JPS5817735B2 - Gamma − Fuhouwa carbon sane ester noseiho - Google Patents
Gamma − Fuhouwa carbon sane ester noseihoInfo
- Publication number
- JPS5817735B2 JPS5817735B2 JP50008673A JP867375A JPS5817735B2 JP S5817735 B2 JPS5817735 B2 JP S5817735B2 JP 50008673 A JP50008673 A JP 50008673A JP 867375 A JP867375 A JP 867375A JP S5817735 B2 JPS5817735 B2 JP S5817735B2
- Authority
- JP
- Japan
- Prior art keywords
- ethyl
- acid
- methyl
- mol
- reaction
- 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
Links
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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、Ｒ２及びＲ３は低級アルキル基でありＲ４
及びＲ５は水素又は低級アルキル基であり、Ｒ４及びＲ
５の少くとも一方は水素である。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein R1, R2 and R3 are lower alkyl groups and R4
and R5 are hydrogen or a lower alkyl group, R4 and R
At least one of 5 is hydrogen.
）で表七されるγ−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 γ-unsaturated carboxylic acid esters shown in Table 7.
更に詳しくは、本発用は一般式
（式中Ｒ２、Ｒ３は低級アルキル基であり、Ｒ４及びＲ
５は水素又は低級アルキル基であり、Ｒ４及びＲ５の少
くとも一方は水素である。More specifically, the present invention is expressed by the general formula (wherein R2 and R3 are lower alkyl groups, R4 and R
5 is hydrogen or a lower alkyl group, and at least one of R4 and R5 is hydrogen.
）で表わされるアリルアルコール誘導体と一般式 （式中Ｒ１は低級アルキル基である。) Allyl alcohol derivatives and general formula (In the formula, R1 is a lower alkyl group.
）で表わされるオルト酢酸エステルとを酸性触媒の存在
下反応させることにより前記一般式（Ｉ）で表わされる
γ一手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-one-handed saturated carboxylic acid ester represented by the general formula (I) by reacting an orthoacetic ester represented by the formula (I) in the presence of an acidic catalyst.
前記一般式ＣＩ）で表わされるγ−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
中間体として有用である。The γ-unsaturated carboxylic acid ester represented by the general formula CI) is useful as an intermediate for the synthesis of units constituting the acid moiety of synthetic pyrethroid compounds, which are attracting attention for their usefulness as insecticides.
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（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 and used from natural sources, 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.
この欠点を解決し、且つ天然ピレスロイドにまさる殺虫
効力を有する化合物の徹底的探索が行なわれた結果、菊
酸のジメチルビニル基を変化させた誘導体の中に持続性
のある優れた殺虫効果を示す合成ピレスロイドが見出さ
れた。As a result of a thorough search for a compound that solves this drawback and has an insecticidal effect superior to that of natural pyrethroids, a derivative of chrysanthemum acid with a modified dimethylvinyl group has shown to have a long-lasting and excellent insecticidal effect. A synthetic pyrethroid was discovered.
ＣＭ。Ｅｌｌｉｏｔｔ ｅｔ ａｌ、、Ｎａｔｕｒｅ、
２４．４．４５６（１９７３）参照〕
本発明は前記の合成ピレスロイド用シクロプロパンカル
ボン酸エステルの先駆体として有用な前記一般式（Ｉ）
で表わされるγ−不飽和カルボン酸エステルを製造する
方法を提供するものである。CM. Elliott et al., Nature.
24.4.456 (1973)] The present invention provides compounds of the general formula (I) useful as precursors of the cyclopropane carboxylic acid esters for synthetic pyrethroids.
The present invention provides a method for producing a γ-unsaturated carboxylic acid ester represented by:
（下記参考側参照）
従来、菊酸のジメチルビニル基を変換するには菊酸自体
を出発原料としオゾン分解後新しい置換基を導入する方
法が提案されている。(See reference side below) Conventionally, in order to convert the dimethylvinyl group of chrysanthemum acid, a method has been proposed in which chrysanthemum acid itself is used as a starting material and a new substituent group is introduced after ozonolysis.
しかし、この従来法は高価な菊酸を用いること及び合成
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 chrysanthemum acid and the long and complicated synthesis route.
〔特開昭４９−４７５３１号及びり、Ｇ、 Ｂｒｏｗｎ
ｅｔ ａｌｌ、Ｊ、Ａｇｒ、Ｆｏｏｄ Ｃｈｅｍ、、
２１．７６７（１９７３：参照〕
更に従来γ−不飽和カルボン酸エステルを製造する方法
としては３−メチルクロチルアルコールとビニルエーテ
ルとを縮合させ、形成せるγ−不飽和アルデヒドを酸化
し、エステル化する方法が提案されている（ Ｊ、Ａｍ
、 Ｃｈｅｍ、 Ｓｏｃ、、８２．４６８１−５（１９
６０）参照〕。[Unexamined Japanese Patent Publication No. 49-47531 and G. Brown
et all, J.Agr., Food Chem.
21.767 (1973: Reference) Furthermore, as a conventional method for producing γ-unsaturated carboxylic acid ester, 3-methylcrotyl alcohol and vinyl ether are condensed, and the γ-unsaturated aldehyde formed is oxidized and esterified. A method has been proposed (J, Am
, Chem, Soc, , 82.4681-5 (19
60)].
しかし、この従来法ではビニルエーテルのような比較的
高価な試剤を必要とするばかりでなく、反応工程も長い
故に工業的方法としては採用し難いものである。However, this conventional method not only requires relatively expensive reagents such as vinyl ether, but also requires a long reaction process, making it difficult to adopt as an industrial method.
本発明者等は斯様な欠点を解決すべく、鋭意検討を重ね
た結果、工業的に有利に菊酸同族体に導き得るγ−不飽
和カルボン酸エステルを製造する一般的方法を完成する
に至ったものである。In order to solve such drawbacks, the present inventors have made extensive studies and have completed a general method for producing γ-unsaturated carboxylic acid esters that can be industrially advantageously led to chrysanthemum acid analogues. This is what we have come to.
本発明の方法で原料化合物として用いる前記一般式（６
）で表わされるアリルアルコール誘導体としては、３−
メチル−２−ブテン−１−オール、４−メチル−３−ペ
ンテン−２−オール、５−メチル−４−ヘキセン−３−
オール、２−メチル−２−ヘプテン−４−オール等を例
示することができる。The general formula (6) used as a raw material compound in the method of the present invention
) as the allyl alcohol derivative represented by 3-
Methyl-2-buten-1-ol, 4-methyl-3-penten-2-ol, 5-methyl-4-hexene-3-
Examples include ol, 2-methyl-2-hepten-4-ol, and the like.
これらのアリルアルコール誘導体はいずれも工業原料か
ら容易に誘導し得る化合物である。All of these allyl alcohol derivatives are compounds that can be easily derived from industrial raw materials.
本発明は酸性触媒の存在を必須とするものであるが、酸
性触媒としては、フェノール、０・ｍ・ｐ−ニトロフェ
ノール、０・ｍ−ｐ−クレゾール、ｏ−ｍ−ｐ−キシレ
ノール、２・６−シメチルフエノール、２・６−ジーｔ
−７”チルフェノール、２・４・６−トリー５ｅｃ−ブ
チルフェノール、２・４・６−トリーｔ−ブチルフェノ
ール、４−メチル−２・６−ジーｔ−ブチルフェノール
、４−メチル−３・５−ジーｔ−プチルフエノーノ瓢ハ
イドロキノン、２・５−ジーＬ−ブチルノ・イドロキノ
ノ、α・β−ナフトールなどのフェノール類、酢酸、プ
ロピオン酸、酪酸、イソ酪酸、シクロヘキサンカルボン
酸、吉草酸などの低級脂肪酸類、安息香酸、ｍ−クロル
安息香酸などの芳香族カルボン酸類、ベンゼンスルホン
酸、バラトルエンスルホン酸などのスルホン酸類、塩酸
、硫酸、リン酸、ホウ酸などの鉱酸、塩化アルミニウム
、塩化亜鉛、塩化鉄、三弗化ホウ素、酢酸第二水銀など
のルイス酸などであるが、式（２）の原料の脱水などの
副反応をさけるために、好ましくはフェノール却、炭素
数２〜６の脂肪酸及び芳香族カルボン酸類などが用いら
れる。The present invention requires the presence of an acidic catalyst, and examples of acidic catalysts include phenol, 0.m.p.-nitrophenol, 0.m.p.-cresol, o.m.p.-xylenol, 2.m.p. 6-dimethylphenol, 2,6-di-t
-7” thylphenol, 2,4,6-tri-5ec-butylphenol, 2,4,6-tri-t-butylphenol, 4-methyl-2,6-di-t-butylphenol, 4-methyl-3,5-di-t-butylphenol Phenols such as t-butylhydroquinone, 2,5-di-L-butylhydroquinone, and α/β-naphthol, lower fatty acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, cyclohexanecarboxylic acid, and valeric acid, benzoic acid acids, aromatic carboxylic acids such as m-chlorobenzoic acid, sulfonic acids such as benzenesulfonic acid and valatoluenesulfonic acid, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid, aluminum chloride, zinc chloride, iron chloride, These include boron trifluoride and Lewis acids such as mercuric acetate, but in order to avoid side reactions such as dehydration of the raw materials of formula (2), phenol, fatty acids having 2 to 6 carbon atoms, and aromatic acids are preferably used. Carboxylic acids and the like are used.
触媒量は原料アリルアルコール誘導体に対し０．００１
〜２０重量％の範囲で使用されるが、好ましくは１〜１
５重量％の範囲である。The amount of catalyst is 0.001 based on the raw material allyl alcohol derivative
It is used in a range of 20% by weight, preferably 1 to 1% by weight.
It is in the range of 5% by weight.
反応溶媒は必ずしも必要としないが、ｎ−オクタン、ト
ルエン、ｏ’ｍ’ｐ−キシレン、ジ−ｎ−ブチルエーテ
ル、ｔ−７”チルアルコール、Ｎ・１Ｎ−ジメチルホル
ムアミドなど反応に関与しないものが用いられる。A reaction solvent is not necessarily required, but one that does not participate in the reaction, such as n-octane, toluene, o'm'p-xylene, di-n-butyl ether, t-7'' methyl alcohol, and N.1N-dimethylformamide, can be used. It will be done.
反応温度は限定的ではないが、反応速度、選択率の面か
ら約１００〜２５０℃の範囲が好ましい。Although the reaction temperature is not limited, it is preferably in the range of about 100 to 250°C from the viewpoint of reaction rate and selectivity.
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
３−メチル−２−ブテン−１−オール４３グ（０，５モ
ル）、オルト酢酸エチル９７ｆ（０，６モル）、フェノ
ール７．０２（０，０７５モル）を混合し９〜１０時間
１３５〜１４０℃に加熱攪拌した。Example 1 43 g (0.5 mol) of 3-methyl-2-buten-1-ol, 97 f (0.6 mol) of ethyl orthoacetate, and 7.02 (0,075 mol) of phenol were mixed to produce 9 to 10 g of 3-methyl-2-buten-1-ol. The mixture was heated and stirred at 135 to 140°C for a period of time.
反応が進行するに伴って生成したエチルアルコールは反
応系外に留去した。Ethyl alcohol produced as the reaction progressed was distilled out of the reaction system.
理論量のエチルアルコールが留出してから加熱を止め、
反応液を室温に戻した。After the theoretical amount of ethyl alcohol has distilled out, stop heating.
The reaction solution was returned to room temperature.
反応液をエーテルで希釈した後、■規定塩酸で充分に振
とうして過剰のオルトエステルを分解した。After diluting the reaction solution with ether, it was thoroughly shaken with normal hydrochloric acid to decompose excess orthoester.
次に飽和重炭酸ナトリウム、水で洗った後乾燥した。It was then washed with saturated sodium bicarbonate, water, and dried.
溶液を濃縮後減圧蒸留することにより３・３−ジメチル
−４−ペンテン酸エチルを６０．８２得た。The solution was concentrated and then distilled under reduced pressure to obtain 60.82 ethyl 3,3-dimethyl-4-pentenoate.
収率７８％０沸点５７〜６０°Ｃ／ １１ ｍｍＨｇ
０生成物の核磁気共鳴吸収（ＣＣ１４δ）
６．１５〜５．６０ （ｍ Ｉ Ｈ）、５．１５〜４．
６８（ｍ２Ｈ）、４．０２（ｑ ２Ｈ）、２．１９（
ｓ２Ｈ）、］、、４５〜１．０５（ｍ ９Ｈ）。Yield 78% 0 Boiling point 57-60°C/11 mmHg
Nuclear magnetic resonance absorption (CC14δ) of 0 product 6.15-5.60 (m I H), 5.15-4.
68 (m2H), 4.02 (q 2H), 2.19 (
s2H), ], 45-1.05 (m 9H).
実施例 ２
４−メチル−３−ペンテン−２−オール５グ（０，０５
モル）とオルト酢酸エチル１７グ（０，１０５モル）を
フラスコに入れ、フェノール０．５１を加え１３０〜１
４０°Ｃで２４時間攪拌する。Example 2 4-methyl-3-penten-2-ol 5 g (0,05
Put 17 g (0,105 mol) of ethyl orthoacetate into a flask, add 0.51 mol of phenol, and make 130 to 1 mol).
Stir at 40°C for 24 hours.
その間生成するエタノールは留去させる。冷却後、過剰
のオルト酢酸エチルを減圧下留去したのち、減圧蒸留に
より３・３−゛ジメチルー４−ヘキセン酸エチルを５．
６′？（収率６４％）得た。Ethanol produced during this time is distilled off. After cooling, excess ethyl orthoacetate was distilled off under reduced pressure, and then ethyl 3,3-dimethyl-4-hexenoate was distilled under reduced pressure.
6'? (yield: 64%).
沸点１０３〜１０５１５７朋Ｈｇ、生成物の赤外吸収（
ＫＢｒ、ＣｒｒＬ’）１７３５．１６００．１１２５．
１０３８．９６５．８４５゜
実施例 ３
５−メチル−４−ヘキセン−３−オール５．６０Ｐ（０
，０４９モル）とオルト酢酸エチル１５８８ｆ（０，０
９８モル）を混合し、フェノール０．５１を加え１４０
℃に加熱する。Boiling point 103-105157 Hg, infrared absorption of product (
KBr, CrrL') 1735.1600.1125.
1038.965.845゜Example 3 5-methyl-4-hexen-3-ol 5.60P (0
,049 mol) and ethyl orthoacetate 1588f (0,0
98 mol), added 0.51 mol of phenol and added 140 mol of
Heat to ℃.
生成するエタノール留去しながら２４時間加熱攪拌を続
げろ。Continue heating and stirring for 24 hours while distilling off the ethanol produced.
その後渡圧下過剰のオルト酢酸エチルを留去し、減圧蒸
留により、３・３−ジメチル−４−ヘプテン酸エチル７
６４グを得た。Thereafter, excess ethyl orthoacetate was distilled off under passing pressure, and ethyl 3,3-dimethyl-4-heptenoate was purified by distillation under reduced pressure.
I got 64g.
沸点１０３〜１０７°Ｃ／３８ｍｍＨｇ０収率８４．５
％。Boiling point 103-107°C/38mmHg0 Yield 84.5
%.
生成物の核磁気共鳴（ＣＣＩ４δ）
５．３５（ｍ ２Ｈ）、４．０３（ｑ ２Ｈ）、２
．１．７（ｓ ２Ｈ）、２．１５〜１．７５ （ｍ
２Ｈ）、１．４０〜１．８０（ｍ ］、２Ｈ）
実施例 ４
２−メチル−２−へブテン−４−オール５０グ（０，０
３９モル）とオルト酢酸エチル１２．６４１（０，０７
８モル）を混合し、フェノール０．４１を加え、１４０
℃に加熱する。Product nuclear magnetic resonance (CCI4δ) 5.35 (m 2H), 4.03 (q 2H), 2
．． 1.7 (s 2H), 2.15-1.75 (m
2H), 1.40-1.80 (m ), 2H) Example 4 2-methyl-2-hebuten-4-ol 50 g (0,0
39 mol) and ethyl orthoacetate 12.641 (0.07
8 mol), added 0.41 phenol, and added 140
Heat to ℃.
実施例３と同様操作後、減圧蒸留により、３・３−ジメ
チル−４−オクテン酸エチル６．７７９を得た。After the same operation as in Example 3, 6.779 ethyl 3,3-dimethyl-4-octenoate was obtained by distillation under reduced pressure.
沸点１１４〜１１６℃／ ３３ ｍｍＨｇ ｏ収率８８
％。Boiling point 114-116℃/33 mmHg o Yield 88
%.
生成物の核磁気共鳴吸収（ＣＣＩ４δ）
５．６０〜５．２０（ｍ ２Ｈ）、４．０２ （ｑ
２Ｈ）、２．１６（ｓ ２Ｈ）、２．１５−１．７５
（ｍ ２Ｈ）、１．６０〜］、、００（ｍ ＩＩＨ
）、０．８７（ｔ３Ｈ）。Nuclear magnetic resonance absorption of product (CCI4δ) 5.60-5.20 (m2H), 4.02 (q
2H), 2.16 (s 2H), 2.15-1.75
(m 2H), 1.60~], 00(m IIH
), 0.87 (t3H).
実施例 ５
３−メチル−２−ブテン−１−オール４．３１とオルト
酢酸エチル１６２１を混合し、硼酸８６ｍ９を加えて１
２０℃に加熱した。Example 5 4.31 3-methyl-2-buten-1-ol and 1621 ml of ethyl orthoacetate were mixed, 86 m9 of boric acid was added, and 1
Heated to 20°C.
２時間後反応混合物を１４５℃〜１５０℃とし、８時間
加熱攪拌を続けその間生成するエタノールは留去した。After 2 hours, the reaction mixture was heated to 145°C to 150°C and heated and stirred for 8 hours, during which time the ethanol produced was distilled off.
その後、ビグローカラムを用いて過剰のオルト酢酸エチ
ルを留去したのち、減圧蒸留により沸点７８〜８０°ｃ
／ ５１ ｍｍＨｇを有する３・３−ジメチル−４−
ペンテン酸エチル６．２５Ｐをえた。After that, excess ethyl orthoacetate was distilled off using a Vigreux column, and the boiling point was 78-80°C by distillation under reduced pressure.
/3,3-dimethyl-4- with 51 mmHg
6.25P of ethyl pentenoate was obtained.
収率８０％。Yield 80%.
生成物の核磁気共鳴吸収（ＣＣＩ、、δ）５．８５（ｄ
、ｄ ］、Ｈ）、５．１０〜４．７０ （ｍ２Ｈ）、
４．０３（ｑ ２Ｈ）、２．１．９ （ｑ、 ２Ｈ）
、１．２３（ｔ ３Ｈ）、１．１２（ｓ ６Ｈ）。Nuclear magnetic resonance absorption (CCI, δ) of the product 5.85 (d
, d], H), 5.10 to 4.70 (m2H),
4.03 (q 2H), 2.1.9 (q, 2H)
, 1.23 (t 3H), 1.12 (s 6H).
実施例 ６
実施例５において、触媒として硼酸の代りにリン酸３滴
を用いた以外は同様の操作を行ない、減圧蒸留により、
沸点８７〜８８℃／ ５８ ｍｒｒｔＨｇを有する３・
３−ジメチル−４−ペンテン酸エチル６．１５２をえた
。Example 6 The same procedure as in Example 5 was performed except that 3 drops of phosphoric acid was used instead of boric acid as a catalyst, and by vacuum distillation,
3. with boiling point 87-88℃/58 mrrtHg
6.152 ethyl 3-dimethyl-4-pentenoate was obtained.
収率７９％。生成物のスペクトルは実施例５でえられた
生成物のスペクトルと一致した。Yield 79%. The spectrum of the product was consistent with that obtained in Example 5.
実施例 ７
３−メチル−２−ブテン−１−オール０．６５１とオル
ト酢酸エチル２４３７を混合し、フェノール５０ｍ９を
加え１２０℃に加熱した。Example 7 0.651 of 3-methyl-2-buten-1-ol and 2437 of ethyl orthoacetate were mixed, 50 m9 of phenol was added, and the mixture was heated to 120°C.
２時間後反応混合物を１４０℃にし２０時間加熱攪拌を
続け、生成するエタノールを留去した。After 2 hours, the reaction mixture was heated to 140°C and continued to be heated and stirred for 20 hours, and the produced ethanol was distilled off.
その後反応液をベンゼンに溶解して全量を５ｍｌとし、
ガスクロマトグラフィーにより定量したところ、収率９
２％で３・３−ジメチル−４−ペンテン酸エチルの生成
を認めた。After that, the reaction solution was dissolved in benzene to make a total volume of 5 ml,
As determined by gas chromatography, the yield was 9.
Formation of ethyl 3,3-dimethyl-4-pentenoate was observed at 2%.
実施例 ８
実施例７において、触媒としてフェノールの代りにハイ
ドロキノン２５〜を用いた以外は同様の操作を行ない、
ガスクロマトグラフィーにより収率５１％で３・３−ジ
メチル−４−ペンテン酸エチルの生成を認めた。Example 8 The same operation as in Example 7 was performed except that hydroquinone 25~ was used instead of phenol as a catalyst,
Gas chromatography confirmed the formation of ethyl 3,3-dimethyl-4-pentenoate in a yield of 51%.
実施例 ９
実施例７において、触媒としてフェノールの代りに酢酸
第二水銀５０Ｉｎ９を用いた以外は同様の操作を行ない
、ガスクロマトグラフィーにより収率６９％で３・３−
ジメチル−４−ペンテン酸エチ。Example 9 The same procedure as in Example 7 was carried out except that mercuric acetate 50In9 was used instead of phenol as a catalyst, and 3.3-
Ethyl dimethyl-4-pentenoate.
ルの生成を認めた。The generation of files was confirmed.
実施例 １０
実施例７において、触媒としてフェノールの代りにイソ
酪酸５０〜を用いた以外は同様の操作を行ない、ガスク
ロマトグラフィーにより収率７０：％で３・３−ジメチ
ル−４−ペンテン酸エチルの生成を認めた。Example 10 The same procedure as in Example 7 was carried out except that isobutyric acid 50~ was used instead of phenol as a catalyst, and ethyl 3,3-dimethyl-4-pentenoate was obtained with a yield of 70:% by gas chromatography. The formation of
実施例 １１
２・５−ジメチル−４−ヘキセン−３−オール３．８り
とオルト酢酸エチル９．７２Ｐとを混合し、シハイドロ
キノン０．１１を加えて、１４０℃に加熱した。Example 11 3.8 P of 2,5-dimethyl-4-hexen-3-ol and 9.72 P of ethyl orthoacetate were mixed, 0.11 P of cyhydroquinone was added, and the mixture was heated to 140°C.
生成するエタノールを留去しながら１８時間加熱攪拌を
続けた。The mixture was heated and stirred for 18 hours while distilling off the produced ethanol.
その後、過剰のオルト酢酸エチルを留去し、次いで減圧
蒸留により沸点９０〜９３℃／ ３０ ｍ７ＩＬＨｇを
有する３・３・６−ドリ８メチル−４−ヘプテン酸エチ
ル１．６１Ｐをえた。Thereafter, excess ethyl orthoacetate was distilled off, and 1.61 P of ethyl 3,3,6-doli-8methyl-4-heptenoate having a boiling point of 90-93°C/30 m7ILHg was obtained by distillation under reduced pressure.
収率２８％。Yield 28%.
生成物の核磁気共鳴吸収（ＣＣＩいδ）
５．６０〜４．９５（ｍ ２Ｈ）、３．９８ （ｑ
２Ｈ）、２．３０〜１．９０（ｍ ＩＨ）、２．２１
（ｓ ２Ｈ）、１．１８（ｔ ３Ｈ）、１．０６（
ｓ ６Ｈ）、０．９５（ｄ ６Ｈ）。Nuclear magnetic resonance absorption (CCI δ) of product 5.60-4.95 (m2H), 3.98 (q
2H), 2.30-1.90 (m IH), 2.21
(s 2H), 1.18(t 3H), 1.06(
s 6H), 0.95 (d 6H).
実施例 １２
３−メチル−２−ブテン−１−オール４．３７（０，０
５モル）、オルト酢酸メチル］８，０グ（０，１５モル
）及び８５％リン酸５７ｍ９（０，５ミリモル）を混合
し１００℃に加熱攪拌して生成したエチルアルコールを
反応系外に留去した。Example 12 3-Methyl-2-buten-1-ol 4.37 (0,0
8.0 g (0.15 mol) of methyl orthoacetate] and 57 m9 (0.5 mmol) of 85% phosphoric acid were heated and stirred at 100°C, and the produced ethyl alcohol was distilled out of the reaction system. I left.
その後、油浴の温度を１５０℃に加熱して反応の進行に
伴って生成したエチルアルコールを系外に留去した。Thereafter, the temperature of the oil bath was heated to 150° C., and the ethyl alcohol produced as the reaction progressed was distilled out of the system.
一夜反応を続けた後、反応混合物を蒸留すると３・３−
ジメチル−４−ペンテン酸メチルが４．１１Ｐが得られ
た。After continuing the reaction overnight, distillation of the reaction mixture yields 3.3-
4.11P of methyl dimethyl-4-pentenoate was obtained.
収率５８％。沸点ニア４℃／ ５０ ｍｍＨｇ 。Yield 58%. Boiling point near 4℃/50 mmHg.
生成物の核磁気共鳴吸収（ＣＤＣ１３δ）：６．１８〜
５．６５ （Ｃ１、Ｉ Ｈ） 、５．１５〜４．８ ｏ
（ｍ。Nuclear magnetic resonance absorption of product (CDC13δ): 6.18~
5.65 (C1, IH), 5.15-4.8 o
(m.
２Ｈ）、３．６０（ｓ、３Ｈ）、２．３０（Ｓ、２Ｈ）
、１．１８ （ｓ、 ６Ｈ） 。2H), 3.60 (s, 3H), 2.30 (S, 2H)
, 1.18 (s, 6H).
実施例 １３
３−メチル−２−ブテン−１−オール１２９グ（１，５
モル）、オルト酢酸メチル５４０グ（４，５モル）及び
８５％リン酸０．７１’（７，５ミリモル）を混合し、
１００℃に加熱攪拌して生成したエチルアルコールを反
応系外に留去した。Example 13 129 g of 3-methyl-2-buten-1-ol (1,5
mol), 540 g (4,5 mol) of methyl orthoacetate and 0.71' (7,5 mmol) of 85% phosphoric acid,
Ethyl alcohol produced by heating and stirring at 100° C. was distilled out of the reaction system.
その後反応混合物を０．５気圧加圧し、１３０°Ｃで加
熱攪拌して、反応の進行に伴って生成したエチルアルコ
ールを系外に留去した。Thereafter, the reaction mixture was pressurized by 0.5 atm, heated and stirred at 130°C, and ethyl alcohol produced as the reaction progressed was distilled out of the system.
２１時間後、反応混合物を蒸留すると、３・３−ジメチ
ル−４−ペンテン酸メチルが１４８７得られた。After 21 hours, the reaction mixture was distilled to yield 1487 methyl 3,3-dimethyl-4-pentenoate.
収率７０％。沸点ニア４℃／ ５０ ｉｍＨｇ 。Yield 70%. Boiling point near 4℃/50 imHg.
生成物の核磁気共鳴吸収（ＣＤＣ１３δ）６．１ ｓ
〜５．６５ （（１，Ｉ Ｈ）、５．１５〜４．８ ｏ
（ｍ、２Ｈ）、３．６０（ｓ、３Ｈ）、２．３０（Ｓ、
２Ｈ）、１．．１８（ｓ、６Ｈ）。Nuclear magnetic resonance absorption of product (CDC13δ) 6.1 s
~5.65 ((1, I H), 5.15 ~ 4.8 o
(m, 2H), 3.60 (s, 3H), 2.30 (S,
2H), 1. ．． 18 (s, 6H).
Claims (1)
れるオルト酢酸エステルとを酸性触媒の存在下反応させ
ることから成る、一般式 で表わされるγ−不飽和カルボン酸エステルの製造方法
。 （式中Ｒ１、Ｒ２及びＲ３は低級アルキル基であり、Ｒ
４及びＲ５は水素又は低級アルキル基であり、Ｒ４及び
Ｒ５の少なくとも一方は水素である。[Scope of Claims] 1. A γ-unsaturated carboxylic acid ester represented by the general formula, which is obtained by reacting an allyl alcohol derivative represented by the general formula with an orthoacetic ester represented by the general formula in the presence of an acidic catalyst. Production method. (In the formula, R1, R2 and R3 are lower alkyl groups, R
4 and R5 are hydrogen or a lower alkyl group, and at least one of R4 and R5 is hydrogen.
Priority Applications (42)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50008673A JPS5817735B2 (en) | 1975-01-22 | 1975-01-22 | Gamma − Fuhouwa carbon sane ester noseiho |
| 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 |
| 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 |
| 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. |
| DE2560240A DE2560240C2 (en) | 1974-09-10 | 1975-09-08 | Hexanoic acid, hexenoic acid and cyclopropanecarboxylic acid esters |
| DE2539895A DE2539895C2 (en) | 1974-09-10 | 1975-09-08 | Process for the preparation of 2-dihalovinylcyclopropanecarboxylic acid esters |
| CH1161375A CH630891A5 (en) | 1974-09-10 | 1975-09-08 | METHOD FOR PRODUCING 2-DIHALOGENVINYLCYCLOPROPANCARBONIC ACID ESTERS. |
| SE7510042A SE435618B (en) | 1974-09-10 | 1975-09-09 | PROCEDURE FOR PREPARING ESTHERS OF DIHALOGENVINYL CYCLEOPROPANCARBOXYL ACIDS |
| DK402075A DK158614C (en) | 1974-09-10 | 1975-09-09 | PROCEDURE FOR PREPARING A DIHALOGENEVINYLYCYCLOPROPANCARBOXYLATE |
| 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 |
| NZ178641A NZ178641A (en) | 1974-09-10 | 1975-09-09 | Esters of vinylcycloprpane carboxylic acids and intermediates |
| 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 |
| DD7500196141A DD128351A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING UNCONDITIONED CARBONIC ACID ESTERS |
| MX487775U MX5591E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR THE PREPARATION OF ESTERS OF DIHALOVINYL CYCLOPROPANOCARBOXYLIC ACIDS |
| MX10052375U MX5451E (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING DIHALOVINYL CYCLOPROPAN CARBOXYLATE |
| DD7500196145A DD128352A5 (en) | 1974-09-10 | 1975-09-10 | PROCESS FOR PREPARING GAMMA-UNACCURATED CARBONIC ACID ESTERS |
| 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 |
| 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 | |
| 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 | |
| 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 |
|---|---|---|---|
| JP50008673A JPS5817735B2 (en) | 1975-01-22 | 1975-01-22 | Gamma − Fuhouwa carbon sane ester noseiho |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5186410A JPS5186410A (en) | 1976-07-29 |
| JPS5817735B2 true JPS5817735B2 (en) | 1983-04-09 |
Family
ID=11699438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50008673A Expired JPS5817735B2 (en) | 1974-09-10 | 1975-01-22 | Gamma − Fuhouwa carbon sane ester noseiho |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5817735B2 (en) |
-
1975
- 1975-01-22 JP JP50008673A patent/JPS5817735B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5186410A (en) | 1976-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Taber et al. | Rhodium-mediated cyclopentane construction can compete with. beta.-hydride elimination: synthesis of (.+-.)-tochuinyl acetate | |
| Ravid et al. | New syntheses in dihydrojasmone series | |
| Crimmins et al. | Intramolecular photocycloaddition-cyclobutane fragmentation: A highly stereoselective total synthesis of (+-)-pentalenic acid | |
| JP2013227345A (en) | Synthesis of half ester | |
| JPS623141B2 (en) | ||
| JPS5817735B2 (en) | Gamma − Fuhouwa carbon sane ester noseiho | |
| US3970673A (en) | Process for preparing bicyclic γ-lactone | |
| KR950014219B1 (en) | (phenylethenyl)phenylopropionic acid and its ester, and metho for producing (benzoylphenyl)-propionic acid or its ester | |
| US4190730A (en) | Preparation of 1,1,1-trihalogeno-4-methyl-3-penten-2-ol | |
| US4237322A (en) | Process for preparation of 1,5-dimethylbicyclo[3,2,1]octan-8-ol | |
| US4591651A (en) | Process for directly converting an aldehyde into an ethylene ester | |
| US4298757A (en) | 2-[2-(2,2-Dihalovinyl)-3,3-dimethylcyclopropyl ]vinyl alkanoates | |
| JP3338101B2 (en) | Process for producing aryl acrylic acids and their esters | |
| US3649672A (en) | Automatic telephone-answering and message-recording apparatus | |
| US2583112A (en) | Process for the oxidation of acetals to acids | |
| Piccolo et al. | Optically active α-and β-naphthalene derivatives—IV: Synthesis and optical purity of 2-methyl-3-and 2, 2-dimethyl-3-(α-and β-naphthyl)-butanes | |
| JPS5933580B2 (en) | Method for producing γ-unsaturated carboxylic acid ester | |
| JPS63290842A (en) | Production of 2-(substituted phenyl)propionic acid or alkyl ester thereof | |
| CA2027010C (en) | 3-substituted 2-hydroxy-3-formylpropionic esters, the preparation thereof and the use thereof for preparing 3-substituted 3-formylacrylic esters | |
| Yamashita et al. | Syntheses of Naphthoquinone Compounds Using Chromium Carbonyl Carbene Complexes. | |
| RU2809284C1 (en) | Method for producing polyfluoralkylmethyl ketones | |
| US3489796A (en) | Method for making high purity and high yield tertiary-amyl acetate | |
| JPS5951530B2 (en) | Method for producing τ-unsaturated carboxylic acid ester | |
| JP3756537B2 (en) | Dimethyldecandial and process for producing the same | |
| US4786748A (en) | Processes for preparing aklylene and dialkyl ketals and alkyl alpha-enol ethers of alpha-acetyl cinnamic acids or esters thereof |