JPH06172313A - Isoquinoline derivative having antifungal activity - Google Patents
Isoquinoline derivative having antifungal activityInfo
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- JPH06172313A JPH06172313A JP20727691A JP20727691A JPH06172313A JP H06172313 A JPH06172313 A JP H06172313A JP 20727691 A JP20727691 A JP 20727691A JP 20727691 A JP20727691 A JP 20727691A JP H06172313 A JPH06172313 A JP H06172313A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明化合物であるテトラヒドロ
イソキノリン誘導体およびその酸付加塩は、新規な化合
物であり、また、本発明は、殺菌剤に関し、特に作物栽
培上有用な農業用殺菌剤に関する。TECHNICAL FIELD The compound of the present invention, a tetrahydroisoquinoline derivative and an acid addition salt thereof, are novel compounds, and the present invention relates to a fungicide, and particularly to an agricultural fungicide useful for crop cultivation.
【０００２】[0002]
【従来技術】テトラヒドロイソキノリン骨格はベンゾフ
ェナントリジンアルカロイドに含まれ、抗癌作用等さま
ざまな生理活性が知られている（例えばＪ．Ａｍ．Ｃｈ
ｅｍ．Ｓｏｃ．１９８３，１０５，２８７３；Ｊ．Ｏ．
Ｃｈｅｍ．１９７８，４３，２８６）。しかし、一般式
（Ｉ）で示されるテトラヒドロイソキノリン誘導体は文
献未記載のものであり、それらの殺菌活性については何
ら知られていない。2. Description of the Related Art Tetrahydroisoquinoline skeleton is contained in benzophenanthridine alkaloids and is known to have various physiological activities such as anticancer activity (for example, J. Am. Ch.
em. Soc. 1983, 105, 2873; O.
Chem. 1978, 43, 286). However, the tetrahydroisoquinoline derivative represented by the general formula (I) has not been described in the literature, and its bactericidal activity is not known at all.
【０００３】[0003]
【発明が解決しようとする課題】農業生産上、作物の病
害を防除し、収量増加を図るためには、農園芸用殺菌剤
の使用は欠くことができない。現在、多くの農園芸用殺
菌剤が使用されているが、中には、その防除効果が不十
分なもの、また環境問題上、あるいは毒性問題上使用が
厳しく限定されているものが多々ある。一方、同一ある
いは同系統の薬剤を長期継続使用する事により、これら
の殺菌剤に耐性を示す植物病原菌が出現し、防除効果の
低下を引き起こすことが数種の植物病害で確認されてい
る。従って、充分な効果を発揮し、環境上及び毒性上の
問題がなく、しかも耐性発現のない農園芸用殺菌剤の開
発が望まれている。In agricultural production, the use of agricultural and horticultural fungicides is indispensable for controlling the diseases of crops and increasing the yield. At present, many agricultural and horticultural fungicides are used, but in many cases, their control effects are insufficient, and their use is severely limited due to environmental problems or toxicity problems. On the other hand, it has been confirmed in several plant diseases that phytopathogenic fungi resistant to these fungicides appear due to continuous use of the same or the same type of agents for a long period of time, causing a decrease in the control effect. Therefore, it is desired to develop a fungicide for agricultural and horticultural use which exerts a sufficient effect, has no problems in terms of environment and toxicity, and does not exhibit resistance.
【０００４】[0004]
【問題を解決するための手段】本発明者らは、新規なテ
トラヒドロイソキノリン誘導体が優れた殺菌活性を持つ
事を見い出し、本発明を完成した。The present inventors have found that the novel tetrahydroisoquinoline derivative has excellent bactericidal activity, and completed the present invention.
【０００５】すなわち、本発明は下記一般式（Ｉ）That is, the present invention is represented by the following general formula (I)
【０００６】[0006]
【化３】 ｛式中、Ｒ1 は、Ｃ1 〜Ｃ10の直鎖または分岐アルキル
基、Ｃ2 〜Ｃ10の直鎖または分岐アルケニル基、Ｃ2 〜
Ｃ10の直鎖または分岐アルキニル基、Ｃ1 〜Ｃ5の直鎖
または分岐ハロゲン化アルキル基、ハロゲン原子または
水素原子を表わし、Ｒ2 はＣ1 〜Ｃ5 の直鎖または分岐
アルキル基、Ｃ2 〜Ｃ5 の直鎖または分岐アルケニル
基、Ｃ2 〜Ｃ5 の直鎖または分岐アルキニル基を表わ
す。｝で示されるテトラヒドロイソキノリン誘導体およ
びその酸付加塩（以下、本発明化合物という）、その製
法および本発明化合物を含有する殺菌剤を提供すること
にある。[Chemical 3] {In the formula, R 1 is a C 1 to C 10 linear or branched alkyl group, a C 2 to C 10 linear or branched alkenyl group, C 2 to
C 10 represents a linear or branched alkynyl group, C 1 to C 5 linear or branched halogenated alkyl group, halogen atom or hydrogen atom, and R 2 represents C 1 to C 5 linear or branched alkyl group, C linear or branched alkenyl group having 2 -C 5, a straight-chain or branched alkynyl group of C 2 -C 5. } The tetrahydroisoquinoline derivative shown by these, and its acid addition salt (henceforth the compound of this invention), its manufacturing method, and providing the fungicide containing this compound.
【０００７】[0007]
【作用】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００８】本発明化合物であるテトラヒドロイソキノ
リン誘導体は、２個の不斉炭素を有するため、下記一般
式（Ｉ−Ａ）、一般式（Ｉ−Ｂ）、一般式（Ｉ−Ｃ）お
よび一般式（Ｉ−Ｄ）の４個の立体異性体が存在する。Since the tetrahydroisoquinoline derivative which is the compound of the present invention has two asymmetric carbons, it has the following general formula (IA), general formula (IB), general formula (IC) and general formula (I-C). There are four stereoisomers of (ID).
【０００９】[0009]
【化４】 ｛式中、Ｒ1 、Ｒ2 は一般式（Ｉ）と同じ意味を表
す。｝ これらの立体異性体は、一般式（Ｉ−Ａ）と一般式（Ｉ
−Ｂ）および一般式（Ｉ−Ｃ）と一般式（Ｉ−Ｄ）の２
個ずつそれぞれ対掌体の組をなしている。そしてこれら
の対掌体の組はカラムクロマトグラフィー、再結晶等の
操作により、各対掌体の組に分離することができる。[Chemical 4] {In the formula, R 1 and R 2 have the same meanings as in formula (I). } These stereoisomers are represented by the general formula (IA) and the general formula (I
-B) and general formula (I-C) and general formula (I-D) 2
Each one forms a pair of antipodes. These enantiomers can be separated into each enantiomer by operations such as column chromatography and recrystallization.
【００１０】本発明化合物を具体的に説明すると、前記
一般式（Ｉ）におけるＲ1 としては、メチル、エチル、
プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ
−ブチル、ｔｅｒｔ−ブチル，ペンチル、イソペンチ
ル、ネオペンチル、ｔｅｒｔ−ペンチル、ヘキシル、イ
ソヘキシル、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−エチル−ブチル、２
−エチル−ブチル、１−エチル−ブチル、２−プロピル
−プロピル、１−プロピル−プロピル等のＣ1 〜Ｃ10の
直鎖または分岐アルキル基；アリル、イソプロペニル、
１−プロペニル、１−メチル−１−プロペニル、２−メ
チル−１−プロペニル、１−メチル−２−プロペニル、
２−ブテニル、１−メチル−２−ブテニル、２−メチル
−２−ブテニル、３−メチル−２−ブテニル、１，１−
ジメチル−２−プロペニル等のＣ2〜Ｃ10の直鎖または
分岐アルケニル基；エチニル、１−プロピニル、２−プ
ロピニル、１−メチル−２−プロピニル、１，１−ジメ
チル−２−プロピニル等のＣ2 〜Ｃ10の直鎖または分岐
アルキニル基；トリフルオロメチル、ジフルオロメチ
ル、トリクロロメチル、ジクロロメチル、ペンタフルオ
ロエチル等のＣ1 〜Ｃ5の直鎖または分岐ハロゲン化ア
ルキル基；フッ素原子、塩素原子、臭素原子、ヨウ素原
子等のハロゲン原子；水素原子を挙げることができる。The compound of the present invention will be described in detail. In the general formula (I), R 1 is methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, sec
-Butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, 3-methyl-pentyl, 2-methyl-pentyl, 1-methyl-pentyl, 3-ethyl-butyl, 2
- ethyl - butyl, 1-ethyl - butyl, 2-propyl - propyl, 1-propyl - the C 1 -C 10, such as propyl linear or branched alkyl group; allyl, isopropenyl,
1-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,
2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1,1-
Linear or branched alkenyl group having C 2 -C 10 dimethyl-2-propenyl; ethynyl, 1-propynyl, 2-propynyl, 1-methyl-2-propynyl, C such 1,1-dimethyl-2-propynyl 2 to C 10 linear or branched alkynyl group; C 1 to C 5 linear or branched halogenated alkyl group such as trifluoromethyl, difluoromethyl, trichloromethyl, dichloromethyl, pentafluoroethyl; fluorine atom, chlorine atom Halogen atoms such as bromine atom and iodine atom; and hydrogen atom.
【００１１】Ｒ2 としてはメチル、エチル、プロピル、
イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、
ｔｅｒｔ−ブチル、ペンチル、イソペンチル、ネオペン
チル、ｔｅｒｔ−ペンチル等のＣ1 〜Ｃ5 の直鎖または
分岐アルキル基、ビニル、アリル、イソプロペニル、１
−プロペニル、１−メチル−１−プロペニル、２−メチ
ル−１−プロペニル、１−メチル−２−プロペニル、２
−ブテニル、１−メチル−２−ブテニル、２−メチル−
２−ブテニル、３−メチル−２−ブテニル、１，１−ジ
メチル−２−プロペニル等のＣ2 〜Ｃ5 の直鎖または分
岐アルケニル基、２−プロピニル、１−メチル−２−プ
ロピニル、１，１−ジメチル−２−プロピニル等のＣ2
〜Ｃ5 の直鎖または分岐アルキニル基を挙げることがで
きる。R 2 is methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, sec-butyl,
C 1 -C 5 linear or branched alkyl groups such as tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, vinyl, allyl, isopropenyl, 1
-Propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2
-Butenyl, 1-methyl-2-butenyl, 2-methyl-
2-butenyl, 3-methyl-2-butenyl, 1,1-dimethyl-2 straight-chain or branched alkenyl group having C 2 -C 5 of propenyl, 2-propynyl, 1-methyl-2-propynyl, 1, C 2 such as 1-dimethyl-2-propynyl
To C 5 straight-chain or branched alkynyl groups.
【００１２】前記一般式（Ｉ）で示されるテトラヒドロ
イソキノリン誘導体の酸付加塩としては、たとえば塩酸
塩、臭化水素酸塩、硫酸塩、硝酸塩、リン酸塩、過塩素
酸塩等の無機酸塩；ギ酸塩、酢酸塩、シュウ酸塩、コハ
ク酸塩、フマル酸塩、アジピン酸塩、ステアリン酸塩、
オレイン酸塩、酒石酸塩等のカルボン酸塩；メタンスル
ホン酸塩、ベンゼンスルホン酸塩、ｐ−トルエンスルホ
ン酸塩等の有機スルホン酸塩等を挙げることができる。Examples of the acid addition salt of the tetrahydroisoquinoline derivative represented by the general formula (I) include inorganic acid salts such as hydrochloride, hydrobromide, sulfate, nitrate, phosphate and perchlorate. Formate, acetate, oxalate, succinate, fumarate, adipate, stearate,
Examples thereof include carboxylic acid salts such as oleic acid salts and tartaric acid salts; organic sulfonic acid salts such as methanesulfonic acid salts, benzenesulfonic acid salts and p-toluenesulfonic acid salts.
【００１３】本発明化合物は例えば下記のような反応に
より製造することができる。The compound of the present invention can be produced, for example, by the following reaction.
【００１４】[0014]
【化５】 ｛式中、Ｒ1 、Ｒ2 は一般式（Ｉ）と同じ意味を表
す。｝ 本発明化合物の製造法において、中間体として用いる一
般式（ＩＩ），一般式（ＩＩＩ）、一般式（ＩＶ）で示
される化合物は公知の方法（Ｍａｒｋ Ｃａｓｈｍａｎ
等， Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９８３，１
０５，２８７３）に従い製造することができる。[Chemical 5] {In the formula, R 1 and R 2 have the same meanings as in formula (I). The compound represented by the general formula (II), the general formula (III) or the general formula (IV) used as an intermediate in the method for producing the compound of the present invention is a known method (Mark Cashman).
Et al., J. Am. Chem. Soc. , 1983, 1
05,2873).
【００１５】一般式（ＩＩＩ）で示されるカルボン酸誘
導体は一般式（ＩＶ）で示される化合物を溶媒存在下、
無水ホモフタル酸と−１０℃ないし２００℃、好ましく
は０℃ないし１００℃で数分から数日間、反応させるこ
とにより製造することができる。The carboxylic acid derivative represented by the general formula (III) is obtained by reacting the compound represented by the general formula (IV) in the presence of a solvent.
It can be produced by reacting with homophthalic anhydride at −10 ° C. to 200 ° C., preferably 0 ° C. to 100 ° C. for several minutes to several days.
【００１６】溶媒としては、アセトニトリル、ジメチル
ホルムアミド、ジメチルスルホキシド、リン酸ヘキサメ
チルトリアミド等の極性溶媒を挙げることができるが、
好ましくはジメチルホルムアミド、アセトニトリル等の
極性溶媒である。Examples of the solvent include polar solvents such as acetonitrile, dimethylformamide, dimethylsulfoxide, and hexamethyltriamide phosphate.
Preferred are polar solvents such as dimethylformamide and acetonitrile.
【００１７】一般式（ＩＩ）で示されるラクタム誘導体
は一般式（ＩＩＩ）で示される化合物を塩基存在下、溶
媒存在下で−１０℃ないし２５０℃、好ましくは５０℃
ないし１８０℃で数分から数日間、反応することにより
製造することができる。The lactam derivative represented by the general formula (II) is the compound represented by the general formula (III) in the presence of a base and a solvent in the range of -10 ° C to 250 ° C, preferably 50 ° C.
It can be produced by reacting at 180 to 180 ° C. for several minutes to several days.
【００１８】塩基としては、炭酸ナトリウム、炭酸カリ
ウム、炭酸水素ナトリウム、炭酸水素カリウム等の無機
塩基が挙げられるが、好ましくは、炭酸ナトリウム、炭
酸カリウム等の炭酸アルカリ塩である。Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate, and alkali carbonate salts such as sodium carbonate and potassium carbonate are preferable.
【００１９】溶媒としては、アセトニトリル、ジメチル
ホルムアミド、ジメチルスルホキシド、リン酸ヘキサメ
チルトリアミド等の極性溶媒を挙げることができるが、
好ましくはジメチルホルムアミド、ジメチルスルホキシ
ド等の極性溶媒である。Examples of the solvent include polar solvents such as acetonitrile, dimethylformamide, dimethylsulfoxide and hexamethyltriamide phosphate.
Preferred are polar solvents such as dimethylformamide and dimethylsulfoxide.
【００２０】本発明化合物は一般式（ＩＩ）で示される
ラクタム誘導体を水素化剤存在下、溶媒存在下で−１０
℃ないし２００℃、好ましくは０℃ないし１３０℃で数
分から数日間、反応することにより製造することができ
る。The compound of the present invention is obtained by converting the lactam derivative represented by the general formula (II) into -10 in the presence of a hydrogenating agent and a solvent.
It can be produced by reacting at 0 to 200 ° C, preferably 0 to 130 ° C for several minutes to several days.
【００２１】反応に用いられる好ましい水素化剤として
は水素化アルミニウムリチウム、ジボラン、水素化ホウ
素ナトリウム、水素化ホウ素リチウム、ソジュウム ビ
ス２−メトキシエトキシ）アルミニウム ハイドライド
などが挙げられる。反応に供される水素化剤の量は、通
常一般式（ＩＩ）で示されるラクタム誘導体１当量に対
して０．２当量から２０当量である。Preferred hydrogenating agents used in the reaction include lithium aluminum hydride, diborane, sodium borohydride, lithium borohydride, sodium bis-2-methoxyethoxy) aluminum hydride and the like. The amount of the hydrogenating agent used in the reaction is usually 0.2 to 20 equivalents relative to 1 equivalent of the lactam derivative represented by the general formula (II).
【００２２】反応に用いられる溶媒の好ましい例として
はエチルエ−テル、テトラヒドロフラン、ジオキサン、
ビス（２−メトキシエチル）エ−テル等のエ−テル類；
ピリジン、トリエチルアミン等の三級アミン類；ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素類；メタノ
−ル等のアルコ−ル類が挙げられる。Preferred examples of the solvent used in the reaction include ethyl ether, tetrahydrofuran, dioxane,
Ethers such as bis (2-methoxyethyl) ether;
Examples include tertiary amines such as pyridine and triethylamine; aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol.
【００２３】本発明化合物および上記一般式（ＩＩ）で
示されるラクタム誘導体は２個の不斉炭素を有するため
４個の立体異性体が存在し、これらの立体異性体は２個
ずつそれぞれ対掌体の組をなしている。そして本発明化
合物および上記一般式（ＩＩ）で示されるラクタム誘導
体の対掌体はカラムクロマトグラフィー、再結晶等の操
作により、容易に各対掌体の組に分離することができ
る。Since the compound of the present invention and the lactam derivative represented by the general formula (II) have two asymmetric carbons, there are four stereoisomers, and each of these stereoisomers is an enantiomer. It is a pair of bodies. The enantiomers of the compound of the present invention and the lactam derivative represented by the general formula (II) can be easily separated into groups of enantiomers by operations such as column chromatography and recrystallization.
【００２４】上記一般式（ＩＩＩ）で示されるカルボン
酸誘導体は３個の不斉炭素を有するため８個の立体異性
体が存在し、これらの立体異性体は２個ずつそれぞれ対
掌体の組をなしている。そして上記一般式（ＩＩＩ）で
示されるカルボン酸誘導体の対掌体はカラムクロマトグ
ラフィー、再結晶等の操作により、容易に各対掌体の組
に分離することができる。Since the carboxylic acid derivative represented by the above general formula (III) has three asymmetric carbons, there are eight stereoisomers, and each of these stereoisomers is a pair of enantiomers. Is doing. The enantiomer of the carboxylic acid derivative represented by the general formula (III) can be easily separated into each enantiomer group by operations such as column chromatography and recrystallization.
【００２５】分離された上記一般式（ＩＩ）で示される
ラクタム誘導体の対掌体の組および本発明化合物の対掌
体の組のうち、３−置換エチル基における１−メチル基
の水素が 1Ｈ−ＮＭＲスペクトル（ＣＤＣｌ3 溶媒）
上、高磁場にあらわれる対掌体の組を高磁場化合物、低
磁場にあらわれる対掌体の組を低磁場化合物とよぶこと
にする。In the isolated pair of enantiomers of the lactam derivative represented by the general formula (II) and the pair of enantiomers of the compound of the present invention, the hydrogen of the 1 -methyl group in the 3-substituted ethyl group is 1 H-NMR spectrum (CDCl 3 solvent)
Above, the pair of antipodes appearing in a high magnetic field is called a high magnetic field compound, and the pair of antipodes appearing in a low magnetic field is called a low magnetic field compound.
【００２６】本発明化合物を有効成分として含む本発明
の農園芸用殺菌剤は、植物病原菌に対して優れた殺菌力
を有し、広範囲にわたる種々の菌類による植物病害の駆
除撲滅のために適用出来る。例えば，イネいもち病(Pyr
icularia oryzae)、イネ紋枯れ病(Rhizoctonia solan
i)、イネごま葉枯れ病 (Cochliobolus miyabeanus)、リ
ンゴうどんこ病(Podosphaera leucotricha) 、リンゴ黒
星病 (Venturia inaequalis)、ナシ黒星病(Venturia na
shicola)、ナシモニリア病(Sclerosinia mali)、カキ炭
そ病(Gloeosporium kaki) 、モモ灰星病(Sclerotinia c
inerea) 、モモ黒星病(Cladosporium carpophilum)、ブ
ドウ灰色かび病(Botrytis cinerea)、ブドウ黒とう病(E
lsinoe ampelina)、ブドウ晩腐病(Glomerella cingulat
a)、テンサイ褐斑病(Cercospora beticola) 、ピ−ナッ
ツ褐斑病(Cercospora arachidicola) 、ピーナッツ黒渋
病(Cercospora personata)、オオムギうどんこ病(Erysi
phegraminis f.sp. hordei)、オムギアイ・スポット病
(Cercosporella herpotrichoides) 、オオムギ紅色雪腐
病(Fusarium nivale) 、コムギうどんこ病(Erysiphegra
minis f.sp. tritici) 、コムギ赤さび病(Puccinia rec
ondita)、コムギ斑点病 (Drechslera sorokiniana) 、
キュウリべと病(Pseudoperonospora cubensis)、キュウ
リうどんこ病(Sphaerotheca fuliginea)、キュウリつる
枯病(Mycosphaerella melonis)、キュウリ灰色かび病(B
otrytis cinerea)、キュウリ黒星病(Cladosporium cucu
merinum)、トマト疫病(Phytophthora infestans)、トマ
ト葉かび病(Cladosporium fulvum) 、トマト灰色かび病
(Botrytis cinerea)、イチゴうどんこ病(Sphaerotheca
humuli) 、ホップ灰色かび病(Botrytis cinerea)、タバ
コうどんこ病(Erysiphe cichoracearum)、バラ黒星病(D
iplocarpon rosae) 、ミカンそうか病(Elsinoe fawceti
i)、ミカン青かび病(Penicillium italicum)、ミカン緑
かび病(Penicillium digitatum)等があげられる。The fungicide for agricultural and horticultural use of the present invention containing the compound of the present invention as an active ingredient has excellent bactericidal activity against phytopathogenic fungi and can be applied for eradication and eradication of plant diseases caused by a wide variety of fungi. . For example, rice blast (Pyr
icularia oryzae), rice blight (Rhizoctonia solan)
i), rice sesame leaf blight (Cochliobolus miyabeanus), apple powdery mildew (Podosphaera leucotricha), apple scab (Venturia inaequalis), pear scab (Venturia na)
shicola), nasimonilia disease (Sclerosinia mali), oyster anthracnose (Gloeosporium kaki), peach scab (Sclerotinia c)
inerea), peach scab (Cladosporium carpophilum), grape gray mold (Botrytis cinerea), grape black rot (E
lsinoe ampelina), late grapevine rot (Glomerella cingulat)
a), sugar beet leaf spot (Cercospora beticola), peanut leaf spot (Cercospora arachidicola), peanut black leaf spot (Cercospora personata), barley powdery mildew (Erysi)
phegraminis f.sp.hordei), Omgiyai spot disease
(Cercosporella herpotrichoides), barley red snow rot (Fusarium nivale), wheat powdery mildew (Erysiphegra)
minis f.sp. tritici), wheat leaf rust (Puccinia rec)
ondita), wheat leaf spot (Drechslera sorokiniana),
Cucumber downy mildew (Pseudoperonospora cubensis), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber vine blight (Mycosphaerella melonis), cucumber gray mold (B)
otrytis cinerea), cucumber scab (Cladosporium cucu)
merinum), tomato blight (Phytophthora infestans), tomato leaf mold (Cladosporium fulvum), tomato gray mold
(Botrytis cinerea), strawberry powdery mildew (Sphaerotheca
humuli), hop gray mold (Botrytis cinerea), tobacco powdery mildew (Erysiphe cichoracearum), rose scab (D)
iplocarpon rosae), mandarin orange scab (Elsinoe fawceti
i), mandarin orange mold (Penicillium italicum), mandarin orange mold (Penicillium digitatum) and the like.
【００２７】これらの中で特に、コムギうどんこ病、コ
ムギさび病、コムギ斑点病、イネいもち病に対して顕著
な効果を示す。また、本発明の農園芸用殺菌剤は、イ
ネ、コムギ等の作物に対してほとんど薬害を与えること
がなく、安全性の高いものである。[0027] Among these, especially, remarkable effects are shown against wheat powdery mildew, wheat rust, wheat spot disease, and rice blast. Further, the agricultural and horticultural fungicide of the present invention is highly safe with almost no chemical damage to crops such as rice and wheat.
【００２８】本発明の農園芸用殺菌剤はテトラヒドロイ
ソキノリン誘導体それ自体を用いてもよいが、通常は担
体、界面活性剤、分散剤、または補助剤等を配合して定
法により、例えば、水和剤、乳剤、粉剤または粒剤に製
剤して用いることができる。これらの製剤は適切な濃度
に希釈して散布するか、または直接施用する。Although the tetrahydroisoquinoline derivative itself may be used as the fungicide for agricultural and horticultural use of the present invention, it is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent or the like by a conventional method, for example, hydration. It can be used by formulating into a drug, emulsion, powder or granule. These preparations are diluted to an appropriate concentration and then sprayed or applied directly.
【００２９】有効成分の配合割合については必要に応じ
て選ばれるが、製剤に対して通常０．５〜８０％の範囲
が適当である。The blending ratio of the active ingredient is selected according to need, but usually 0.5 to 80% is suitable for the preparation.
【００３０】本発明の農園芸用殺菌剤の施用量は、使用
される化合物の種類、対象病害、被害の程度、環境条
件、使用する剤型などによって変動するが、粉剤及び粒
剤の様にそのまま使用する場合は有効成分として１０ア
ール当り１〜５０００ｇ好ましくは、５〜１０００ｇの
範囲から選ぶのがよい。又、乳剤または水和剤のように
最終的に液状で使用する場合は、０．１〜１００００ｐ
ｐｍ、好ましくは１〜３０００ｐｐｍの範囲から選ぶの
がよい。The application rate of the fungicide for agricultural and horticultural use of the present invention varies depending on the type of compound used, target disease, degree of damage, environmental conditions, dosage form used, and the like, but like powder and granules. When used as it is, the active ingredient is preferably selected from the range of 1 to 5000 g per 10 ares, preferably 5 to 1000 g. When it is finally used in a liquid state such as an emulsion or a wettable powder, it is 0.1 to 10,000 p
pm, preferably in the range of 1 to 3000 ppm.
【００３１】[0031]
【実施例】次に、実施例によって本発明を具体的に説明
するが、本発明はこれらの実施例のみに限定されるもの
ではない。下記実施例中の部は重量部を意味する。 参考例１ ２−メチル−３−（１−メチル−２−フェニルエチル）
−１−オキソ−１，２，３，４−テトラヒドロイソキノ
リンの製造 ２−メチル−３−（１−メチル−２−フェニルエチル）
−１−オキソ−４−ヒドロキシカルボニル−１，２，
３，４−テトラヒドロイソキノリン４．９４ｇのジメチ
ルスルホキシド（２０ｍｌ）溶液に炭酸ナトリウム３．
２４ｇを加え、１５０℃で２時間反応した。反応終了
後、溶媒を減圧留去、残遙を酢酸エチルで抽出し飽和食
塩水で洗浄後、無水硫酸マグネシウムで乾燥を行った。
溶媒を減圧下留去後、残渣をシリカゲルカラムクロマト
グラフィ−［展開溶媒：ｎ−ヘキサン−酢酸エチル（４
／１）］で単離精製し、２−メチル−３−（１−メチル
−２−フェニルエチル）−１−オキソ−１，２，３，４
−テトラヒドロイソキノリンの対掌体の組をそれぞれ分
取した（２．１９ｇ）。３−置換エチル基における１−
メチル基の水素のスペクトルとして、高磁場化合物は
０．６１(d,3H,J=7Hz)を、低磁場化合物は０．８３(d,3
H,J=7Hz)をそれぞれ観測した。EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. Parts in the following examples mean parts by weight. Reference Example 1 2-Methyl-3- (1-methyl-2-phenylethyl)
Preparation of -1-oxo-1,2,3,4-tetrahydroisoquinoline 2-methyl-3- (1-methyl-2-phenylethyl)
-1-oxo-4-hydroxycarbonyl-1,2,
A solution of 4.94 g of 3,4-tetrahydroisoquinoline in dimethyl sulfoxide (20 ml) was added with sodium carbonate 3.
24 g was added, and the mixture was reacted at 150 ° C. for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, the residue was extracted with ethyl acetate, washed with saturated saline, and dried with anhydrous magnesium sulfate.
After evaporating the solvent under reduced pressure, the residue was subjected to silica gel column chromatography- [Developing solvent: n-hexane-ethyl acetate (4
/ 1)] and isolated and purified to give 2-methyl-3- (1-methyl-2-phenylethyl) -1-oxo-1,2,3,4.
-Each set of antipodes of tetrahydroisoquinoline was separated (2.19 g). 1-in the 3-substituted ethyl group
As for the hydrogen spectrum of the methyl group, 0.61 (d, 3H, J = 7Hz) is for the high magnetic field compound and 0.83 (d, 3) for the low magnetic field compound.
H, J = 7 Hz) was observed respectively.
【００３２】＜高磁場化合物＞1 Ｈ−ＮＭＲ （溶媒：ＣＤＣｌ3 、δｐｐｍ） 0.61(d,3H,J=7Hz),2.05-2.20(m,1H),2.45(dd,1H,J=13H
z,11Hz),2.74(dd,1H,J=13Hz,5Hz),2.97(d,1H,J=15Hz),
3.15(S,3H),3.32(dd,1H,J=16Hz,7Hz),3.40-3.45(m,1H),
7.00-7.42(m,8H),8.05(d,1H,J=6Hz) ＩＲ （ｃｍ-1：ＮａＣｌ） 2960,2930,1650,1610,1580,1480 ｎD 24.5＝１．５５６６ ＜低磁場化合物＞1 Ｈ−ＮＭＲ （溶媒：ＣＤＣｌ3 、δｐｐｍ） 0.83(d,3H,J=7Hz),2.00-2.20(m,2H),2.65(dd,1H,J=20H
z,10Hz),3.00(d,1H,J=15Hz),3.25(s,3H),3.38(dd,1H,J=
16Hz,7Hz),3.45-3.52(m,1H),6.98-7.45(m,8H),8.05(d,1
H,J=6Hz) ＩＲ （ｃｍ-1：ＮａＣｌ） 2960,2930,1640,1605,1580,1470 ｎD 24.5＝１．５７９０<High magnetic field compound> 1 H-NMR (solvent: CDCl 3 , δppm) 0.61 (d, 3H, J = 7Hz), 2.05-2.20 (m, 1H), 2.45 (dd, 1H, J = 13H)
z, 11Hz), 2.74 (dd, 1H, J = 13Hz, 5Hz), 2.97 (d, 1H, J = 15Hz),
3.15 (S, 3H), 3.32 (dd, 1H, J = 16Hz, 7Hz), 3.40-3.45 (m, 1H),
7.00-7.42 (m, 8H), 8.05 (d, 1H, J = 6Hz) IR (cm -1 : NaCl) 2960,2930,1650,1610,1580,1480 n D 24.5 = 1.5566 <Low magnetic field compound> 1 H-NMR (solvent: CDCl 3 , δppm) 0.83 (d, 3H, J = 7Hz), 2.00-2.20 (m, 2H), 2.65 (dd, 1H, J = 20H
z, 10Hz), 3.00 (d, 1H, J = 15Hz), 3.25 (s, 3H), 3.38 (dd, 1H, J =
16Hz, 7Hz), 3.45-3.52 (m, 1H), 6.98-7.45 (m, 8H), 8.05 (d, 1
H, J = 6Hz) IR (cm -1 : NaCl) 2960,2930,1640,1605,1580,1470 n D 24.5 = 1.5790
【００３３】参考例２ ２−メチル−３−（１−メチル−２−フェニルエチル）
−１−オキソ−４−ヒドロキシカルボニル−１，２，
３，４−テトラヒドロイソキノリンの製造 Ｎ−（２−メチル−３−フェニルプロピリデン）メチル
アミン７．８６ｇのアセトニトリル（３０ｍｌ）溶液
に、無水ホモフタル酸６．０ｇを加え、室温下６時間反
応した。反応終了後、１０％水酸化ナトリウム水溶液で
抽出、水層を冷やしながら１０％塩酸水溶液で酸性にし
たのち、エーテル抽出、飽和食塩水で洗浄後、無水硫酸
マグネシウムで乾燥を行った。溶媒を減圧下留去後、２
−メチル−３−（１−メチル−２−フェニルエチル）−
１−オキソ−４−ヒドロキシカルボニル−１，２，３，
４−テトラヒドロイソキノリン４．９４ｇを得た。 ＩＲ （ｃｍ-1：ＮａＣｌ） 3400,2960,1720,1630,1580,1260Reference Example 2 2-methyl-3- (1-methyl-2-phenylethyl)
-1-oxo-4-hydroxycarbonyl-1,2,
Production of 3,4-tetrahydroisoquinoline To a solution of 7.86 g of N- (2-methyl-3-phenylpropylidene) methylamine in acetonitrile (30 ml) was added 6.0 g of homophthalic anhydride, and the mixture was reacted at room temperature for 6 hours. After completion of the reaction, the mixture was extracted with a 10% aqueous sodium hydroxide solution, acidified with a 10% aqueous hydrochloric acid solution while cooling the aqueous layer, extracted with ether, washed with saturated brine, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, 2
-Methyl-3- (1-methyl-2-phenylethyl)-
1-oxo-4-hydroxycarbonyl-1,2,3,
4.94 g of 4-tetrahydroisoquinoline was obtained. IR (cm -1 : NaCl) 3400,2960,1720,1630,1580,1260
【００３４】実施例１ ２−メチル−３−（１−メチル−２−フェニルエチル）
−１，２，３，４−テトラヒドロイソキノリン（高磁場
化合物）（化合物番号１）の製造 ２−メチル−３−（１−メチル−２−フェニルエチル）
−１−オキソ−１，２，３，４−テトラヒドロイソキノ
リン（高磁場化合物）０．７３ｇのＴＨＦ（３０ｍｌ）
溶液に水素化リチウムアルミニウム０．３０ｇを加え、
室温下２時間反応した。反応終了後、水０．３ｍｌ、１
５％水酸化ナトリウム水溶液０．３ｍｌさらに水０．９
ｍｌをゆっくり加えた後酢酸エチルで抽出し、生じた沈
澱をセライト濾過した。濾液を飽和食塩水洗後、無水硫
酸マグネシウムで乾燥を行った。溶媒を減圧下留去後、
残遙をシリカゲルカラムクロマトグラフィ−［展開溶
媒：ｎ−ヘキサン−酢酸エチル（６／１）］で精製し、
２−メチル−３−（１−メチル−２−フェニルエチル）
−１，２，３，４−テトラヒドロイソキノリン（高磁場
化合物）０．５１ｇを得た。同様な方法により本発明化
合物を得た。その代表例を表１と表２に示す。Example 1 2-Methyl-3- (1-methyl-2-phenylethyl)
Preparation of -1,2,3,4-tetrahydroisoquinoline (high magnetic field compound) (Compound No. 1) 2-methyl-3- (1-methyl-2-phenylethyl)
-1-oxo-1,2,3,4-tetrahydroisoquinoline (high magnetic field compound) 0.73 g THF (30 ml)
0.30 g of lithium aluminum hydride was added to the solution,
The reaction was carried out at room temperature for 2 hours. After completion of the reaction, 0.3 ml of water, 1
5% sodium hydroxide aqueous solution 0.3 ml and water 0.9
After slowly adding ml, the mixture was extracted with ethyl acetate, and the formed precipitate was filtered through Celite. The filtrate was washed with saturated brine and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure,
The residue is purified by silica gel column chromatography- [developing solvent: n-hexane-ethyl acetate (6/1)],
2-methyl-3- (1-methyl-2-phenylethyl)
0.51 g of -1,2,3,4-tetrahydroisoquinoline (high magnetic field compound) was obtained. The compound of the present invention was obtained by the same method. Typical examples are shown in Tables 1 and 2.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】実施例２（水和剤） 本発明化合物（Ｎｏ．１）１０部を担体材料としてジー
クライト［商品名、国峰工業株）製］８７．３部界面活
性剤としてネオペレックス［商品名、花王アトラス
（株）製］１．３５部及びソルポール８００Ａ［商品
名、東邦化学工業（株）製］１．３５部と共に混合粉砕
して１０％水和剤を得た。 実施例３（乳剤） 本発明化合物（Ｎｏ．２）５部をキシレン８５部，界面
活性剤としてソルポール８００Ａ１０部を混合溶解し、
５％乳剤を得た。 実施例４（粉剤） 本発明化合物（Ｎｏ．３）２部を珪藻土５部，およびク
レー９３部を均一に混合粉砕して２％粉剤を得た。 実施例５（粒剤） 本発明化合物（Ｎｏ．４）１０部をベントナイト５０
部、クニライト［商品名、国峰工業（株）製］３５部及
び界面活性剤としてソルポール８００Ａ５部を混合粉砕
した後、水１０部を加えて均一に撹拌し、直径０．７ｍ
ｍの篩穴から押し出し乾燥後１〜２ｍｍの長さに切断し
て１０％粒剤を得た。Example 2 (Wettable powder) 10 parts of the compound of the present invention (No. 1) as a carrier material, Sieglite [trade name, manufactured by Kunimine Industry Co., Ltd.] 87.3 parts as a surfactant Neoperex [trade name] , Manufactured by Kao Atlas Co., Ltd.] and 1.35 parts of Solpol 800A [trade name, manufactured by Toho Chemical Industry Co., Ltd.] were mixed and pulverized to obtain a 10% wettable powder. Example 3 (Emulsion) 5 parts of the compound of the present invention (No. 2) was mixed and dissolved with 85 parts of xylene and 10 parts of Solpol 800A as a surfactant.
A 5% emulsion was obtained. Example 4 (Dust) 2 parts of the compound of the present invention (No. 3) was uniformly mixed and pulverized with 5 parts of diatomaceous earth and 93 parts of clay to obtain a 2% powder. Example 5 (Granule) Bentonite 50 was added with 10 parts of the compound of the present invention (No. 4).
Part, Kunilite [trade name, manufactured by Kunimine Industry Co., Ltd.] and 50 parts of Solpol 800A as a surfactant are mixed and pulverized, and then 10 parts of water is added and uniformly stirred to obtain a diameter of 0.7 m.
It was extruded through a sieve hole of m and dried, and then cut into a length of 1 to 2 mm to obtain 10% granules.
【００３８】次に試験例をあげ、本発明化合物の農園芸
用殺菌剤としての有用性をさらに明らかにする。 試験例１ コムギうどんこ病予防効果試験 ８ｃｍ×８ｃｍプラスチック製ポットにコムギ種子（品
種：農林６１号）を播種し温室内で育成させた。第一葉
が完全に展開したコムギ幼苗に、実施例２に準じて調製
した水和剤を有効成分濃度が所定の濃度になるように水
で希釈した液を散布した。風乾後、コムギうどんこ病菌
を接種し、２５℃の恒温室に入れた。接種７日後下記基
準によりポット全体の被害度を調査し、防除価を算出し
た。Next, test examples will be given to further clarify the usefulness of the compound of the present invention as an agricultural and horticultural fungicide. Test Example 1 Wheat Powdery Mildew Prevention Effect Test Wheat seeds (variety: Norin 61) were sown in an 8 cm × 8 cm plastic pot and grown in a greenhouse. To a wheat seedling in which the first leaf was completely developed, a wettable powder prepared according to Example 2 was sprayed with a liquid diluted with water so that the concentration of the active ingredient became a predetermined concentration. After air-drying, wheat powdery mildew was inoculated and placed in a thermostatic chamber at 25 ° C. 7 days after the inoculation, the damage level of the entire pot was investigated according to the following criteria, and the control value was calculated.
【００３９】被害度（％）＝１００ ×｛（ｎ1 ×１）
＋（ｎ2 ×２）＋（ｎ3 ×３）＋（ｎ4 ×４）｝／４Ｎ Ｎ ：調査全葉数 ｎ0 ：発病なしの葉数 ｎ1 ：病斑面積率２５％未満の発病葉数 ｎ2 ：病斑面積率２５〜５０％の発病葉数 ｎ3 ：病斑面積率５０〜７５％の発病葉数 ｎ4 ：病斑面積率７５％以上の発病葉数 防除価（％）＝１００×｛１−（処理区の被害度）／
（無処理区の被害度）｝ 防除効力は、防除価が、９０％以上の時「５」、８０％
以上９０％未満の時４」、７０％以上８０％未満の時
「３」、６０％以上７０％未満の時「２」、５０％以上
６０％未満の時「１」、５０％未満の時「０」として６
段階に評価し、それぞれ５，４，３，２，１，０で示
す。得られた結果を表３に示す。Damage level (%) = 100 × {(n 1 × 1)
+ (N 2 × 2) + (n 3 × 3) + (n 4 × 4)} / 4N N: total number of leaves investigated n 0 : number of leaves without disease n 1 : diseased area ratio less than 25% Number of leaves n 2 : Number of diseased leaves with lesion area ratio of 25 to 50% n 3 : Number of diseased leaves with lesion area ratio of 50 to 75% n 4 : Number of diseased leaves with lesion area ratio of 75% or more Control value (% ) = 100 × {1- (degree of damage of treatment area) /
(Damage level of untreated area)} The control efficacy is "5", 80% when the control value is 90% or more.
When 90% or more and less than 90% 4 ", When 70% or more and less than 80%" 3 ", When 60% or more and less than 70%" 2 ", When 50% or more and less than 60%" 1 ", When less than 50% 6 as "0"
It was evaluated in stages and shown as 5, 4, 3, 2, 1, 0, respectively. The results obtained are shown in Table 3.
【００４０】[0040]
【表３】 [Table 3]
【００４１】試験例２ コムギうどんこ病治療効果試験 ８ｃｍ×８ｃｍプラスチック製ポットにコムギ種子（品
種：農林６１号）を播種し温室内で育成させた。第一葉
が完全に展開したコムギ幼苗に、コムギうどんこ病菌を
接種し、２５℃の恒温室に入れた。１日、２日および３
日経過後、実施例２に準じて調製した水和剤を有効成分
濃度が１００ｐｐｍになるように水で希釈した液を散布
した。風乾後、再び２５℃の恒温室に入れた。接種７日
後下記基準によりポット全体の被害度を調査し、試験例
１と同様にして防除価を算出し、防除効力も評価した。
化合物番号８について、防除効力は、１日、２日および
３日経過後いずれの場合も５であった。Test Example 2 Wheat Powdery Mildew Treatment Effect Test Wheat seeds (variety: Norin 61) were sown in an 8 cm × 8 cm plastic pot and grown in a greenhouse. Wheat seedlings with fully developed first leaves were inoculated with wheat powdery mildew and placed in a thermostatic chamber at 25 ° C. 1st, 2nd and 3rd
After a lapse of days, a wettable powder prepared according to Example 2 was diluted with water so that the concentration of the active ingredient was 100 ppm, and then sprayed. After air drying, it was placed again in a thermostatic chamber at 25 ° C. Seven days after the inoculation, the degree of damage of the entire pot was investigated according to the following criteria, the control value was calculated in the same manner as in Test Example 1, and the control effect was also evaluated.
The control efficacy of compound No. 8 was 5 in all cases after 1 day, 2 days and 3 days.
【００４２】試験例３ コムギ赤さび病予防効果試験 ８ｃｍ×８ｃｍプラスチック製ポットにコムギ種子（品
種：農林６１号）を播種し温室内で育成させた。第一葉
が完全に展開したコムギ幼苗に、実施例２に準じて調製
した水和剤を有効成分濃度が５００ｐｐｍになるように
水で希釈した液を散布した。風乾後、コムギ赤さび病菌
を接種し、２５℃の恒温室に入れた。接種７日後ポット
全体の病斑数を調査し、下記の式に従って防除価を算出
し、試験例１と同様にして防除効力を評価した。Test Example 3 Wheat Leaf Rust Preventive Effect Test Wheat seeds (variety: Norin 61) were sown in an 8 cm × 8 cm plastic pot and grown in a greenhouse. To a wheat seedling with completely developed first leaves, a wettable powder prepared according to Example 2 was sprayed with a solution diluted with water so that the concentration of the active ingredient was 500 ppm. After air-drying, wheat leaf rust fungus was inoculated and placed in a thermostatic chamber at 25 ° C. 7 days after the inoculation, the number of lesions in the entire pot was examined, the control value was calculated according to the following formula, and the control effect was evaluated in the same manner as in Test Example 1.
【００４３】防除価（％）＝１００×｛１−（処理区病
斑数）／（無処理区病斑数）｝ 得られた結果を表４に示す。Control value (%) = 100 × {1- (number of treated lesions) / (number of untreated lesions)} The results obtained are shown in Table 4.
【００４４】[0044]
【表４】 [Table 4]
【００４５】試験例４ イネいもち病予防効果試験 ８ｃｍ×８ｃｍプラスチック製ポットにイネ種子（品
種：ヤマホウシ）を播種し温室内で育成させた。２．５
〜３葉期に、実施例２に準じて調製した水和剤を有効成
分濃度が５００ｐｐｍになるように水で希釈した液を散
布した。風乾後、イネいもち病菌を接種し、２５℃の恒
温室に入れた。接種７日後ポット全体の病斑数を調査
し、試験例３と同様にして防除価を算出し、防除効力も
評価した。例えば、化合物番号１０について、防除効力
は５であった。Test Example 4 Rice Blast Prevention Effect Test Rice seeds (variety: porcupine) were sown in an 8 cm × 8 cm plastic pot and grown in a greenhouse. 2.5
At the ~ 3 leaf stage, a wettable powder prepared according to Example 2 was sprayed with a solution diluted with water so that the concentration of the active ingredient was 500 ppm. After air drying, rice blast fungus was inoculated and placed in a thermostatic chamber at 25 ° C. Seven days after the inoculation, the number of lesions on the entire pot was examined, and the control value was calculated in the same manner as in Test Example 3 to evaluate the control efficacy. For example, with respect to Compound No. 10, the control efficacy was 5.
【００４６】[0046]
【発明の効果】本発明化合物である新規なテトラヒドロ
イソキノリン誘導体は、イネ、コムギ等の作物に対して
ほとんど薬害を与えることなく、コムギうどんこ病、コ
ムギさび病、コムギ斑点病、イネいもち病などの植物病
原菌に対して優れた殺菌力を有する農園芸用殺菌剤とし
て有用である。INDUSTRIAL APPLICABILITY The novel tetrahydroisoquinoline derivative which is the compound of the present invention gives almost no phytotoxicity to crops such as rice and wheat, and has powdery mildew of wheat, rust of wheat, leaf spot of wheat, blast of rice blast, etc. It is useful as an agricultural and horticultural fungicide having excellent bactericidal activity against the above plant pathogens.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年７月３１日[Submission date] July 31, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【化１】 ｛式中、Ｒ１は、Ｃ１〜Ｃ１０の直鎖または分岐アルキ
ル基、Ｃ２〜Ｃ１０の直鎖または分岐アルケニル基、Ｃ
２〜Ｃ１０の直鎖または分岐アルキニル基、Ｃ１〜Ｃ５
の直鎖または分岐ハロゲン化アルキル基、ハロゲン原子
または水素原子を表わし、Ｒ２はＣ１〜Ｃ５の直鎖また
は分岐アルキル基、Ｃ２〜Ｃ５の直鎖または分岐アルケ
ニル基、Ｃ２〜Ｃ５の直鎖または分岐アルキニル基を表
わす。｝[Chemical 1] {In the formula, R 1 is a C 1 to C 10 linear or branched alkyl group, a C 2 to C 10 linear or branched alkenyl group, C 1
2 to C 10 linear or branched alkynyl group, C 1 to C 5
Represents a straight chain or branched halogenated alkyl group, a halogen atom or a hydrogen atom, and R 2 represents a C 1 to C 5 straight chain or branched alkyl group, a C 2 to C 5 straight chain or branched alkenyl group, C 2 Represents a C 5 straight or branched alkynyl group. }
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項４[Name of item to be corrected] Claim 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【化２】 ｛式中、Ｒ１、Ｒ２は一般式（Ｉ）と同じ意味を表
す。｝[Chemical 2] {In the formula, R 1 and R 2 have the same meanings as in formula (I). }
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】[0006]
【化３】 ｛式中、Ｒ１は、Ｃ１〜Ｃ１０の直鎖または分岐アルキ
ル基、Ｃ２〜Ｃ１０の直鎖または分岐アルケニル基、Ｃ
２〜Ｃ１０の直鎖または分岐アルキニル基、Ｃ１〜Ｃ５
の直鎖または分岐ハロゲン化アルキル基、ハロゲン原子
または水素原子を表わし、Ｒ２はＣ１〜Ｃ５の直鎖また
は分岐アルキル基、Ｃ２〜Ｃ５の直鎖または分岐アルケ
ニル基、Ｃ２〜Ｃ５の直鎖または分岐アルキニル基を表
わす。｝で示されるテトラヒドロイソキノリン誘導体お
よびその酸付加塩（以下、本発明化合物という）、その
製法および本発明化合物を含有する殺菌剤を提供するこ
とにある。[Chemical 3] {In the formula, R 1 is a C 1 to C 10 linear or branched alkyl group, a C 2 to C 10 linear or branched alkenyl group, C 1
2 to C 10 linear or branched alkynyl group, C 1 to C 5
Represents a straight chain or branched halogenated alkyl group, a halogen atom or a hydrogen atom, and R 2 represents a C 1 to C 5 straight chain or branched alkyl group, a C 2 to C 5 straight chain or branched alkenyl group, C 2 Represents a C 5 straight or branched alkynyl group. } The tetrahydroisoquinoline derivative shown by these, and its acid addition salt (henceforth the compound of this invention), its manufacturing method, and providing the fungicide containing this compound.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】[0009]
【化４】 ｛式中、Ｒ１、Ｒ２は一般式（Ｉ）と同じ意味を表
す。｝ これらの立体異性体は、一般式（Ｉ−Ａ）と一般式（Ｉ
−Ｂ）および一般式（Ｉ−Ｃ）と一般式（Ｉ−Ｄ）の２
個ずつそれぞれ対掌体の組をなしている。そしてこれら
の対掌体の組はカラムクロマトグラフィー、再結晶等の
操作により、各対掌体の組に分離することができる。[Chemical 4] {In the formula, R 1 and R 2 have the same meanings as in formula (I). } These stereoisomers are represented by the general formula (IA) and the general formula (I
-B) and general formula (I-C) and general formula (I-D) 2
Each one forms a pair of antipodes. These enantiomers can be separated into each enantiomer by operations such as column chromatography and recrystallization.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】[0014]
【化５】 ｛式中、Ｒ１、Ｒ２は一般式（Ｉ）と同じ意味を表
す。｝ 本発明化合物の製造法において、中間体として用いる一
般式（ＩＩ），一般式（ＩＩＩ）、一般式（ＩＶ）で示
される化合物は公知の方法（Ｍａｒｋ Ｃａｓｈｍａｎ
等， Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９８３，１
０５，２８７３）に従い製造することができる。[Chemical 5] {In the formula, R 1 and R 2 have the same meanings as in formula (I). The compound represented by the general formula (II), the general formula (III) or the general formula (IV) used as an intermediate in the method for producing the compound of the present invention is a known method (Mark Cashman).
Et al., J. Am. Chem. Soc. , 1983, 1
05,2873).
Claims (7)
イソキノリン誘導体およびその酸付加塩。 【化１】 ｛式中、Ｒ1 は、Ｃ1 〜Ｃ10の直鎖または分岐アルキル
基、Ｃ2 〜Ｃ10の直鎖または分岐アルケニル基、Ｃ2 〜
Ｃ10の直鎖または分岐アルキニル基、Ｃ1 〜Ｃ5の直鎖
または分岐ハロゲン化アルキル基、ハロゲン原子または
水素原子を表わし、Ｒ2 はＣ1 〜Ｃ5 の直鎖または分岐
アルキル基、Ｃ2 〜Ｃ5 の直鎖または分岐アルケニル
基、Ｃ2 〜Ｃ5 の直鎖または分岐アルキニル基を表わ
す。｝1. A tetrahydroisoquinoline derivative represented by the following general formula (I) and an acid addition salt thereof. [Chemical 1] {In the formula, R 1 is a C 1 to C 10 linear or branched alkyl group, a C 2 to C 10 linear or branched alkenyl group, C 2 to
C 10 represents a linear or branched alkynyl group, C 1 to C 5 linear or branched halogenated alkyl group, halogen atom or hydrogen atom, and R 2 represents C 1 to C 5 linear or branched alkyl group, C linear or branched alkenyl group having 2 -C 5, a straight-chain or branched alkynyl group of C 2 -C 5. }
水素が 1Ｈ−ＮＭＲスペクトル（ＣＤＣｌ3 溶媒）上、
高磁場にあらわれる対掌体の組あるいはそのひとつであ
る請求項１に記載のテトラヒドロイソキノリン誘導体お
よびその酸付加塩。2. The hydrogen of the 1-methyl group in the 3-substituted ethyl group is 1 H-NMR spectrum (CDCl 3 solvent),
The tetrahydroisoquinoline derivative and the acid addition salt thereof according to claim 1, which are a pair of enantiomers appearing in a high magnetic field or one of them.
水素が 1Ｈ−ＮＭＲスペクトル（ＣＤＣｌ3 溶媒）上、
低磁場にあらわれる対掌体の組あるいはそのひとつであ
る請求項１に記載のテトラヒドロイソキノリン誘導体お
よびその酸付加塩。3. The hydrogen of the 1-methyl group in the 3-substituted ethyl group is 1 H-NMR spectrum (CDCl 3 solvent),
The tetrahydroisoquinoline derivative and the acid addition salt thereof according to claim 1, which are a pair of enantiomers appearing in a low magnetic field or one of them.
導体を水素化剤により還元することを特徴とする請求項
１に記載の一般式（Ｉ）で示されるテトラヒドロイソキ
ノリン誘導体の製法。 【化２】 ｛式中、Ｒ1 、Ｒ2 は一般式（Ｉ）と同じ意味を表
す。｝4. The method for producing a tetrahydroisoquinoline derivative represented by the general formula (I) according to claim 1, wherein the lactam derivative represented by the following general formula (II) is reduced by a hydrogenating agent. [Chemical 2] {In the formula, R 1 and R 2 have the same meanings as in formula (I). }
トラヒドロイソキノリン誘導体および／またはその酸付
加塩を有効成分として含有する殺菌剤。5. A bactericide containing the tetrahydroisoquinoline derivative represented by the general formula (I) according to claim 1 and / or an acid addition salt thereof as an active ingredient.
誘導体および／またはその酸付加塩を有効成分として含
有する殺菌剤。6. A bactericide containing the tetrahydroisoquinoline derivative according to claim 2 and / or an acid addition salt thereof as an active ingredient.
誘導体および／またはその酸付加塩を有効成分として含
有する殺菌剤。7. A bactericide containing the tetrahydroisoquinoline derivative according to claim 3 and / or an acid addition salt thereof as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03207276A JP3136676B2 (en) | 1991-07-25 | 1991-07-25 | Isoquinoline derivative with bactericidal effect |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03207276A JP3136676B2 (en) | 1991-07-25 | 1991-07-25 | Isoquinoline derivative with bactericidal effect |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06172313A true JPH06172313A (en) | 1994-06-21 |
| JP3136676B2 JP3136676B2 (en) | 2001-02-19 |
Family
ID=16537116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03207276A Expired - Fee Related JP3136676B2 (en) | 1991-07-25 | 1991-07-25 | Isoquinoline derivative with bactericidal effect |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3136676B2 (en) |
-
1991
- 1991-07-25 JP JP03207276A patent/JP3136676B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3136676B2 (en) | 2001-02-19 |
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