JPS58170743A

JPS58170743A - Novel amide derivative

Info

Publication number: JPS58170743A
Application number: JP5125682A
Authority: JP
Inventors: Makoto Takeda; 真武田; Mitsumasa Minafuji; 皆藤　光雅
Original assignee: Mitsubishi Petrochemical Co Ltd
Current assignee: Mitsubishi Petrochemical Co Ltd
Priority date: 1982-03-31
Filing date: 1982-03-31
Publication date: 1983-10-07

Abstract

NEW MATERIAL:The compound of formula I (X is Cl or Br). EXAMPLE:2-Cyanoethyl-2,3-dibromopropionamide. USE:Disinfectant, antiseptic, herbicide, etc. and their intermediates. PROCESS:The compound of formula 1 can be prepared by the addition reaction of Cl or Br to the double bond of the novel 2-cyanoethylacrylamide of formula 2. The addition reaction is carried out using a halogenated hydrocarbon (e.g. chloroform, dichloromethane, etc.) or water as the solvent. When the former compound is used as the solvent, the side reactions are suppressed; however, the use of the latter compound may cause the hydrolysis of amide. The novel compound of formula 2 can be prepared by reacting 2-methyleneglutaronitrile of formula 3 with hydrogen peroxide in an alkaline aqueous solution in the presence of sodium tungstate.

Description

【発明の詳細な説明】本発明は、次の一般式（１）で表わされるｌ−シアノエ
チル−２，３−ジハロプロピオンアミドに関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to l-cyanoethyl-2,3-dihalopropionamide represented by the following general formula (1).

ＨｇＸＨ！　ＮＯＣＣ−ＣＨｍ　ＣＨｘ　−ｃＮ　　　　（１
）〔式中、ｘｈ塩素または臭素を表わす、〕本発明化合
物は、文献未記載の新規化合物であり、殺菌剤、防腐剤
、除草剤等として、あるいはそれらの中間体として有用
なものである。HgX H! NOCC-CHm CHx-cN (1
) [where xh represents chlorine or bromine] The compound of the present invention is a novel compound not described in any literature, and is useful as a fungicide, preservative, herbicide, etc., or as an intermediate thereof.

本発明化合物は、例えば次のような方法で製造すること
ができる。The compound of the present invention can be produced, for example, by the following method.

（１）−（１）１式中、Ｘは前記と同じ〕即ち、２−シアノヱチルアクリルアミド（２）の二重結
合部分に塩素または臭素を付加することＫより得るヒと
が出来る。(1)-(1) In formula 1, X is the same as above] That is, the compound obtained from K can be obtained by adding chlorine or bromine to the double bond portion of 2-cyanoethyl acrylamide (2).

上記のハロゲン付加反応は、クロロホルム、ジクロルメ
タン郷のハロゲン化脚化水素または水を溶媒として行わ
れる。前者を溶媒とする場合は、副反応なし、高収率？
Ｉｉ的物（１）を得ることが出来る。後者を溶媒とする
場合はアミドの加水分解の副反応が起る場合がある。The above halogen addition reaction is carried out using chloroform, dichloromethane, hydrogen halogenide, or water as a solvent. If the former is used as a solvent, will there be no side reactions and high yield?
Ii property (1) can be obtained. When the latter is used as a solvent, a side reaction of amide hydrolysis may occur.

上記反応の出発物質（吟も新規化合物であるが、既に本
発明者勢Ｆｉ特顧［５＠−１４０７１４号として、出願
済みでろ抄、そこで開示した通ね、下記の式で示す方法
によ抄合成される。Although the starting material for the above reaction (Gin) is also a new compound, it has already been filed as a special report by the present inventors as Fi. be synthesized.

即ち、２−メチレンゲルタロニトリルをタンクステン酸
ナトリウムの存在下、アルカリ水溶液中で、過駿化水素
と反応させることＫよね得られる。That is, it can be obtained by reacting 2-methylene geltalonitrile with hydrogen perhydrogen in the presence of sodium tankstate in an alkaline aqueous solution.

次に実施例をあげて本発明を具体的に示す。Next, the present invention will be specifically illustrated with reference to Examples.

５００Ｈの反応器に２−シアノエチルアクリルアミド１
．Ｏｆ　（８，１ｍｍｏｊ）、りｏロホルＡｌ０ＣＣを
入れ、６０℃で攪拌し、これに臭素１．４　ｆ　（８，
８ｖｎｖｍＯ１）を滴下した。滴下終了１１．６０Ｃで
さらに１時間攪拌した後、放冷し、溶液を濃縮して淡褐
色粘稠液体２．１２を得た。：カラムクロマトグラフイ
ーによる精製で、２−シアノエチル−２，３−ジブロム
プロピオンアミド１．９　Ｆ　（６，７ｖｍｍｏｌ　）
を白色結晶として得た。（収率８３慢）本化合物融点：
　ｓ　４．５〜９６．ＯＣＩＲ（ＫＢｒ）：３４５０，３３２０，３０２０゜２９
５０．２２４５，１６８０゜１５９０．１４３５，１３７５゜１２２０．１０１５，７４０ｍ−１ＮＭＲ：　　　ａ　　　（ＣＤ　　　Ｃ１ｍ　　）２．
１−２．９　　　（ｓ＊、　　　４Ｉ（、ＣＨ意　　Ｃ
Ｈｘ　　　　）３．９　　　（ｓ、　　２Ｈ，−ＣＨｘ
　　Ｂｒ　）６．１−７．０　（ｂｍ、　２　Ｈ，−Ｃ
ｏｇ　ＮＨ＊　）ＭｊＬ！Ｉｌｌ　　：鍋／・（相対強
ｆ）２０５（２，６）、２０３（２，６，Ｍ”−ＢＦ）
。2-cyanoethyl acrylamide 1 in a 500H reactor
．． Of (8,1 mmoj), Riophorol Al0CC was added, stirred at 60°C, and 1.4 f of bromine (8,
8vnvmO1) was added dropwise. After the addition was completed, the mixture was stirred for an additional 1 hour at 11.60C, allowed to cool, and the solution was concentrated to obtain a pale brown viscous liquid 2.12. : 2-cyanoethyl-2,3-dibromopropionamide 1.9 F (6,7 vmmol) was purified by column chromatography.
was obtained as white crystals. (Yield 83%) Melting point of this compound:
s 4.5-96. OC IR (KBr): 3450, 3320, 3020°29
50.2245,1680°1590.1435,1375°1220.1015,740m-1 NMR: a (CD C1m)2.
1-2.9 (s*, 4I(, CH i C
Hx ) 3.9 (s, 2H, -CHx
Br)6.1-7.0 (bm, 2H, -C
og NH* ) MjL! Ill: Pot/・(relative strength f) 205 (2, 6), 203 (2, 6, M”-BF)
.

５６２（ＴＯ）、１６０（Ｔｏ）、８０　（８０）。562 (TO), 160 (To), 80 (80).

５３（１００）、４４（１１３）、４１（５２）ｓｏｃ
ｃの反応器に２−シアンエチルアクリルアミド３．０ｆ
（２４，２ｍ調・ｔ）、クロロホルム２０ｓｇｔ−入れ
、５５〜６０℃で攪拌し、これに塩素ガスをゆつくりと
１時間吹き込んだ、放冷後、溶液を濃縮して無色透明粘
稠液体５．２２を得、これをカラムクロマトグラフィー
で精製して、２−シアノエチル−２，３−ジクロルゾロ
ビオンアミド３．４ｆ　（１７，４密ｍｏｌ）を白色結
晶として得た。（収率７２％）本化合物の物性値は次の
通りである。53 (100), 44 (113), 41 (52) soc
3.0f of 2-cyanoethyl acrylamide in the reactor c.
(24.2 m/t), 20 sgt of chloroform was added, stirred at 55 to 60°C, and chlorine gas was slowly blown into this for 1 hour. After cooling, the solution was concentrated to form a colorless transparent viscous liquid. .22 was obtained, and this was purified by column chromatography to obtain 2-cyanoethyl-2,3-dichlorozolobionamide 3.4f (17,4 mol) as white crystals. (Yield: 72%) The physical properties of this compound are as follows.

融点：　６２．５〜６４．２℃ ＩＲ（ＫＢｒ）：３４４５，３３１０，３０００゜２９
５０．２２５０，１６７５゜１５８０．１４４０．１３８５゜１２７０．１０３５．７４０ｍ　’ ＮＭＲ：　Ｊ　（ＣＤ　ＣＬｓ　）２．１−Ｌ９いｍ、　　４　Ｈ，−ＣＨ意−ＣＨ意−）
３．９　　　（ｄｄ、　２　Ｈ，−ＣＨ雪Ｃｔ）６．４
−７．２　　　（ｂｓ、　　２　　Ｈ，−ＣＯＮＨ意　
　）Ｍａｓｍ　　：　ｍ　／　ｅ　（相対強度）１６０
（０，４）、１５９（１，２，Ｍ＋−Ｃｔ）。Melting point: 62.5-64.2°C IR (KBr): 3445, 3310, 3000°29
50.2250,1675゜1580.1440.1385゜1270.1035.740m' NMR: J (CD CLs) 2.1-L9m, 4H, -CH -CH -)
3.9 (dd, 2 H, -CH snow Ct) 6.4
-7.2 (bs, 2 H, -CONH)
) Masm: m/e (relative intensity) 160
(0,4), 159(1,2,M+-Ct).

１５５　（０，７）、１５３（４，０）、１５１（６，
２）。155 (0,7), 153 (4,0), 151 (6,
2).

１１８（１５）、１１７（３３）、１１６（４？）。118 (15), 117 (33), 116 (4?).

１１５（１００）、８０（１５）、？？（１２）。115 (100), 80 (15),? ? (12).

Claims

[Claims] A cyanethyl-2,3-dihalopropionamide represented by the general formula %, where XFi represents chlorine or bromine.