JPS5817451B2 - Production method of γ↓-chloro↓-δ↓-unsaturated carboxylic acid ester - Google Patents
Production method of γ↓-chloro↓-δ↓-unsaturated carboxylic acid esterInfo
- Publication number
- JPS5817451B2 JPS5817451B2 JP50028606A JP2860675A JPS5817451B2 JP S5817451 B2 JPS5817451 B2 JP S5817451B2 JP 50028606 A JP50028606 A JP 50028606A JP 2860675 A JP2860675 A JP 2860675A JP S5817451 B2 JPS5817451 B2 JP S5817451B2
- Authority
- JP
- Japan
- Prior art keywords
- ethyl
- acid ester
- dimethyl
- unsaturated carboxylic
- carboxylic acid
- 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
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は一般式
（式中Ｒ１はアルコール残基であり、Ｒ２、Ｒ３、Ｒ４
及びＲ５は水素又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 (wherein R1 is an alcohol residue, R2, R3, R4
and R5 is hydrogen or a lower alkyl group.
）で表わされるγ−クロルーδ−不飽和カルボン酸エス
テルを製造する方法に関するものである。) The present invention relates to a method for producing a γ-chloro-δ-unsaturated carboxylic acid ester represented by:
前記一般式（Ｉ）で表わされるγ−・・ローδ−不飽和
カルボン酸エステル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
単位の合成用中間体である。The γ-rho δ-unsaturated carboxylic acid ester represented by the general formula (I) is an intermediate for the synthesis of the unit constituting the acid moiety of synthetic pyrethroid compounds, which are attracting attention for their usefulness as insecticides. be.
即ち、前記一般式（Ｉ）の化合物を塩基の存在下閉環さ
せるこトニよりジクロルビニル基を持つシクロプロパン
カルボン酸エステルに誘導できる（下記参考側参照）。That is, by ring-closing the compound of the general formula (I) in the presence of a base, a cyclopropanecarboxylic acid ester having a dichlorovinyl group can be derived (see the reference side below).
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
、ジハロビニル基を持つシクロプロパンカルボン酸エス
テルが低毒性、持続性共に優秀であることが明らかとな
った（Ｍ−Ｅｌｌｉｏｔｔ、 ｅｔ ａｌ、。As a result of testing many compounds to solve this drawback, it became clear that cyclopropanecarboxylic acid ester having a dihalobinyl group has low toxicity and excellent durability (M-Elliott, et al.).
Ｎａｔｕｒｅ、 ２４６，１６９（１９７３））。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〔特開昭４９−４７５３１ある
いはり、Ｇ−Ｂｒｏｗｎ、 ｅｔ ａｌ、。Conventionally, methods for synthesizing this type of compound include (1) a method using natural chrysanthemum acid as a starting material [see JP-A-49-47531, G-Brown, et al.
Ｊ−Ａｇｒ、 ＦｏｏｄＣｈｅｍ、 、 ２１．７６
７（１９７３））（２）ジハロブタジェンヘジアゾ酢酸
エステルを付加させる方法（Ｊ−Ｆａｒｋａｓ、ｅｔａ
ｌｌ、 Ｃｏ１１．Ｃｚｅｃｋ、 Ｃｈｅｍ、 Ｃｏｍ
ｍ０、２４゜２２３０ （１９５９））が提案されてい
る。J-Agr, FoodChem, , 21.76
7 (1973)) (2) Method for adding diazoacetate to dihalobutadiene (J-Farkas, eta
ll, Co11. Czeck, Chem, Com
m0, 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、工業的に有利にジクロルヒニル基ヲ持つ
シクロプロパンカルボン酸エステルに誘導し得る前記一
般式（Ｔ）の化合物の簡便な製造方法を完成するに至っ
たものである。The present inventors have made intensive studies to solve these drawbacks of the conventional methods, and have found that the compound of the general formula (T) can be industrially advantageously derived into a cyclopropanecarboxylic acid ester having a dichlorohinyl group. This led to the completion of a simple manufacturing method.
本発明の方法は原料として一般式
〔式中Ｒ１はアルコール残基であり、Ｒ２、Ｒ３Ｒ４及
びＲ５は水素又は低級アルキル基である。The method of the present invention uses a raw material having the general formula [where R1 is an alcohol residue and R2, R3R4 and R5 are hydrogen or a lower alkyl group].
で表わされるδ−トリクロルメチル−γ−不飽和カルボ
ン酸エステルを用いるものである。A δ-trichloromethyl-γ-unsaturated carboxylic acid ester represented by the following formula 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カ
ルボン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・・ロゲン化炭素を付加せしめ、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）。This compound can be easily formed, for example, by adding a tetra-logenated carbon to a γ-unsaturated carboxylic acid ester formed from an allyl alcohol derivative and an orthocarboxylic acid ester, and then treating it with a specific amount of base (
(See reference side below).
前記一般式（社）で表わされるδ−トリクロルメチル−
γ−不飽和カルボン酸エステルとしては、３．３−ジメ
チル−５−トリクロルメチル−４−ペンテン酸メチル、
３，３−ジメチル−５−トリクロルメチル−４−ペンテ
ン酸エチル、２．３．３− トＩＪメチルー５−ト’Ｊ
クロルメチル−４−ペンテン酸エチル、３，３．５−
４リメチル−５−トリクロルメチル−４−ペンテン酸エ
チル、３−メｆルー５− ） ！Ｊ クロルメチル−４
−ペンテン酸エチル、５−トリクロルメチル−４−ペン
テン酸エチル、３，３−ジメチル−５−トリクロルメチ
ル−４、−−−−ヘンテン酸ツメタフエノキシベンジル
エステル、３，３−ジメチル−５−トリクロルメチル−
４−ペンテン酸（７）５−ヘンシル−３−フリルメチル
エステル、２−エチル−３，３−ジメチル−５−トリク
ロルメチル−４−ペンテン酸エチル等ヲ例示することが
できる。δ-Trichloromethyl- represented by the general formula (Company)
Examples of the γ-unsaturated carboxylic acid ester include methyl 3,3-dimethyl-5-trichloromethyl-4-pentenoate;
Ethyl 3,3-dimethyl-5-trichloromethyl-4-pentenoate, 2.3.3-toIJmethyl-5-to'J
Ethyl chloromethyl-4-pentenoate, 3,3.5-
Ethyl 4-trimethyl-5-trichloromethyl-4-pentenoate, 3-methyl-5-)! J Chlormethyl-4
-Ethyl pentenoate, 5-trichloromethyl-4-ethyl pentenoate, 3,3-dimethyl-5-trichloromethyl-4, ----hentenoic acid tumetaphenoxybenzyl ester, 3,3-dimethyl-5- trichloromethyl-
Examples include 4-pentenoic acid (7) 5-hensyl-3-furylmethyl ester, ethyl 2-ethyl-3,3-dimethyl-5-trichloromethyl-4-pentenoate, and the like.
本発明は前記一般式旺で表わされるδ−トリクロルメチ
ル−γ−不飽和カルボン酸エステルを加熱下または酸性
触媒存在下異性化することを必須の要件とするものであ
る。An essential requirement of the present invention is that the δ-trichloromethyl-γ-unsaturated carboxylic acid ester represented by the above general formula is isomerized under heating or in the presence of an acidic catalyst.
この加熱処理は５０８Ｃ〜２００℃で行なわれる。This heat treatment is performed at 508C to 200C.
５０°Ｃ以下では反応が著しく遅く、又２００℃以上で
は副生物が形成するので好捷しくない。If the temperature is below 50°C, the reaction will be extremely slow, and if it is above 200°C, by-products will be formed, which is not preferable.
好ましい加熱温度は１００〜１７０℃である。The preferred heating temperature is 100 to 170°C.
又、本異性化反応は酸性触媒の存在により達成すること
もできる。Moreover, this isomerization reaction can also be achieved by the presence of an acidic catalyst.
酸性触媒としては酢酸、プロピオン酸、酪酸、イソ酪酸
等の低級脂肪酸類、フェノール、ハイドロキノン等のフ
ェノール類、塩化アルミニウム、塩化亜鉛、三弗化硼素
等のルイス酸を好適に用いることが出来る。As the acidic catalyst, lower fatty acids such as acetic acid, propionic acid, butyric acid, and isobutyric acid, phenols such as phenol and hydroquinone, and Lewis acids such as aluminum chloride, zinc chloride, and boron trifluoride can be suitably used.
これらの酸性触媒の使用量は原料化合物に対して一般に
は０．０５〜１０モル係で充分である。The amount of these acidic catalysts to be used is generally from 0.05 to 10 mol based on the raw material compound.
酸性触媒の使用の場合加熱処理を併用することにより反
応を加速出来るものであり、このことも本発明の実施態
様である。In the case of using an acidic catalyst, the reaction can be accelerated by combined use of heat treatment, and this is also an embodiment of the present invention.
本発明は溶媒を用いずに実施できるが、所望ならば反応
に直接関与しない溶媒、例えばベンゼン、トルエン、キ
シレン、テトラリン、高沸点石油エーテル、ジメトキシ
エタン、ジグライムなどの高沸点エーテル類等を用いて
も一面に差支えない。The present invention can be carried out without using a solvent, but if desired, a solvent that does not directly participate in the reaction may be used, such as high-boiling ethers such as benzene, toluene, xylene, tetralin, high-boiling petroleum ether, dimethoxyethane, and diglyme. There is no problem in one aspect.
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.
実施例 １
３、３−ツメｆルー５−トリクロルメチル−４−ペンテ
ン酸エチル５４７■（２ミＩＪモル）ヲテトラリン２
ｍｌに溶解し、アルゴン雰囲気下、１５０°Ｃに２４時
間加熱した。Example 1 Ethyl 3,3-5-trichloromethyl-4-pentenoate 547■ (2 IJ mol) Tetralin 2
ml and heated at 150°C for 24 hours under an argon atmosphere.
その後、減圧蒸留により沸点８８〜９０°Ｃ／ ０．２
ｍｍＨｇを有する３、３−ジメチル−４，６，６−４
リクロル−５−ヘキセン酸エチル３５６ｍ９をえた。Then, by distillation under reduced pressure, the boiling point is 88-90°C/0.2
3,3-dimethyl-4,6,6-4 with mmHg
356 m9 of ethyl chlor-5-hexenoate was obtained.
収率６５係生成物の赤外吸収（ＫＢｒｃｍ ）、１
７３５゜１６１３核磁気共鳴吸収（ＣＣ１４，δ）５．
９６（ｄ ＩＨ）、４．８５（ｄ ＩＨＬ４．０６
（（１２Ｈ）、 ２．４ｘ（ｄ ＩＨ）。Yield: 65 Infrared absorption of product (KBrcm), 1
735°1613 nuclear magnetic resonance absorption (CC14, δ)5.
96 (d IH), 4.85 (d IHL4.06
((12H), 2.4x(d IH).
２．２３（ｄ ＩＨ）、１．２３（ｔ ３Ｈ）。2.23 (d IH), 1.23 (t 3H).
１、ＩＮｓ ６Ｈ）・
実施例 ２
３．３−ジメチル−５−トリクロルメチル−４−ヘンテ
ン酸エチル５４７ａ？（２ミリモル）ヲキシレン２ｍｌ
に溶解し、イソ酪酸３０■を加えたのち、アルゴン雰囲
気下加熱還流を６時間行なった。1, INs 6H)・Example 2 Ethyl 3.3-dimethyl-5-trichloromethyl-4-henthenate 547a? (2 mmol) Woxylene 2 ml
After adding 30 μm of isobutyric acid, the mixture was heated under reflux under an argon atmosphere for 6 hours.
溶媒留去後、減圧蒸留により、沸点８５〜８６°Ｃ／
０．１ ｍｍＨｇを有する３、３〜ジメチル−４，６，
６−ドリクロルー５−ヘキセン酸エチル４１６〜を得た
。After distilling off the solvent, reduce the boiling point to 85-86°C by distillation under reduced pressure.
3,3-dimethyl-4,6, with 0.1 mmHg
Ethyl 6-dolychloro-5-hexenoate 416 was obtained.
収率７６％得られた生成物のスペクトルは、実施例１の
生成物のスペクトルと一致した。The spectrum of the product obtained in 76% yield matched that of the product of Example 1.
実施例 ３
３．３−ジメチル−５−トリクロルメチル−４−ペンテ
ン酸エチル５４７〜をアルボッ８Ｍｔ下、１５０℃１０
時間加熱した。Example 3 Ethyl 3.3-dimethyl-5-trichloromethyl-4-pentenoate 547 ~ was heated at 150°C under 8Mt of Albod at 10
heated for an hour.
その後、減圧蒸留により、沸点８４〜８５°Ｃ／ ０．
０９ ｍｍＨｇを有する油状体として３，３−ジメチル
−４，６，６−４リクロル−５−ヘキセン酸エチル２４
６〜をえた。Then, by vacuum distillation, the boiling point was 84-85°C/0.
Ethyl 3,3-dimethyl-4,6,6-4lichloro-5-hexenoate 24 as an oil with 0.09 mmHg
I got 6~.
収率４５係。Yield: 45.
この生成物はＩＲ１ＮＭＲスペクト。ルおよびガスクロ
マトグラフィーで、実施例１でえられた生成物と比較同
定した。This product has an IR1 NMR spectrum. The product was compared with the product obtained in Example 1 by gas chromatography and gas chromatography.
実施例 ４
実施例２において、溶媒として、ジグライム２ｍｌを用
い、１５０℃に加熱した以外は同様の操作を行なうこと
により３，３−ジメチル−４，６，６−ドリクロルー５
−ヘキセン酸エチル３８３〜を得た。Example 4 3,3-dimethyl-4,6,6-dolychloro-5 was obtained by performing the same operation as in Example 2 except that 2 ml of diglyme was used as the solvent and heated to 150°C.
-Ethyl hexenoate 383- was obtained.
収率７０％。生成物はスペクトル及びガスクロマトグラ
フィーにより比較同定した。Yield 70%. The product was comparatively identified by spectroscopy and gas chromatography.
実施例 ５
３、３−ツメｆルー５−ト１）クロルメチル−４−ペン
テン酸エチル２７４〜に塩化アルミニウム３０ｍ９を加
え、室温で２４時間攪拌した。Example 5 30 m9 of aluminum chloride was added to 274~ of ethyl chloromethyl-4-pentenoate (3,3-thume root 5-t), and the mixture was stirred at room temperature for 24 hours.
生成物をガスクロマトグラフィーで調べたところ、収率
３０係で、３，３−ジメチル−４，６，６−ドリクロル
ー５−ヘキセン酸エチルが生成していることが確認され
た。When the product was examined by gas chromatography, it was confirmed that ethyl 3,3-dimethyl-4,6,6-dolychloro-5-hexenoate was produced at a yield of 30%.
実施例 ６
２．３．３４リメチル−５−トリクロルメチル−４−ペ
ンテン酸エチル２８８〜ヲキシレン１ｍｌに溶解し、フ
ェノール３０ｒｎ９を加えたのち、アルゴン雰囲気下、
１０時間加熱還流した。Example 6 2.3.34 Ethyl-5-trichloromethyl-4-pentenoate 288 ~ After dissolving in 1 ml of xylene, adding phenol 30rn9, under argon atmosphere,
The mixture was heated under reflux for 10 hours.
冷却後、溶媒を留去したのち、減圧蒸留により、沸点９
１〜９３°Ｃ／ ０．１２ ｍｍＨｇを有する油状体と
して、２，３．３−４リメチル−４，６，６−４リクロ
ル−５−ヘキセン酸エチル１９６１ｎ９ヲ得ｋ。After cooling, the solvent was distilled off, and the boiling point was reduced to 9 by distillation under reduced pressure.
Ethyl 2,3.3-4-limethyl-4,6,6-4-lichloro-5-hexenoate 1961n9 was obtained as an oil with a temperature of 1-93°C/0.12 mmHg.
収率６８係。Yield: 68.
生成物の核磁気共鳴吸収（ＣＣ１４，δ）５．９５，５
．９４（ｄ ＩＨ）、４．７７．４．６２（ｄ Ｉ
Ｈ）、 ４．０３．４．０２ （ｑ ２Ｈ）。Nuclear magnetic resonance absorption of product (CC14, δ) 5.95,5
．． 94 (d IH), 4.77.4.62 (d I
H), 4.03.4.02 (q 2H).
２．８０〜２．３５（ｍ ＩＨ）、１．２２（ｔ３Ｈ
）、１．３５〜ｏ、９ｏ（ｍ ９Ｈ）一実施例 ７
参考例１と同様の方法により合成した３、３−ジメチル
−５〜トリクロルメチル−４−ペンテン酸ｍ−フェノキ
シベンジル４２７、５〜をキシレン２ｍｌに溶解し、イ
ソ酪酸３０〜を加えた。2.80-2.35 (m IH), 1.22 (t3H
), 1.35-o,9o (m 9H) Example 7 m-phenoxybenzyl 3,3-dimethyl-5-trichloromethyl-4-pentenoate 427,5- synthesized by the same method as Reference Example 1 was dissolved in 2 ml of xylene, and 30~ of isobutyric acid was added.
この溶液をアルゴン雰囲気下に６時間加熱還流した。The solution was heated to reflux under an argon atmosphere for 6 hours.
溶媒留去後、シリカゲルカラムクロマトグラフィーを行
ない、３，３−ジメチル−４，６，６−ドリクロルー５
−ヘキセン酸ｍ−フェノキシベンシル２９１■を得た。After distilling off the solvent, silica gel column chromatography was performed to obtain 3,3-dimethyl-4,6,6-dolychloro-5.
291 ml of m-phenoxybenzyl-hexenoate was obtained.
収率６８係。原料の核磁気共鳴吸収（ＣＣ１４，δ）
７．４〜６．７（ｍ ９ＨＬ ６．２３（ｄ ＩＨ
）。Yield: 68. Nuclear magnetic resonance absorption of raw material (CC14, δ) 7.4-6.7 (m 9HL 6.23 (d IH
).
５．９５ （ｄ ＩＨ）、 ４．９３ （ｓ ２Ｈ
）。5.95 (d IH), 4.93 (s 2H
).
２．３３（ｓ ２Ｈ）、１．１８（ｓ ６Ｈ）生成
物の核磁気共鳴吸収（ＣＣ１４，δ）７．５〜６．ｓ（
ｍ ９Ｈ）、５．９５（ｄ ｉｎ）。Nuclear magnetic resonance absorption (CC14, δ) of 2.33 (s 2H), 1.18 (s 6H) products 7.5-6. s(
m 9H), 5.95 (d in).
４．９５ （ｓ ２Ｈ）、 ４．８５ （ｄ ＩＨ
）。4.95 (s 2H), 4.85 (d IH
).
２．４０（ｄ ＩＨ）、２．２２（ｄ ＩＨ）。2.40 (d IH), 2.22 (d IH).
１．１０（ｓ ６Ｈ）
参考例 １
３．３−ジメチル−４−ブロム−５−４リクロルメチル
吉草酸エチル７０９〜（２ｍｍ０１ ）の無水テトラヒ
ドロフラン溶液２ｍｌを１６３ｍＦ？（２，４ｍｍｏ
ｌ ）のナトリウムエトキシドを懸濁させた無水テトラ
ヒドロフラン２０ｍ１の溶液に水冷下部下し、室温下、
一晩攪拌を続けた。1.10 (s 6H) Reference Example 1 2ml of an anhydrous tetrahydrofuran solution of ethyl 3.3-dimethyl-4-bromo-5-4lichloromethylvalerate 709~(2mm01) was heated to 163mF? (2,4 mmo
A solution of 20 ml of anhydrous tetrahydrofuran in which sodium ethoxide (1) was suspended was added to a water-cooled bottom, and at room temperature,
Stirring was continued overnight.
次いで氷水にあけ、エーテル抽出し乾燥した。Then, it was poured into ice water, extracted with ether, and dried.
溶媒を留去後、減圧下、蒸留し沸点８３〜８５°Ｃ１０
，１ｍｍ Ｈｇを有する３、３−ジメチル−５−トリク
ロルメチル−４−ヘンテン酸エチルを４４８〜得り。After distilling off the solvent, it is distilled under reduced pressure to a boiling point of 83-85°C10
, 1 mm Hg was obtained from 448~.
収率８２係（純度８５係以上）１つ
純粋な生成物の核磁気共鳴吸収（ＣＣ１４，δ）６．１
３（ｑ、２Ｈ）、４°０７ （ｑ 、 ２Ｈ） 、２°
２９（ｓ、２Ｈ）、１．５０〜１．００（ｍ、９Ｈ）。Yield: 82 (Purity: 85 or higher) Nuclear magnetic resonance absorption of one pure product (CC14, δ) 6.1
3 (q, 2H), 4°07 (q, 2H), 2°
29 (s, 2H), 1.50-1.00 (m, 9H).
参考例 ２
２．３．３−トリメチル−４−ブロム−５−トジクロル
メチル吉草酸エチル７３７■（２ｍｍｏ ｌ ｅを無水
テトラヒドロフラン２０ ｍｌの溶解し、氷冷した。Reference Example 2 737 ml of ethyl 2.3.3-trimethyl-4-bromo-5-todichloromethylvalerate (2 mmole) was dissolved in 20 ml of anhydrous tetrahydrofuran and cooled on ice.
この溶液に、ナトリウムエトキシド１６３〜（２，４ミ
リモル）を少しづつ加えた。To this solution, 163-(2.4 mmol) of sodium ethoxide was added in portions.
５時間後、氷冷した希塩酸にあけ、エーテル抽出し、水
、重曹水、飽和食塩水で洗滌したのち、乾燥した。After 5 hours, the mixture was poured into ice-cooled diluted hydrochloric acid, extracted with ether, washed with water, aqueous sodium bicarbonate, and saturated brine, and then dried.
溶媒留去後減圧蒸留により、沸点９２〜９５℃１０．２
ｍｍ Ｈｇを有する２、３．３−）ジメチル−５−トリ
クロルメチル−４−ペンテン酸エチル４３０ｍｇを得た
。After distilling off the solvent, the boiling point was 92-95℃10.2 by distillation under reduced pressure.
430 mg of ethyl 2,3.3-)dimethyl-5-trichloromethyl-4-pentenoate with mm Hg were obtained.
収率７５係。生成物の核磁気共鳴吸収（ＣＣ１４，δ）
６．１５（ｑ ２Ｈ）、４．０７（ｑ ２Ｈ）。Yield: 75. Nuclear magnetic resonance absorption of product (CC14, δ)
6.15 (q 2H), 4.07 (q 2H).
２．７０〜２．１０（ｍ ＩＨ）、１．２４（ｔ３Ｈ
）、１．３０〜０．９０（ｍ ９Ｈ）参考例 ３
３．３−ジメチル−４，６，６−）リクロルー５−ヘキ
セン酸エチル５４７７Ｑ（２ミリモル）全無水エチルア
ルコール２ｍｌに溶解した。2.70-2.10 (m IH), 1.24 (t3H
), 1.30 to 0.90 (m 9H) Reference Example 3 3.3-Dimethyl-4,6,6-)lichloro-5-hexenoate ethyl 5477Q (2 mmol) was dissolved in 2 ml of total anhydrous ethyl alcohol.
この溶液を、金属ナトリウム５７■（２，５ミリモル）
を溶解した無水エチルアルコール１０ｍ１に滴下Ｌ、５
時間室温で攪拌した。Add this solution to 57 μm (2.5 mmol) of metallic sodium
Dropped into 10 ml of absolute ethyl alcohol dissolved in L, 5
Stirred at room temperature for an hour.
その後、反応液を氷水冷却して塩化水素の無水エチルア
ルコール溶液を滴下して中和した。Thereafter, the reaction solution was cooled with ice water, and anhydrous ethyl alcohol solution of hydrogen chloride was added dropwise to neutralize it.
１／１０の体積に濃縮した後、エーテルを加え、氷水に
あけ、エーテル層を炭酸水素ナトリウム水溶液、飽和食
塩水で洗滌、乾燥した。After concentrating to 1/10 volume, ether was added, poured into ice water, and the ether layer was washed with an aqueous sodium bicarbonate solution and saturated brine, and dried.
溶媒を留去した後、減圧蒸留により、沸点７５〜７６°
Ｃ１０，２５皿Ｈｇを有する２−４２，２−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４３６ｒｎ？ヲ得た。After distilling off the solvent, reduce the boiling point to 75-76° by distillation under reduced pressure.
C10,2-42,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate with 25 Hg 436rn? I got it.
収率９２係。Yield: 92.
生成物中のトランス異性体の由来する核磁共鳴吸収（δ
、ＣＣ１４）：５．５６（ａ ＩＨ）。Nuclear magnetic resonance absorption (δ
, CC14): 5.56 (a IH).
４．０５（ｂｑ ２Ｈ）、２．１２（ｄｄ ＩＨ）
１．４７（ａ ＩＨ）、１．５０〜１．１ｏ（ｍ９Ｈ
）・
なお、６．２２ （ｄ ）、 ２．３５〜２．１０
（ｍ ）にシス体に由来する吸収が認められた。4.05 (bq 2H), 2.12 (dd IH)
1.47 (a IH), 1.50-1.1o (m9H
)・In addition, 6.22 (d), 2.35 to 2.10
Absorption derived from the cis isomer was observed in (m).
シスとトランスの比は核磁気共鳴吸収よりおよそ２：８
であった。The ratio of cis to trans is approximately 2:8 from nuclear magnetic resonance absorption.
Met.
参考例 ４
３．３−ジメチル−４，６，６−）ジクロル−５−ヘキ
セン酸エチル５４７〜（２ミリモル）全乾燥テトラヒド
ロフラン２ｍｌに溶解した。Reference Example 4 Ethyl 3.3-dimethyl-4,6,6-)dichloro-5-hexenoate 547 ~ (2 mmol) was dissolved in 2 ml of completely dry tetrahydrofuran.
この溶液をナトリウムｔ−ブトキシド２８８■（３ミリ
モル）を加えた乾燥テトラヒドロフラン１０ｍ１に滴下
し、室温で２時間攪拌した。This solution was added dropwise to 10 ml of dry tetrahydrofuran to which 288 μm (3 mmol) of sodium t-butoxide had been added, and the mixture was stirred at room temperature for 2 hours.
その後反応液を氷水に注いだのち、エーテル抽出し、乾
燥した。Thereafter, the reaction solution was poured into ice water, extracted with ether, and dried.
溶媒を留去したのち、減圧蒸留により、沸点７８〜７９
°Ｃ／ ０．３５ 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４２７７７２１；ＪｔＪｉｔ。After distilling off the solvent, the boiling point is 78-79 by distillation under reduced pressure.
Ethyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate 4277721 with °C/0.35 mmHg; JtJit.
収率９０係。Yield: 90.
生成物のスペクトルは、参考例３で得られた化合物とほ
ぼ一致した。The spectrum of the product almost matched that of the compound obtained in Reference Example 3.
シスとトランスの比はおよそ１：９であった。The cis to trans ratio was approximately 1:9.
参考例 ５
２．３．３−）ジメチル−４，６，６−４リクロルー５
−ヘキセン酸エチル５７５■（２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１２０■（
５０％、２．５ミリモル）を分散させた無水ジメトキシ
エタン１０ｍ１に滴下した。Reference example 5 2.3.3-)dimethyl-4,6,6-4lichloro-5
- A solution of 575 μm (2 mmol) of ethyl hexenoate in 5 ml of anhydrous dimethoxyethane was added with 120 μm (2 mmol) of sodium hydride (
50%, 2.5 mmol) was added dropwise to 10 ml of anhydrous dimethoxyethane dispersed therein.
その後加熱還流を５時間続け、冷却した。氷冷しだ希塩
酸で中和したのち、エーテル抽出し、炭素水素す） Ｉ
Ｊウム水溶液、飽和食塩水で洗滌し乾燥した。Thereafter, heating under reflux was continued for 5 hours, and the mixture was cooled. After cooling with ice and neutralizing with dilute hydrochloric acid, extracting with ether and removing carbon hydrogen)
It was washed with an aqueous solution of Jum and a saturated saline solution and dried.
溶媒留去後、減圧蒸留により、沸点７５〜７８°Ｃ／
０．１ ｍｍ Ｈｇを有する１−メチル−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３６０■を得だ。After distilling off the solvent, reduce the boiling point to 75-78°C by distillation under reduced pressure.
1-methyl-2-(2,2
360 μm of ethyl (-dichlorovinyl)-3,3-dimethylcyclo-propanecarboxylate was obtained.
収率７２チ。生成物の核磁気共鳴吸収（ＣＣ１４，δ）
：６．２６．５．５７（ｄ ＩＦＩ）、 ４．１０
（ｑ２Ｈ）、２．２８，１．５２（ｄ ＩＢ）、１．
３９〜ｏ、ｃ＋ｏ（ｍ １２Ｈ）。Yield: 72 cm. Nuclear magnetic resonance absorption of product (CC14, δ)
:6.26.5.57 (d IFI), 4.10
(q2H), 2.28, 1.52 (d IB), 1.
39~o, c+o (m 12H).
Claims (1)
ボン酸エステルを加熱下または酸性触媒存在下、異性化
せしめることを特徴とする、一般式で表わされるγ−ク
ロルーδ−不飽和カルボン酸エステルの製造方法〔式中
Ｒ１はアルコール残基であり、Ｒ２、Ｒ３、Ｒ４及びＲ
５は水素又は低級アルキル基である。 〕。[Scope of Claims] 1 A compound represented by the general formula, characterized by isomerizing a δ-totrylolmethyl-γ-unsaturated carboxylic acid ester represented by the general formula under heating or in the presence of an acidic catalyst. [In the formula, R1 is an alcohol residue, R2, R3, R4 and R
5 is hydrogen or a lower alkyl group. ].
Priority Applications (45)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50028606A JPS5817451B2 (en) | 1975-03-11 | 1975-03-11 | Production method of γ↓-chloro↓-δ↓-unsaturated carboxylic acid ester |
| 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 |
| 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 |
| 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 |
| 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 |
| NZ178641A NZ178641A (en) | 1974-09-10 | 1975-09-09 | Esters of vinylcycloprpane carboxylic acids and intermediates |
| 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 |
| 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 |
| DD7500196143A DD128298A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR THE PREPARATION OF TRIHALOGENCYCLOPROPANCARBOSE ACID ESTERS |
| DD188270A DD122678A5 (en) | 1974-09-10 | 1975-09-10 | |
| MX10052375U MX5451E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING DIHALOVINYL CYCLOPROPAN CARBOXYLATE |
| BE159921A BE833278A (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR OBTAINING SUBSTITUTE CYCLOPROPANES, PARTICULARLY USEFUL AS PYRETHROID INSECTICIDES |
| DD7500196145A DD128352A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING GAMMA-UNACCURATED CARBONIC ACID ESTERS |
| MX487775U MX5591E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR THE PREPARATION OF ESTERS OF DIHALOVINYL CYCLOPROPANOCARBOXYLIC ACIDS |
| CS616475A CS212300B2 (en) | 1974-09-10 | 1975-09-10 | Method of preparation of esters of the dihalogenvinylcyclopropancarboxyl acid |
| TR2087675A TR20876A (en) | 1974-09-10 | 1975-09-10 | MANUFACTURING PROCEDURE OF THE ESTERS OF DIHALO-VINYLICYCLOPROPANKARBOXYLED ACIDS |
| DD7500196141A DD128351A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING UNCONDITIONED CARBONIC ACID ESTERS |
| DD7500196142A DD128297A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING CYCLOPROPANCARBOXIC 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 |
| FR7639508A FR2351943A1 (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 |
| FR7639509A FR2351944A1 (en) | 1975-02-24 | 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 |
| TR2086879A TR20868A (en) | 1974-11-30 | 1979-09-06 | MANUFACTURING PROCEDURE OF THE ESTERS OF DIHALO-OENYLICYCLOPROPANKARBOXYLIC 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 |
|---|---|---|---|
| JP50028606A JPS5817451B2 (en) | 1975-03-11 | 1975-03-11 | Production method of γ↓-chloro↓-δ↓-unsaturated carboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51105013A JPS51105013A (en) | 1976-09-17 |
| JPS5817451B2 true JPS5817451B2 (en) | 1983-04-07 |
Family
ID=12253224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50028606A Expired JPS5817451B2 (en) | 1974-09-10 | 1975-03-11 | Production method of γ↓-chloro↓-δ↓-unsaturated carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5817451B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0548347B2 (en) * | 1985-10-04 | 1993-07-21 | Shiiiteku Inc |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49103520A (en) * | 1973-02-03 | 1974-10-01 |
-
1975
- 1975-03-11 JP JP50028606A patent/JPS5817451B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49103520A (en) * | 1973-02-03 | 1974-10-01 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0548347B2 (en) * | 1985-10-04 | 1993-07-21 | Shiiiteku Inc |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51105013A (en) | 1976-09-17 |
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