JPS5821901B2 - Method for producing 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester - Google Patents

Method for producing 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester

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Publication number
JPS5821901B2
JPS5821901B2 JP1238975A JP1238975A JPS5821901B2 JP S5821901 B2 JPS5821901 B2 JP S5821901B2 JP 1238975 A JP1238975 A JP 1238975A JP 1238975 A JP1238975 A JP 1238975A JP S5821901 B2 JPS5821901 B2 JP S5821901B2
Authority
JP
Japan
Prior art keywords
acid ester
dichlorovinyl
trans
producing
cis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP1238975A
Other languages
Japanese (ja)
Other versions
JPS5188939A (en
Inventor
近藤聖
根岸章
松井清英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sagami Chemical Research Institute
Original Assignee
Sagami Chemical Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sagami Chemical Research Institute filed Critical Sagami Chemical Research Institute
Priority to JP1238975A priority Critical patent/JPS5821901B2/en
Priority to IN1621/CAL/75A priority patent/IN142702B/en
Priority to IL4796575A priority patent/IL47965A/en
Priority to US06/606,807 priority patent/US4681953A/en
Priority to AU84256/75A priority patent/AU491852B2/en
Priority to IE1891/75A priority patent/IE43065B1/en
Priority to CA000234464A priority patent/CA1212685A/en
Priority to GR7302A priority patent/GR82690B/el
Priority to GB336177A priority patent/GB1520446A/en
Priority to GB52795/76A priority patent/GB1520445A/en
Priority to GB36340/75A priority patent/GB1520443A/en
Priority to GB50530/76A priority patent/GB1520444A/en
Priority to NLAANVRAGE7510479,A priority patent/NL185513C/en
Priority to CH1161375A priority patent/CH630891A5/en
Priority to DE2539895A priority patent/DE2539895C2/en
Priority to DE2560240A priority patent/DE2560240C2/en
Priority to NZ178641A priority patent/NZ178641A/en
Priority to FR7527596A priority patent/FR2318143A1/en
Priority to NO75753085A priority patent/NO147792C/en
Priority to SU752170851A priority patent/SU664558A3/en
Priority to DK402075A priority patent/DK158614C/en
Priority to NZ18303575A priority patent/NZ183035A/en
Priority to SE7510042A priority patent/SE435618B/en
Priority to DD7500196145A priority patent/DD128352A5/en
Priority to DD7500196141A priority patent/DD128351A5/en
Priority to MX10052375U priority patent/MX5451E/en
Priority to DD7500196143A priority patent/DD128298A5/en
Priority to TR2087675A priority patent/TR20876A/en
Priority to MX487775U priority patent/MX5591E/en
Priority to DD7500196142A priority patent/DD128297A5/en
Priority to DD188270A priority patent/DD122678A5/xx
Priority to BE159921A priority patent/BE833278A/en
Priority to FR7621447A priority patent/FR2318144A1/en
Priority to FR7621448A priority patent/FR2333774A1/en
Publication of JPS5188939A publication Critical patent/JPS5188939A/en
Priority to IN1919/CAL/1976A priority patent/IN143561B/en
Priority to NO763933A priority patent/NO148414C/en
Priority to NO763934A priority patent/NO763934L/no
Priority to DK263479A priority patent/DK158461C/en
Priority to CA000339362A priority patent/CA1210776A/en
Priority to CH722281A priority patent/CH641146A5/en
Publication of JPS5821901B2 publication Critical patent/JPS5821901B2/en
Priority to US06/507,998 priority patent/US4833266A/en
Priority to US07/343,318 priority patent/US4999451A/en
Expired legal-status Critical Current

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Description

【発明の詳細な説明】 本発明は一般式 （式中Ｒ１は低級アルキル基である。[Detailed description of the invention] The present invention is based on the general formula (In the formula, R1 is a lower alkyl group.

）で表わされルトランス型２−（２・２−−）クロルビ
ニル）＝３・３−ジメチルシクロプロパンカルボン酸エ
ステルを優位成分とするシス及びトランス混合物の製造
方法に関するものである。The present invention relates to a method for producing a cis and trans mixture represented by 2-(2.2--)chlorovinyl)=3.3-dimethylcyclopropanecarboxylic acid ester represented by the following formula.

更に詳しくは本発明は一般式 （式中Ｒ１は低級アルキル基であり、Ｘはハロゲンであ
る。More specifically, the present invention is based on the general formula (where R1 is a lower alkyl group and X is a halogen).

）で表わされるγ−ハロカルボン酸エステルをアルコー
ル中アルカル金属アルコキシドで処理することを特徴と
する、前記一般式（Ｉ）で表わされるトランス型２−（
２・２−ジクロルビニル）−３・３−ジメチルシクロプ
ロパンカルボン酸エステルを優位成分とするシス及びト
ランス混合物を製造する方法に関するものである。) is treated with an alkali metal alkoxide in alcohol to obtain the trans-type 2-(
The present invention relates to a method for producing a cis and trans mixture containing 2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester as a predominant component.

前記一般式（Ｉ）で表わされる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。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より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
、前記一般式（Ｉ）で表わされるトランス型２−（２・
２−ジクロルビニル）−３・３−ジメチルシクロプロパ
ンカルボン酸エステルとこのシス異性体とを８：２の割
合で含有するエステル混合物が低毒性、持続性共に優秀
であることが明らかとなったＣ Ｍ、Ｅ １ｌｉｏｔｔ
ｅｔ ａｌ 、、Ｎａｔｕｒｅ １２４６．１６９（１
９７３））。In order to solve this drawback, many compounds were tested, and as a result, the trans-type 2-(2.
It has been revealed that an ester mixture containing 2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester and its cis isomer in a ratio of 8:2 has excellent low toxicity and long-lasting properties. ,E 1liott
et al., Nature 1246.169(1
973)).

従来、この種の化合物の合成法としてし慎１）天然の葉
酸を出発物質とする方法特開昭４９−４７５３１号及び
り、Ｇ、 Ｂｒｏｗｎ ｅｔ ａｌ、、 Ｊ。Conventionally, there have been several methods for synthesizing this type of compound: 1) A method using natural folic acid as a starting material; JP-A-49-47531;

Ａｇｒ 、 Ｆｏｏｄ Ｃｈｅｍ 、、 ２１．７６
７（１９７３：（２）ジハロブタジェンにジアゾ酢酸エ
ステルを附加させる方法（Ｊ、 Ｆａｒｋａｓ ｅｔ
ａｌ 、、Ｃｏ１１゜Ｃｚｅｃｈ 、Ｃｈｅｍ、Ｃ
ｏｍｍ、、 ２４．２２３゜（１９５９）、ｌ及び（３
）３・３−ジメチル−４−ブロム−５−トリクロロメチ
ル吉草酸エチルをテトラヒドロフラン中カリウムｔ−ブ
トキシドで処理する方法〔日本化学会第３１秋季年会講
演予稿集ＩＰ ５８（１９７４）参照〕が提案されてい
る。Agr, Food Chem,, 21.76
7 (1973: (2) Method for adding diazoacetate to dihalobutadiene (J, Farkas et
al,,Co11゜Czech,Chem,C
omm,, 24.223゜(1959), l and (3
) A method was proposed in which ethyl 3,3-dimethyl-4-bromo-5-trichloromethylvalerate was treated with potassium t-butoxide in tetrahydrofuran [see Proceedings of the 31st Autumn Annual Meeting of the Chemical Society of Japan, IP 58 (1974)]. has been done.

しかし上記（１）及堕２）の従来法はいずれも原料化合
物が高価であり、合成経路が長く且つ高価な助剤を必要
とする等の欠点がある。However, the conventional methods (1) and (2) above all have drawbacks such as expensive raw material compounds, long synthetic routes, and the need for expensive auxiliaries.

又、上記（３）の方法ではシス及びトランス型シクロプ
ロパンカルボン酸エステルのはｒｌ ： １の混合物が
得られるのみであり、従ってトランス：シス＝８＝２の
組成を所望する場合には更に異性化を行なう必要がある
。In addition, in the method (3) above, only a mixture of cis and trans cyclopropane carboxylic acid esters with rl: 1 is obtained, so if a composition of trans:cis=8=2 is desired, further isomerization is required. It is necessary to carry out the conversion.

本発明者等は従来法の斯様な欠点を解決し且つ所望の比
を有するシス及びトランス体の混合物を直接製造する方
法について鋭意検討を重ねた結果、トランス体を優位に
含むシクロプロパンカルボン酸エステル混合物を製造す
る方法を完成するに至ったものである。The present inventors have conducted intensive studies on a method for directly producing a mixture of cis and trans isomers having a desired ratio while overcoming such drawbacks of the conventional methods. This has led to the completion of a method for producing ester mixtures.

本発明の方法は原料として前記一般式（９）で表わされ
るγ−ハロ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 a γ-halocarboxylic acid ester represented by the general formula (9) above as a raw material.

この化合物は例えば、アリルアルコール誘導体とオルト
酢酸エステルとから形成されるγ−不飽和カルボン酸エ
ステルに四塩化炭素又はブロムトリクロルメタンを付加
せしめることにより容易に形成できる。This compound can be easily formed, for example, by adding carbon tetrachloride or bromotrichloromethane to a γ-unsaturated carboxylic ester formed from an allyl alcohol derivative and orthoacetic ester.

本発明は、前記一般式（ＩＩ）で表わされるγ−ハロカ
ルボン酸エステルを特定溶媒中特定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 requires that the γ-halocarboxylic acid ester represented by the general formula (II) be treated with a specific base in a specific solvent.

即ち、特定溶媒として炭素数１〜４個の低級アルコール
である所のメタノール、エタノール、プロパツール、イ
ンプロパツール、ブタノール等を用いるこが必必須であ
り、又塩基としては、ナトリウムメトキシド、ナトリウ
ムエトキシド、カリウムメトキシド、カリウムエトキシ
ド等の如きアルカリ金属アルコキシド等を用いることが
必要である。That is, it is essential to use lower alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, propatool, impropatol, butanol, etc. as a specific solvent, and as a base, sodium methoxide, sodium It is necessary to use alkali metal alkoxides such as ethoxide, potassium methoxide, potassium ethoxide, and the like.

塩基の使用量は原料に対して２モル当量若しくはや〜過
剰量用いれば十分である。It is sufficient to use the base in an amount of 2 molar equivalents or a slight excess amount based on the raw material.

反応温度としては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 room temperature to the reflux temperature of the solvent from the viewpoint of ease of operation.

前記の条件下で本発明を実施することにより、従来全く
予幼しなかった所望のトランス体及びシス体の混合物を
形成出来るばかりでなく、反応操作例えば反応時間も数
時間という短時間で十分である。By carrying out the present invention under the above conditions, it is not only possible to form a desired mixture of trans and cis isomers, which has not been possible in the past, but also a short reaction time of several hours is sufficient for the reaction operation. be.

更にはｙ定量的収率で目的を達成できることが明らかと
なった。Furthermore, it became clear that the objective could be achieved with a quantitative yield.

以下実施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 with reference to Examples below.

実施例 １ 金属ナトリウム１．０１ ？ （４４ｍｍｏｌｅ）を無
水コタノール８０ｒｕｌにとかし氷水冷却下に３・３−
ジメチル−４−クロル−５−トリクロルメチル吉草酸エ
チル６．２０ｆ（２０ｍｍｏｌｅ ）の無水エタノール
溶液（２０ｍｌ）を滴下した。Example 1 Sodium metal 1.01? (44 mmole) was dissolved in 80 rul of anhydrous cotanol and cooled with ice water.
An anhydrous ethanol solution (20 ml) of 6.20 f (20 mmole) of ethyl dimethyl-4-chloro-5-trichloromethylvalerate was added dropwise.

滴下後室温でさらに１時間攪拌し３０分間加熱還流した
。After the dropwise addition, the mixture was further stirred at room temperature for 1 hour and heated under reflux for 30 minutes.

反応液を再び氷水潜動して塩化水素の無水エタノール溶
液を滴下して中和した。The reaction solution was submerged in ice water again, and a solution of hydrogen chloride in absolute ethanol was added dropwise to neutralize it.

析出した固体な濾別して濾液を１／１０の体積に濃縮し
た後エーテルで希釈した。The precipitated solid was filtered off, the filtrate was concentrated to 1/10 volume, and then diluted with ether.

エーテル溶液を飽和重そう水、飽和食塩水で洗滌後乾燥
した。The ether solution was washed with saturated deuterated water and saturated brine, and then dried.

溶媒を留去後残液を減圧蒸留すると、沸点７２〜７４℃
／ ０．４ ｍｍＨｇを有する２−（２・２ジクロルビ
ニル）−３・３−ジメチルシクロプロパンカルボン酸エ
チル４．４７グが得られた。After distilling off the solvent, the residual liquid is distilled under reduced pressure, resulting in a boiling point of 72-74°C.
4.47 g of ethyl 2-(2.2-dichlorovinyl)-3.3-dimethylcyclopropanecarboxylate having a value of /0.4 mmHg were obtained.

（収率９４％）。ガスクロマトグラフィ（１０％ＱＦ−
１．ｉｎ、カラム温度１３５℃）でこのシクロプロパン
カルボン酸エステルのシス−トランス異性体比を調べた
結果シス：トランス＝３４：６６であることがわかった
。(Yield 94%). Gas chromatography (10% QF-
1. As a result of examining the cis-trans isomer ratio of this cyclopropane carboxylic acid ester at a column temperature of 135° C., it was found that cis:trans = 34:66.

実施例 ２ 金属カリウム８６０Ｑ？（２２ｍｍｏｌｅ ）を無水エ
タノール８０ｍ１にとかし氷水冷却下に３・３−ジメチ
ル−４−クロル−５−トリクロルメチル吉草酸エチル３
．１ ｏｙ（ｌ Ｏｍｍｏｌｅ ）無水エタノール溶液
（２Ｑ’ｍｌ）を滴下した。Example 2 Metal potassium 860Q? Ethyl 3,3-dimethyl-4-chloro-5-trichloromethylvalerate was dissolved in 80 ml of absolute ethanol and cooled with ice water.
．． 1 oy (l Ommole) absolute ethanol solution (2Q'ml) was added dropwise.

滴下後室温で１時間攪拌しさらに３０分間加熱還流した
。After the dropwise addition, the mixture was stirred at room temperature for 1 hour and further heated under reflux for 30 minutes.

以下実施例１と同様の操作により２．３（ｌの２−（２
・２−ジクロルビニル）−３・３−ジメチルシクロプロ
パンカルボン酸エチルが得られた。Hereinafter, by the same operation as in Example 1, 2.3 (2 - (2 of 1)
- Ethyl 2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate was obtained.

（収率９６％）ガスクロマトグラフィによる生成比はシ
ス：トランス−２６： ７４であった。(Yield: 96%) The production ratio determined by gas chromatography was cis:trans-26:74.

実施例 ３ 金属ナトリウＡ ５７５１ｎ９（２５ｍｍｏｌｅ ）を
無水メタノール８０ｍ１にとかし氷水冷却下に３・３−
シメチル−４−クロル−５−トリクロルメチル吉草酸エ
チ／１／３．１０ ？ （］、 ＯｍｍＯ，ｔｅ ）の
無水メタノール溶液（２０ｍｌ）を滴下した。Example 3 Sodium metal A 5751n9 (25 mmole) was dissolved in 80 ml of anhydrous methanol and cooled with ice water to form 3.3-
Ethyl dimethyl-4-chloro-5-trichloromethylvalerate/1/3.10? An anhydrous methanol solution (20 ml) of (], OmmO,te) was added dropwise.

滴下後室温で１時間攪拌し、さらに３０分間加熱還流し
た。After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and further heated under reflux for 30 minutes.

以下実施例１と同様の操作により沸点６８°〜７０℃／
０．２ ｍｍＨｇを有する２−（２・２−ジクロルビ
ニル）−３・３−ジメチルシクロプロパンカルボン酸メ
チル２．０９Ｓ’が得られた。Hereinafter, by the same operation as in Example 1, the boiling point was 68° to 70°C/
Methyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate 2.09S' having 0.2 mmHg was obtained.

（収率９３％）ガスクロマトグラフィによる生成比はシ
ス：トランス−２３ニア７であった。(Yield: 93%) The production ratio determined by gas chromatography was cis:trans-23 near 7.

実施例 ４ 金属ナトリウム５７５１ｎ９のかわりに金属カリウム８
６０〜を用いた以外は実施例３と同様の方法により２．
１３Ｓ’の２−（２・２−ジクロルビニル）−３・３−
ジメチルシクロプロパンカルボン酸メチノヒが得られた
。Example 4 Metallic potassium 8 instead of metallic sodium 5751n9
2. by the same method as in Example 3 except that 60~ was used.
13S'2-(2,2-dichlorovinyl)-3,3-
Dimethylcyclopropanecarboxylic acid methynohyde was obtained.

（収率９５％）、ガスクロマトグラフィによる生成比は
シス：トランス−２５＝７５であった。(yield 95%), and the production ratio by gas chromatography was cis:trans-25=75.

Claims (1)

【特許請求の範囲】 １ 一般式 で表わされるｒ−ハロカルボン酸エステルを炭素数１〜
４個の低級アルコール中アルカリ金属アルコキシドで処
理することを特徴とする、一般式で表わされるトランス
型２−（２・２−ジクロルビニル）−３・３−ジメチル
シクロプロパンカルボン酸エステルを優位成分とするシ
ス及びトランス混合物の製造方法（式中、Ｒ１及びＲ２
は低級アルキル基であり、Ｘはハロゲンである。 ）。[Scope of Claims] 1 An r-halocarboxylic acid ester represented by the general formula having 1 to 1 carbon atoms
The predominant component is trans-type 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester represented by the general formula, which is characterized by treatment with an alkali metal alkoxide in four lower alcohols. Method for producing cis and trans mixtures (wherein R1 and R2
is a lower alkyl group, and X is a halogen. ).
JP1238975A 1974-09-10 1975-01-31 Method for producing 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester Expired JPS5821901B2 (en)

Priority Applications (42)

Application Number Priority Date Filing Date Title
JP1238975A JPS5821901B2 (en) 1975-01-31 1975-01-31 Method for producing 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester
IN1621/CAL/75A IN142702B (en) 1974-09-10 1975-08-20
IL4796575A IL47965A (en) 1974-09-10 1975-08-20 Process for the preparation of esters of dihalovinylcyclopropane-carboxylic acids
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
GR7302A GR82690B (en) 1974-09-10 1975-09-01
GB336177A GB1520446A (en) 1974-09-10 1975-09-03 Process for the preparation of esters of vinyl-cyclopropanecarboxylic acids
GB52795/76A GB1520445A (en) 1974-09-10 1975-09-03 Cyclopropanecarboxylates
GB36340/75A GB1520443A (en) 1974-09-10 1975-09-03 Process for the preparation of esters of dihalovinycyclo-propanecarboxylic acids
GB50530/76A GB1520444A (en) 1974-09-10 1975-09-03 Preparation of unsaturated ethers and esters
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
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
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
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
NZ178641A NZ178641A (en) 1974-09-10 1975-09-09 Esters of vinylcycloprpane carboxylic acids and intermediates
SE7510042A SE435618B (en) 1974-09-10 1975-09-09 PROCEDURE FOR PREPARING ESTHERS OF DIHALOGENVINYL CYCLEOPROPANCARBOXYL ACIDS
DD188270A DD122678A5 (en) 1974-09-10 1975-09-10
BE159921A BE833278A (en) 1974-09-10 1975-09-10 PROCESS FOR OBTAINING SUBSTITUTE CYCLOPROPANES, PARTICULARLY USEFUL AS PYRETHROID INSECTICIDES
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
DD7500196143A DD128298A5 (en) 1974-09-10 1975-09-10 PROCESS FOR THE PREPARATION OF TRIHALOGENCYCLOPROPANCARBOSE ACID ESTERS
TR2087675A TR20876A (en) 1974-09-10 1975-09-10 MANUFACTURING PROCEDURE OF THE ESTERS OF DIHALO-VINYLICYCLOPROPANKARBOXYLED ACIDS
MX487775U MX5591E (en) 1974-09-10 1975-09-10 PROCESS FOR THE PREPARATION OF ESTERS OF DIHALOVINYL CYCLOPROPANOCARBOXYLIC ACIDS
DD7500196142A DD128297A5 (en) 1974-09-10 1975-09-10 PROCESS FOR PREPARING CYCLOPROPANCARBOXIC ACID ESTERS
DD7500196145A DD128352A5 (en) 1974-09-10 1975-09-10 PROCESS FOR PREPARING GAMMA-UNACCURATED CARBONIC ACID ESTERS
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
IN1919/CAL/1976A IN143561B (en) 1974-09-10 1976-10-20
NO763934A NO763934L (en) 1974-09-10 1976-11-18
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
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
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
JP1238975A JPS5821901B2 (en) 1975-01-31 1975-01-31 Method for producing 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ester

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JPS5188939A JPS5188939A (en) 1976-08-04
JPS5821901B2 true JPS5821901B2 (en) 1983-05-04

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