JPS5821902B2 - Alpha cyclopropane carbonate ester - Google Patents
Alpha cyclopropane carbonate esterInfo
- Publication number
- JPS5821902B2 JPS5821902B2 JP1991775A JP1991775A JPS5821902B2 JP S5821902 B2 JPS5821902 B2 JP S5821902B2 JP 1991775 A JP1991775 A JP 1991775A JP 1991775 A JP1991775 A JP 1991775A JP S5821902 B2 JPS5821902 B2 JP S5821902B2
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- Prior art keywords
- acid ester
- general formula
- represented
- monosubstituted
- ethyl
- Prior art date
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Description
【発明の詳細な説明】
本発明は一般式
（式中Ｒ，Ｒ１、Ｒ２及びＲ３は低級アルキル基であり
、Ｘは同−又は異なるハロゲンである。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (where R, R1, R2 and R3 are lower alkyl groups, and X is the same or different halogens).
）で表わされるα一置換シクロプロパンカルボン酸エス
テルの製造方法に関するものである。) The present invention relates to a method for producing an α-monosubstituted cyclopropanecarboxylic acid ester represented by:
更に詳しくは本発明は一般式
（式中Ｒ，Ｒ”、Ｒ２及びＲ３は低級アルキル基であり
、Ｘはハロゲンであり、４個のＸは同一あるいは異なる
ものでもよい。More specifically, the present invention relates to the general formula (where R, R'', R2 and R3 are lower alkyl groups, X is a halogen, and the four X's may be the same or different.
）で表わされるα−置換−γ−ハロカルボン酸エステル
を塩基で処理することを特徴とする、前記一般式（Ｉ）
で表わさレルα一置換シクロプロパンカルボン酸エステ
ルを製造する方法並びに一般式
（式中Ｒ，Ｒ”、Ｒ２及びＲ３は低級アルキル基である
。) The α-substituted-γ-halocarboxylic acid ester represented by formula (I) is treated with a base.
A method for producing a monosubstituted cyclopropane carboxylic acid ester represented by the general formula (where R, R'', R2 and R3 are lower alkyl groups).
）で表わされるα一置換−γ−不飽和カルボン酸エステ
ルに四ハロゲン化炭素をラジカル反応条件下付加させて
形成せる前記一般式（ｎ）で表わされるｒ−ハロカルボ
ン酸エステルを塩基で処理することを特徴とする、前記
一般式（Ｉ）で表わされるα（換シクロプロパンカルボ
ン酸エステルを製造する方法に関するものである。) Treating the r-halocarboxylic acid ester represented by the general formula (n), which is formed by adding carbon tetrahalide to the α-monosubstituted-γ-unsaturated carboxylic acid ester represented by the formula (n), under radical reaction conditions, with a base. The present invention relates to a method for producing an α(substituted cyclopropanecarboxylic acid ester) represented by the general formula (I), which is characterized by the following.
前記一般式（Ｉ）で表わされるα一置換シクロプロパン
カルボン酸は、殺虫剤としてその有用性が注目されてい
る合成ピレスロイド系化合物の酸部分を構成する単位で
ある。The α-monosubstituted cyclopropanecarboxylic acid represented by the general formula (I) is a unit constituting the acid moiety of a synthetic pyrethroid compound that is attracting attention for its usefulness as an insecticide.
従来、殺虫剤としてはＤＤＴやＢＨＣが使用されて来た
が、その残留毒性の故に無公害性の殺虫剤が強く要望さ
れているのが現状である。Conventionally, DDT and BHC have been used as insecticides, but due to their residual toxicity, there is currently a strong demand for non-polluting insecticides.
この観点から古くより天然物から抽出し使用されて来た
ピレスロイドがその低公害及び殺虫能力の故に新たに注
目を集めている。From this point of view, pyrethroids, which have been extracted from natural products and used since ancient times, are newly attracting attention due to their low pollution and insecticidal ability.
天然ピレスロイド系殺虫剤の使用上の欠陥は生分解が早
い点にある。A disadvantage in the use of natural pyrethroid insecticides is that they biodegrade quickly.
この欠点を解決すべく多くの化合物がテストされた結果
、２一位にジハロビニル基を持つシクロプロパンカルボ
ン酸エステルが持続性のある優れた殺虫効果を示すこと
が明らかとなった。As a result of testing many compounds to solve this drawback, it became clear that a cyclopropanecarboxylic acid ester having a dihalobinyl group at the 21-position exhibits a long-lasting and excellent insecticidal effect.
ＣＭ。Ｅｌｌｉｏｔｔ ｅｔ ａｌ 、、Ｎａｔｕｒｅ
１２４６．１６９（１９７３）、ｌ。CM. Elliott et al., Nature
1246.169 (1973), l.
一方、シクロプロパンカルボン酸の１一位に単純な置換
基を導入した場合、置換基を持たない場合に比べ殺虫効
果が増大されることも知られている。On the other hand, it is also known that when a simple substituent is introduced at the 11-position of cyclopropanecarboxylic acid, the insecticidal effect is increased compared to when there is no substituent.
本発明者等は斯様な点を考慮し２一位にジノ・ロビニル
基及び１一位に置換基を有するシクロプロパンカルボン
酸エステルが理想的殺虫剤と成り得ることを期待し、そ
の製造方法について検討を重ねて来た。Considering these points, the present inventors expected that a cyclopropanecarboxylic acid ester having a dino-rovinyl group at the 21st position and a substituent at the 11th position could be an ideal insecticide, and developed a method for producing the same. I've been thinking about it a lot.
本発明はこの目的に合致した新規なジハロビニル基ヲ持
つα一置換シクロプロパンカルボン酸エステルの新規な
製造方法を提供するものである。The present invention provides a novel method for producing an α-monosubstituted cyclopropane carboxylic acid ester having a novel dihalobinyl group that meets this objective.
従来、１一位に置換基を持つシクロプロパンカルボン酸
エステルの合成法としては２一位に各種の置換基を導入
した３・３−ジメチルシクロプロパンカルボン酸エステ
ルを出発物質とする方法〔特開昭４９−７２２３７号参
照〕が提案されている。Conventionally, as a method for synthesizing cyclopropanecarboxylic acid ester having a substituent at the 11-position, a method using a 3,3-dimethylcyclopropanecarboxylic acid ester with various substituents introduced at the 21-position as a starting material [JP-A [See No. 72,237/1972] has been proposed.
しかし、この従来法は原料化合物を得るために高価な葉
酸を用いることおよび合成経路が長く煩雑である等の欠
点がある。However, this conventional method has drawbacks such as the use of expensive folic acid to obtain the raw material compound and the long and complicated synthetic route.
本発明の方法は原料として前記一般式（■）で表わされ
るα−置換−γ−ハロカルボン酸エステル及び前記一般
式（ＩＩＩ）で表わされるα−置換−γ−不飽和カルボ
ン酸エステルを用いるものである。The method of the present invention uses an α-substituted-γ-halocarboxylic acid ester represented by the above-mentioned general formula (■) and an α-substituted-γ-unsaturated carboxylic acid ester represented by the above-mentioned general formula (III) as raw materials. be.
このα−置換−γ−不飽和カルボン酸エステルは例えば
アリルアルコール誘導体とオルトカルボン酸エステルを
反応させることにより容易に製造出来る（下記参考側参
照）。This α-substituted-γ-unsaturated carboxylic acid ester can be easily produced, for example, by reacting an allyl alcohol derivative with an orthocarboxylic acid ester (see the reference side below).
又他方の出発物質である四ハロゲン化炭素としては四塩
化炭素、四臭化炭素、−臭化三塩化炭素、三臭化二塩化
炭素、−沃化三フツ化炭素等を例示することができる。Examples of the carbon tetrahalide which is the other starting material include carbon tetrachloride, carbon tetrabromide, -carbon trichloride bromide, carbon tribromide dichloride, -carbon trifluoride iodide, etc. .
本発明は、前記一般式（Ｉ［）で表わされるα一置換−
γ−ハロカルボン酸エステルを塩基で処理することを必
須要件とするものである。The present invention provides α-monosubstituted −
It is an essential requirement that the γ-halocarboxylic acid ester be treated with a base.
塩基としては水酸化ナトリウム、水酸化カリウム等のア
ルカリ金属水酸化物、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−ブレキシド等のアルカリ金
属アルコキシド、水酸化ナトリウム等のアルカリ金属ハ
イドライド、ナトリウムアミド等のアルカリ金属アミド
、１・５−ジアザビシクロ〔３・４・０〕ノネン−５（
ＤＢＮ）、ナフタレンナトリウム、トリエチルアミン等
を例示することができるが、反応効率が高い点で水素化
ナトリウム又はアルカリ金属アルコキシドの使用が好ま
しい。Examples of bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-brexide, alkali metal hydrides such as sodium hydroxide, and alkalis such as sodium amide. Metal amide, 1,5-diazabicyclo[3.4.0]nonene-5 (
DBN), naphthalene sodium, triethylamine, etc., but sodium hydride or alkali metal alkoxide is preferably used because of its high reaction efficiency.
塩基の使用量は原料に対して１．５モル当量以上、好ま
しくは２モル〜５モル当量である。The amount of the base used is 1.5 molar equivalents or more, preferably 2 to 5 molar equivalents, based on the raw material.
この塩基処理工程の反応は溶媒中で行なうのが好ましく
溶媒としてはメタノール、エタノール、ｔ−ブタノール
等のアルコール、エーテル、テトラヒドロフラン、ジメ
トキシエタン等のエーテル類、ベンゼン、トルエン等の
芳香族炭化水素類、Ｎ−Ｎ−ジメチルホルムアミド（Ｄ
ＭＦ’）等を例示することが出来る。The reaction in this base treatment step is preferably carried out in a solvent, such as alcohols such as methanol, ethanol and t-butanol, ethers such as ether, tetrahydrofuran and dimethoxyethane, aromatic hydrocarbons such as benzene and toluene, N-N-dimethylformamide (D
MF') etc. can be exemplified.
反応温度として＋ｉ、室温乃至溶媒の還流温度が操作が
容易である観点から好ましい。The reaction temperature is preferably +i, room temperature or the reflux temperature of the solvent from the viewpoint of ease of operation.
又、本発明のα−置換−ｒ−不飽和カルボン酸エステル
と四・・ロゲン化炭素との反応はラジカル反応条件下で
行なうことを必須要件とするものである。Further, it is essential that the reaction between the α-substituted-r-unsaturated carboxylic acid ester and the tetra-logenated carbon of the present invention be carried out under radical reaction conditions.
ラジカル反応条件とゆラジカル反応開始剤を存在せしめ
るか又は光を照射することによって達成できるものであ
る。This can be achieved by radical reaction conditions and the presence of a radical reaction initiator or by irradiation with light.
ラジカル反応開始剤としては、アゾビスイソブチロニト
リル（ＡＩＢＮ）、過酸化ベンゾイル（ＢＰＯ）、過酸
化アセチル、過酸化ジ−ｔ−ブチル、過酢酸を一ブチル
、過安臭香酸ｔ−ブチル、過フタール酸ｔ−ブチル、ｔ
−ブチルハイドロパーオキシドを例示することが出来る
。Radical reaction initiators include azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), acetyl peroxide, di-t-butyl peroxide, monobutyl peracetic acid, and t-butyl perbenbrozoate. , t-butyl perphthalate, t
-Butyl hydroperoxide can be exemplified.
これらのラジカル反応開始剤はいわゆる接触量用いれば
充分である。It is sufficient to use a so-called contact amount of these radical reaction initiators.
反応にあっては原料化合物を等モル用い、溶媒は特に必
要としないが、所望ならば反応に直接関与しない溶媒、
例えば二硫化炭素あるいはベンゼン等の炭化水素系溶媒
を用いてもよい。In the reaction, equimolar amounts of starting compounds are used, and no solvent is particularly required, but if desired, a solvent that does not directly participate in the reaction,
For example, a hydrocarbon solvent such as carbon disulfide or benzene may be used.
又、四塩化炭素の如き液状物質をハロダン什済りとして
用いる場合にはそれ自体を多量に用いて反応を行なうこ
とが出来る。Further, when a liquid substance such as carbon tetrachloride is used as the halodane, a large amount of the substance itself can be used to carry out the reaction.
ラジカル反応開始法として光を用いる場合には室温乃至
１００°Ｃ１その他のラジカル開始剤を用いる場合には
７０°Ｃ〜１５０℃で反応を行なうのが好ましい。When light is used as a radical reaction initiation method, the reaction is preferably carried out at room temperature to 100°C, and when other radical initiators are used, the reaction is preferably carried out at 70°C to 150°C.
以下実施例及び参考例により本発明を更に詳細に説明す
る。The present invention will be explained in more detail below using Examples and Reference Examples.
実施例 １
２・３・３−１−ＩＪメチル−４−ペンテン酸エチル１
．７（１（０，０１モル）を−臭化三塩化炭素５ｍｌに
溶解し、過酸化ベンゾイル５０１ｎ９を加え、アルゴン
雰囲気下油浴を１３０℃に加熱し、激しく還流を続ける
。Example 1 Ethyl 2.3.3-1-IJ methyl-4-pentenoate 1
．． 7 (1 (0.01 mol)) is dissolved in 5 ml of carbon trichloride bromide, benzoyl peroxide 501n9 is added, the oil bath is heated to 130° C. under an argon atmosphere, and vigorous reflux is continued.
１０時間後過剰の一臭化三塩化炭素を留去し、減圧蒸留
により沸点１１５〜１２０℃／ ０．５ ｍｍＨｇを有
する２−３−３−）ジメチル−４−ブロモ−５−トリク
ロロメチル吉草酸エチルを３．０１得た。After 10 hours, excess carbon monobromide trichloride was distilled off, and 2-3-3-)dimethyl-4-bromo-5-trichloromethylvaleric acid having a boiling point of 115-120°C/0.5 mmHg was obtained by distillation under reduced pressure. 3.01 ethyl was obtained.
収率８１％。生成物のＮＭＲ（δ ＣＣｌ４）： ４．
６０〜３．８０ （ｍ、’３Ｉ（）、３．７０〜３．１
０ （ｍ。Yield 81%. NMR of product (δ CCl4): 4.
60-3.80 (m, '3I(), 3.70-3.1
0 (m.
２Ｈ）、３．１０〜２．７０ （ｍ、ＬＨ）、１．６０
〜０．９５ （ｍ、 １２Ｈ）。2H), 3.10-2.70 (m, LH), 1.60
~0.95 (m, 12H).
実施例 シ
２・３・３−Ｈメチル−４−ペンテン酸エチル１．３６
Ｐ（８ミＩＪモル）を四塩化炭素２０ｒｎｌに溶解し、
耐圧管に入れ、過酸化ベンゾイル５０〜を加え、アルゴ
ン置換したのち密栓し、油浴を１３０〜１４０℃に加熱
する。Example Ethyl 2-3-3-H methyl-4-pentenoate 1.36
Dissolve P (8 mmol) in 20rnl of carbon tetrachloride,
The tube is placed in a pressure-resistant tube, and 50~50% of benzoyl peroxide is added thereto, the atmosphere is replaced with argon, the tube is sealed tightly, and the oil bath is heated to 130-140°C.
その後５時間毎に過酸化ベンゾイル５０〜を加え、合計
２０時間加熱したのち、冷却し炭酸水素ナトリウム水溶
液、更に食塩水で洗浄し、乾燥する。Thereafter, 50~ of benzoyl peroxide was added every 5 hours, and after heating for a total of 20 hours, the mixture was cooled, washed with an aqueous sodium bicarbonate solution, and further with brine, and dried.
溶媒留去後、減圧蒸留により沸点１０６〜１０７°ｃ
／ ０．３ ｍｒＩＬＨｇを示す油状体として、２・３
・３−トリメチル−４−クロロ−５−トリクロロメチル
吉草酸エチルを１，８１１得た。After distilling off the solvent, the boiling point is 106-107°C by distillation under reduced pressure.
/ 0.3 mrILHg as an oily body, 2.3
- 1,811 ethyl 3-trimethyl-4-chloro-5-trichloromethylvalerates were obtained.
収率７０％。生成物のＮＭＲ（δ ＣＣｌ４）： ４．
４３〜３．８５ （ｍ、 ３Ｈ）、３．４５〜３．０
０ （ｍ１２Ｈ）、２．９７〜２．６３ （ｍ１１ Ｈ
）、１．３５０．９５ （ｍ、 １２Ｈ）。Yield 70%. NMR of product (δ CCl4): 4.
43-3.85 (m, 3H), 3.45-3.0
0 (m12H), 2.97-2.63 (m11H
), 1.350.95 (m, 12H).
実施例 ３
実施例２の操作により得られた２・３・３−トリメチル
−４−クロロ−５−トリクロロメチル吉草酸エチル１．
３Ｐ（４ミリモル）の無水ジメトキシエタン５ｍｌ溶液
を水素化ナトリウム５００〜（５０％、１０ミリモル）
を分散させた無水ジメトキシエタン１５７ｄに滴下する
。Example 3 Ethyl 2,3,3-trimethyl-4-chloro-5-trichloromethylvalerate obtained by the procedure of Example 21.
A solution of 3P (4 mmol) in 5 ml of anhydrous dimethoxyethane was added to 500 ~ (50%, 10 mmol) of sodium hydride.
is added dropwise to 157d of anhydrous dimethoxyethane in which it is dispersed.
終了後、加熱還流を２０時間続け、冷却する。After completion, heating under reflux is continued for 20 hours and then cooled.
希塩酸で中和したのちエーテル抽出し、食塩水で洗浄し
乾燥する。After neutralizing with dilute hydrochloric acid, extract with ether, wash with brine, and dry.
溶媒留去後、減圧蒸留により沸点７１〜７６℃１０、０
８ ｍｍＨｇを有する１−メチル−２−（２−２−ジク
ロロビニル）−３・３−ジメチルシクロプロパンカルボ
ン酸エチル５５０ｍｇを得た。After distilling off the solvent, reduce the boiling point to 71-76℃10.0 by distillation under reduced pressure.
550 mg of ethyl 1-methyl-2-(2-2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate having 8 mmHg was obtained.
収率５５％。Yield 55%.
生成物のＮＭＲ（δ ＣＣｌ４）： ６．２６．５−５
７ （ｄ、ＬＨ）、４．１０（ｂ、ｑｌ、２Ｈ）、２．
２８．１．５２（ｄ、ＩＨ）、１．４０〜０．９０（ｍ
、１２Ｈ）。NMR of product (δ CCl4): 6.26.5-5
7 (d, LH), 4.10 (b, ql, 2H), 2.
28.1.52 (d, IH), 1.40-0.90 (m
, 12H).
実施例 ４
実施例１の操作により得られた２・３・３−トリメチル
−４−ブロモ−５−トリクロロメチル吉草酸エチル３６
８．５Ｉｎ９（１ミ１，１モル）の無水テトラヒドロフ
ラン１ｒｒＬｌ溶液をカリウムｔ−ブトキシド２２４７
７２９（２ミＩＪモル）を懸濁させた無水テトラヒドロ
フラン１０ｒｒＬｌ溶液に滴下し、終了後５時間加熱還
流する。Example 4 Ethyl 2,3,3-trimethyl-4-bromo-5-trichloromethylvalerate 36 obtained by the procedure of Example 1
A solution of 8.5 In9 (1 mol) in 1 rr Ll of anhydrous tetrahydrofuran was dissolved in 2247 ml of potassium t-butoxide.
729 (2 mmol) was added dropwise to a 10 rr Ll solution of anhydrous tetrahydrofuran, and after completion of the addition, the mixture was heated under reflux for 5 hours.
その後氷水にあげエーテル抽出し乾燥する。Then, it is placed in ice water, extracted with ether, and dried.
溶媒留去後、減圧蒸留により１−メチル−２−（２・２
−ジクロロビニル）−３・３−ジメチルシクロプロボン
カルボン酸エチル５５〜を得た。After distilling off the solvent, 1-methyl-2-(2.2
-dichlorovinyl)-3,3-dimethylcycloprovonecarboxylic acid ethyl 55~ was obtained.
生成物のＮＭＲは実施例３で得られた生成物のＮＭＲと
一致した。The NMR of the product was consistent with that of the product obtained in Example 3.
収率２２％。参考例 １
３−メチル−２−ブテン−１−オール３．４４１（０，
０４モル）とオルトプロピオン酸エチル１４．０８′ｙ
（０，０８モル）を混合しフェノール０．３５？を加え
、１４０℃に加熱する。Yield 22%. Reference example 1 3-methyl-2-buten-1-ol 3.441 (0,
04 mol) and ethyl orthopropionate 14.08'y
(0.08 mol) and phenol 0.35? and heat to 140°C.
生成するエタノールを留去しながら２４時間加熱攪拌を
続ける。Continue heating and stirring for 24 hours while distilling off the ethanol produced.
冷却後減圧下過剰のオルトプロピオン酸エチルを留去し
た後、減圧蒸留を行ない、沸点９０〜ｂ
−４−ペンテン酸エチル４．７６ Ｐを得た。After cooling, excess ethyl orthopropionate was distilled off under reduced pressure, and then vacuum distillation was performed to obtain 4.76 P of ethyl orthopropionate with a boiling point of 90 to b -4-pentenoate.
収率７０％。Yield 70%.
核磁気共鳴吸収（δ ＣＣｌ４）：６゜１０〜５．５５
（ｍ、 Ｌ Ｈ）、５．１０〜４．７０ （ｍ。Nuclear magnetic resonance absorption (δ CCl4): 6°10-5.55
(m, L H), 5.10-4.70 (m.
２Ｈ）、４．０５ （ｑ１２ Ｈ）、２．２５（ｑｌｌ
Ｈ）、１．２２（ｔ、３Ｈ）、１．２０〜０．９５（ｍ
、９Ｈ）。2H), 4.05 (q12 H), 2.25 (qll
H), 1.22 (t, 3H), 1.20-0.95 (m
, 9H).
参考例 ２
シンナミルアルコール２．６１’（０，０２モル）とオ
ルトプロピオン酸エチル７．０４Ｐ（０，０４モル）を
混合し、フェノール０．３１存在下参考例１と同様操作
を行なった。Reference Example 2 Cinnamyl alcohol 2.61' (0.02 mol) and ethyl orthopropionate 7.04P (0.04 mol) were mixed and the same operation as in Reference Example 1 was carried out in the presence of 0.31 phenol.
その後、減圧蒸留により２−メチル−３−フェニル−４
−ペンテン酸エチル２．０１’を得た。Then, by distillation under reduced pressure, 2-methyl-3-phenyl-4
-2.01' of ethyl pentenoate was obtained.
収率４９％。沸点１０４℃／１、５ ｍｍＨｇ″Ｏ
核磁気共鳴吸収（δ ＣＣＩ、） ： ７．１２（ｂｓ
、５Ｈ）、６．３０〜４．８０ （ｍ１３Ｈ）、４．２
６〜３．２０（ｍ、３Ｈ）、３．００〜２．５０ （ｍ
１１Ｈ）、１．４０〜０．７８ （ｍ、 ６Ｈ） 。Yield 49%. Boiling point 104℃/1,5 mmHg''O Nuclear magnetic resonance absorption (δ CCI,): 7.12 (bs
, 5H), 6.30-4.80 (m13H), 4.2
6-3.20 (m, 3H), 3.00-2.50 (m
11H), 1.40-0.78 (m, 6H).
Claims (1)
塩基で処理することを特徴とする、一般式テ表ワされる
α一置換シクロプロパンカルボン酸エステルの製造方法
（式中Ｒ，Ｒ’、Ｒ２又はＲ３は低級アルキル基であり
、Ｘは同−又は異なるハロゲンである。 ）。２ 一般式 で表わされるα一置換−γ−不飽和カルボン酸エステル
に一般式ＣＸ４で表わされる四ハロゲン化炭素をラジカ
ル反応条件下付加させ、形成せる、一般式 で表わされるα一置換−γ−ハロカルボン酸エステルを
塩基で処理することを特徴とする、一般式で表わされる
α一置換シクロプロパンカルボン酸エステルの製造方法
（式中Ｒ，Ｒ１、Ｒ２及びＲ３□は低級アルキル基であ
り、Ｘは同−又は異なるハロゲンである。 ）。[Claims] A method for producing an α-monosubstituted cyclopropanecarboxylic acid ester represented by the general formula (formula R, R', R2 or R3 is a lower alkyl group, and X is the same or different halogen). 2 α-monosubstituted-γ- represented by the general formula, which is formed by adding a carbon tetrahalide represented by the general formula CX4 to the α-mono-substituted-γ-unsaturated carboxylic acid ester represented by the general formula under radical reaction conditions. A method for producing an α-monosubstituted cyclopropanecarboxylic acid ester represented by the general formula, which comprises treating a halocarboxylic acid ester with a base (wherein R, R1, R2 and R3□ are lower alkyl groups, and X is (same or different halogens).
Priority Applications (45)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1991775A JPS5821902B2 (en) | 1975-02-19 | 1975-02-19 | Alpha cyclopropane carbonate ester |
| IL53593A IL53593A (en) | 1974-09-10 | 1975-08-20 | halo hexan-(hexen)ioc and 2-haloethyl cyclopropanecarboxylic acid derivatives as intermediates for the preparatiionof esters fo dihalovinylcyclopropane anecarboxylic acids |
| IN1621/CAL/75A IN142702B (en) | 1974-09-10 | 1975-08-20 | |
| US06/606,807 US4681953A (en) | 1974-09-10 | 1975-08-22 | Process for preparing dihalovinylcyclopropanecarboxylates |
| AU84256/75A AU491852B2 (en) | 1975-08-26 | Preparation of certain cyclopropane-carboxylate esters | |
| IE1891/75A IE43065B1 (en) | 1974-09-10 | 1975-08-28 | Process for the preparation of esters of dihalovinyl-cyclopropanecarboxylic acids |
| CA000234464A CA1212685A (en) | 1974-09-10 | 1975-08-29 | Process for the preparation of esters of dihalovinylcyclopropanecarboxylic acids |
| GB336177A GB1520446A (en) | 1974-09-10 | 1975-09-03 | Process for the preparation of esters of vinyl-cyclopropanecarboxylic acids |
| GB50530/76A GB1520444A (en) | 1974-09-10 | 1975-09-03 | Preparation of unsaturated ethers and esters |
| GB36340/75A GB1520443A (en) | 1974-09-10 | 1975-09-03 | Process for the preparation of esters of dihalovinycyclo-propanecarboxylic acids |
| GB52795/76A GB1520445A (en) | 1974-09-10 | 1975-09-03 | Cyclopropanecarboxylates |
| NLAANVRAGE7510479,A NL185513C (en) | 1974-09-10 | 1975-09-05 | PROCESS FOR THE PREPARATION OF A DIHALOGENIC VINYL CYCLOPROPANIC CARBOXYLATE. |
| CH1161375A CH630891A5 (en) | 1974-09-10 | 1975-09-08 | METHOD FOR PRODUCING 2-DIHALOGENVINYLCYCLOPROPANCARBONIC ACID ESTERS. |
| DE2539895A DE2539895C2 (en) | 1974-09-10 | 1975-09-08 | Process for the preparation of 2-dihalovinylcyclopropanecarboxylic acid esters |
| DE2560240A DE2560240C2 (en) | 1974-09-10 | 1975-09-08 | Hexanoic acid, hexenoic acid and cyclopropanecarboxylic acid esters |
| SE7510042A SE435618B (en) | 1974-09-10 | 1975-09-09 | PROCEDURE FOR PREPARING ESTHERS OF DIHALOGENVINYL CYCLEOPROPANCARBOXYL ACIDS |
| SU752170851A SU664558A3 (en) | 1974-09-10 | 1975-09-09 | Method of obtaining esters of dihaloidvinylcyclopropancarboxylic acids |
| DK402075A DK158614C (en) | 1974-09-10 | 1975-09-09 | PROCEDURE FOR PREPARING A DIHALOGENEVINYLYCYCLOPROPANCARBOXYLATE |
| NZ18303575A NZ183035A (en) | 1974-09-10 | 1975-09-09 | Esters of hexanoic or hexenoic acid derivatives ethyl-2-( , , -trichloroethyl)-3,3-dimenthyl-cyclopropane-carboxylate and 1,1-diethoxy-1-(3-methyl-2-buten-1-yloxy)-ethane |
| NZ178641A NZ178641A (en) | 1974-09-10 | 1975-09-09 | Esters of vinylcycloprpane carboxylic acids and intermediates |
| HU19475A HU185211B (en) | 1974-09-10 | 1975-09-09 | Process for producing hexane-carboxylic acid derivatives |
| FR7527596A FR2318143A1 (en) | 1974-09-10 | 1975-09-09 | PROCESS FOR OBTAINING SUBSTITUTE CYCLOPROPANES, IN PARTICULAR USEFUL AS PYRETHROID INSECTICIDES |
| NO75753085A NO147792C (en) | 1974-09-10 | 1975-09-09 | PROCEDURE FOR PREPARING ESTERS OF DIHALOGEN-VINYL CYCLOPROPANCARBOXYL ACIDS |
| DD7500196145A DD128352A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING GAMMA-UNACCURATED CARBONIC ACID ESTERS |
| DD7500196142A DD128297A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING CYCLOPROPANCARBOXIC ACID ESTERS |
| DD7500196141A DD128351A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING UNCONDITIONED CARBONIC ACID ESTERS |
| MX10052375U MX5451E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING DIHALOVINYL CYCLOPROPAN CARBOXYLATE |
| DD188270A DD122678A5 (en) | 1974-09-10 | 1975-09-10 | |
| TR2087675A TR20876A (en) | 1974-09-10 | 1975-09-10 | MANUFACTURING PROCEDURE OF THE ESTERS OF DIHALO-VINYLICYCLOPROPANKARBOXYLED ACIDS |
| DD7500196143A DD128298A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR THE PREPARATION OF TRIHALOGENCYCLOPROPANCARBOSE ACID ESTERS |
| BE159921A BE833278A (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR OBTAINING SUBSTITUTE CYCLOPROPANES, PARTICULARLY USEFUL AS PYRETHROID INSECTICIDES |
| MX487775U MX5591E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR THE PREPARATION OF ESTERS OF DIHALOVINYL CYCLOPROPANOCARBOXYLIC ACIDS |
| FR7621447A FR2318144A1 (en) | 1974-09-10 | 1976-07-13 | PROCESS FOR OBTAINING VINYLCYCLOPROPANE CARBOXYLATES |
| FR7621448A FR2333774A1 (en) | 1974-09-10 | 1976-07-13 | SUBSTITUTE HARLOCARBOXYLATES, USED AS INTERMEDIARIES FOR THE MANUFACTURE OF PYRETHROID INSECTICIDES |
| SU762402853A SU969700A1 (en) | 1974-09-10 | 1976-09-24 | Esters of substituted 4,6,6,6-tetrahalodihexanoic acid as intermediate compounds for producing dihalovinylcyclopropane carboxylates |
| IN1919/CAL/1976A IN143561B (en) | 1974-09-10 | 1976-10-20 | |
| NO763933A NO148414C (en) | 1974-09-10 | 1976-11-18 | 4,6,6,6-TETRAHALOGENCARBOXYLIC ACID ESTERS FOR USE AS INTERMEDIATE IN THE PREPARATION OF ESTERS OF DIHALOGENVINYL-CYCLOPROPANCARBOXYL ACIDS |
| NO763934A NO763934L (en) | 1974-09-10 | 1976-11-18 | |
| IL53593A IL53593A0 (en) | 1974-09-10 | 1977-12-13 | Intermediates for the preparation of esters of dihalovinylcyclopropanecarboxylic acids |
| DK263479A DK158461C (en) | 1974-09-10 | 1979-06-22 | 4,6,6,6-TETRAHALOGENCARBOXYLIC ACID ESTERS USED AS INTERMEDIATES IN THE PREPARATION OF DIHALOGEN-VINYLYCYCLOPROPANCARBOXYLATES |
| TR2086679A TR20866A (en) | 1974-09-10 | 1979-09-06 | MANUFACTURING PROCEDURE OF THE ESTERS OF DIHALO-VINYLICYCLOPROPANKARBOXYLIC ACIDS |
| CA000339362A CA1210776A (en) | 1974-09-10 | 1979-11-07 | Process for the preparation of esters of dihalovinylcyclopropanecarboxylic acids |
| CH722281A CH641146A5 (en) | 1974-09-10 | 1981-11-10 | Process for the preparation of 2-dihalovinylcyclopropanecarboxylic acid esters |
| US06/507,998 US4833266A (en) | 1974-09-10 | 1983-06-27 | Process for preparing dihalovinylcyclopropanecarboxylates |
| US07/343,318 US4999451A (en) | 1974-09-10 | 1989-04-26 | Process for preparing dihalovinylcyclopropanecarboxylates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1991775A JPS5821902B2 (en) | 1975-02-19 | 1975-02-19 | Alpha cyclopropane carbonate ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5198246A JPS5198246A (en) | 1976-08-30 |
| JPS5821902B2 true JPS5821902B2 (en) | 1983-05-04 |
Family
ID=12012560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1991775A Expired JPS5821902B2 (en) | 1974-09-10 | 1975-02-19 | Alpha cyclopropane carbonate ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5821902B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS595503A (en) * | 1982-06-09 | 1984-01-12 | シビエ・プロジエクト−ル | Opposing headlight for vehicle |
-
1975
- 1975-02-19 JP JP1991775A patent/JPS5821902B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS595503A (en) * | 1982-06-09 | 1984-01-12 | シビエ・プロジエクト−ル | Opposing headlight for vehicle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5198246A (en) | 1976-08-30 |
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