JPS58185535A - Halogeno-3-phenylbutylaldehyde and its preparation - Google Patents

Abstract

NEW MATERIAL:A halogeno-3-phenylbutylaldehyde shown by the formula I (X is halogen, nitro, or haloalkyl; n is 0, 1, or 2; Y is H or halogen). EXAMPLE:2,2,4-Trichloro-3-(2,3-dichlorophenyl)butylaldehyde. USE:An intermediate for a fungicide, and an intermediate for synthesizing a 3- phenylpyrrole derivative useful as drugs, agricultural chemicals or their intermediates. PROCESS:A diazonium salt obtained easily from an aniline shown by the formula IIis reacted with a crotonaldehyde shown by the formula III (Y2 is H or halogen) in a water-containing solvent such as acetone, etc. in the presence of a catalyst such as cupric chloride, cupric bromide, etc. at 10-30 deg.C, to give a compound shown by the formula I .

Description

【発明の詳細な説明】 本発明は新規な化合物及びその製造方法に関し、詳しく
は一般式 （式中、Ｘは・・口ｒ／Ｉｆｉ、子、ニトロ基又はノ・
ロｒルキル基を、Ｙは水素原子又はハロダン原子を、ｎ
はＯｌｌ又は２ｔ−示す。）で表わされる化合物及びそ
の製造方法である、 本発明の化合物は、医薬、農薬又はその中間体として有
用な３−フェニルビロール誘導体の製造用中間体として
有用である。例えば下記反応酸に示す如く、本発明化合
物をアンモニアあるいはアノモニア水と反応させること
により、殺菌剤とし”１１１３−フェニル−４−クロロ
−ビロール誘導体が得られる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound and a method for producing the same, and more specifically, the present invention relates to a novel compound and a method for producing the same.
lorkyl group, Y is a hydrogen atom or a halodane atom, n
indicates Oll or 2t-. ) and a method for producing the same The compound of the present invention is useful as an intermediate for producing 3-phenylvirol derivatives useful as medicines, agricultural chemicals, or intermediates thereof. For example, as shown in the reaction acid below, by reacting the compound of the present invention with ammonia or aqueous ammonia, a 1113-phenyl-4-chloro-pyrrol derivative can be obtained as a disinfectant.

ｔ　　ａｚ 特開昭５４−１０３８６５ （式中、！及びｎは前記と同一の意味を示す。）で表わ
されるアニリン類から容易に得られるノア、ｌニウム塩
と、一般式　０ｊＯＨ，ＯＨ＝　ＯＹ、ＣＨＯ（ＩＩ　
）（式中、Ｙ３は水嵩原子又は）・ログン原子を示゛ｔ
０）で表わされるクロトンアルデヒド類とを反応させる
ことにより製造することができる。反応は水父は含水溶
媒中触媒の存在下ｌＯ℃〜３０’Ｃで１０〜２４時間行
う。含水溶媒としてはアセトン、アセトニトリル、酢酸
等が用いられ、触媒としては塩化第二銅、美化第二銅等
が用いられる。通常のメールワイン反応と同様、本発明
の方法に於いても、前記一般式（１）で表わされるクロ
トンアルデヒド類を過剰に添加することにより収率の向
上を計ることができる。添加量はジアゾニウム塩に対し
、等モル−１０１跨モルが好ましい。t az JP 54-103865 (In the formula, ! and n have the same meanings as above.) Noah, lium salt easily obtained from anilines represented by the general formula 0jOH,OH= OY, CHO(II)
) (In the formula, Y3 represents a water bulk atom or a )・logon atom.
It can be produced by reacting with crotonaldehydes represented by 0). The reaction is carried out in a water-containing solvent in the presence of a catalyst at lO<0>C to 30<0>C for 10 to 24 hours. As the water-containing solvent, acetone, acetonitrile, acetic acid, etc. are used, and as the catalyst, cupric chloride, beautified cupric, etc. are used. As in the usual Mehlwein reaction, in the method of the present invention as well, the yield can be improved by adding an excess of crotonaldehyde represented by the general formula (1). The amount added is preferably equivalent to -101 moles relative to the diazonium salt.

反応終了後は適当な有機溶媒で、抽出し丸後、溶媒を留
去Ｉ２、残留油状物を減圧蒸留することにより、本発明
化合物を好収率で得ることができる８゜壕だ蒸Ｍ１．て
単離することなく未反応のクロトンアルデヒド類を減圧
留去した後残渣をそのまま次の反応に用いることもでき
る。After the completion of the reaction, the compound of the present invention can be obtained in good yield by extraction with an appropriate organic solvent, distilling off the solvent I2, and distilling the residual oil under reduced pressure. The unreacted crotonaldehyde can be distilled off under reduced pressure without being isolated, and the residue can be used as it is in the next reaction.

父、本発明化合物は蒸留操作において若干の熱分解が生
じ、収率が低下する恐れがあるが、反応混合物に亜硫酸
水素す）　ＩＪウムを添加することＫより本発明化合物
を亜硫酸水素ナトリウム付加体として沈醸させて、分ａ
ｔ−九後、亜硫酸水素ナトリウムを脱離し７て本発明化
合物を単離することもできる。However, the compound of the present invention undergoes some thermal decomposition during the distillation operation, which may reduce the yield. Let it settle as a minute a
After t-9, the compound of the invention can also be isolated by eliminating sodium bisulfite.

次に実施例を挙げて本発明の製造方法について−更に詳
（７〈説明する。Next, the manufacturing method of the present invention will be explained in further detail with reference to Examples.

実施例１ ａｚ　　ｏｚ ２．３−ジクロロアニリン８．２　ｆ　（０，０５モル
）、水１０ｍ及び換塩酸１５−からなる溶液に、亜硝酸
ソーダ３．８ｆを水８−に溶かした溶液を０〜２℃で滴
下した。加分間攪拌した後、枦遇してジアゾニウム塩の
水溶液とした。Example 1 A solution of 3.8 f of sodium nitrite dissolved in 8 m of water was added to a solution consisting of 8.2 f (0.05 mol) of az oz 2.3-dichloroaniline, 10 m of water, and 15 m of dichlorochloric acid. It was added dropwise at ~2°C. After stirring for an additional period of time, an aqueous solution of diazonium salt was prepared.

２．４−ジクロロクロトンアルデヒド４．７ｔ（０，０
３３モル）とアセトン加−と、塩化カリウム９．２ｆの
混合液に先に調製したジアゾニウム塩水浴液を０〜５℃
で加えた。飽和酢酸ソーダ水溶液でｐＨ２に調整し、塩
化第二銅ｌｔを加えて１５〜加ｔで１８時間反応させた
。反応終了後エーテル３０ｍｇで３回抽出し、飽和食塩
水で水洗、硫酸マグネシウムで乾燥後エーテルを留去し
た。得られた油状９ｄを蒸留して目的物４．８Ｆを得た
。2.4-dichlorocrotonaldehyde 4.7t (0,0
33 mol) and acetone, and the previously prepared diazonium salt water bath solution was added to a mixture of 9.2 f potassium chloride at 0 to 5°C.
I added it. The pH was adjusted to 2 with a saturated aqueous solution of sodium acetate, cupric chloride (lt) was added, and the mixture was reacted for 18 hours at 15 to 100 t. After the reaction was completed, the mixture was extracted three times with 30 mg of ether, washed with saturated brine, dried over magnesium sulfate, and then the ether was distilled off. The obtained oil 9d was distilled to obtain the target product 4.8F.

収率４５−１融点７６℃、沸点１４０〜１４８℃１０．
３−Ｈｆ実施例２ アニリン１．７　ｆ　（０，０１８モル）、水８−及び
濃塩酸６−からなる溶液に亜硝酸ソーダ１．３　ｆを水
４−に浴かした溶液を滴下し実施例１と一様にしてジア
ゾニウム塩水溶液を調製した。Yield 45-1 Melting point 76°C, Boiling point 140-148°C 10.
3-Hf Example 2 A solution of 1.3 f of sodium nitrite in 4- of water was added dropwise to a solution consisting of 1.7 f (0,018 mol) of aniline, 8- of water, and 6- of concentrated hydrochloric acid. A diazonium salt aqueous solution was prepared in the same manner as in Example 1.

２．４−ジクロルクロトンアルデヒド７．５ｆ（０，０
５３モル）とアセトン１８−と酢酸ソーダ１．９２の混
合液に、先に調製したジアゾニウム塩水溶液を０〜５℃
で加えた。これに塩化リチウム１．２Ｖ、塩化第二銅０
．３５　ｔを加え１５〜２０℃で１８時間反応させた。2.4-dichlorocrotonaldehyde 7.5f (0,0
53 mol), acetone 18 and sodium acetate 1.92, add the previously prepared diazonium salt aqueous solution to 0 to 5°C.
I added it. To this, lithium chloride 1.2V, cupric chloride 0
．． 35 t was added and reacted at 15 to 20°C for 18 hours.

反応液からアセトンを留去してエーテル切−で２回抽出
後、抽出液を硫酸マグネシウムで乾燥ｌ−てエーテルを
留去した。残留した油状物を蒸留し７て目的物１．９　
ｔを得た。Acetone was distilled off from the reaction solution and extracted twice with ether. The extract was dried over magnesium sulfate and the ether was distilled off. Distill the remaining oily substance to obtain the desired product 1.9
I got t.

収率４１１Ｇ、沸点９６〜９７℃７０．１５　ｗｍ　Ｈ
ｆ実施例３ ｔ ２−クロルアニリン２　Ｆ　（０，０１５６モル）、水
９ｄ及び湊塩酸６ＷＩｔからなる溶液に、亜硝酸ソーダ
１．２　Ｆを水４−に溶かした溶液を滴下し、実施例１
と一様にしてジアゾニウム塩水溶液を調製した。Yield 411G, boiling point 96-97℃ 70.15 wm H
f Example 3 A solution of 1.2 F of sodium nitrite dissolved in 4- of water was added dropwise to a solution consisting of 2-chloroaniline 2 F (0,0156 mol), 9 d of water, and 6 WIt of Minato hydrochloric acid, and 1
A diazonium salt aqueous solution was prepared in the same manner as above.

２．４−ジクロルクロトンアルデヒド６．５ｖ５．０．
０４６７モル）、アセトン１８−及び酢酸ソーダ１．７
Ｖの混合、液中に０．〜５℃で、先に調製したジアゾニ
ウム塩水溶液を加え九。これに塩化リチウム０．９ノ、
塩化第二銅０．２ｔを加え、１５〜２０℃でｎ時間反応
させた。以下実施例２と同様にして目的物２．２９を得
た。2.4-dichlorocrotonaldehyde 6.5v5.0.
0467 mol), acetone 18 and sodium acetate 1.7
Mixing of V, 0. At ~5°C, add the previously prepared diazonium salt aqueous solution. To this, lithium chloride 0.9,
0.2 t of cupric chloride was added, and the mixture was reacted at 15 to 20°C for n hours. Thereafter, in the same manner as in Example 2, target product 2.29 was obtained.

沸点１０１〜１１５℃／　ｔＪ、ｌ　ｍＨｒ、収４４９
．０　％実施例４ ２−ニトロアニリン２．３　ｆ　（０，０１６モル）、
水９１、濃塩酸６−からなる浴液Ｋ、亜硝酸ソーダ１．
２　ｔを水４ｄに溶がした溶液を滴下し、実施例１と同
様に［７て・ノアゾニウム塩水浴液を調製しり、。Boiling point 101-115℃/tJ, l mHr, yield 449
．． 0% Example 4 2-nitroaniline 2.3 f (0,016 mol),
Bath solution K consisting of 91 parts of water, 6 parts of concentrated hydrochloric acid, 1 part of sodium nitrite.
A solution of 2t dissolved in 4d of water was added dropwise, and a noazonium salt bath solution was prepared in the same manner as in Example 1.

２．４−・ジクロルクロトンアルデヒド６．７２（（１
，０４８２モル）とアセトン１８ｓ＋ｔと酢酸ソーダ１
．７１の混合液中に、先に調製したジアゾニウム塩水溶
液を０〜５℃で加えた。これに塩化リチウムｌｔ及び塩
化俯二鋼０．３　ｖを加え１５〜２０℃でｎ時間反応さ
せた。2.4-dichlorocrotonaldehyde 6.72 ((1
,0482 mol), acetone 18s+t, and sodium acetate 1
．． The previously prepared diazonium salt aqueous solution was added to the mixture of No. 71 at 0 to 5°C. To this, lithium chloride lt and 0.3 v of chlorinated steel were added, and the mixture was reacted at 15 to 20°C for n hours.

以下実施例２と同様圧して目的物１４１を得た。Thereafter, the same pressure as in Example 2 was applied to obtain the target object 141.

沸点１５５〜１６８℃／２■Ｈｆ、収率３１慢実施例５ ２−アミノペンシトリフルオライド２．６ｔ（０，ＯＬ
６モルラ、水９−及び濃塩酸６−から彦る耐液に、亜硝
酸ソーダ１．２ｔを水４−に溶かした溶液を滴下し、実
施例１と同様にしてジアゾニウム塩水溶液を調製した。Boiling point 155-168°C/2■Hf, yield 31% Example 5 2-aminopencitrifluoride 2.6t (0,OL
A diazonium salt aqueous solution was prepared in the same manner as in Example 1 by adding dropwise a solution of 1.2 t of sodium nitrite dissolved in 4 mol of water to a liquid containing 6 mol of water, 9 ml of water, and 6 ml of concentrated hydrochloric acid.

２．４−ジクロルクロトンアルデヒド６．７ｔ（０，０
４８２モル）とアセトン１８　ｍ　、酢酸ソーダ２ｖの
混合液中に、先に調製したジアゾニウム塩水溶液を０〜
５℃で加えた。これに塩化リチウム１を及び塩化第二銅
０．３ｔを加え、１５〜２０℃で１８時間反応させた１
、 以下実施例２と同様にして目的物２．３ｆを得た。１収
率４５．１　％　、沸点９３〜９７℃１０．３ｗＨｆ’
実施例６ ２．３−ノクロロアニリン４．１　ｔ　（０，０２５モ
ル）、水５−および濃塩酸７．５−からなる溶液に亜硝
酸ソーダ１．９ｆを水４−に溶がした溶液を０〜２℃で
滴下した。そのままの温度でｍ分間攪拌した後、濾過し
てノアゾニウム塩の水溶液とした。このジアゾニウ′ム
塩の水溶液を２，４−ノクロロクロトンアルデヒド３４
．７５　ｆ　（０，２５％　ル）、アセト７５　ｍ。2.4-dichlorocrotonaldehyde 6.7t (0,0
482 mol), acetone 18 m, and sodium acetate 2 v, add the previously prepared diazonium salt aqueous solution from 0 to
Added at 5°C. 1 of lithium chloride and 0.3 t of cupric chloride were added to this and reacted at 15 to 20°C for 18 hours.
Then, in the same manner as in Example 2, a target object 2.3f was obtained. 1 yield 45.1%, boiling point 93-97℃ 10.3wHf'
Example 6 A solution of 1.9 f of sodium nitrite dissolved in 4 of water in a solution consisting of 4.1 t (0,025 mol) of 2.3-nochloroaniline, 5 of water, and 7.5 of concentrated hydrochloric acid. was added dropwise at 0 to 2°C. After stirring for m minutes at the same temperature, the mixture was filtered to obtain an aqueous solution of noazonium salt. This aqueous solution of diazonium salt was dissolved in 2,4-nochlorocrotonaldehyde 34
．． 75 f (0,25% le), acetate 75 m.

塩化カリウム１．８６　ｆ　（ｔ）、０２５モル）の混
合物の中に０〜５℃で加え、飽和酢酸ソーダ水溶液でｐ
Ｈを４．１に調整した後、塩化第二銅０．５　Ｆ　（０
，００３７モル）を加えて１５〜２０℃で５時間反応さ
せた。反応終了後、エーテル３０−で３回抽出し、エー
テル抽出液を飽和食塩水３０−で２回水洗後硫酸マグネ
シウムで乾燥後エーテルを留去し、油状物の蒸留により
４．６５　Ｆの２．２．４−トリクロロ−３−（２，３
−ノクロロフェニル）プチルアルデヒ）’　（Ｋｐ　１
４０〜１４８℃７０．３　ＨＰ、　ｍｐ　７６℃）が得
られた。Potassium chloride (1.86 f(t), 025 mol) was added at 0 to 5°C, and p.
After adjusting H to 4.1, cupric chloride 0.5 F (0
,0037 mol) was added thereto and reacted at 15 to 20°C for 5 hours. After the reaction was completed, extraction was carried out three times with 30-mL ether, the ether extract was washed twice with 30-mL saturated brine, dried over magnesium sulfate, the ether was distilled off, and the oil was distilled to give 4.65 F. 2,4-trichloro-3-(2,3
-nochlorophenyl)butyraldehy)' (Kp 1
40-148°C 70.3 HP, mp 76°C) was obtained.

収率ＳＳＳ 本発明化合物の代表例を第１表に示す。Yield SSS Representative examples of the compounds of the present invention are shown in Table 1.

第１表Table 1

Claims (2)

【特許請求の範囲】[Claims] （１）　　一般式 （式中、Ｘは・・ロダン原子、ニトロ基又は・・ロアル
キル基を、ｎは０、ｌ又は２を、Ｙは水素原子父は・・
ロダン原子を示す。）で表わされる化合物。(1) General formula (wherein, X is a rodan atom, a nitro group, or a loalkyl group, n is 0, l or 2, Y is a hydrogen atom, and the parent is...
Showing a Rodan atom. ). （２）一般式 （式中、Ｘは）・ロダン原子、ニトロ基又はノ・ロアル
キル基を、ｎは０、ｌ又は２を、Ｙｌはハロｒ／原子を
示す。）で表わされる化合物（式中、！、は水素原子又
はハロダン原子を示す。）で表わされるクロトンアルデ
ヒド類と反応させることを特徴とする一般式 （式中、Ｘ及びｎは前記と同一の意味を示し、Ｙは水素
原子又は塩素原子を示す。）で表わされる化合物の製造
方法。(2) General formula (wherein, X represents) a rhodane atom, a nitro group or a no-roalkyl group, n represents 0, 1 or 2, and Yl represents a halo r/atom. ) (wherein, ! represents a hydrogen atom or a halodane atom). and Y represents a hydrogen atom or a chlorine atom).