (2-Chlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (34, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.2Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.2Hz), 4.22 (2H, s), 7.26 (3H, m), 7.37 (1H, m) ppm
3- (3-Chlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (35, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.9, Δν = 76.9Hz), 3.53 (2H, ABq, J = 14.6, Δν = 8.0Hz), 4.22 (2H, s), 7.27 (3H, s), 7.37 (1H, s) ppm
3- (4-Chlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (36, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 17.0, Δν = 77.0Hz), 3.51 (2H, s), 4.21 (2H, s), 7.30 (4H, s) ppm
3- (2,3-Dichlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (37, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.99 (2H, ABq, J = 16.9, Δν = 76.6Hz), 3.52 (2H, ABq, J = 11.6, Δν = 6.3Hz), 4.38 (2H, s), 7.12 -7.16 (1H, m), 7.38-7.46 (2H, m) ppm
3- (2,4-Dichlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (38, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 74.2Hz), 3.52 (2H, d, J = 1.9Hz), 4.32 (2H, s), 7.21 (1H, dd , J = 8.4,1.9Hz), 7.41 (1H, d, J = 1.9), 7.47 (1H, d, J = 8.4Hz) ppm
3- (2,5-dichlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (39, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.00 (2H, ABq, J = 16.5, Δν = 73.9Hz), 3.53 (2H, d, J = 2.3Hz), 4.32 (2H, s), 7.21 (1H, dd , J = 8.5,2.3Hz), 7.32 (1H, d, J = 8.5Hz), 7.52 (1H, d, J = 2.3Hz) ppm
3- (2,6-dichlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (40, mp80-81)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 3.06 (2H, ABq, J = 16.6, Δν = 73.9Hz), 3.57 (2H, ABq, J = 11.2, Δν = 11.4Hz), 4.63 (2H, s), 7.14 -7.35 (3H, m) ppm
3- (3,4-Dichlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (41, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.99 (2H, ABq, J = 16.6, Δν = 75.4Hz), 3.52 (2H, d, J = 2.0Hz), 4.19 (2H, s), 7.23 (1H, dd , J = 8.0,1.7Hz), 7.39 (1H, d, J = 8.0Hz), 7.48 (1H, d, J = 1.7Hz) ppm
3- (3,5-dichlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (42, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 17.2, Δν = 74.9Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.3Hz), 4.18 (2H, s), 7.25 (1H, s), 7.27 (2H, s) ppm
3- (2,4,6-Trichlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (44, Amorphous)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 3.05 (2H, ABq, J = 16.7, Δν = 74.5Hz), 3.57 (2H, ABq, J = 11.3, Δν = 10.8Hz), 4.59 (2H, s), 7.36 (2H, s) ppm
3- (3-Chloro-4-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (45, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.36 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 75.2Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.2Hz), 4.19 (2H, s), 7.11-7.36 (3H, m) ppm
3- (2,4-Dichloro-3-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (48, oil)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 2.49 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 74.0Hz), 3.52 (2H, d, J = 1.9Hz), 4.34 (2H, s ), 7.21-7.34 (2H, m) ppm
3- (2,5-Dichloro-4-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (49, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.33 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 73.8Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.8Hz), 4.30 (2H, s), 7.27 (1H, s), 7.49 (1H, s) ppm
3- (2-Bromobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (50, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.9, Δν = 75.2Hz), 3.53 (2H, d, J = 2.1Hz), 4.38 (2H, s), 7.14-7.18 (1H) , m), 7.24-7.31 (1H, m), 7.50-7.59 (2H, m) ppm
3- (3-Bromobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (51, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.6, Δν = 75.1Hz), 3.53 (2H, d, J = 2.1Hz), 4.21 (2H, s), 7.15-7.34 (2H , m), 7.38-7.53 (2H, m) ppm
3- (4-Bromobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (52, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.98 (2H, ABq, J = 16.7, Δν = 75.6Hz), 3.52 (2H, d, J = 1.8Hz), 4.20 (2H, s), 7.23-7.28 (2H , m), 7.42-7.47 (2H, m) ppm
3- (2-Fluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (53, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.01 (2H, ABq, J = 16.8, Δν = 74.5Hz), 3.53 (2H, d, J = 2.1Hz), 4.29 (2H, s), 7.01-7.14 (2H , m), 7.23-7.31 (1H, m), 7.44 (1H, t, J = 7.7Hz) ppm
3- (3-Fluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (54, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.4Hz), 3.52 (2H, d, J = 2.1Hz), 4.24 (2H, s), 6.97-7.32 (4H , m) ppm
3- (4-Fluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (55, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 75.1Hz), 3.52 (2H, ABq, J = 11.1, Δν = 6.8Hz), 4.23 (2H, s), 6.96 -7.05 (2H, m), 7.31-7.38 (2H, m) ppm
3- (2,3-Difluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (56, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 74.7Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.4Hz), 4.31 (2H, d, J = 1.4Hz), 7.02-7.22 (3H, m) ppm
3- (2,4-Difluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (57, oil)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 74.1Hz), 3.51 (2H, ABq, J = 11.2, Δν = 7.2Hz), 4.24 (2H, s), 6.75 -6.88 (2H, m), 7.37-7.49 (1H, m) ppm
3- (2,5-Difluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (58, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.18 (2H, ABq, J = 16.7, Δν = 74.6Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.5Hz), 4.25 (2H, s), 6.92 -7.05 (2H, m), 7.14-7.23 (1H, m) ppm
3- (2,6-Difluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (59, mp58-61)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.03 (2H, ABq, J = 16.7, Δν = 75.2Hz), 3.55 (2H, ABq, J = 11.2, Δν = 9.8Hz), 4.35 (2H, s), 6.87 -6.96 (2H, m), 7.19-7.31 (1H, m) ppm
3- (3,4-Difluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (60, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.6, Δν = 75.3Hz), 3.52 (2H, ABq, J = 11.3, Δν = 6.9Hz), 4.19 (2H, s), 7.06 -7.23 (3H, m) ppm
3- (3,5-Difluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (61, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.19 (2H, ABq, J = 16.7, Δν = 75.4Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.3Hz), 4.21 (2H, s), 6.66 -6.95 (3H, m) ppm
3- (2-Fluoro-3-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (64, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.28 (3H, d, J = 2.1Hz), 3.00 (2H, ABq, J = 16.8, Δν = 74.5Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.5Hz), 4.28 (2H, s), 6.98 (1H, t, J = 7.57Hz), 7.08-7.12 (1H, m), 7.21-7.28 (1H, m) ppm
3- (3-Fluoro-4-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (65, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.25 (3H, d, J = 1.9Hz), 3.00 (2H, ABq, J = 16.7, Δν = 75.2Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.2Hz), 4.21 (2H, s), 7.01-7.17 (3H, m) ppm
3- (2,3,5,6-tetrafluoro-4-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (66, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.24 (3H, dt, J = 12.8,2.0Hz), 2.85 (1H, dd, J = 16.8,5.2Hz), 3.18 (1H, dd, J = 16.8,5.9Hz) ), 3.53 (2H, ABq, J = 3.5, Δν = 3.0Hz),
4.35 (2H, d, J = 22.4Hz) ppm
3- (2-Fluoro-3-chlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (67, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 74.1Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.1Hz), 4.29 (2H, s), 7.04 (1H, t, J = 7.9Hz), 7.28-7.40 (2H, m) ppm
3- (2-Chloro-4-fluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (68, oil)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 73.8Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.1Hz), 4.33 (2H, s), 6.95 (1H, td, J = 8.4,2.6Hz), 7.14 (1H, dd, J = 8.4,2.6Hz), 7.50 (1H, dd, J = 8.4,6.1Hz) ppm
3- (2-Chloro-6-fluorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (70, oil)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.04 (2H, ABq, J = 16.7, Δν = 76.4Hz), 3.55 (2H, ABq, J = 11.2, Δν = 10.5Hz), 4.47 (2H, d, J = 1.6Hz), 6.97-7.26 (3H, m) ppm
3- (2-Trifluoromethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (71, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 73.5Hz), 3.54 (2H, ABq, J = 11.2, Δν = 8.8Hz), 4.46 (2H, s), 7.35 -7.43 (1H, m), 7.49-7.56 (1H, m), 7.64-7.71 (2H, m) ppm
3- (3-Trifluoromethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (72, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.4Hz), 3.51 (2H, d, J = 2.0Hz), 4.30 (2H, s), 7.44-7.64 (4H , m) ppm
3- (4-Trifluoromethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (73, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 75.7Hz), 3.52 (2H, d, J = 1.9Hz), 4.29 (2H, s), 7.53 (2H, d , J = 8.4Hz), 7.57 (2H, d, J = 8.4Hz) ppm 3- (2,4-bistrifluoromethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (74, Amorphous )
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.01 (2H, ABq, J = 16.7, Δν = 74.4Hz), 3.55 (2H, ABq, J = 11.8, Δν = 8.9Hz), 4.49 (2H, s), 7.78 (1H, d, J = 7.9Hz), 7.90 (2H, d, J = 7.9Hz) ppm
3- (3.5-Bistrifluoromethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (75, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.01 (2H, ABq, J = 17.0, Δν = 75.6Hz), 3.52 (2H, ABq, J = 11.2, Δν = 6.8Hz), 4.34 (2H, s), 7.79 (1H, br), 7.86 (2H, br) ppm
3- (2-Fluoro-4-trifluoromethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (76, mp46-48)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.16 (2H, ABq, J = 16.8, Δν = 74.8Hz), 3.52 (2H, ABq, J = 11.3, Δν = 6.9Hz), 4.31 (2H, s), 7.33 (1H, d, J = 9.3Hz), 7.38 (1H, d, J = 9.3Hz), 7.62 (1H, t, J = 7.3Hz) ppm
3- (2-Methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (77, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 74.3Hz), 3.51 (2H, ABq, J = 18.3, Δν = 8.6Hz), 3.87 (3H, s), 4.29 (2H, s), 6.86-6.95 (2H, m), 7.23-7.39 (2H, m) ppm
3- (3-Methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (78, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 75.3Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.7Hz), 3.81 (3H, s), 4.24 (2H, s), 6.80-6.97 (3H, m), 7.21-7.28 (1H, m) ppm
3- (4-Methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (79, mp32-33)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 74.9Hz), 3.52 (2H, d, J = 2.1Hz), 3.80 (3H, s), 4.22 (2H, s ), 6.85 (2H, d, J = 8.6Hz), 7.30 (2H, d, J = 8.6Hz) ppm
3- (2,3-Dimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (80, oil)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 3.06 (2H, ABq, J = 17.0, Δν = 77.0Hz), 3.53 (2H, d, J = 2.3Hz), 3.86 (3H, s), 3.89 (3H, s ), 4.31 (2H, s), 6.83-6.91 (1H, m), 6.97-7.05 (2H, m) ppm
3- (2,4-Dimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (81, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.99 (2H, ABq, J = 16.6, Δν = 73.8Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.7Hz), 3.80 (3H, s), 3.84 (3H, s), 4.24 (2H, s), 6.41-6.45 (2H, m), 7.25-7.30 (1H, m) ppm
3- (2,5-Dimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (82, mp50-53)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.6, Δν = 73.9Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.9Hz), 3.77 (3H, s), 3.83 (3H, s), 4.26 (2H, s), 6.78-6.80 (2H, m), 6.97 (1H, d, J = 1.6Hz) ppm
3- (2,6-Dimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (83, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.06 (2H, ABq, J = 16.6, Δν = 75.5Hz), 3.55 (2H, ABq, J = 11.2, Δν = 10.9Hz), 3.85 (6H, s), 4.40 (2H, s), 6.55 (2H, d, J = 8.4Hz), 7.22 (1H, t, J = 8.4Hz) ppm
3- (3,4-Dimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (84, mp95-97)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 77.5Hz), 3.53 (2H, d, J = 2.3Hz), 3.87 (3H, s), 3.89 (3H, s ), 4.20 (2H, s), 6.79-6.94 (3H, m) ppm
3- (3,5-Dimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (85, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3h, s), 3.01 (2H, ABq, J = 16.7, Δν = 75.4Hz), 3.53 (2H, d, J = 2.7Hz), 3.79 (6H, s), 4.21 (2H, s ), 6.38 (1H, t, J = 2.3Hz), 6.53 (2H, d, J = 2.2Hz) ppm
3- (3,4,5-Trimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (87, Amorphous)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.01 (2H, ABq, J = 16.7, Δν = 75.9Hz), 3.53 (2H, d, J = 2.5Hz), 3.84 (3H, s), 3.86 (6H, s ), 4.22 (2H, s), 6.61 (2H, s) ppm
3- (2-Ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (88, oil)
1H-NMR (200MHz, CDClThree) δ: 1.44 (3H, t, J = 7.0Hz), 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 73.8Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.2Hz), 4.09 (2H, q, J = 7.0Hz), 4.31 (2H, s), 6.84-6.93 (2H, m), 7.20-7.29 (1H, m), 7.35-7.40 (1H, m) ppm
3- (3-Ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (89, oil)
1H-NMR (200MHz, CDClThree) δ: 1.41 (3H, t, J = 7.0Hz), 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.1Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.5Hz), 4.03 (2H, q, J = 7.0Hz), 4.23 (2H, s), 6.78-6.95 (3H, m), 7.21 (1H, d, J = 7.3Hz) ppm
3- (4-Ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (90, mp64)
1H-NMR (200MHz, CDClThree) δ: 1.41 (3H, t, J = 7.0Hz), 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 75.1Hz), 3.52 (2H, d, J = 2.2Hz), 4.02 (2H, q, J = 7.0Hz), 4.22 (2H, s), 6.84 (2H, d, J = 8.6Hz), 7.28 (2H, d, J = 7.6Hz) ppm
3- (2-Isopropyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (92, oil)
1H-NMR (200MHz, CDClThree) δ: 1.36 (6H, d, J = 6.1Hz), 1.54 (3H, s), 2.99 (2H, ABq, J = 16.9, Δν = 73.4Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.7Hz), 4.28 (2H, s), 4.61 (1H, quintet, J = 6.3Hz), 6.83-6.91 (2H, m), 7.18-7.26 (1H, m), 7.27-7.40 (1H, m) ppm
3- (3-Isopropyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (93, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.2Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.6Hz), 4.23 (2H, s), 4.55 (1H, quintet, J = 6.1Hz), 6.77-7.18 (3H, m), 7.24 (1H, d, J = 8.1Hz) ppm
3- (4-Isopropyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (94, mp34-36)
1H-NMR (200MHz, CDClThree) δ: 1.33 (3H, d, J = 6.2Hz), 1.54 (3H, s), 3.00 (2H, ABq, J = 16.6, Δν = 74.8Hz), 3.52 (2H, d, J = 2.2Hz), 4.22 (2H, s), 4.53 (1H, septet, J = 6.2Hz), 6.83 (2H, d, J = 8.7Hz), 7.27 (2H, d, J = 8.7Hz) ppm
3- (2-Methoxy-3-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (95, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2,22-2.27 (1H, m), 2.31 (3H, s), 3.01 (2H, ABq, J = 16.8, Δν = 74.5Hz), 3.54 (2H, ABq, J = 11.2, Δν = 8.8Hz), 3.80 (3H, s), 4.32 (2H, s), 6.95-7.02 (1H, m), 7.13 (1H, d, J = 6.0Hz) ppm
3- (3-Methyl-4-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (97, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.31 (3H, s), 3.02 (2H, ABq, J = 16.8, Δν = 74.4Hz), 3.54 (2H, ABq, J = 11.1, Δν = 9.0Hz), 3.81 (3H, s), 4.32 (2H, s), 6.95-7.27 (3H, m) ppm
3- (3-Methoxy-4-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (98, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.19 (3H, s), 3.01 (2H, ABq, J = 16.8, Δν = 75.6Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.7Hz), 3.83 (3H, s), 4.24 (2H, s), 6.86 (2H, d, J = 5.6Hz), 7.08 (1H, d, J = 7.7Hz) ppm
3- (2-Ethoxy-3-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (99, oil)
1H-NMR (200MHz, CDClThree) δ: 1.44 (3H, t, J = 7.2Hz), 1.55 (3H, s), 2.30 (3H, s), 3.01 (2H, ABq, J = 16.9, Δν = 73.9Hz), 3.54 (2H, d , J = 3.0Hz), 3.93 (2H, q, J = 7.2Hz), 4.32 (2H, s), 6.98-7.02 (1H, m), 7.12 (1H, d, J = 6.1Hz), 7.23-7.26 (1H, m) ppm
3- (2-Isopropyloxy-3-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (100, oil)
1H-NMR (200MHz, CDClThree) δ: 1.32 (6H, d, J = 6.2Hz), 1.58 (3H, s), 2.29 (3H, s), 3.01 (2H, ABq, J = 16.7, Δν = 73.6Hz), 3.53 (2H, ABq , J = 5.9, Δν = 6.2Hz), 4.24-4.38 (1H, m), 4.34 (2H, s) ppm
3- (3-Chloro-2-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (101, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.01 (2H, ABq, J = 16.9, Δν = 74.4Hz), 3.53 (2H, ABq, J = 11.1, Δν = 8.6Hz), 3.94 (3H, s), 4.31 (2H, s), 6.98-7.05 (1H, m), 7.29-7.37 (2H, m) ppm
3- (4-Chloro-2-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (102, mp63-64)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.98 (2H, ABq, J = 16.7, Δν = 74.5Hz), 3.52 (2H, ABq, J = 11.0, Δν = 7.1Hz), 3.86 (3H, s), 4.23 (2H, s), 6.85-6.92 (2H, m), 7.31 (1H, d, J = 7.7Hz) ppm
3- (2-Chloro-5-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (103, mp50-54)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 72.9Hz), 3.53 (2H, ABq, J = 11.2, Δν = 8.0Hz), 3.78 (3H, s), 4.33 (2H, s), 6.78 (1H, dd, J = 8.8,3.0Hz), 7.06 (1H, d, J = 3.0Hz), 7.26 (1H, d, J = 8.8Hz) ppm
3- (5-Chloro-2-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (104, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 74.3Hz), 3.53 (2H, ABq, J = 11.1, Δν = 7.6Hz), 3.85 (3H, s), 4.23 (2H, s), 6.79 (1H, d, J = 8.8Hz), 7.22 (1H, dd, J = 8.8,2.7Hz), 7.36 (1H, d, J = 2.7Hz) ppm
3- (4-Chloro-3-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (105, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 75.7Hz), 3.43 (2H, ABq, J = 11.3, Δν = 7.3Hz), 3.91 (3H, s), 4.22 (2H, s), 6.88-6.98 (2H, m), 7.30 (1H, d, J = 8.1Hz) ppm
3- (3,5-dichloro-2-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (106, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.01 (2H, ABq, J = 16.8, Δν = 74.5Hz), 3.54 (2H, ABq, J = 11.3, Δν = 8.7Hz), 3.91 (3H, s), 4.26 (2H, s), 7.31-7.35 (2H, m) ppm
3- (2,6-Dimethoxy-3-chlorobenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (107, oil)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.05 (2H, ABq, J = 16.6, Δν = 75.3Hz), 3.56 (2H, ABq, J = 11.2, Δν = 11.6Hz), 3.85 (3H, s), 3.92 (3H, s), 4.39 (2H, s), 6.63 (1H, d, J = 8.9Hz), 7.28 (1H, d, J = 8.9Hz) ppm
3- (2-Chloro-3,4-dimethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (108, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.6, Δν = 72.7Hz), 3.53 (2H, d, J = 2.6Hz), 3.87 (6H, s), 4.33 (2H, s ), 6.79 (1H, d, J = 8.5Hz), 7.23 (1H, d, J = 8.5Hz) ppm
3- (3,5-dichloro-4-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (109, mp41-47)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 74.5Hz), 3.53 (2H, ABq, J = 11.3, Δν = 7.7Hz), 3.89 (3H, s), 4.15 (2H, s), 7.32 (2H, s) ppm
3- (3-Chloro-2-ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (110, oil)
1H-NMR (200MHz, CDClThree) δ: 1.46 (3H, t, J = 7.0Hz), 3.00 (3H, s), (2H, ABq, J = 16.8, Δν = 74.1Hz), 3.52 (2H, d, J = 2.2Hz), 4.11 (2H, q, J = 7.0Hz), 4.32 (2H, s), 7.00 (1H, t, J = 7.8Hz), 7.32 (2H, t, J = 2.4Hz) ppm
3- (4-Chloro-2-ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (111, oil)
1H-NMR (200MHz, CDClThree) δ: 1.44 (3H, t, J = 7.0Hz), 1.53 (3H, s), 2.98 (2H, ABq, J = 16.7, Δν = 73.9Hz), 3.51 (2H, d, J = 1.8Hz), 4.06 (2H, q, J = 7.0Hz), 4.23 (2H, s), 6.83-6.89 (2H, m), 7.31 (1H, d, J = 7.9Hz) ppm
3- (2-Chloro-5-ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (112, oil)
1H-NMR (200MHz, CDClThree) δ: 1.40 (3H, t, J = 7.0Hz), 1.54 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 73.0Hz), 3.53 (2H, ABq, J = 11.3, Δν = 7.8Hz), 4.00 (2H, q, J = 7.0Hz), 4.33 (2H, s), 6.77 (1H, dd, J = 8.8,3.0Hz), 7.05 (1H, d, J = 3.0Hz), 7.25 (1H, d, J = 8.8Hz) ppm
3- (5-Chloro-2-ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (113, oil)
1H-NMR (200MHz, CDClThree) δ: 1.43 (3H, t, J = 7.0Hz), 1.54 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 73.8Hz), 3.53 (2H, ABq, J = 11.3, Δν = 7.4Hz), 4.05 (2H, q, J = 7.0Hz), 4.24 (2H, s), 6.77 (1H, d, J = 8.7Hz), 7.18 (1H, dd, J = 8.7,2.7Hz), 7.36 (1H, d, J = 2.7Hz) ppm
3- (4-Chloro-3-ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (114, oil)
1H-NMR (200MHz, CDClThree) δ: 1.47 (3H, t, J = 7.0Hz), 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 75.7Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.9Hz), 4.11 (2H, q, J = 7.0Hz), 4.20 (2H, s), 6.88 (1H, dd, J = 8.1,2.0Hz), 6.96 (1H, d, J = 2.0Hz), 7.29 (1H, d, J = 8.1Hz) ppm
3- (3,5-dichloro-2-ethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (115, oil)
1H-NMR (200MHz, CDClThree) δ: 1.46 (3H, t, J = 7.0Hz), 1.55 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 74.1Hz), 3.53 (2H, d, J = 2.2Hz), 4.12 (2H, q, J = 7.0Hz), 4.32 (2H, s), 7.28 (1H, d, J = 1.8Hz) ppm
3- (4-Chloro-2-isopropyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (116, oil)
1H-NMR (200MHz, CDClThree) δ: 1.36 (6H, d, J = 6.0Hz), 1.53 (3H, s), 2.97 (2H, ABq, J = 16.7, Δν = 73.4Hz), 3.52 (2H, d, J = 2.0Hz), 4.21 (2H, s), 4.57 (1H, quintet, J = 6.0Hz), 6.82-6.87 (2H, m), 7.30 (1H, d, J = 8.7Hz) ppm
3- (2-Chloro-5-isopropyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (117, oil)
1H-NMR (200MHz, CDClThree) δ: 1.32 (6H, d, J = 6.1Hz), 1.54 (3H, s), 2.99 (2H, ABq, J = 16.3, Δν = 73.6Hz), 3.52 (2H, d, J = 2.4Hz), 4.32 (2H, s), 4.51 (1H, quintet, J = 6.0Hz), 6.75 (1H, dd, J = 8.6,3.0Hz), 7.05 (1H, d, J = 3.0Hz), 7.24 (1H, d , J = 8.6Hz) ppm
3- (5-Chloro-2-isopropyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (118, oil)
1H-NMR (200MHz, CDClThree) δ: 1.35 (6H, d, J = 6.1Hz), 1.55 (3H, s), 2.99 (2H, ABq, J = 16.6, Δν = 73.6Hz), 3.53 (2H, ABq, J = 11.2, Δν = 7.8Hz), 4.22 (2H, s), 4.55 (1H, quintet, J = 5.9Hz), 6.78 (1H, d, J = 8.8Hz), 7.18 (1H, dd, J = 8.8,2.7Hz), 7.35 (1H, d, J = 2.7Hz) ppm
3- (4-Chloro-3-isopropyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (119, oil)
1H-NMR (200MHz, CDClThree) δ: 1.38 (6H, d, J = 6.0Hz), 1.53 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 76.0Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.0Hz), 4.20 (2H, s), 4.56 (1H, quintet, J = 6.0Hz), 6.87 (1H, dd, J = 8.1,2.0Hz), 6.99 (1H, d, J = 2.0Hz), 7.29 (1H, d, J = 8.1Hz) ppm
3- (2-Fluoro-6-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (120, mp56-59)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.04 (2H, ABq, J = 16.8, Δν = 75.2Hz), 3.40 (2H, ABq, J = 11.2, Δν = 10.4Hz), 3.88 (3H, s), 4.36 (2H, d, J = 1.2Hz), 6.67-6.75 (2H, m), 7.17-7.29 (1H, m) ppm
3- (2-Ethoxy-3-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (121, oil)
1H-NMR (200MHz, CDClThree) δ: 1.39 (3H, t, J = 7.1Hz), 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 73.6Hz), 3.53 (2H, ABq, J = 11.2, Δν = 8.6Hz), 4.19 (2H, q, J = 7.1Hz), 4.31 (2H, s), 6.82-6.87 (1H, m), 7.00 (2H, d, J = 4.6Hz) ppm
3- (2-Ethoxy-6-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (122, oil)
1H-NMR (200MHz, CDClThree) δ: 1.42 (3H, t, J = 7.0Hz), 1.56 (3H, s), 3.06 (2H, ABq, J = 16.8, Δν = 74.4Hz), 3.55 (2H, ABq, J = 11.0, Δν = 10.7Hz), 3.85 (3H, s), 4.07 (2H, q, J = 7.0Hz), 4.40 (2H, s), 6.53 (2H, d, J = 8.2Hz), 7.20 (1H, t, J = 8.2Hz) ppm
3- (3-Methoxy-2-propyloxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (123, oil)
1H-NMR (200MHz, CDClThree) δ: 1.04 (3H, t, J = 7.45), 1.54 (3H, s), 1.81 (2H, septet, J = 7.1Hz), 3.00 (2H, ABq, J = 16.7, Δν = 74.0Hz), 3.53 (2H, ABq, J = 11.2, Δν = 8.2Hz), 3.84 (3H, s), 3.99 (2H, t, J = 6.9Hz), 4.31 (2H, s), 6.99 (2H, d, J = 5.5 Hz) ppm
3- (2-Isopropyloxy-3-methoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (124, oil)
1H-NMR (200MHz, CDClThree) δ: 1.29 (6H, d, J = 6.2Hz), 1.55 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 72.1Hz), 3.53 (2H, ABq, J = 11.2, Δν = 9.0Hz), 3.83 (3H, s), 4.34 (2H, s), 4.59 (1H, quintet, J = 6.1Hz), 6.81-6.85 (1H, m), 6.94-7.03 (2H, m) ppm
3- (2,3-Methylenedioxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (125, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.02 (2H, ABq, J = 16.8, Δν = 76.4Hz), 3.52 (2H, ABq, J = 11.1, Δν = 7.3Hz), 4.28 (2H, s), 5.99 (2H, s), 6.73-6.90 (3H, m) ppm
3- (3,4-Methylenedioxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (126, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.6, Δν = 74.9Hz), 3.53 (2H, d, J = 2.4Hz), 4.19 (2H, s), 5.95 (2H, s ), 6.72-6.86 (3H, m) ppm
3- (2,3-Ethylenedioxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (127, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 74.9Hz), 3.53 (2H, ABq, J = 11.2, Δν = 8.0Hz), 4.24-4.34 (6H, m) , 6.74-6.84 (2H, m), 6.94 (1H, dd, J = 6.1,3.2Hz) ppm
3- (2-Methyl-3,4-ethylenedioxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (131, mp83-85)1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.22 (3H, s), 3.01 (2H, ABq, J = 16.9, Δν = 74.2Hz), 3.54 (2H, ABq, J = 11.1, Δν = 9.2Hz), 4.20 -4.31 (6H, m), 6.68 (1H, d, J = 8.4Hz), 6.83 (1H, d, J = 8.3Hz) ppm
3- (4-Trifluoromethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (142, oil)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.3Hz), 3.52 (2H, ABq, J = 11.3, Δν = 6.9Hz), 4.24 (2H, s), 7.16 (2H, d, J = 8.7Hz), 7.41 (2H, d, J = 8.7Hz) ppm
3- (2-Difluoromethoxy-3-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (143, oil)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 2.33 (3H, s), 3.14 (2H, ABq, J = 17.5, Δν = 76.6Hz), 4.15 (2H, ABq, J = 11.4, Δν = 15.6Hz), 4.33 (2H, s), 6.43 (1H, t, J = 74.0Hz), 7.13-7.17 (2H, m), 7.37 (1H, dd, J = 6.3,2.3Hz) ppm
3- (2-Difluoromethoxy-4-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (144, oil)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 2.34 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 73.5Hz), 3.52 (2H, d, J = 2.1Hz), 4.27 (2H, s ), 6.53 (1H, t, J = 74.0Hz), 6.94-7.01 (2H, m), 7.37 (1H, d, J = 7.8Hz) ppm
3- (2-Difluoromethoxy-5-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (145, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.32 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 73.1Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.6Hz), 4.27 (2H, s), 6.51 (1H, t, J = 73.9Hz), 7.04-7.12 (2H, m), 7.28 (1H, d, J = 1.6Hz) ppm
3- (3-Difluoromethoxy-4-methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (146, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.27 (3H, s), 2.99 (2H, ABq, J = 16.6, Δν = 75.1Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.2Hz), 4.22 (2H, s), 6.50 (1H, t, J = 74.1Hz), 7.10-7.20 (3H, m) ppm
3- (3-Chloro-2-difluoromethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (147, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 73.4Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.4Hz), 4.36 (2H, s), 6.06 (1H, t, J = 74.4Hz), 7.18 (1H, t, J = 7.9Hz), 7.04 (1H, dd, J = 7.9,1.7Hz), 7.50 (1H, dd, J = 1.8,1.7Hz) ppm
3- (2-Chloro-5-difluoromethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (148, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 74.0Hz), 3.52 (2H, ABq, J = 11.3, Δν = 7.3Hz), 4.34 (2H, s), 6.49 (1H, t, J = 73.4Hz), 7.02 (1H, dd, J = 8.8,2.9Hz), 7.33 (1H, d, J = 2.9Hz), 7.37 (1H, d, J = 8.8Hz) ppm
3- (5-Chloro-2-difluoromethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (149, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 73.6Hz), 3.52 (2H, d, J = 2.3Hz), 4.25 (2H, s), 6.53 (1H, t , J = 73.3Hz), 7.08 (1H, d, J = 8.8Hz), 7.26 (1H, dd, J = 8.8,2.5Hz), 7.50 (1H, d, J = 2.5Hz) ppm
3- (4-Chloro-3-difluoromethoxybenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (150, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 75.5Hz), 3.52 (2H, ABq, J = 10.4, Δν = 6.9Hz), 4.21 (2H, s), 6.54 (1H, t, J = 73.4Hz), 7.08-7.41 (3H, m) ppm
3- (2-Methoxymethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (151, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.01 (2H, ABq, J = 16.5, Δν = 74.3Hz), 3.41 (3H, s), 3.54 (2H, ABq, J = 11.2, Δν = 8.5Hz), 4.37 (2H, s), 4.56 (2H, s), 7.26-7.45 (4H, m) ppm
3- (2-Ethoxymethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (152, oil)
1H-NMR (200MHz, CDClThree) δ: 1.26 (3H, t, J = 7.0Hz), 1.55 (3H, s), 3.00 (2H, ABq, J = 16.9, Δν = 74.3Hz), 3.52-3.62 (4H, m), 4.38 (2H , s), 4.60 (2H, s), 7.25-7.45 (4H, m) ppm
3- (2- (2,2,2-trifluoroethoxymethyl) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (153, oil)1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.00 (2H, ABq, J = 17.8, Δν = 82.4Hz), 3.53 (2H, d, J = 2.4Hz), 3.86 (2H, q, J = 8.8Hz), 4.35 (2H, s), 4.80 (2H, s), 7.3-7.5 (4H, m) ppm
3- (3- (2,2,2-trifluoroethoxymethyl) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (154, oil)1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 75.4Hz), 3.52 (2H, d, J = 2.0Hz), 3.84 (2H, q, J = 8.6Hz), 4.27 (2H, s), 4.67 (2H, s), 7.29-7.36 (4H, m) ppm
3- (2- (2-methoxyethoxy) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (155, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 73.6Hz), 3.52 (2H, ABq, J = 9.5, Δν = 6.5Hz), 3.78 (2H, t, J = 4.8Hz), 4.18 (2H, t, J = 4.8Hz), 4.31 (2H, s), 6.86-6.96 (2H, m), 7.21-7.40 (2H, m) ppm
3- (3- (2-methoxyethoxy) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (156, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.7, Δν = 75.1Hz), 3.52 (2H, ABq, J = 12.0, Δν = 7.5Hz), 3.45 (3H, s), 3.75 (2H, t, J = 4.7Hz), 4.12 (2H, t, J = 4.7Hz), 4.23 (2H, s), 6.82-6.98 (3H, m), 7.23 (1H, t, J = 7.4Hz) ppm
3- (2- (2,2-dimethoxyethoxy) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (157, oil)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 2.98 (2H, ABq, J = 17.1, Δν = 73.8Hz), 3.47 (6H, s), 3.52 (2H, s), 4.23 (2H, d, J = 5.7Hz ), 4.30 (2H, s), 4.75 (1H, t, J = 5.9Hz), 6.89-6.93 (2H, m), 7.21-7.41 (2H, m) ppm
3- (3- (2,2-dimethoxyethoxy) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (158, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.00 (2H, ABq, J = 16.8, Δν = 75.1Hz), 3.46 (6H, s), 3.52 (2H, d, J = 2.4Hz), 4.00 (2H, d , J = 5.2Hz), 4.23 (2H, s), 4.72 (1H, t, J = 5.2Hz), 6.82-6.87 (1H, m), 6.96-7.20 (2H, m), 7.23-7.28 (1H, m) ppm
3- (2- (2,2-ethylenedioxyethoxy) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (159, mp79-80.5)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 2.99 (2H, ABq, J = 16.7, Δν = 73.1Hz), 3.52 (2H, ABq, J = 11.1, Δν = 7.4Hz), 3.93-4.08 (4H, m) , 4.09 (2H, d, J = 3.6Hz), 4.31 (2H, s), 5.33 (1H, t, J = 3.7Hz), 6.86-6.96 (2H, m), 7.20-7.29 (1H, m), 7.38 (1H, dd, J = 7.5,0.8Hz) ppm
3- (3- (2,2-ethylenedioxyethoxy) benzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (160, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.99 (2H, ABq, J = 16.8, Δν = 74.9Hz), 3.52 (2H, ABq, J = 11.2, Δν = 7.7Hz), 3.92-4.10 (6H, m) , 4.23 (2H, s), 5.29 (1H, t, J = 4.0Hz), 6.82-6.99 (3H, m), 7.19-7.27 (1H, m) ppm
3- (α-Methylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (161, oil)
1H-NMR (200MHz, CDClThree) δ: 1.49 (s), 1.51 (s) (3H), 1.75 (d, J = 7.0Hz), 1.76 (d, J = 7.0Hz) (3H), 2.92 (ABq, J = 16.7, Δν = 74.5 Hz), 2.95 (ABq, J = 16.7, Δν = 74.1Hz) (2H), 3.46 (2H, s), 4.79 (q, J = 7.0Hz), 4.79 (q, J = 7.0Hz) (1H), 7.23-7.42 (5H, m) ppm
3- (α, α-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (162, oil)
1H-NMR (200MHz, CDClThree) δ: 1.37 (3H, s), 1.91 (6H, s), 2.61 (2H, ABq, J = 17.1, Δν = 77.3Hz), 3.30 (2H, ABq, J = 11.2, Δν = 11.9Hz), 7.25 -7.39 (3H, m), 7.56-7.60 (2H, m) ppm
3- (α-Isopropylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (165, oil)
1H-NMR (200MHz, CDClThree) δ: 0.89 (d, J = 6.7Hz) +0.89 (d, J = 6.7Hz) (3H), 1.09 (d, J = 6.7Hz) +1.10 (d, J = 6.7Hz) (3H), 1.43 (3H, s), 2.16-2.24 (1H, m), 2.69 (1H, dd, J = 17.1,12.1Hz), 3.07 (1H, dd, J = 16.7,14.4Hz), 3.36 (2H, ABq, J = 13.4, Δν = 7.0Hz), 4.44 (d, J = 7.9Hz) +4.46 (d, J = 7.7Hz) (1H), 7.22-7.32 (5H, m) ppm
3- (α, 2-Dimethylbenzyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (166, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (s) +1.56 (s) (3H), 1.76 (d, J = 6.9Hz) +1.78 (d, J = 6.9Hz) (3H), 2.42 (3H, s), 2.96 (ABq, J = 16.6, Δν = 73.0Hz) +2.96 (ABq, J = 16.8, Δν = 71.3Hz) (2H), 3.49 (2H, d, J = 2.7Hz), 5.01 (1H, q, J = 6.9Hz) , 7.16-7.23 (3H, m), 7.40-7.44 (1H, m) ppm
3- (4-chromanyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (167, mp83-84)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 2.38-2.48 (2H, m), 2.84 (d, J = 16.9Hz) +2.92 (d, J = 16.8Hz) (1H), 3.14 (d, J = 16.7Hz ) +3.21 (d, J = 16.7Hz) (1H), 3.50-3.64 (2H, m), 4.31-4.37 (2H, m), 5.00 (1H, t, J = 6.4Hz), 6.79-6.93 (2H , m), 7.13-7.21 (1H, m), 7.28-7.33 (1H, m) ppm
3- (1- (1,2,3,4-terolahydronaphthyl) thio) -5-chloromethyl-5-methyl-2-isoxazoline (169, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 1.89-2.32 (4H, m), 2.74-3.65 (6H, m), 5.08 (1H, brs), 7.08-7.21 (3H, m), 7.38-7.42 (1H, m) ppm
3-Benzylthio-5-trifluoromethyl-5-methyl-2-isoxazoline (179, mp56-59)
1H-NMR (200MHz, CDClThree) δ: 1.60 (3H, d, J = 1.9Hz), 2.97 (1H, dd, J = 7.1,0.8Hz), 3.34 (1H, d, J = 17.2Hz), 4.28 (3H, s), 7.30- 7.38 (5H, m) ppm
[0116]
[Example 2]
3-Benzylsulfinyl-5-chloromethyl-5-methyl-2-isoxazoline(Compound No. 1001) and3-Benzylsulfonyl-5-chloromethyl-5-methyl-2-isoxazoline(Compound No. 2001) (Step C)
(1) 3-Benzylsulfinyl-5-chloromethyl-5-methyl-2-isoxazoline (Step C-1)
926.7 mg of 3-benzylthio-5-chloromethyl-5-methyl-2-isoxazoline (Compound No. 1) prepared by the method of Example 1 was dissolved in 20 ml of 1,2-dichloroethane and stirred with m-chloro. 892.4 mg of perbenzoic acid was added at room temperature. After further stirring at room temperature for 45 minutes, a saturated aqueous sodium sulfite solution was added to the reaction solution, and the mixture was extracted with methylene chloride. The organic layer was washed with an aqueous sodium hydrogen carbonate solution and brine successively. After drying over anhydrous sodium sulfate, filtration and evaporation of the solvent, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1), and 710.9 mg (72% of the desired product) having a melting point of 60-65 ° C. )
[0117]
1H-NMR (200MHz, CDClThree) δ: 1.54 (s) +1.56 (s) (3H), 2.85 (2H, ABq, J = 17.9, Δν = 201.3Hz), 3.43-3.57 (2H, m), 4.16-4.36 (2H, m), 7.30-7.42 (5H, m) ppm
(2) 3-Benzylsulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (Steps C-1 and C-2)
13-3.1 mg of 3-benzylthio-5-chloromethyl-5-methyl-2-isoxazoline (Compound No. 1) prepared by the method of Example 1 was dissolved in 5 ml of methylene chloride, and m-chloroperbenzoic acid was stirred. 5 ml of 385 mg of methylene chloride solution was added dropwise at room temperature. After further stirring at room temperature for 2 hours, a saturated aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was extracted with methylene chloride. The organic layer was washed with an aqueous sodium bicarbonate solution and brine successively. After drying over anhydrous sodium sulfate, filtration and evaporation of the solvent, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1), and 86.2 mg (58%) of the desired product having a melting point of 87-88 ° C. )
[0118]
1H-NMR (200MHz, CDClThree) δ: 1.50 (3H, s), 2.98 (2H, ABq, J = 17.9, Δν = 86.1Hz), 3.49 (2H, s), 4.60 (2H, s), 7.43 (5H, m) ppm
The compounds produced according to the method of Example 2 (1) and the method of Example 2 (2) are shown below.
[0119]
3- (2-Methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2002, oil)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 2.46 (3H, s), 3.03 (2H, ABq, J = 17.7, Δν = 88.4Hz), 3.52 (2H, s), 4.69 (2H, s), 7.23-7.40 (4H, m) ppm
3- (3-Methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2003, mp51-54)
1H-NMR (200MHz, CDClThree) δ: 1.50 (3H, s), 2.37 (3H, s), 2.97 (2H, ABq, J = 17.8, Δν = 84.9Hz), 3.48 (2H, s), 4.56 (2H, s), 7.20-7.30 (4H, m) ppm
3- (4-Methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2004, mp99-101)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H.s), 2.37 (3H, s), 2.97 (2H, ABq, J = 17.9, Δν = 78.5Hz), 3.49 (2H, s), 4.56 (2H, s), 7.22 (2H , d, J = 8.1 Hz), 7.31 (2H, d, J = 8.1 Hz) ppm
3- (2,3-Dimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2005, Amorphous)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 2.33 (3H, s), 2.34 (3H, s), 3.01 (2H, ABq, J = 17.5, Δν = 88.3Hz), 3.52 (2H, br), 4.72 (2H , s), 7.09-7.24 (3H, m) ppm
3- (2,4-Dimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2006, oil)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 2.33 (3H, s), 2.41 (3H, s), 3.02 (2H, ABq, J = 17.8, Δν = 80.6Hz), 3.51 (2H, s), 4.64 (2H) , s), 7.03-7.13 (2H, m), 7.24-7.27 (1H, m) ppm
3- (2,5-Dimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2007, oil)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 2.33 (3H, s), 2.41 (3H, s), 3.03 (2H, ABq, J = 17.9, Δν = 88.7Hz), 3.52 (2H, s), 4.64 (2H) , s), 7.14-7.17 (3H, m) ppm
3- (2,6-Dimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2008, Amorphous)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 2.48 (6H, s), 3.17 (2H, ABq, J = 17.8, Δν = 85.7Hz), 3.58 (2H, d, J = 1.8Hz), 4.85 (2H, s ), 7.08-7.26 (3H, m) ppm
3- (3,4-Dimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2009, mp87-88)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 2.28 (6H, s), 2.96 (2H, ABq, J = 17.8, Δν = 75.5Hz), 3.47 (2H, s), 4.53 (2H, s), 7.16 (3H , s) ppm
3- (3,5-Dimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2010, mp73-75)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 2.33 (6H, s), 2.97 (2H, ABq, J = 17.9, Δν = 84.4Hz), 3.48 (2H, s), 4.52 (2H, s), 7.03 (3H) , br) ppm
3- (2,4,6-Trimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2011, mp121-123)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 2.29 (3H, s), 2.43 (6H, s), 3.14 (2H, ABq, J = 17.7, Δν = 78.6Hz), 3.56 (2H, s), 4.80 (2H) , s), 6.94 (2H, s) ppm
3- (2-Ethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2012, oil)
1H-NMR (200MHz, CDClThree) δ: 1.24 (3H, t, J = 7.5Hz), 1.53 (3H, s), 2.81 (2H, q, J = 7.5Hz), 3.02 (2H, ABq, J = 17.9, Δν = 88.7Hz), 3.52 (2H, s), 4.71 (2H, s), 7.20-7.41 (4H, m) ppm
3- (4-Ethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2014, mp112-113)
1H-NMR (200MHz, CDClThree) δ: 1.24 (3H, t, J = 7.7Hz), 1.50 (3H, s), 2.67 (2H, q, J = 7.7Hz), 2.96 (2H, ABq, J = 18.0, Δν = 80.8Hz), 3.47 (2H, s), 4.57 (2H, s), 7.24 (2H, d, J = 8.1Hz), 7.34 (2H, d, J = 8.1Hz) ppm
3- (2,6-Diethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2015, mp58-61)
1H-NMR (200MHz, CDClThree) δ: 1.24 (6H, t, J = 7.5Hz), 1.57 (3H, s), 2.85 (4H, q, J = 7.5Hz), 3.13 (2H, ABq, J = 17.7, Δν = 86.3Hz), 3.56 (2H, s), 4.89 (2H, s), 7.17 (2H, d, J = 7.7Hz), 7.26-7.36 (1H, m) ppm
3- (4-npropylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2019, mp101-103)
1H-NMR (200MHz, CDClThree) δ: 0.94 (3H, t, J = 7.3Hz), 1.49 (3H, s), 1.64 (2H, sextet, J = 7.3Hz), 2.61 (2H, t, J = 7.3Hz), 2.95 (2H, ABq, J = 17.9, Δν = 84.5Hz), 3.48 (2H, s), 4.56 (2H, s), 7.22 (2H, d, J = 8.3Hz), 7.34 (2H, d, J = 8.3Hz) ppm
3- (2-Isopropylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2020, mp76-78)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.08 (2H, ABq, J = 17.9, Δν = 90.9Hz), 3.23-3.36 (1H, m), 3.54 (2H, ABq, J = 11.7, Δν = 5.8Hz) , 4.75 (2H, s), 7.18-1.42 (4H, m) ppm
3- (4-tert-Butylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2031, mp108-110)
1H-NMR (200MHz, CDClThree) δ: 1.32 (9H, s), 1.49 (3H, s), 2.94 (2H, ABq, J = 17.8, Δν = 81.2Hz), 3.46 (2H, d, J = 1.3Hz), 4.57 (2H, s ), 7.35 (2H, d, J = 8.6Hz), 7.44 (2H, d, J = 8.6Hz) ppm
3- (2- (5,6,7,8-tetrahydronaphthyl) sulfonyl) -5-chloromethyl-5-methyl-2-isoxazoline (2033, mp69-73)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 1.76-1.82 (4H, m), 2.74-2.77 (4H, m), 2.98 (2H, ABq, J = 18.0, Δν = 73.0Hz), 3.47 (2H, s) , 4.52 (2H, s), 7.09-7.18 (3H, m) ppm
3- (2-Chlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2034, mp92-94)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.08 (2H, ABq, J = 17.9, Δν = 83.2Hz), 3.54 (2H, ABq, J = 11.8, Δν = 7.9Hz), 4.58 (2H, s), 7.33 -7.42 (4H, m) ppm
3- (3-Chlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2035, mp95-97)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.08 (2H, ABq, J = 17.8, Δν = 83.6Hz), 3.54 (2H, d, J = 1.4Hz), 4.57 (2H, s), 7.32-7.43 (4H , m) ppm
3- (4-Chlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2036, mp89-90)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.10 (2H, ABq, J = 17.8, Δν = 82.4Hz), 3.54 (2H, d, J = 2.4Hz), 4.58 (2H, s), 7.38 (4H, s ) ppm
3- (2,3-dichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2037, mp71-73)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.17 (2H, ABq, J = 17.7, Δν = 81.4Hz), 3.57 (2H, ABq, J = 11.8, Δν = 10.1Hz), 4.90 (2H, s), 7.27 (1H, t, J = 7.9Hz), 7.46-7.57 (2H, m) ppm
3- (2,4-Dichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2038, mp111-113)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.21 (2H, ABq, J = 17.7, Δν = 80.7Hz), 3.69 (2H, ABq, J = 11.8, Δν = 10.7Hz), 4.82 (2H, s), 7.33 (1H, dd, J = 8.4,2.0Hz), 7.49-7.53 (2H, m) ppm
3- (2,5-dichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2039, mp135-136)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.20 (2H, ABq, J = 17.7, Δν = 81.7Hz), 3.59 (2H, ABq, J = 11.7, Δν = 11.5Hz), 4.81 (2H, s), 7.33 (1H, dd, J = 8.6,2.2Hz), 7.42 (1H, d, J = 8.6Hz), 7.56 (1H, d, J = 2.2Hz) ppm
3- (2,6-dichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2040, mp147-148)
1H-NMR (200MHz, CDClThree) δ: 1.63 (3H, s), 3.29 (2H, ABq, J = 17.8, Δν = 83.0Hz), 3.62 (2H, d, J = 4.7Hz), 5.15 (2H, s), 7.29-7.45 (3H , m) ppm
3- (3,4-Dichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2041, mp88-90)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.17 (2H, ABq, J = 17.8, Δν = 80.5Hz), 3.56 (2H, ABq, J = 11.8, Δν = 10.7Hz), 4.56 (2H, s), 7.29 (1H, dd, J = 8.3,2.0Hz), 7.50 (1H, d, J = 8.4Hz), 7.54 (1H, d, J = 2.0Hz) ppm
3- (3,5-dichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2042, mp96-98)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.16 (2H, ABq, J = 18.0, Δν = 81.6Hz), 3.57 (2H, ABq, J = 11.9, Δν = 11.5Hz), 4.55 (2H, s), 7.34 (2H, d, J = 1.8Hz), 7.42 (1H, t, J = 1.8Hz) ppm
3- (2,3,5-Trichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2043, mp124-127)
1H-NMR (200MHz, CDClThree) δ: 1.60 (3H, s), 3.21 (2H, ABq, J = 17.9, Δν = 81.6Hz), 3.59 (2H, ABq, J = 11.7, Δν = 11.5Hz), 4.81 (2H, s), 7.31 -7.56 (2H, m) ppm
3- (2,4,6-Trichlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2044, mp137-139)
1H-NMR (200MHz, CDClThree) δ: 1.64 (3H, s), 3.32 (2H, ABq, J = 17.8, Δν = 83.4Hz), 3.63 (2H, ABq, J = 11.7, Δν = 12.2Hz), 5.11 (2H, s), 7.45 (2H, s) ppm
3- (3-Chloro-4-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2045, mp79-83)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.39 (3H, s), 3.09 (2H, ABq, J = 17.8, Δν = 81.7Hz), 3.53 (2H, ABq, J = 9.6, Δν = 6.0Hz), 4.54 (2H, s), 7.17-7.40 (3H, m) ppm 3- (3-Methyl-4-chlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2046, mp88-90)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.39 (3H, s), 3.09 (2H, ABq, J = 17.8, Δν = 81.3Hz), 3.53 (2H, ABq, J = 11.7, Δν = 6.5Hz), 4.55 (2H, s), 7.17-7.40 (3H, m) ppm
3- (3,4-Dichloro-2-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2047, mp86-90)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 2.54 (3H, s), 3.20 (2H, ABq, J = 17.9, Δν = 82.7Hz), 3.59 (2H, ABq, J = 11.7, Δν = 11.5Hz), 4.72 (2H, s), 7.25 (1H, d, J = 8.0Hz), 7.37 (1H, d, J = 8.4Hz) ppm
3- (2,4-Dichloro-3-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2048, mp110-112)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 2.52 (3H, s), 3.18 (2H, ABq, J = 17.9, Δν = 77.8Hz), 3.57 (2H, ABq, J = 11.6, Δν = 9.2Hz), 4.86 (2H, s), 7.35 (2H, s) ppm
3- (2,5-dichloro-4-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2049, mp116-118)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 2.37 (3H, s), 3.19 (2H, ABq, J = 18.0, Δν = 78.5Hz), 3.58 (2H, ABq, J = 11.8, Δν = 9.7Hz), 4.77 (2H, s), 7.35 (1H, s), 7.53 (1H, s) ppm
3- (2-Bromobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2050, mp73-75)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.12 (2H, ABq, J = 17.9, Δν = 81.5Hz), 3.56 (2H, ABq, J = 11.5, Δν = 9.5Hz), 4.89 (2H, s), 7.28 -7.38 (2H, m), 7.57-7.68 (2H, m) ppm
3- (3-Bromobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2051, mp90)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.09 (2H, ABq, J = 17.6, Δν = 83.5Hz), 3.54 (2H, d, J = 2.4Hz), 4.57 (2H, s), 7.29-7.42 (2H , m), 7.56 (2H, d, J = 7.8Hz) ppm
3- (4-Bromobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2052, mp114-115)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.10 (2H, ABq, J = 17.6, Δν = 81.8Hz), 3.54 (2H, d, J = 2.4Hz), 4.57 (2H, s), 7.31 (2H, d , J = 8.3Hz), 7.56 (2H, d, J = 8.3Hz) ppm
3- (2-Fluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2053, mp82-84)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.95 (2H, ABq, J = 17.7, Δν = 81.9Hz), 3.56 (2H, ABq, J = 11.6, Δν = 8.2Hz), 4.68 (2H, s), 7.14 -7.25 (2H, m), 7.37-7.51 (2H, m) ppm
3- (3-Fluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2054, mp95-97)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 3.09 (2H, ABq, J = 17.7, Δν = 83.3Hz), 3.53 (2H, ABq, J = 11.7, Δν = 7.6Hz), 4.60 (2H, s), 7.12 -7.23 (3H, m), 7.34-7.41 (1H, m) ppm
3- (4-Fluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2055, mp75-76)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 3.10 (2H, ABq, J = 17.8, Δν = 83.4Hz), 3.53 (2H, ABq, J = 11.7, Δν = 7.5Hz), 4.58 (2H, s), 7.06 -7.15 (2H, m), 7.38-7.45 (2H, m) ppm
3- (2,3-Difluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2056, mp83-85)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.22 (2H, ABq, J = 17.9, Δν = 81.2Hz), 3.59 (2H, ABq, J = 11.8, Δν = 10.6Hz), 4.70 (2H, s), 7.13 -7.26 (3H, m) ppm
3- (2,4-Difluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2057, mp81)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 3.21 (2H, ABq, J = 17.7, Δν = 80.6Hz), 3.58 (2H, ABq, J = 11.7, Δν = 10.6Hz), 4.64 (2H, s), 6.86 -7.01 (2H, m, 7.43-7.55 (1H, m) ppm
3- (2,5-Difluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2058, mp127-129)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.22 (2H, ABq, J = 17.7, Δν = 80.8Hz), 3.58 (2H, ABq, J = 11.7, Δν = 10.5Hz), 4.65 (2H, s), 7.08 -7.25 (3H, m) ppm
 3- (2,6-Difluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2059, mp92-93)
1H-NMR (200MHz, CDClThree) δ: 1.62 (3H, s), 3.27 (2H, ABq, J = 17.7, Δν = 82.3Hz), 3.61 (2H, ABq, J = 11.6, Δν = 10.6Hz), 4.37 (2H, s), 6.97 -7.05 (2H, m), 7.37-7.46 (1H, m) ppm
3- (3,4-Difluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2060, mp104)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.17 (2H, ABq, J = 17.8, Δν = 80.8Hz), 3.56 (2H, ABq, J = 11.7, Δν = 10.9Hz), 4.57 (2H, s), 7.12 -7.34 (3H, m) ppm
3- (3,5-Difluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2061, mp108-110)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.17 (2H, ABq, J = 17.8, Δν = 81.3Hz), 3.57 (2H, ABq, J = 11.9, Δν = 11.1Hz), 4.59 (2H, s), 6.88 -7.02 (3H, m) ppm
3- (2-Fluoro-3-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2064, mp96-97)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.31 (3H, d, J = 2.0Hz), 3.14 (2H, ABq, J = 17.8, Δν = 84.1Hz), 3.55 (2H, ABq, J = 11.7, Δν = 6.2Hz), 4.66 (2H, s), 7.09 (1H, t, J = 7.7Hz), 7.28 (2H, q, J = 7.3Hz) ppm
3- (3-Fluoro-4-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2065, mp88-89)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.29 (3H, d, J = 1.9Hz), 3.07 (2H, ABq, J = 17.9, Δν = 78.2Hz), 3.52 (2H, s), 4.56 (2H, s ), 7.08-7.27 (3H, br) ppm
3- (2,3,5,6-tetrafluoro-4-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2066, mp115-117)
1H-NMR (200MHz, CDClThree) δ: 1.62 (3H, d, J = 7.1Hz), 2.29 (3H, dt, J = 13.1,2.2Hz), 3.09 (1H, dd, J = 17.8,11.7Hz), 3.41-3.69 (3H, m ), 4.70 (2H, d, J = 20.5Hz) ppm
3- (2-Fluoro-3-chlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2067, mp90-92)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.38 (2H, ABq, J = 17.8, Δν = 81.1Hz), 3.58 (2H, ABq, J = 11.7, Δν = 10.4Hz), 4.69 (2H, s), 7.12 -7.20 (1H, m), 7.37-7.52 (2H, m) ppm
3- (2-Chloro-4-fluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2068, mp80-82)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.20 (2H, ABq, J = 17.9, Δν = 81.4Hz), 3.59 (2H, ABq, J = 11.7, Δν = 11.0Hz), 4.81 (2H, s), 7.07 (1H, td, J = 8.6,2.7Hz), 7.12-7.25 (1H, m), 7.56 (1H, dd, J = 8.6,5.9Hz) ppm
3- (2-Chloro-6-fluorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2070, mp118)
1H-NMR (200MHz, CDClThree) δ: 1.63 (3H, s), 3.27 (2H, ABq, J = 17.8, Δν = 82.8Hz), 3.62 (2H, ABq, J = 11.7, Δν = 11.1Hz), 4.91 (2H, d, J = 1.6Hz), 7.12-7.39 (3H, m) ppm
3- (2-Trifluoromethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2071, mp78)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.21 (2H, ABq, J = 17.8, Δν = 80.3Hz), 3.58 (2H, ABq, J = 11.7, Δν = 9.8Hz), 4.87 (2H, s), 7.55 -7.64 (2H, m), 7.77 (2H, d, J = 7.4Hz) ppm
3- (3-Trifluoromethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2072, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.14 (2H, ABq, J = 17.8, Δν = 84.6Hz), 3.54 (2H, d, J = 2.6Hz), 4.67 (2H, s), 7.59-7.70 (4H , m) ppm
3- (4-Trifluoromethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2073, mp107-109)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.14 (2H, ABq, J = 18.0, Δν = 81.2Hz), 3.55 (2H, ABq, J = 11.8, Δν = 9.4Hz), 4.68 (2H, s), 7.58 (2H, d, J = 8.3Hz), 7.69 (2H, d, J = 8.3Hz) ppm
3- (2,4-Bistrifluoromethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2074, mp84-85)
1H-NMR (200MHz, CDClThree) δ: 1.62 (3H, s), 3.30 (2H, ABq, J = 17.6, Δν = 78.9Hz), 3.62 (2H, ABq, J = 11.8, Δν = 13.4Hz), 4.93 (2H, s), 7.91 (2H, br.d, J = 2.6Hz), 8.02 (1H, br) ppm
3- (3,5-Bistrifluoromethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2075, mp105-106)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 3.23 (2H, ABq, J = 17.7, Δν = 82.3Hz), 3.58 (2H, ABq, J = 11.9, Δν = 12.7Hz), 4.75 (2H, s), 7.92 (3H, br) ppm
3- (2-Fluoro-4-trifluoromethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2076, mp93-94)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.25 (2H, ABq, J = 17.6, Δν = 79.7Hz), 3.59 (2H, ABq, J = 11.8, Δν = 11.9Hz), 4.74 (2H, s), 7.41 -7.51 (2H, m), 7.67 (1H, t, J = 7.0Hz) ppm
3- (2-Methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2077, mp85-87)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.05 (2H, ABq, J = 17.8, Δν = 85.5Hz), 3.49 (2H, s), 3.87 (3H, s), 4.71 (2H, s), 6.93-7.00 (2H, m), 7.39-7.45 (2H, m) ppm
3- (3-Methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2078, oil)
1H-NMR (200MHz, CDClThree) δ: 1.50 (3H, s), 2.96 (2H, ABq, J = 17.9, Δν = 82.1Hz), 3.49 (2H, s), 3.82 (3H, s), 4.56 (2H, s), 6.92-7.01 (3H, m), 7.27-7.34 (1H, m) ppm
3- (4-Methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2079, mp84-85)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 3.00 (2H, ABq, J = 17.6, Δν = 81.2Hz), 3.50 (2H, s), 3.82 (3H, s), 4.54 (2H, s), 6.93 (2H) , d, J = 8.7Hz), 7.34 (2H, d, J = 8.7Hz) ppm
3- (2,3-Dimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2080, mp94-95)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.11 (2H, ABq, J = 17.8, Δν = 71.4Hz), 3.56 (2H, ABq, J = 11.4, Δν = 13.8Hz), 3.86 (3H, s), 3.93 (3H, s), 4.69 (2H, s), 6.95-7.13 (3H, m) ppm
3- (2,4-Dimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2081, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.06 (2H, ABq, J = 17.8, Δν = 82.3Hz), 3.50 (2H, s), 3.83 (3H, s), 3.85 (3H, s), 6.49-6.56 (2H, m), 4.63 (2H, s), 7.34 (1H, d, J = 8.3Hz) ppm
3- (2,5-Dimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2082, mp92-94)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 3.06 (2H, ABq, J = 17.9, Δν = 83.1Hz), 3.50 (2H, s), 3.78 (3H, s), 3.83 (3H, s), 4.67 (2H) , s), 6.89-7.00 (3H, m) ppm
3- (2,6-Dimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2083, mp128-130)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.13 (2H, Abq, J = 17.7, Δν = 87.9Hz), 3.53 (2H, s), 3.87 (6H, s), 4.80 (2H, s), 6.60 (2H) , d, J = 8.4Hz), 7.33 (1H, t, J = 7.3Hz) ppm
3- (3,4-Dimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2084, mp117-118)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 3.01 (2H, ABq, J = 17.8, Δν = 83.0Hz), 3.51 (2H, s), 3.90 (6H, s), 4.55 (2H, s), 6.86-6.99 (3H, m) ppm
3- (3,5-Dimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2085, mp128-128.5)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 2.97 (2H, ABq, J = 17.9, Δν = 79.1Hz), 3.50 (2H, s), 3.80 (6H, s), 4.52 (2H, s), 6.49 (1H) , t, J = 2.2Hz), 6.55 (2H, d, J = 2.2Hz) ppm
3- (3,4,5-Trimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2087, mp105-106)
1H-NMR (200MHz, CDClThree) δ: 1.52 (3H, s), 3.04 (2H, ABq, J = 17.9, Δν = 88.3Hz), 3.52 (2H, d, J = 1.8Hz), 3.86 (3H, s), 3.87 (6H, s ), 4.54 (2H, s), 6.63 (2H, s) ppm
3- (2-Ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2088, mp97-99)
1H-NMR (200MHz, CDClThree) δ: 1.45 (3H, t, J = 7.0Hz), 1.51 (3H, s), 2.99 (2H, ABq, J = 17.8, Δν = 87.0Hz), 3.48 (2H, s), 4.09 (2H, q , J = 7.0Hz), 4.73 (2H, s), 6.91-7.03 (2H, m), 7.33-7.46 (2H, m) ppm
3- (3-Ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2089, mp86-88)
1H-NMR (200MHz, CDClThree) δ: 1.42 (3H, t, J = 7.0Hz), 1.55 (3H, s), 2.96 (2H, ABq, J = 17.9, Δν = 81.9Hz), 3.49 (2H, s), 4.04 (2H, q , J = 7.0Hz), 4.55 (2H, s), 6.92-6.99 (3H, m), 7.27-7.31 (1H, m) ppm
3- (4-Ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2090, mp104-105)
1H-NMR (200MHz, CDClThree) δ: 1.42 (3H, t, J = 7.0Hz), 1.51 (3H, s), 2.99 (2H, ABq, J = 18.0, Δν = 82.3Hz), 3.50 (2H, s), 4.04 (2H, d , J = 7.0Hz), 4.53 (2H, s), 6.91 (2H, d, J = 8.6Hz), 7.32 (2H, d, J = 8.4Hz) ppm
3- (2,6-diethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2091, mp81-82)
1H-NMR (200MHz, CDClThree) δ: 1.43 (6H, t, J = 7.0Hz), 1.55 (3H, s), 3.02 (2H, ABq, J = 17.8, Δν = 89.8Hz), 3.50 (2H, s), 4.08 (4H, q , J = 7.0Hz), 4.85 (2H, s), 6.55 (2H, d, J = 8.3Hz), 7.27 (1H, t, J = 8.3Hz) ppm
3- (2-Isopropyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2092, mp89-92)
1H-NMR (200MHz, CDClThree) δ: 1.37 (6H, d, J = 6.0Hz), 1.51 (3H, s), 2.98 (2H, ABq, J = 17.7, Δν = 83.7Hz), 3.48 (2H, s), 4.61 (1H, quintet , J = 6.1Hz), 4.71 (2H, s), 6.91-6.99 (2H, m), 7.30-7.46 (2H, m) ppm
3- (3-Isopropyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2093, mp66-68)
1H-NMR (200MHz, CDClThree) δ: 1.50 (3H, s), 2.68 (6H, d, J = 6.1Hz), 2.96 (2H, ABq, J = 17.8, Δν = 83.4Hz), 3.48 (2H, s), 4.53-4.59 (3H , m), 6.90-6.98 (3H, m), 7.30-7.34 (1H, m) ppm
3- (4-Isopropyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2094, mp76-78)
1H-NMR (200MHz, CDClThree) δ: 1.35 (3H, d, J = 6.2Hz), 1.51 (3H, s), 3.00 (2H, ABq, J = 17.8, Δν = 82.5Hz), 3.50 (2H, s), 4.53 (2H, s ), 4.53 (1H, dept, J = 6.2Hz), 6.90 (2H, d, J = 8.6Hz), 7.31 (2H, d, J = 8.6Hz) ppm
3- (2-Methoxy-3-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2095, mp110-113)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.34 (3H, s), 3.08 (3H, s), 3.11 (2H, ABq, J = 17.5, Δν = 77.9Hz), 3.55 (2H, ABq, J = 12.1, Δν = 11.1Hz), 4.67 (2H, s), 7.04-7.12 (1H, m), 7.23-7.35 (2H, m) ppm
3- (3-Methyl-4-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2097, mp110-111)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.34 (3H, s), 3.10 (2H, ABq, J = 17.6, Δν = 77.5Hz), 3.54 (2H, ABq, J = 11.4, Δν = 10.8Hz), 3.80 (3H, s), 4.67 (2H, s), 7.04-7.12 (1H, m), 7.23-7.34 (2H, m) ppm
3- (3-Methoxy-4-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2098, mp86-88)
1H-NMR (200MHz, CDClThree) δ: 1.50 (3H, s), 2.22 (3H, s), 2.96 (2H, ABq, J = 17.8, Δν = 83.2Hz), 3.48 (2H, s), 3.85 (3H, s), 4.56 (2H) , s), 6.87-6.92 (2H, m), 7.15 (1H, d, J = 7.4Hz) ppm
3- (2-Ethoxy-3-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2099, oil)
1H-NMR (200MHz, CDClThree) δ: 1.41 (3H, t, J = 7.1Hz), 1.56 (3H, s), 2.31 (3H, s), 3.08 (2H, ABq, J = 17.8, Δν = 75.0Hz), 3.55 (2H, ABq , J = 11.5, Δν = 12.0Hz), 3.93 (2H, q, J = 7.1Hz), 4.65 (2H, s), 7.07 (1H, t, J = 7.5Hz), 7.25 (1H, m), 7.34 (1H, d, J = 7.5Hz) ppm
3- (2-Isopropyloxy-3-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2100, mp105-106)
1H-NMR (200MHz, CDClThree) δ: 1.30 (6H, d, J = 6.2Hz), 1.56 (3H, s), 2.30 (3H, s), 2.96 (2H, ABq, J = 17.7, Δν = 70.0Hz), 3.51 (2H, ABq , J = 11.4, Δν = 6.7Hz), 4.22 (1H, quintet, J = 6.1Hz), 4.64 (2H, s), 7.07 (1H, t, J = 7.8Hz), 7.24 (1H, d, J = 7.6Hz), 7.36 (1H, d, J = 7.8Hz) ppm
3- (3-Chloro-2-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2101, mp83-85)
1H-NMR (200MHz, CDClThree) δ: 1.59 (3H, s), 3.18 (2H, ABq, J = 17.7, Δν = 81.7Hz), 3.59 (2H, ABq, J = 11.6, Δν = 14.3Hz), 3.97 (3H, s), 4.70 (2H, s), 7.07-7.15 (1H, m), 7.39-7.46 (2H, m) ppm
3- (4-Chloro-2-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2102, mp110-112)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.14 (2H, ABq, J = 17.8, Δν = 83.2Hz), 3.54 (2H, s), 3.88 (3H, s), 4.68 (2H, s), 6.94-7.02 (2H, m), 7.36 (1H, d, J = 8.1Hz) ppm
3- (2-Chloro-5-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2103, mp101-103)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.12 (2H, ABq, J = 17.9, Δν = 80.8Hz), 3.56 (2H, ABq, J = 11.6, Δν = 8.8Hz), 3.82 (3H, s), 4.79 (2H, s), 6.91 (1H, dd, J = 8.9,3.0Hz), 7.10 (1H, d, J = 3.1Hz), 7.35 (1H, d, J = 8.9Hz) ppm
3- (5-Chloro-2-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2104, mp109-111)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.14 (2H, ABq, J = 17.9, Δν = 83.4Hz), 3.55 (2H, ABq, J = 11.7, Δν = 5.7Hz), 3.87 (3H, s), 4.68 (2H, s), 6.89 (1H, d, J = 8.8Hz), 7.34 (1H, dd, J = 8.8,2.5Hz), 7.41 (1H, d, J = 2.5Hz) ppm
3- (4-Chloro-3-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2105, mp91-93)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.10 (2H, ABq, J = 17.7, Δν = 85.0Hz), 3.54 (2H, ABq, J = 11.7, Δν = 14.6Hz), 3.93 (3H, s), 4.58 (2H, s), 6.93-7.00 (2H, m), 7.40 (1H, d, J = 8.0Hz) ppm
3- (3,5-Dichloro-2-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2106, mp85-87)1H-NMR (200MHz, CDClThree) δ: 1.61 (3H, s), 3.24 (2H, ABq, J = 17.9, Δν = 81.9Hz), 3.61 (2H, ABq, J = 11.6, Δν = 15.2Hz), 3.96 (3H, s), 4.68 (2H, s), 7.39 (1H, d, J = 2.6Hz), 7.44 (1H, d, J = 2.6Hz) ppm
3- (2,6-Dimethoxy-3-chlorobenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2107, mp85-88)
1H-NMR (200MHz, CDClThree) δ: 1.61 (3H, s), 3.20 (2H, ABq, J = 17.6, Δν = 84.4Hz), 3.61 (2H, ABq, J = 11.4, Δν = 15.5Hz), 3.87 (3H, s), 3.96 (3H, s), 4.78 (2H, s), 6.70 (1H, d, J = 8.9Hz), 7.37 (1H, d, J = 8.9Hz) ppm
3- (2-Chloro-3,4-dimethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2108, oil)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 3.17 (2H, ABq, J = 17.8, Δν = 81.0Hz), 3.57 (2H, ABq, J = 11.6, Δν = 8.1Hz), 3.88 (3H, s), 3.90 (3H, s), 4.78 (2H, s), 6.89 (1H, d, J = 8.9Hz), 7.29 (1H, d, J = 8.9Hz) ppm
3- (3,5-Dichloro-4-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2109, mp126-127)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 3.38 (2H, ABq, J = 17.8, Δν = 77.9Hz), 3.58 (2H, ABq, J = 11.8, Δν = 11.5Hz), 3.92 (3H, s), 4.51 (2H, s), 7.83 (2H, s) ppm
3- (3-Chloro-2-ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2110, oil)
1H-NMR (200MHz, CDClThree) δ: 1.46 (3H, t, J = 7.0Hz), 1.59 (3H, s), 3.15 (2H, ABq, J = 17.8, Δν = 79.8Hz), 3.58 (2H, ABq, J = 11.6, Δν = 14.5Hz), 4.12 (2H, q, J = 7.2Hz), 4.68 (2H, s), 7.17 (1H, t, J = 8.0Hz), 7.41 (1H, q, J = 1.6Hz), 7.45 (1H , q, J = 1.8Hz) ppm
3- (4-Chloro-2-ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2111, mp118)
1H-NMR (200MHz, CDClThree) δ: 1.45 (3H, t, J = 6.9Hz), 1.54 (3H, s), 3.09 (2H, ABq, J = 17.6, Δν = 84.2Hz), 3.53 (2H, s), 4.08 (2H, q , J = 6.9Hz), 4.69 (2H, s), 6.92-7.00 (2H, m), 7.36 (1H, d, J = 8.1Hz) ppm
3- (2-Chloro-5-ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2112, mp113-114)
1H-NMR (200MHz, CDClThree) δ: 1.42 (3H, t, J = 7.0Hz), 1.54 (3H, s), 3.10 (2H, ABq, J = 17.8, Δν = 80.6Hz), 3.55 (2H, d, J = 3.3Hz), 4.03 (2H, q, J = 7.0Hz), 4.77 (2H, s), 6.89 (1H, dd, J = 8.8, 3.1Hz), 7.08 (1H, d, J = 3.1Hz), 7.34 (1H, d , J = 8.8Hz) ppm
3- (5-Chloro-2-ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2113, mp75-77)
1H-NMR (200MHz, CDClThree) δ: 1.44 (3H, t, J = 7.0Hz), 1.55 (3H, s), 3.09 (2H, ABq, J = 17.8, Δν = 84.2Hz), 3.55 (2H, s), 4.07 (2H, q , J = 7.0Hz), 4.69 (2H, s), 6.86 (1H, d, J = 8.8Hz), 7.31 (1H, dd, J = 8.8,2.6Hz), 7.40 (1H, d, J = 2.6Hz ) ppm
3- (4-Chloro-3-ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2114, mp85-88)
1H-NMR (200MHz, CDClThree) δ: 1.48 (3H, t, J = 7.0Hz), 1.53 (3H, s), 3.08 (2H, ABq, J = 17.8, Δν = 85.3Hz), 3.53 (2H, ABq, J = 11.7, Δν = 8.2Hz), 4.13 (2H, q, J = 7.0Hz), 4.56 (2H, s), 6.92 (1H, dd, J = 8.0,2.0Hz), 6.98 (1H, d, J = 2.0Hz), 7.38 (1H, d, J = 8.0Hz) ppm
3- (3,5-dichloro-2-ethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2115, mp78-80)
1H-NMR (200MHz, CDClThree) δ: 1.45 (3H, t, J = 6.8Hz), 1.61 (3H, s), 3.21 (2H, ABq, J = 17.8, Δν = 80.5Hz), 3.60 (2H, ABq, J = 11.4, Δν = 15.2Hz), 4.15 (2H, q, J = 6.8Hz), 4.66 (2H, s), 7.40 (1H, d, J = 2.4Hz), 7.44 (1H, d, J = 2.6Hz) ppm
3- (4-Chloro-2-isopropyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2116, mp92-95)
1H-NMR (200MHz, CDClThree) δ: 1.38 (6H, d, J = 6.0Hz), 1.54 (3H, s), 3.09 (2H, ABq, J = 17.7, Δν = 82.3Hz), 3.53 (2H, d, J = 1.4Hz), 4.58 (1H, m), 4.68 (2H, s), 6.92 (1H, m), 6.97 (1H, d, J = 1.9Hz), 7.35 (1H, d, J = 7.9Hz) ppm
3- (2-Chloro-5-isopropyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2117, mp53-57)
1H-NMR (200MHz, CDClThree) δ: 1.33 (6H, d, J = 6.0Hz), 1.56 (3H, s), 3.10 (2H, ABq, J = 17.8, Δν = 80.5Hz), 3.55 (2H, ABq, J = 11.6, Δν = 7.9Hz), 4.53 (1H, quintet, J = 6.1Hz), 4.77 (2H, s), 6.87 (1H, dd, J = 8.9,3.0Hz), 7.07 (1H, d, J = 3.0Hz), 7.33 (1H, d, J = 8.9Hz) ppm
3- (5-Chloro-2-isopropyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2118, mp64-66)
1H-NMR (200MHz, CDClThree) δ: 1.36 (6H, d, J = 6.1Hz), 1.55 (3H, s), 3.10 (2H, ABq, J = 17.8, Δν = 82.4Hz), 3.54 (2H, ABq, J = 11.6, Δν = 7.0Hz), 4.57 (1H, quintet, J = 6.0Hz), 4.68 (2H, s), 6.86 (1H, d, J = 8.8Hz), 7.30 (1H, dd, J = 8.8,2.6Hz), 7.40 (1H, d, J = 2.6Hz) ppm
3- (4-Chloro-3-isopropyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2119, mp94-95)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 3.09 (2H, ABq, J = 17.8, Δν = 85.8Hz), 3.54 (2H, ABq, J = 11.7, Δν = 7.5Hz), 4.56 (2H, s), 4.59 (1H, quintet, J = 6.3Hz), 6.91 (1H, dd, J = 8.1,1.9Hz), 7.01 (1H, d, J = 1.9Hz), 7.38 (1H, d, J = 8.1Hz) ppm
3- (2-Fluoro-6-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2120, mp105-107)
1H-NMR (200MHz, CDClThree) δ: 1.60 (3H, s), 3.20 (2H, ABq, J = 17.8, Δν = 84.3Hz), 3.58 (2H, ABq, J = 11.5, Δν = 7.2Hz), 3.91 (3H, s), 4.76 (2H, d, J = 1.2Hz), 6.74-6.82 (2H, m), 7.30-7.41 (1H, m) ppm
3- (2-Ethoxy-3-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2121, oil)
1H-NMR (200MHz, CDClThree) δ: 1.38 (3H, t, J = 7.0Hz), 1.56 (3H, s), 3.07 (2H, ABq, J = 17.8, Δν = 67.1Hz), 3.55 (2H, ABq, J = 11.4, Δν = 15.5Hz), 3.85 (2H, s), 4.15 (2H, q, J = 7.0Hz), 4.68 (2H, d, J = 1.5Hz), 6.93-6.98 (1H, m), 7.05-7.09 (2H, m) ppm
3- (2-Ethoxy-6-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2122, mp105-108)
1H-NMR (200MHz, CDClThree) δ: 1.43 (3H, t, J = 7.0Hz), 1.50 (3H, s), 3.08 (2H, ABq, J = 17.7, Δν = 88.6Hz), 3.52 (2H, s), 3.86 (3H, s ), 4.09 (2H, q, J = 7.0Hz), 4.82 (2H, s), 6.57 (2H, d, J = 8.4Hz), 7.30 (1H, t, J = 8.4Hz) ppm
3- (3-Methoxy-2-propyloxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2123, oil)
1H-NMR (200MHz, CDClThree) δ: 1.02 (3H, t, J = 7.4Hz), 1.54 (3H, s), 1.79 (2H, septet, J = 7.2Hz), 3.03 (2H, ABq, J = 17.6, Δν = 63.6Hz), 3.54 (2H, ABq, J = 11.5, Δν = 14.6Hz), 3.85 (3H, s), 4.02 (2H, t, J = 6.7Hz), 4.67 (2H, q, J = 13.8Hz), 6.92-6.99 (1H, m), 7.03-7.08 (2H, m) ppm
3- (2-Isopropyloxy-3-methoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2124, mp95-98)
1H-NMR (200MHz, CDClThree) δ: 1.27 (6H, dd, J = 6.1,2.7Hz), 1.53 (3H, s), 3.07 (2H, ABq, J = 17.7, Δν = 50.6Hz), 3.53 (2H, ABq, J = 11.3, Δν = 15.6Hz), 3.84 (3H, s), 4.64 (1H, septet, J = 6.3Hz), 4.64 (2H, ABq, J = 13.8, Δν = 16.4Hz), 6.92-6.97 (1H, m), 7.07-7.10 (2H, m) ppm
3- (2,3-Methylenedioxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2125, mp121-122)1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.13 (2H, ABq, J = 17.8, Δν = 85.2Hz), 3.54 (2H, ABq, J = 11.7, Δν = 6.2Hz), 4.60 (2H, s), 6.02 (2H, s), 6.85-6.95 (3H, m) ppm
3- (3,4-Methylenedioxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2126, mp81-83)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.07 (2H, ABq, J = 17.4, Δν = 76.7Hz), 3.52 (2H, s), 4.51 (2H, s), 6.00 (2H, s), 6.80-6.90 (3H, m) ppm
3- (2,3-Ethylenedioxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2127, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.08 (2H, ABq, J = 17.8, Δν = 88.8Hz), 3.52 (2H, s), 4.25-4.34 (4H, m), 4.67 (2H, s), 6.82 -7.01 (3H, m) ppm
3- (3,4-Ethylenedioxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2128, mp74-76)
1H-NMR (200MHz, CDClThree) δ: 1.52 (3H, s), 2.99 (2H, ABq, J = 18.0, Δν = 71.3Hz), 3.50 (2H, s), 4.25 (4H, s), 4.46 (2H, s), 6.88 (2H) , s), 6.91 (1H, s) ppm
3- (2-Methyl-3,4-ethylenedioxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2131, mp110-112)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.26 (3H, s), 3.03 (2H, ABq, J = 18.0, Δν = 75.9Hz), 3.52 (2H, s), 4.24-4.28 (4H, m), 4.61 (2H, s), 6.76 (1H, d, J = 8.4Hz), 6.87 (1H, d, J = 8.5Hz) ppm
3- (4-Trifluoromethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2142, mp106-107)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 3.12 (2H, ABq, J = 17.6, Δν = 85.0Hz), 3.54 (2H, ABq, J = 11.8, Δν = 8.8Hz), 4.62 (2H, s), 7.27 (2H, d, J = 8.4Hz), 7.49 (2H, d, J = 8.4Hz) ppm
3- (2-Difluoromethoxy-3-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2143, oil)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 2.35 (3H, s), 3.20 (2H, ABq, J = 17.7, Δν = 77.8Hz), 3.58 (2H, ABq, J = 11.7, Δν = 8.9Hz), 4.73 (1H, s), 6.47 (1H, t, J = 73.3Hz), 7.26-7.34 (2H, m), 7.43 (1H, dd, J = 7.0,1.8Hz) ppm
3- (2-Difluoromethoxy-4-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2144, oil)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 2.39 (3H, s), 3.19 (2H, ABq, J = 17.8, Δν = 77.3Hz), 3.57 (2H, ABq, J = 11.6, Δν = 9.0Hz), 4.70 (2H, s), 6.52 (1H, t, J = 73.7Hz), 7.04-7.11 (2H, m), 7.40 (1H, d, J = 7.7Hz) ppm
3- (2-Difluoromethoxy-5-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2145, mp64)
1H-NMR (200MHz, CDClThree) δ: 1.58 (3H, s), 2.36 (3H, s), 3.20 (2H, ABq, J = 17.8, Δν = 80.0Hz), 3.57 (2H, ABq, J = 11.7, Δν = 9.8Hz), 4.68 (2H, s), 6.51 (1H, t, J = 73.8Hz), 7.18 (2H, dd, J = 1.8,8.3Hz), 7.26 (1H, d, J = 1.8Hz) ppm
3- (3-Difluoromethoxy-4-methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2146, mp63-65)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 2.31 (3H, s), 3.10 (2H, ABq, J = 17.8, Δν = 78.8Hz), 3.53 (2H, d, J = 1.4Hz), 4.58 (2H, s ), 6.54 (1H, t, J = 73.6Hz), 7.16-7.21 (3H, m) ppm
3- (3-Chloro-2-difluoromethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2147, oil)
1H-NMR (200MHz, CDClThree) δ: 1.60 (3H, s), 3.24 (2H, ABq, J = 17.8, Δν = 78.7Hz), 3.58 (2H, ABq, J = 11.7, Δν = 11.2Hz), 4.76 (2H, s), 6.60 (1H, t, J = 73.6Hz), 7.30-7.34 (1H, m), 7.52-7.56 (2H, m) ppm
3- (2-Chloro-5-difluoromethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2148, mp85-86)
1H-NMR (200MHz, CDClThree) δ: 1.60 (3H, s), 3.21 (2H, ABq, J = 17.8, Δν = 80.6Hz), 3.58 (2H, ABq, J = 11.7, Δν = 10.7Hz), 4.83 (2H, s), 6.53 (1H, t, J = 72.8Hz), 7.16 (1H, dd, J = 8.8,2.8Hz), 7.36 (1H, d, J = 2.8Hz), 7.47 (1H, d, J = 8.8Hz) ppm
3- (5-Chloro-2-difluoromethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2149, oil)
1H-NMR (200MHz, CDClThree) δ: 1.60 (3H, s), 3.24 (2H, ABq, J = 17.8, Δν = 80.6Hz), 3.59 (2H, ABq, J = 11.7, Δν = 12.4Hz), 4.71 (2H, s), 6.52 (1H, t, J = 73.2Hz), 7.20 (1H, d, J = 8.8Hz), 7.41 (1H, dd, J = 8.8,2.6Hz), 7.52 (1H, d, J = 2.6Hz) ppm
3- (4-Chloro-3-difluoromethoxybenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2150, oil)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.18 (2H, ABq, J = 17.8, Δν = 80.8Hz), 3.56 (2H, ABq, J = 11.9, Δν = 10.3Hz), 4.59 (2H, s), 6.57 (1H, t, J = 72.9Hz), 7.26 (1H, dd, J = 8.2,2.0Hz), 7.34 (1H, br), 7.50 (1H, d, J = 8.2Hz) ppm
3- (2-Methoxymethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2151, oil)
1H-NMR (200MHz, CDClThree) δ: 1.54 (3H, s), 3.04 (2H, ABq, J = 18.0, Δν = 81.8Hz), 3.41 (3H, s), 3.54 (2H, ABq, J = 12.7, Δν = 5.7Hz), 4.61 (2H, s), 4.83 (2H, s), 7.36-7.49 (4H, m) ppm
3- (2-Ethoxymethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2152, oil)
1H-NMR (200MHz, CDClThree) δ: 1.25 (3H, t, J = 7.0Hz), 1.54 (3H, s), 3.04 (2H, ABq, J = 17.8, Δν = 81.3Hz), 3.47-4.14 (4H, m), 4.66 (2H , s), 4.86 (2H, s), 7.33-7.48 (4H, m) ppm
3- (2- (2,2,2-trifluoroethoxymethyl) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2153, mp <40)
1H-NMR (200MHz, CDClThree) δ: 1.56 (3H, s), 3.13 (2H, ABq, J = 17.8, Δν = 83.7Hz), 3.56 (2H, d, J = 3.2Hz), 3.86 (2H, q, J = 8.8Hz), 4.83 (2H, s), 4.87 (2H, s), 7.4-7.5 (4H, m) ppm
3- (3- (2,2,2-trifluoroethoxymethyl) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2154, mp <40)
1H-NMR (200MHz, CDClThree) δ: 1.53 (3H, s), 3.07 (2H, ABq, J = 17.6, Δν = 80.5Hz), 3.51 (2H, d, J = 1.6Hz) 3.86 (2H, q, J = 8.8Hz), 4.62 (2H, s), 4.70 (2H, s), 7.41-7.43 (4H, m) ppm
3- (2- (2-methoxyethoxy) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2155, oil)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 3.03 (2H, ABq, J = 17.8, Δν = 78.1Hz), 3.45 (3H, s), 3.50 (2H, d, J = 1.5Hz), 3.77 (2H, t , J = 4.8Hz), 4.17 (2H, t, J = 4.8Hz), 4.73 (2H, s), 6.94-7.05 (2H, m), 7.32-7.46 (2H, m) ppm
3- (3- (2-methoxyethoxy) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2156, oil)
1H-NMR (200MHz, CDClThree) δ: 1.50 (3H, s), 2.96 (2H, ABq, J = 17.7, Δν = 82.3Hz), 3.46 (3H, s), 3.49 (2H, s), 3.76 (2H, t, J = 4.6Hz ), 4.13 (2H, t, J = 4.6Hz), 4.56 (2H, s), 6.99 (3H, d, J = 3.5Hz), 7.27-7.36 (1H, m) ppm
3- (2- (2,2-dimethoxyethoxy) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2157, oil)
1H-NMR (200MHz, CDClThree) δ: 1.52 (3H, s), 3.03 (2H, ABq, J = 17.8, Δν = 80.2Hz), 3.48 (6H, s), 3.51 (2H, d, J = 1.5Hz), 4.04 (2H, d , J = 5.3Hz), 4.74 (3H, t), 6.93-7.06 (2H, m), 7.33-7.46 (2H, m) ppm
3- (3- (2,2-dimethoxyethoxy) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2158, mp55-58)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 2.98 (2H, ABq, J = 17.9, Δν = 81.4Hz), 3.47 (6H, s), 3.50 (2H, s), 4.02 (2H, d, J = 5.2Hz ), 4.56 (2H, s), 4.72 (1H, t, J = 5.2Hz), 6.96-7.03 (3H, m), 7.26-7.34 (1H, m) ppm
3- (2- (2,2-ethylenedioxyethoxy) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2159, oil)
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 3.04 (2H, ABq, J = 17.7, Δν = 76.1Hz), 3.50 (2H, ABq, J = 11.6, Δν = 5.7Hz), 3.92-4.07 (4H, m) , 4.09 (2H, d, J = 3.8Hz), 4.73 (2H, s), 5.30 (1H, t, J = 3.7Hz), 6.94-7.07 (2H, m), 7.33-7.48 (2H, m) ppm
3- (3- (2,2-ethylenedioxyethoxy) benzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2160, mp74-76)
1H-NMR (200MHz, CDClThree) δ: 1.50 (3H, s), 2.97 (2H, ABq, J = 17.9, Δν = 81.6Hz), 3.49 (2H, s), 3.96-4.11 (6H, m), 4.55 (2H, s), 5.29 (1H, t, J = 3.8Hz), 6.97-7.03 (3H, m), 7.26-7.32 (1H, m) ppm
3- (α-Methylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2161, mp62-64)
1H-NMR (200MHz, CDClThree) δ: 1.36 (s) +1.47 (s) (3H), 1.88 (3H, d, J = 7.2Hz), 2.69 (ABq, J = 17.9, Δν = 179.4Hz) +2.70 (s) (2H), 3.31 (ABq, J = 11.5, Δν = 17.7Hz) +3.45 (s) (2H), 4.58 (q, J = 7.2Hz) +4.59 (q, J = 7.2Hz) (1H), 7.39-7.45 (5H , m) ppm
3- (α, α-Dimethylbenzylsulfonyl) -5-chloromethyl-5-methyl-2-isoxazoline (2162, mp102-105)
1H-NMR (200MHz, CDClThree) δ: 1.32 (3H, s), 1.95 (6H, s), 2.26 (2H, ABq, J = 18.0, Δν = 88.6Hz), 3.31 (2H, ABq, J = 11.5, Δν = 10.0Hz), 7.41 -7.47 (3H, m), 7.60-7.65 (2H, m) ppm
3- (α-Isopropylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2165, mp75-80)
1H-NMR (200MHz, CDClThree) δ: 0.92 (3H, d, J = 6.7Hz), 1.31 (d, J = 6.6Hz) +1.33 (d, J = 6.6Hz) (3H), 1.19 (s) +1.40 (s) (3H) , 1.82-3.38 (5H, m), 4.18 (d, J = 8.7Hz) +4.20 (d, J = 8.2Hz) (1H), 7.42 (5H, s) ppm
3- (α, 2-Dimethylbenzyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2166, oil)
1H-NMR (200MHz, CDClThree) δ: 1.31 (s) +1.55 (s) (3H), 1.83 (3H, d, J = 7.0Hz), 2.41 (3H, d, J = 1.9Hz), 2.71 (ABq, J = 18.0, Δν = 202.4Hz) +2.73 (ABq, J = 16.9, Δν = 25.8Hz) (2H), 3.25 (ABq, J = 11.5, Δν = 29.5Hz) +3.48 (d, J = 2.1Hz) (2H), 7.21- 7.34 (3H, m), 7.56-7.61 (1H, m) ppm
3- (4-chromanyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2167, oil)
1H-NMR (200MHz, CDClThree) δ: 1.55 (3H, s), 2.39-2.47 (1H, m), 2.72-2.96 (1H, m), 2.99 (d, J = 4.8Hz) +3.02 (ABq, J = 17.9, Δν = 143.2Hz ) (2H), 3.45 (s) +3.57 (ABq, J = 11.8, Δν = 15.2Hz) (2H), 4.22-4.30 (1H, m), 4.46-4.60 (1H, m), 4.66-4.72 (1H , m), 6.91-7.01 (2H, m), 7.30-7.34 (1H, m), 7.47-7.51 (1H, m) ppm
3- (1-Indanyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (2168, oil)
1H-NMR (200MHz, CDClThree) δ: 1.38 (s) +1.52 (s) (3H), 2.35-3.59 (8H, m), 4.92 (1H, dt, J = 8.9,3.3Hz), 7.28-7.37 (3H, m), 7.64 ( 1H, d, J = 7.3Hz) ppm
3- (1- (1,2,3,4-terolahydronaphthyl) sulfonyl) -5-chloromethyl-5-methyl-2-isoxazoline (2169, oil)
1H-NMR (200MHz, CDClThree) δ: 1.38 (s) +1.50 (s) (3H), 2.18-2.29 (2H, m), 2.61-2.85 (4H, m), 2.79 (2H, ABq, J = 17.9, Δν = 176.0Hz), 3.36 (d, J = 4.3Hz) +3.51 (d, J = 3.2Hz) (2H), 4.67-4.72 (1H, m), 7.17-7.35 (3H, m), 7.54-7.60 (1H, m) ppm
3-Benzylsulfonyl-5- (2-chloroethyl) -5-methyl-2-isoxazoline (2170, mp74-75)
1H-NMR (200MHz, CDClThree) δ: 1.39 (3H, s), 2.13 (2H, t, J = 7.3Hz), 2.86 (2H, ABq, J = 17.6, Δν = 32.9Hz), 3.49 (2H, t, J = 7.3Hz), 4.61 (2H, s), 7.43 (5H, s) ppm
 3-Benzylsulfonyl-5-difluoromethyl-5-methyl-2-isoxazoline (2178, mp78-80)
1H-NMR (200MHz, CDClThree) δ: 1.47 (3H, s), 3.02 (2H, ABq, J = 18.1, Δν = 95.4Hz), 4.61 (2H, s), 5.65 (1H, t, J = 55.5Hz), 7.35-7.46 (5H , br) ppm
3-Benzylsulfonyl-5-trifluoromethyl-5-methyl-2-isoxazoline (2179, mp106-107)
1H-NMR (200MHz, CDClThree) δ: 1.57 (3H, s), 3.11 (2H, ABq, J = 18.3, Δν = 79.9Hz), 4.62 (2H, s), 7.43 (5H, s) ppm
3-Benzylsulfonyl-5-chloromethyl-5-ethyl-2-isoxazoline (2181, oil)
1H-NMR (200MHz, CDClThree) δ: 0.92 (3H, t, J = 7.4Hz), 1.81 (2H, q, J = 7.4Hz), 3.00 (2H, ABq, J = 18.0, Δν = 51.0Hz), 3.51 (2H, ABq, J = 11.8, Δν = 7.0Hz), 4.60 (2H, s), 7.42 (5H, s) ppm
[0120]
[Example 3]
3-Benzylthio-5-chloromethyl-5-ethyl-2-isoxazoline(Compound No. 181) (Step E)
3-Benzylthio-5-hydroxymethyl-5-ethyl-2-isoxazoline (3.03 g) and triphenylphosphine (3.38 g) produced according to the method of Example 1 were dissolved in carbon tetrachloride (30 ml) and refluxed overnight. After cooling to room temperature, the reaction solution was filtered, the solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 40: 1) to obtain 1.13 g (28%) of the oily desired product.
[0121]
1H-NMR (200MHz, CDClThree) δ: 0.98 (3H, t, j = 7.4Hz), 1.85 (2H, q, J = 7.4Hz), 2.98 (2H, ABq, J = 16.9, Δν = 50.9Hz), 3,55 (2H, ABq , J = 11.3, Δν = 17.5Hz), 4.26 (2H, s), 7.28-7.41 (5H, m) ppm
[0122]
[Example 4]
3-Benzylthio-5-difluoromethyl-5-methyl-2-isoxazoline(Compound No. 178) (Steps H and I)
(1) 3-Benzylthio-5-formyl-5-methyl-2-isoxazoline (Step H)
0.11 ml of oxalyl chloride was dissolved in 3 ml of methylene chloride, cooled to −60 ° C., and then a mixed solution of 0.15 ml of N, N-dimethylsulfoxide and 1.9 ml of methylene chloride was added dropwise. After stirring at −60 ° C. for 20 minutes, 2 ml of 244.3 mg of 3-benzylthio-5-hydroxymethyl-5-methyl-2-isoxazoline prepared according to the method of Example 1 was added dropwise, Stir at 60 ° C. for 20 minutes. Further, 0.43 ml of triethylamine was added to the reaction solution, followed by stirring for 1 hour and 40 minutes at −60 ° C. for 30 minutes while warming to room temperature. Water was added to the reaction solution and the mixture was extracted with methylene chloride. The organic layer was washed with water, 1N hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. After filtration and evaporation of the solvent, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 238.1 mg (98%) of the oily target product.
[0123]
1H-NMR (200MHz, CDClThree) δ: 1.51 (3H, s), 3.09 (2H, ABq, J = 16.5, Δν = 103.9Hz), 4.26 (2H, d, J = 1.2Hz), 7.28-7.40 (5H, m), 9.62 (1H , s) ppm
(2) 3-Benzylthio-5-difluoromethyl-5-methyl-2-isoxazoline (Compound No. 178) (Step I)
220.8 mg of 3-benzylthio-5-formyl-5-methyl-2-isoxazoline produced by the method of (1) was dissolved in 4.4 ml of methylene chloride, and diethylaminosulfur trifluoride (DAST) 0. 5 ml was added. After stirring for 2 hours, the ice-water bath was removed and the temperature was raised to room temperature. After further stirring for 12 hours, ice was added to the reaction solution, followed by extraction with methylene chloride. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. After filtration and evaporation of the solvent, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain 116.4 mg (48%) of the oily desired product.
[0124]
1H-NMR (200MHz, CDClThree) δ: 1.49 (3H, s), 3.04 (2H, ABq, J = 16.9, Δν = 80.6Hz), 4.27 (2H, s), 5.68 (1H, t, J = 56.0Hz), 7.23-7.42 (5H , m) ppm
[0125]
[Formulation example]
[0126]
[Formulation Example 1]
(Wettable powder)
A wettable powder was obtained by thoroughly pulverizing and mixing 25% of Compound No. 2161, 2.5% sodium dodecylbenzenesulfonate, 2.5% calcium ligninsulfonate and 70% diatomaceous earth.
[0127]
[Formulation Example 2]
(emulsion)
Mix well 30% of the compound No. 2 compound, 2.68% of calcium dodecylbenzenesulfonate, 4.92% of polyoxyethylene alkyl ether, 0.4% of polyoxyethylene nonylphenyl ether calcium phosphate and 62% of xylene. To obtain an emulsion.
[0128]
[Formulation Example 3]
(Granule)
Compound No. 2011 compound 5%, white carbon 1%, lignin sulfonic acid calcium salt 5%, bentonite 20% and clay 69% are thoroughly pulverized and mixed, water is added and kneaded well, granulated and dried. A granule was obtained.
[0129]
[Formulation Example 4]
(Hydrated granules)
Compound No. 162, compound 80%, special polycarboxylic acid sodium salt 1.25%, water 3.75%, dodecylbenzenesulfonic acid sodium salt 3%, dextrin 7% and titanium oxide 5%, then mixed The mixture was pulverized with an air mill, added to a rotating mixer or a fluidized bed mixer, and granulated by spraying water. When most of the particles became 1.0-0.15 mm, the granules were taken out, dried and sieved. The oversized material was pulverized to obtain 1.0-0.15 mm granules.
[0130]
[Formulation Example 5]
(Aqueous suspension)
Compound No. 2170 No. 2170 compound, sodium dioctyl sulfosuccinate 0.7 part, propylene glycol 0.15 part, lignin sulfonate calcium salt 10 parts, water 44.15 parts and propylene glycol 10 parts solid particles 5 microns Milled together in a ball mill, sand mill or roller mill until reduced to the following diameter. To 90 parts of this pulverized slurry, 10 parts of 0.05% (W / W) xanthan gum aqueous solution was added and mixed to obtain an aqueous suspension.
[0131]
【The invention's effect】
The compound (I) of the present invention has a herbicidal action and can be used as a herbicide. Its action is generally stronger on monocotyledonous plants than on dicotyledonous plants. For example, in paddy fields, by treating the flooded soil before or after germination of the weeds, particularly strong weeds of paddy fields such as Tainubie, Himetariinubie, and Kainubie are effectively controlled, and conventional herbicides are also used. It can also control perennial weeds such as pine beetle, firefly, crocodile, and scallops, and perennial weeds such as Urikawa and Omodaka. It is also possible to effectively control broad-leaved weeds such as Sphagnum family weeds, crickets, and scorpions.
[0132]
On the other hand, for paddy rice, there is an advantage that the selectivity is large, and transplanted rice is not affected by phytotoxicity and the treatment application range is wide.
[0133]
In addition, in the field, by treating the soil before weed germination, or by treating the foliage after germination, the field weeds are red and red weeds such as azaza, shiroza and koakaza, the cruciferous weeds such as mustard, It can effectively control Amaranthus weeds such as Inubiyu, Aogaeto, Inokozuchi, and solanaceae weeds such as Inuhizuki. It is possible to control cyperaceae weeds such as hamasge extremely strongly, while crops such as corn, beet, cotton and soybean do not suffer from phytotoxicity.
[0134]
Next, a biological test example is given and the effect is shown concretely.
[0135]
[Test example]
[0136]
[Test Example 1]
Paddy weed germination pretreatment
100cm2 The pot was filled with paddy soil, and the seeds of Tainubie and firefly that had been awakened from dormancy were mixed in 1 cm of the surface layer. Moreover, seedlings of paddy rice at the 2-leaf stage were transplanted to be submerged and grown in a greenhouse. Three days later, the prescribed dosage was treated with flooded soil using a wettable powder prepared according to Formulation Example 1, and after 21 days, the investigation was conducted according to the following criteria. The results are shown in Table 2.
(Criteria)
0: Growth inhibition rate 0-10%
1: Growth inhibition rate 11-30%
2: Growth inhibition rate 31-50%
3: Growth inhibition rate 51-70%
4: Growth inhibition rate 71-90%
5: Growth inhibition rate 91-100%
[0137]
[Test Example 2]
Tainubier 1.5 leaf treatment
In the same manner as in Test Example 1, a predetermined amount was treated with flooded soil at 1.5 leaves of Tainubier using a wettable powder prepared according to Formulation Example 1, and the investigation was conducted 21 days later. The results are shown in Table 2 (the determination criteria are the same as in Test Example 1).
[0138]
In Table 2, Comparison 1, Comparison 2, and Comparison 3 refer to Comparison Compound 1, Comparison Compound 2, and Comparison Compound 3, respectively.
[0139]
Comparative compound 1 is (5-chloromethyl-3-phenylsulfonyl-2-isoxazoline) and is a compound described in Heterocycles, Vol. 22, No. 10, page 2187 (1984).
[0140]
Comparative compound 2 is (5-cyano-5-methyl-3-benzylthio-2-isoxazoline), and is a compound described in JP-A-5-105672.
[0141]
Comparative compound 3 is (5-cyano-5-methyl-3- (3-trifluoromethylbenzyl) sulfonyl-2-isoxazoline), and is a compound described in JP-A-5-105672.
[0142]
The fact that these comparative compounds have herbicidal activity is not described in the above literature.
[0143]
[Table 2]
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
Figure 0003810838
[0144]
[Test Example 3]
Pretreatment of field crop weeds
60cmThree Then, a square pot with a depth of 4 cm was filled with Kureha Horticulture soil, seeded with various test weeds and crop seeds, and covered with about 1 cm of soil. Using these emulsions prepared according to Formulation Example 2, a predetermined dose was uniformly sprayed into these pots. After treatment, these pots were grown in a greenhouse. On the 21st day after the treatment, the herbicidal effect on each weed and the phytotoxicity on the crop were investigated according to the following criteria. The results are shown in Table 3.
[0145]
In the table, BG is barnyardgrass, CR is crabgrass, FO is foxtail, JO is sorghum sorghum (PA), NU is yellow mussels (se) Indicates lambsquarters, MU indicates mustard, and PI indicates pigweed.
[0146]
(Criteria)
0: Growth inhibition rate 0-9%
1: Growth inhibition rate 10-19%
2: Growth inhibition rate 20-29%
3: Growth inhibition rate 30-39%
4: Growth inhibition rate 40-49%
5: Growth inhibition rate 50-59%
6: Growth inhibition rate 60-69%
7: Growth inhibition rate 70-79%
8: Growth inhibition rate 80-89%
9: Growth inhibition rate 90-99%
10: Growth inhibition rate 100%
[0147]
[Table 3]
Figure 0003810838
[0148]
[Test Example 4]
Field crop foliage treatment
60cmThree Then, a square pot with a depth of 4 cm was filled with Kureha Horticulture soil, seeded with various test weeds and crop seeds, and covered with about 1 cm of soil. These pots were used to grow plants in the greenhouse. When each plant reached the 2-3 leaf stage (about 10 days after sowing), a predetermined dose was uniformly sprayed onto the foliage of these pots using an emulsion prepared according to Formulation Example 2. . On the 14th day after the treatment, the herbicidal effect on each weed and the phytotoxicity on the crop were investigated. The results are shown in Table 4 (judgment criteria and abbreviations are the same as in Test Example 3).
[0149]
[Table 4]
Figure 0003810838

Claims (7)

下記一般式（Ｉ）
Figure 0003810838
［式中、Ｒ1 は、同一又は異なった１乃至３個のハロゲン原子により置換された低級アルキル基を示し、Ｒ2 は、低級アルキル基を示し、Ｒ3 及びＲ4 は同一又は異なって、水素原子又は低級アルキル基を示し、Ｒ5 は、ハロゲン原子、低級アルキル基（当該低級アルキル基は、置換基群ａから選ばれる同一又は異なった１乃至３個の置換基により置換されていても良い）又は低級アルコキシ基（当該低級アルコキシ基は、置換基群ａから選ばれる同一又は異なった１乃至３個の置換基により置換されていても良く、また、近接する当該低級アルコキシ基が２個結合して低級アルキレンジオキシ基を形成しても良く、当該低級アルキレンジオキシ基は同一又は異なった１乃至４個のハロゲン原子により置換されていても良い）を示すか、又は、Ｒ4 とＲ5 が一緒になって低級アルキレン基又は低級アルキレンオキシ基を形成しても良く（ｍが２以上の場合、Ｒ5 は同一又は異なっていても良い）、ｍは０、１、２、３、４又は５を示し、ｎは０、１又は２を示す。
（置換基群ａ）
ハロゲン原子、低級アルコキシ基（当該低級アルコキシ基は同一又は異なった１乃至３個のハロゲン原子により置換されていても良く、また、近接する当該低級アルコキシ基が２個結合して低級アルキレンジオキシ基を形成しても良い）］
で表わされる化合物。The following general formula (I)
Figure 0003810838
 [Wherein, R 1 represents a lower alkyl group substituted with 1 to 3 halogen atoms which are the same or different, R 2 represents a lower alkyl group, and R 3 and R 4 are the same or different, Represents a hydrogen atom or a lower alkyl group, and R 5 represents a halogen atom, a lower alkyl group (the lower alkyl group may be substituted with 1 to 3 substituents selected from the same or different substituent group a). Good) or a lower alkoxy group (the lower alkoxy group may be substituted by the same or different 1 to 3 substituents selected from the substituent group a, and two adjacent lower alkoxy groups may be substituted. May be bonded to form a lower alkylenedioxy group, and the lower alkylenedioxy group may be substituted with the same or different 1 to 4 halogen atoms), or R 4 and R 5 may combine to form a lower alkylene group or a lower alkyleneoxy group (when m is 2 or more, R 5 may be the same or different), and m is 0, 1, 2 3, 4 or 5 is shown, and n is 0, 1 or 2.
(Substituent group a)
A halogen atom, a lower alkoxy group (the lower alkoxy group may be substituted by the same or different 1 to 3 halogen atoms, and two adjacent lower alkoxy groups are bonded to form a lower alkylenedioxy group; May be formed)]
A compound represented by 下記一般式（Ｉ）
Figure 0003810838
［式中、Ｒ1 は、同一又は異なった１乃至３個のハロゲン原子により置換された炭素数１個又は２個のアルキル基を示し、Ｒ2 は、炭素数１個又は２個のアルキル基を示し、Ｒ3 及びＲ4 は同一又は異なって、水素原子又は炭素数１個乃至３個のアルキル基を示し、Ｒ5 は、ハロゲン原子、炭素数１個乃至３個のアルキル基又は炭素数１個乃至３個アルコキシ基（近接する当該アルコキシ基が２個結合して炭素数１又は２個のアルキレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは０、１又は２を示し、ｎは０又は２を示す。］
で表わされる化合物。The following general formula (I)
Figure 0003810838
 [Wherein, R 1 represents an alkyl group having 1 or 2 carbon atoms substituted with 1 to 3 halogen atoms which are the same or different, and R 2 represents an alkyl group having 1 or 2 carbon atoms] R 3 and R 4 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents a halogen atom, an alkyl group having 1 to 3 carbon atoms or a carbon number 1 to 3 alkoxy groups (two adjacent alkoxy groups may be bonded to form an alkylenedioxy group having 1 or 2 carbon atoms) (when m is 2, R 5 is the same) Or m may be 0, 1 or 2, and n represents 0 or 2. ]
A compound represented by 下記一般式（Ｉ）
Figure 0003810838
［式中、Ｒ1 は、１個乃至３個の塩素原子により置換された炭素数１個又は２個のアルキル基を示し、Ｒ2 は、メチル基を示し、Ｒ3 及びＲ4 は同一又は異なって、水素原子又はメチル基を示し、Ｒ5 は、弗素原子、塩素原子、臭素原子、メチル基、エチル基、イソプロピル基、メトキシ基、エトキシ基、イソプロピルオキシ基（近接する当該メトキシ基、エトキシ基が２個結合してメチレンジオキシ基、エチレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは０、１又は２を示し、ｎは０又は２を示す。］で表わされる化合物。The following general formula (I)
Figure 0003810838
 [Wherein R 1 represents an alkyl group having 1 or 2 carbon atoms substituted by 1 to 3 chlorine atoms, R 2 represents a methyl group, and R 3 and R 4 are the same or Differently, it represents a hydrogen atom or a methyl group, and R 5 represents a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, an isopropyloxy group (the adjacent methoxy group, ethoxy group Two groups may be bonded to form a methylenedioxy group or an ethylenedioxy group) (when m is 2, R 5 may be the same or different), and m is 0, 1 or 2 is shown, and n is 0 or 2. ] The compound represented by this. 下記一般式（Ｉ）
Figure 0003810838
［式中、Ｒ1 は、クロロメチル基を示し、Ｒ2 は、メチル基を示し、Ｒ3 及びＲ4 は、水素原子を示し、Ｒ5 は、弗素原子、塩素原子、メチル基、エチル基、メトキシ基、エトキシ基（近接する当該メトキシ基、エトキシ基が２個結合してメチレンジオキシ基、エチレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは１又は２を示し、ｎは２を示す。］
で表わされる化合物。The following general formula (I)
Figure 0003810838
 [Wherein R 1 represents a chloromethyl group, R 2 represents a methyl group, R 3 and R 4 represent a hydrogen atom, and R 5 represents a fluorine atom, a chlorine atom, a methyl group, an ethyl group. , A methoxy group, and an ethoxy group (two adjacent methoxy groups and ethoxy groups may be bonded to form a methylenedioxy group and an ethylenedioxy group) (when m is 2, R 5 is the same) Or may be different), m represents 1 or 2, and n represents 2. ]
A compound represented by 下記一般式（Ｉ）
Figure 0003810838
［式中、Ｒ1 は、クロロメチル基を示し、Ｒ2 は、メチル基を示し、Ｒ3 及びＲ4 は、水素原子を示し、Ｒ5 は、塩素原子、エチル基、メトキシ基（近接する当該メトキシ基が２個結合してメチレンジオキシ基を形成しても良い）を示し（ｍが２の場合、Ｒ5 は同一又は異なっていても良い）、ｍは１又は２を示し、ｎは２を示す。］
で表わされる化合物。The following general formula (I)
Figure 0003810838
 [Wherein, R 1 represents a chloromethyl group, R 2 represents a methyl group, R 3 and R 4 represent a hydrogen atom, and R 5 represents a chlorine atom, an ethyl group, or a methoxy group (adjacent to each other). Two methoxy groups may be bonded to form a methylenedioxy group) (when m is 2, R 5 may be the same or different), m represents 1 or 2, and n Indicates 2. ]
A compound represented by 請求項１乃至５に記載の化合物を有効成分として含有する農薬。An agrochemical containing the compound according to claim 1 as an active ingredient. 請求項１乃至５に記載の化合物を有効成分として含有する除草剤。A herbicide containing the compound according to claim 1 as an active ingredient.
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EP1203768B1 (en) 1999-08-10 2006-03-01 Kumiai Chemical Industry Co., Ltd. Isoxazoline derivatives and herbicides containing the same as the active ingredient
JP4465133B2 (en) * 2001-02-08 2010-05-19 クミアイ化学工業株式会社 Isoxazoline derivatives and herbicides containing the same as active ingredients
UA78071C2 (en) * 2002-08-07 2007-02-15 Kumiai Chemical Industry Co Herbicidal composition
JP4570015B2 (en) * 2003-07-14 2010-10-27 クミアイ化学工業株式会社 2-Isoxazoline derivatives and herbicides containing them as active ingredients
ATE383074T1 (en) * 2004-04-30 2008-01-15 Syngenta Participations Ag HERBICIDE COMPOSITION
EP1789401B1 (en) * 2004-09-03 2010-03-03 Syngenta Limited Isoxazoline derivatives and their use as herbicides
ES2333977T3 (en) * 2004-10-05 2010-03-03 Syngenta Limited ISOXAZOLINE DERIVATIVES AND ITS USE AS HERBICIDES.
WO2007006409A2 (en) * 2005-07-07 2007-01-18 Bayer Cropscience Ag Herbicide-safener combination
GB0526044D0 (en) * 2005-12-21 2006-02-01 Syngenta Ltd Novel herbicides
RU2448964C2 (en) * 2006-01-20 2012-04-27 Шеринг Корпорейшн CARBOCYCLIC AND HETEROCYCLIC ARYLSULFONES AS γ-SECRETASE INHIBITORS
EP2065373A1 (en) 2007-11-30 2009-06-03 Bayer CropScience AG Chiral 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl) sulfinyl]-4,5-dihydroisoxazole derivatives, methods for their preparation and their use as herbicides and plant growth regulators
AR108940A1 (en) 2016-07-04 2018-10-10 Kumiai Chemical Industry Co TRANSGENIC PLANT THAT HAS RESISTANCE TO HERBICIDES
CN114075149A (en) * 2020-08-20 2022-02-22 宁夏苏融达化工有限公司 Difluorophenyl-containing heterocyclic compound and application thereof
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