JPS5822463B2 - Cyclopropane carbonate cyclopropane carbonate - Google Patents
Cyclopropane carbonate cyclopropane carbonateInfo
- Publication number
- JPS5822463B2 JPS5822463B2 JP50028607A JP2860775A JPS5822463B2 JP S5822463 B2 JPS5822463 B2 JP S5822463B2 JP 50028607 A JP50028607 A JP 50028607A JP 2860775 A JP2860775 A JP 2860775A JP S5822463 B2 JPS5822463 B2 JP S5822463B2
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- Prior art keywords
- ethyl
- general formula
- cyclopropane
- sodium
- carbonate
- 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Ｒ１は低級アルキル基又は５−ベンジルフリルメ
チル基であり、Ｒ２は水素原子又は低級アルキル基であ
り、Ｙ及びＺは・・ロゲンである。Detailed Description of the Invention The present invention is based on the general formula (wherein R1 is a lower alkyl group or a 5-benzylfurylmethyl group, R2 is a hydrogen atom or a lower alkyl group, and Y and Z are... .
）で表わされる置換ビニル基を有するシクロプロパンカ
ルボン酸誘導体の製造方法に関するものである。) The present invention relates to a method for producing a cyclopropanecarboxylic acid derivative having a substituted vinyl group represented by:
前記一般式（１）で表わされるシクロプロパンカルボン
酸誘導体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 cyclopropanecarboxylic acid derivative represented by the general formula (1) 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り、 Ｄ、 ＴやＢ、 Ｈ，Ｃ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, D, T, B, H, and C have been used as insecticides, but due to their residual toxicity, there is 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性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 attracting new 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）の様なジハロビニル基ヲ持つシクロ
プロパンカルボン酸エステルが低毒性、持続性共に優秀
であることが明らかとなったＣ Ｍ、 Ｅ １ｌｉｏｔ
ｔ ｅｔ −ａｌ 、、Ｎａｔｕｒｅ 、 ２４６．
１６９（１９７３））。As a result of testing many compounds to solve this drawback, it became clear that cyclopropanecarboxylic acid ester having a dihalobinyl group as shown in the general formula (I) has excellent low toxicity and long-lasting properties. M, E 1liot
t et -al, Nature, 246.
169 (1973)).
従来この種の化合物の合成法としては（１）天然の菊酸
を出発物質とする方法ＣＤ、Ｇ、Ｂｒｏｗｎ、ｅｔ。Conventional methods for synthesizing this type of compound include (1) a method using natural chrysanthemum acid as a starting material; CD, G. Brown, et.
ａｌｏ、Ｊ、Ａｇｒ、ＦｏｏｄＣｈｅｍｏ、Ｕ、７６７
（１９７３））。alo, J, Agr, FoodChemo, U, 767
(1973)).
（２）ジハロブタジェンジアゾ酢酸エステルを付加させ
る方法（Ｊ、 Ｆａｒｋａｓ 、ｅｔ 。(2) Method of adding dihalobutadiene diazoacetate (J, Farkas, et.
ａｌｏ、Ｃｏ１１ 、Ｃｚｅｃｈ、 Ｃｈｅｍ、 Ｃｏ
ｍｍ、、２４．２２３０（１９５９））が提案されてい
る。alo, Co11, Czech, Chem, Co
mm, 24.2230 (1959)) has been proposed.
しかしこれら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, all of these conventional methods have drawbacks such as expensive starting compounds, long synthetic routes, and the need for expensive auxiliaries.
本発明者等は従来法の斯様な欠点を解決すべく鋭意検討
を重ねた結果、工業的に有利にシクロプロパンカルボン
酸誘導体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 made extensive studies to solve these drawbacks of the conventional methods, and as a result have completed an industrially advantageous method for producing cyclopropanecarboxylic acid derivatives.
本発明の方法は、原料として一般式
（式中Ｒ１、Ｒ２、Ｙ及びＺは前記に同じであり、Ｘは
ハロゲンである。The method of the present invention uses a raw material having the general formula (wherein R1, R2, Y and Z are the same as above, and X is a halogen).
但し、Ｒ２が水素原子のときＸ、Ｙ及びＺの少なくとも
一つは臭素原子である。However, when R2 is a hydrogen atom, at least one of X, Y and Z is a bromine atom.
）で表わされるシクロプロパンカルボン酸エステルを用
いるものである。) is used.
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
テルに四ハロゲン化炭素、クロロホルム、ジブロムメタ
ン等を付加せしめ、次いで特定量の塩基で処理すること
により容易に形成できる（下記参考側参照〕前記一般式
（ＴＩ）で表わされるシクロプロパンカルボン酸エステ
ルとしては、２−（２・２・２−トリフロムエチル）−
３・３−ジメチルシクロプロパンカルボン酸エチル、２
−（２−クロル−２２−ジブロムエチル）−３・３−ジ
メチルシクロプロパンカルボン酸エチル、２−（２−ブ
ロム−２・２−）クロルエチル）−３・３−ジメチルシ
クロプロパンカルボン酸エチル等を例示することができ
る。This compound can be easily formed, for example, by adding carbon tetrahalide, chloroform, dibromomethane, etc. to a γ-unsaturated carboxylic ester formed from an allyl alcohol derivative and orthoacetic ester, and then treating it with a specific amount of base. (See reference side below) As the cyclopropanecarboxylic acid ester represented by the general formula (TI), 2-(2.2.2-trifluoromethyl)-
Ethyl 3,3-dimethylcyclopropanecarboxylate, 2
Examples include ethyl -(2-chloro-22-dibromoethyl)-3,3-dimethylcyclopropanecarboxylate, ethyl 2-(2-bromo-2,2-)chloroethyl)-3,3-dimethylcyclopropanecarboxylate, etc. can do.
本発明は前記一般式（ｎ）で表わされるシクロプロパン
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 requires that the cyclopropanecarboxylic acid ester represented by the general formula (n) 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、カリウムメトキシド、ナトリウムｔ−
ブトキシド、カリウムｔ−ブトキシド、ナトリウムｔ−
アミルオキシド等のアルカリ金属アルコキシド、水素化
すトリウム、水素化カ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及び１
・５−ジアザビシクロ〔３・４・０〕ノネン−５（ＤＢ
Ｎ）、■・５−ジアザビシクロ〔５・４・０〕ウンデセ
ン−５（ＤＢＵ）、２−ジメチルアミノ−１−ピロリ）
ン等の有機アミン類、ｎ−ブチルリチウム、Ｓ−ブチル
リチウム、ジイソプロピルアミンリチウム等の有機リチ
ウム化合物などを例示することができるが、反応効率が
高い点でアルカリ金属アルコキシドあるいはアルカリ金
属ノ・イドライドの使用：が好ましい。As the base, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, and sodium t-
butoxide, potassium t-butoxide, sodium t-butoxide
Alkali metal alkoxides such as amyl oxide, alkali metal hydrides such as thorium hydride and potassium hydride, alkali metal amides such as sodium amide, and 1
・5-Diazabicyclo[3.4.0]nonene-5 (DB
N), ■・5-diazabicyclo[5.4.0]undecene-5 (DBU), 2-dimethylamino-1-pyrroli)
Examples include organic amines such as n-butyllithium, S-butyllithium, and organic lithium compounds such as diisopropylamine lithium. Use: is preferred.
塩基の使用量は原料に対して１モル当量以上好ましくは
１〜２モル当量である。The amount of the base used is 1 molar equivalent or more, preferably 1 to 2 molar equivalents, based on the raw material.
反応は溶媒中で行なうのが好ましく、メタノール、エタ
ノール等のアルコール系溶媒、Ｎ−Ｎ−ジメチルホルム
アミド（ＤＭＦ）、ジメチルスルｉホキシト（ＤＭＳＯ
）等の非プロトン系極性溶媒あるいはベンゼン、トルエ
ン等の炭化水素類等を例示することができる。The reaction is preferably carried out in a solvent, such as alcoholic solvents such as methanol and ethanol, N-N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), etc.
) and hydrocarbons such as benzene and toluene.
有機アミン類を用いる場合にはこれを過剰に用いて溶媒
としての役割を兼ねさせてもよい。When using organic amines, they may be used in excess to also serve as a solvent.
反応温度は室温〜１５０℃、好ましくは５０℃乃至溶媒
の還流温度で行なうのが操作が容易である点で好ましい
。The reaction temperature is preferably room temperature to 150°C, preferably 50°C to the reflux temperature of the solvent, for ease of operation.
以下参考例及び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 below with reference to Reference Examples and Examples.
参考例 １
ｔ−７”チルアルコール（４ｏｍｉ）とヘキサン（２０
ｍｌ）に３・３−ジメチル−４−ブロム−５−トリブロ
ムメチル吉草酸エチル９．８Ｐ（２０ミリモル）を溶解
した。Reference example 1 t-7” methyl alcohol (4omi) and hexane (20
ml) was dissolved with 9.8 P (20 mmol) of ethyl 3,3-dimethyl-4-bromo-5-tribromomethylvalerate.
この溶液にナトリウムアミド（９７５〜、２５ミリモル
）を水冷下に少しづつ加えた。Sodium amide (975~, 25 mmol) was added little by little to this solution while cooling with water.
反応混合物を１時間攪拌したのち、室温でさらに１時間
攪拌を続げ１規定塩酸を加えた。After the reaction mixture was stirred for 1 hour, stirring was continued for another 1 hour at room temperature, and 1N hydrochloric acid was added.
水で希釈後エーテル抽出し、抽出液を重曹水および食塩
水で洗浄後乾燥した。After diluting with water, the mixture was extracted with ether, and the extract was washed with an aqueous sodium bicarbonate solution and brine, and then dried.
濃縮後、粗生成物を減圧蒸留して沸点１１０〜１１５℃
／ ０．２ ｍｍＨｇを有する２−（２・２・２−トリ
ブロムエチル）−３・３−ジメチルシクロプロパンカル
ボン酸エチル（シス／トランス−１／１）６．９？を得
た。After concentration, the crude product is distilled under reduced pressure to a boiling point of 110-115℃.
/ Ethyl 2-(2.2.2-tribromoethyl)-3.3-dimethylcyclopropanecarboxylate (cis/trans-1/1) with 0.2 mmHg 6.9? I got it.
収率８５％。核磁気共鳴吸収（ＣＣＩ４）δ４．０６（
ｄｑ、２Ｈ）、３．３〜２．９ （ｍ、２Ｈ）、２．５
〜］、、 ７ （ｍ、２Ｈ）、１．３８（ｓ、６Ｈ）、
］、、３５（ｄｔ、３Ｈ）。Yield 85%. Nuclear magnetic resonance absorption (CCI4) δ4.06 (
dq, 2H), 3.3-2.9 (m, 2H), 2.5
~],, 7 (m, 2H), 1.38 (s, 6H),
],,35(dt,3H).
実施例 １
２−（２・２・２−トリブロムエチル）−３・３−ジメ
チルシクロプロパンカルボン酸エチル２．０３？（５ミ
リモル）を無水エチルアルコール１０ｒｎ１２に溶解し
た。Example 1 Ethyl 2-(2.2.2-tribromoethyl)-3.3-dimethylcyclopropanecarboxylate 2.03? (5 mmol) was dissolved in 10rn12 absolute ethyl alcohol.
この溶液を金属すトリウム１３０７％を溶解した無水エ
チルアルコール４−０ｍ１！に滴下し、滴下後３時間加
熱還流した。This solution is 4-0 ml of anhydrous ethyl alcohol with 1307% of sodium metal dissolved in it! After the dropwise addition, the mixture was heated under reflux for 3 hours.
反応液を氷水冷却して乾燥塩化水素を徐々に吹き込み中
和した。The reaction solution was cooled with ice water and neutralized by gradually blowing dry hydrogen chloride into it.
１／１０の体積に濃縮後エーテルで希釈して水、炭酸水
素ナトリウム水溶液、水で順次洗浄してから乾燥した。After concentrating to 1/10 volume, it was diluted with ether, washed successively with water, an aqueous sodium bicarbonate solution, and water, and then dried.
溶媒を留去後、減圧蒸留により沸点９５〜９７℃／ ０
．３ ｍｍＨｇを有する２−（２・２−ジブロムビニル
）−３・３−ジメチルシクロプロパンカルボン酸エチル
１．０６ ｙ ヲ得り。After distilling off the solvent, reduce the boiling point to 95-97℃/0 by distillation under reduced pressure.
．． 1.06 y of ethyl 2-(2,2-dibromvinyl)-3,3-dimethylcyclopropanecarboxylate with 3 mmHg was obtained.
収率６５％。Yield 65%.
生成物の核磁気共鳴吸収（δＣＣｌ４）： ６．７０及
び６．０７（ｄ、ＬＨ）、４．０５（（１，２Ｈ）、２
．４５〜１．４０ （ｍ、 ２Ｈ）、１．３５〜ｉ、
ｉ 、ｏ （ｍ１９Ｈ）。Nuclear magnetic resonance absorption of the product (δCCl4): 6.70 and 6.07 (d, LH), 4.05 ((1,2H), 2
．． 45-1.40 (m, 2H), 1.35-i,
i, o (m19H).
このうちトランス異性体に由来する核磁気共鳴吸収（Ｃ
ＣＩいδ）；６．０７（ｄ、ＩＨ）、４．０５ （ｑ、
２Ｈ）、２．４０〜２．００（ｄ、ｄ、ＩＨ）、１
．５３（ｄ、］、 Ｈ） ］、、２６ （ｔ、３Ｈ：１
．２７（Ｓ、３Ｈ）、］、、２１ （ｓ、３Ｈ）。Of these, nuclear magnetic resonance absorption (C
CI δ); 6.07 (d, IH), 4.05 (q,
2H), 2.40-2.00 (d, d, IH), 1
．． 53(d, ], H) ], 26 (t, 3H:1
．． 27 (S, 3H),], 21 (s, 3H).
シス異性体に由来する核磁気共鳴吸収（ＣＣ１４、δ）
； ６．７０ （ｂｄ、 Ｉ Ｈ）、４．０５（ｑ
、２Ｈ）、２．２０〜１．６０ （ｍ、２Ｈ）、１．３
５〜１．１０（ｍ、９Ｈ）。Nuclear magnetic resonance absorption derived from cis isomer (CC14, δ)
; 6.70 (bd, IH), 4.05 (q
, 2H), 2.20-1.60 (m, 2H), 1.3
5-1.10 (m, 9H).
実施例 ２
２−（２−７”ロム−２・２−−）’；’ロルエチル）
−３・３−ジメチルシクロプロパンカルボン酸エチル１
．６１’（５ミリモル）を無水エチルアルコールｌ□ｍ
７に溶解した。Example 2 2-(2-7"Rom-2・2--)';'lolethyl)
-3,3-dimethylcyclopropanecarboxylic acid ethyl 1
．． 61' (5 mmol) in 1□m of absolute ethyl alcohol
It was dissolved in 7.
この溶液を金属ナトリウム１３０〜を溶解した無水エチ
ルアルコール４０ｍ１に滴下し、滴下後３時間加熱還流
した。This solution was added dropwise to 40 ml of anhydrous ethyl alcohol in which ~130~ of metallic sodium was dissolved, and after the dropwise addition, the mixture was heated under reflux for 3 hours.
以下実施例１と同様の操作により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ｏ、ｓｏｙを得た。Thereafter, by the same operation as in Example 1, ethyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate o,soy was obtained.
収率６８％。Yield 68%.
実施例 ３
実施例２において、２−（２−ブロム−２・２−ジクロ
ルエチル）−３・３−ジメチルシクロプロパンカルボン
酸エチル１．６（ｌの代りに２−（２−クロル−２・２
−ジブロムエチル）−３・３−）メｆ−ルシクロプロパ
ンカルボン酸エチル１．８１Ｐを用いた以外はすべて同
様の操作により、２−（２−クロル−２−ブロムビニル
）−３・３−ジメチルシクロプロパンカルボン酸エチル
８４０ｒｎ９を得た。Example 3 In Example 2, 2-(2-bromo-2,2-dichloroethyl)-3,3-dimethylcyclopropanecarboxylate 1.6
2-(2-chloro-2-bromvinyl)-3,3-dimethylcyclo-2-(2-chloro-2-bromvinyl)-3,3-dimethylcyclo Ethyl propanecarboxylate 840rn9 was obtained.
収率６０％。沸点８４〜８８℃１０、３ ｍｍＨｇ。Yield 60%. Boiling point 84-88°C 10.3 mmHg.
実施例 ４
実施例２において、２−（２−ブロム−２・２−ジクロ
ルエチル）−３・３−ジメチルシクロプロパンカルボン
酸エチル１．６０Ｐの代りに１−メチル−２−（２・２
・２−トリクロルエチル）−３・３−ジメチルシクロプ
ロパンカルボン酸エチル１．９４ ｆを用いた以外はす
べて同様の操作によす、１−、、＜チル−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６９０〜を得た。Example 4 In Example 2, 1-methyl-2-(2.2
・Ethyl 2-trichloroethyl)-3,3-dimethylcyclopropanecarboxylate The same procedure was followed except that 1.94 f was used.
-Dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid ethyl 690~ was obtained.
収率５５％。沸点７５〜７７℃１０、ｌｍｍＨｇ。Yield 55%. Boiling point 75-77°C 10, lmmHg.
生成物の核磁気共鳴吸収（ＣＣＩ４）δ：６２６．５．
５７ （ｄ１］、 Ｈ）、４．１０ （ｂｑ、２Ｈ）、
２．２８．１．５２（ｄｌ １Ｈ）、１．４０〜０．９
０ （ｍ、 ｌ ２Ｈ）。Nuclear magnetic resonance absorption (CCI4) δ of product: 626.5.
57 (d1], H), 4.10 (bq, 2H),
2.28.1.52 (dl 1H), 1.40-0.9
0 (m, l 2H).
実施例 ５
２−（２・２・２−トリブロムエチル）−３・３−ジメ
チルシクロプロパンカルボン酸の５−ベンジル−３−フ
リルメチルエステル５４９〜ヲ無水ジオキザン３ｍｌに
溶解した。Example 5 549 to 549 5-benzyl-3-furyl methyl ester of 2-(2,2,2-tribromoethyl)-3,3-dimethylcyclopropanecarboxylic acid was dissolved in 3 ml of anhydrous dioxane.
この溶液を金属ナトリウム３５〜から調製したナトリウ
ムエトキシドの無水ジオキサ７１０ｍ１懸濁液に滴下し
、滴下後３時間加熱還流した。This solution was added dropwise to a suspension of 710 ml of anhydrous dioxa of sodium ethoxide prepared from 35~ of metallic sodium, and heated under reflux for 3 hours after the dropwise addition.
その後実施例１と同様操作を行ない、溶媒を留去する事
により、３・３−シメチル−２−（２・２−シフロムビ
ニル）−シクロプロパンカルボン酸の５−ベンジル−３
−フリルメチルエステル２５０〜を得た。Thereafter, by carrying out the same operation as in Example 1 and distilling off the solvent, 5-benzyl-3
-Furyl methyl ester 250~ was obtained.
収率５４％。このものをｎ−ヘキサンより再結晶するこ
とにより融点６５℃を有する純粋なトランス異性体を得
た。Yield 54%. This product was recrystallized from n-hexane to obtain a pure trans isomer having a melting point of 65°C.
生成物の核磁気共鳴吸収（δＣＤＣ１３）ニア、０７（
ｍ、６Ｈ）、６．ｏｔ（ｄ、 ＩＨ）、５．８９（ｓ
、ＬＨ）、４−．８１（ｓ、２Ｈ）、３．８５ （ｓ、
２Ｈ）、２．１２（ｍ、１． Ｈ）、］−，５７（ｄ、
Ｈ）、］−，２０（Ｓ、３Ｈ）、１．１−２ （ｓ、
３Ｈ）。Nuclear magnetic resonance absorption (δCDC13) of product near, 07(
m, 6H), 6. ot(d, IH), 5.89(s
, LH), 4-. 81 (s, 2H), 3.85 (s,
2H), 2.12(m, 1.H), ]-,57(d,
H),]-,20(S,3H),1.1-2(s,
3H).
Claims (1)
で処理することを特徴とする、一般式で表わされる置換
ビニル基を有するシクロプロパンカルボン酸誘導体の製
法〔式中Ｒ１は低級アルキル基又は５−ベンジルフリル
メチル基であり、Ｒ２は水素原子又は低級アルキル基で
あり、Ｘ、Ｙ及びＺはハロゲンである。 但し、Ｒ２が水素原子の場合、Ｘ、Ｙ及びＺの少なくと
も一つは臭素原子である。 〕。[Claims] 1. A method for producing a cyclopropane carboxylic acid derivative having a substituted vinyl group represented by the general formula, which comprises treating a cyclopropane carboxylic acid ester represented by the general formula with a base [wherein R1 is It is a lower alkyl group or a 5-benzylfurylmethyl group, R2 is a hydrogen atom or a lower alkyl group, and X, Y and Z are halogen. However, when R2 is a hydrogen atom, at least one of X, Y and Z is a bromine atom. ].
Priority Applications (45)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50028607A JPS5822463B2 (en) | 1975-03-11 | 1975-03-11 | Cyclopropane carbonate cyclopropane carbonate |
| IN1621/CAL/75A IN142702B (en) | 1974-09-10 | 1975-08-20 | |
| 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 |
| 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 |
| 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. |
| DE2560240A DE2560240C2 (en) | 1974-09-10 | 1975-09-08 | Hexanoic acid, hexenoic acid and cyclopropanecarboxylic acid esters |
| 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 |
| 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 |
| 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 |
| 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 |
| AT694975A AT347917B (en) | 1974-11-30 | 1975-09-09 | PROCESS FOR THE PRODUCTION OF 2-DIHALOGEN VINYLCYCLOPROPANCARBON ACID ESTERS |
| DK402075A DK158614C (en) | 1974-09-10 | 1975-09-09 | PROCEDURE FOR PREPARING A DIHALOGENEVINYLYCYCLOPROPANCARBOXYLATE |
| SU752170851A SU664558A3 (en) | 1974-09-10 | 1975-09-09 | Method of obtaining esters of dihaloidvinylcyclopropancarboxylic acids |
| DD7500196142A DD128297A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING CYCLOPROPANCARBOXIC ACID ESTERS |
| MX487775U MX5591E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR THE PREPARATION OF ESTERS OF DIHALOVINYL CYCLOPROPANOCARBOXYLIC ACIDS |
| DD7500196145A DD128352A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING GAMMA-UNACCURATED CARBONIC ACID ESTERS |
| 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 |
| MX10052375U MX5451E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING DIHALOVINYL CYCLOPROPAN CARBOXYLATE |
| CS616475A CS212300B2 (en) | 1974-09-10 | 1975-09-10 | Method of preparation of esters of the dihalogenvinylcyclopropancarboxyl acid |
| 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 |
| FR7621448A FR2333774A1 (en) | 1974-09-10 | 1976-07-13 | SUBSTITUTE HARLOCARBOXYLATES, USED AS INTERMEDIARIES FOR THE MANUFACTURE OF PYRETHROID INSECTICIDES |
| FR7621447A FR2318144A1 (en) | 1974-09-10 | 1976-07-13 | PROCESS FOR OBTAINING VINYLCYCLOPROPANE 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 | |
| FR7639510A FR2351946A1 (en) | 1974-11-30 | 1976-12-29 | 2-(Dihalovinyl) cyclopropane carboxylate insecticides prodn. - by reacting alkenol and orthoformate, addition of carbon tetrahalide, basic cyclisation and dehydrohalogenation |
| 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 |
| 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 |
|---|---|---|---|
| JP50028607A JPS5822463B2 (en) | 1975-03-11 | 1975-03-11 | Cyclopropane carbonate cyclopropane carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51146440A JPS51146440A (en) | 1976-12-16 |
| JPS5822463B2 true JPS5822463B2 (en) | 1983-05-09 |
Family
ID=12253250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50028607A Expired JPS5822463B2 (en) | 1974-09-10 | 1975-03-11 | Cyclopropane carbonate cyclopropane carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5822463B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5159839A (en) * | 1974-10-23 | 1976-05-25 | Sankyo Co | SHIKUROPUROPANKARUBONSANJUDOTAINO SEIZOHO |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5159839A (en) * | 1974-10-23 | 1976-05-25 | Sankyo Co | SHIKUROPUROPANKARUBONSANJUDOTAINO SEIZOHO |
-
1975
- 1975-03-11 JP JP50028607A patent/JPS5822463B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5159839A (en) * | 1974-10-23 | 1976-05-25 | Sankyo Co | SHIKUROPUROPANKARUBONSANJUDOTAINO SEIZOHO |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51146440A (en) | 1976-12-16 |
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