JPS5849529B2 - Method for producing halogenated alcohol and halogenated ester from ester - Google Patents
Method for producing halogenated alcohol and halogenated ester from esterInfo
- Publication number
- JPS5849529B2 JPS5849529B2 JP54100574A JP10057479A JPS5849529B2 JP S5849529 B2 JPS5849529 B2 JP S5849529B2 JP 54100574 A JP54100574 A JP 54100574A JP 10057479 A JP10057479 A JP 10057479A JP S5849529 B2 JPS5849529 B2 JP S5849529B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- halogenated
- mixture
- producing
- yield
- 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
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、脂肪族モノカルボン酸のエステルとハロゲン
化エチレンの混合液にイオン化放射線を照射することに
よってハロゲン化不飽和アルコールとハロゲン化不飽和
エステルの混合物を製造する方法に関するものである。Detailed Description of the Invention The present invention provides a method for producing a mixture of a halogenated unsaturated alcohol and a halogenated unsaturated ester by irradiating a mixture of an aliphatic monocarboxylic acid ester and a halogenated ethylene with ionizing radiation. It is related to.
本発明者らは、先に種々のアルコールとハロゲン化エチ
レンとの混合物にイオン化放射線を照射することにより
、ハロゲン化アルコールを製造する方法を提案した（米
国特許第３３５４０６５）。The present inventors previously proposed a method for producing halogenated alcohols by irradiating mixtures of various alcohols and halogenated ethylene with ionizing radiation (US Pat. No. 3,354,065).
提案した方法の生成物の一つにハロゲン化不飽和アルコ
ールがある。One of the products of the proposed process is a halogenated unsaturated alcohol.
本発明の方法によれば、エステルとハロゲン化エチレン
より、このようなハロゲン化不飽和アルコールを合成す
るとともにハロゲン化不飽和エステルが合成できること
を明らかにした。It has been revealed that, according to the method of the present invention, such a halogenated unsaturated alcohol can be synthesized from an ester and a halogenated ethylene, as well as a halogenated unsaturated ester.
本発明に従うと、一般式
（式中のＲ１、Ｒ２およびＲ３は水素原子またはアルキ
ル基である）で表わされる脂肪族モノカルボン酸エステ
ルと、
一般式
（式中のＸ１、Ｘ２、Ｘ３およびＸ４はハロゲン原子で
ある）で表わされるハロゲン化エチレンとを反応させて
、
一般式
で表わされるハロゲン化不飽和アルコールと、一般式
（各式中のＲ，、Ｒ２、Ｒ３、Ｘ，、Ｘ２ およびＸ３
は前記と同じ意味をもつ）で表わされるハロゲン化不飽
和エステルとの混合物を製造するに当り、イオン化放射
線を照射することを特徴とする方法である。According to the present invention, an aliphatic monocarboxylic acid ester represented by the general formula (wherein R1, R2, and R3 are hydrogen atoms or alkyl groups) and a general formula (wherein X1, X2, X3, and X4 are The halogenated unsaturated alcohol represented by the general formula and the general formula (R, , R2, R3, X, X2 and
This method is characterized by irradiating ionizing radiation when producing a mixture with a halogenated unsaturated ester represented by (has the same meaning as above).
本発明方法において原料として用いられる脂肪族モノカ
ルボン酸エステルは、カルボン酸の酸性水素原子を置換
したアルキル基のａ位置に少なくとも１個の水素原子を
有するエステルであれば、このアルキル基は直鎖状、枝
分れ状のいずれでもよい。The aliphatic monocarboxylic acid ester used as a raw material in the method of the present invention is an ester having at least one hydrogen atom at the a-position of the alkyl group substituted for the acidic hydrogen atom of the carboxylic acid, so long as the alkyl group has a straight chain. It may be either shaped or branched.
またエステルを構成する脂肪族モノカルボン酸のアルキ
ル基は、炭素数１〜１０までのものであれば直鎖状、枝
分れ状のいずれでもよく、たとえば、酢酸メチル、酢酸
エチル、酢酸プロビル、酢酸イソプロビル、酢酸ブチル
、プロピオン酸メチル、メチルエチル酢酸メチルなどが
好適である。The alkyl group of the aliphatic monocarboxylic acid constituting the ester may be linear or branched as long as it has 1 to 10 carbon atoms, and examples include methyl acetate, ethyl acetate, probyl acetate, Isoprobyl acetate, butyl acetate, methyl propionate, methyl ethyl acetate, and the like are preferred.
ハロゲン化エチレンとしてはフッ素原子、塩素原子、臭
素原子を含むもの、たとえばテトラフルオロエチレン、
テトラクロロエチレン、テトラブロムエチレンなどが用
いられる。Examples of halogenated ethylene include those containing fluorine atoms, chlorine atoms, and bromine atoms, such as tetrafluoroethylene,
Tetrachloroethylene, tetrabromoethylene, etc. are used.
本発明方法においては、この脂肪族カルボン酸エステル
とハロゲン化エチレンを１００：１ないし１：１００モ
ル比で混合して使用できるが、特に４二１モル混合物が
有利である。In the process of the present invention, the aliphatic carboxylic acid ester and the halogenated ethylene can be used as a mixture in a molar ratio of 100:1 to 1:100, but a 421 molar mixture is particularly advantageous.
本発明方法において、照射温度は常温より２００℃まで
が好適であり、反応温度が高いときは生成物中のハロゲ
ン化不飽和エステルの含有率が減少し、・・ロゲン化不
飽和アルコールの含有率が増す。In the method of the present invention, the irradiation temperature is preferably from room temperature to 200°C, and when the reaction temperature is high, the content of halogenated unsaturated ester in the product decreases, and the content of halogenated unsaturated alcohol increases.
照射を常温付近で行なえば、この逆でハロゲン化不飽和
エステルの含有率が高い。Conversely, if irradiation is performed at around room temperature, the content of halogenated unsaturated esters will be high.
放射線の照射量は１〜１ ０ ０ Ｍｒａｄで、通常照
射時間は１０〜１０００時間程度である。The radiation dose is 1 to 100 Mrad, and the irradiation time is usually about 10 to 1000 hours.
照射時間は線量率によって若干ことなるが、照射時間の
長い方が収率が良い結果を与える。The irradiation time varies slightly depending on the dose rate, but a longer irradiation time will give a better yield.
線源としては、コバル｝−６０，セシウムー１３７など
の放射性同位元素が好ましいが、放射線発生機も使用で
きる。As the radiation source, radioactive isotopes such as cobal}-60 and cesium-137 are preferred, but radiation generators can also be used.
本発明方法により得られるハロゲン化不飽和アルコール
およびハロゲン化不飽和エステルは、いずれも有機アセ
チレン化合物の合成原料、香料、高分子原料、難燃処理
剤、農薬などとして有用である。The halogenated unsaturated alcohols and halogenated unsaturated esters obtained by the method of the present invention are both useful as raw materials for the synthesis of organic acetylene compounds, fragrances, polymer raw materials, flame retardants, agricultural chemicals, and the like.
次に本発明を実施例によって、さらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
酢酸メチル７．４１’（０．１０モル）とテトラクロロ
エチレン４．１４Ｐ（０．０２５モル）の混合物を、減
圧下に封管中に封入し、コ・＜ノレトー６０を用い線量
率ＩＸ １ ０ ５Ｒ／ｈｒで２００時間照射した。Example 1 A mixture of methyl acetate 7.41' (0.10 mol) and tetrachloroethylene 4.14P (0.025 mol) was sealed in a sealed tube under reduced pressure, and the dose rate was adjusted to IX using Co. Irradiation was performed at 105 R/hr for 200 hours.
照射後、未反応原料を留去して油分０．３２？を得た。After irradiation, unreacted raw materials are distilled off to reduce the oil content to 0.32? I got it.
この油分より２・３・３−トリクロロ−２−プロペン−
１−オール０．１２？（収率２．９％）およびｂｐ ７
４．５ 〜７ ６．０℃／８ｍｍＨｇ （ｄ４１．４
１３０、２０
ｎＤ１．４８７３）の１−アセトキシー２−３−３−ト
リクロロー２−プロペン０．２１１（収率４．０％）を
得た。From this oil, 2,3,3-trichloro-2-propene-
1-all 0.12? (yield 2.9%) and bp 7
4.5 ~7 6.0℃/8mmHg (d41.4
130, 20 nD 1.4873) of 1-acetoxy 2-3-3-trichloro-2-propene (0.211 (yield 4.0%)) was obtained.
実施例 ２
酢酸エチル１９６Ｐ（１．２モル）とテトラクロロエチ
レン４９．７５Ｐ（０．３モル）の混合物ヲ減圧下に封
管中に封じ、コバルト−６０をγ線源として、線量率１
×１０５Ｒ／ｈ八温度２５℃で１９６時間照射した。Example 2 A mixture of ethyl acetate 196P (1.2 mol) and tetrachlorethylene 49.75P (0.3 mol) was sealed in a sealed tube under reduced pressure, and cobalt-60 was used as a γ-ray source at a dose rate of 1.
×105R/h8 Irradiation was performed at a temperature of 25°C for 196 hours.
照射後未反応原料を留去し、油分１３．１：ｌを得た。After irradiation, unreacted raw materials were distilled off to obtain an oil content of 13.1:1.
この油分を分留して、３・４・４−トリクロロ−３−ブ
テンー２−オー・ル０．７Ｍ’（収率１．３％）および
ｂｐ ７１．０〜７２０℃／ ８ｍｍＨｇ （ ｄ２０
１． ２ ９ ３ ２、ｎ ２０１．４７８４）の２−
アセトヤン−３・４・４−トリクロロー３−ブテン７．
６１ｆ（収率１１．６％）を得た。This oil was fractionated to give 3,4,4-trichloro-3-buten-2-ol 0.7M' (yield 1.3%) and bp 71.0-720℃/8mmHg (d20
1. 2 9 3 2, n 201.4784) 2-
Acetoyan-3,4,4-trichloro-3-butene7.
61f (yield 11.6%) was obtained.
実施例 ３
酢酸エチル８．８１Ｐ（０．１０モル）とテトラクロロ
エチレン４．１４ｆ（０．０２５モル）の混合物を実施
例２と同様にして封じた後、コバルト−６０よりのγ線
を４９９時間常温で照射した。Example 3 After sealing a mixture of 8.81P (0.10 mol) of ethyl acetate and 4.14f (0.025 mol) of tetrachlorethylene in the same manner as in Example 2, the gamma rays from cobalt-60 were exposed to room temperature for 499 hours. It was irradiated with
照射後未反応原料を留去し、油分１．２０Ｐを得た。After irradiation, unreacted raw materials were distilled off to obtain 1.20 P of oil.
この油分より３・４・４−トリクロロー３−ブテンー２
−オール０．１２Ｐ（収率４．４％）および２アセトキ
シー３・４・４−トリクロロー３−ブテン０．５４Ｐ（
収率１０．０％）を得た。From this oil, 3,4,4-trichloro-3-butene-2
-ol 0.12P (yield 4.4%) and 2acetoxy3,4,4-trichloro-3-butene 0.54P (
A yield of 10.0%) was obtained.
実施例 ４
酢酸プロビル１ ０． ２ １ Ｐ （ ０． １ ０
モル）とテトラクロロエチレン４．１４Ｐ（０．０２５
モル）の混合物を、減圧下に封管中に封じ、コバルト−
６０をγ線源として、線量率１×１０５Ｒ／ｈｒで２５
℃の温度で２００時間照射した。Example 4 Probyl acetate 1 0. 2 1 P (0.1 0
mole) and tetrachlorethylene 4.14P (0.025
A mixture of cobalt (mol) was sealed in a sealed tube under reduced pressure and
60 as a gamma ray source, 25 at a dose rate of 1 x 105R/hr.
It was irradiated for 200 hours at a temperature of °C.
照射後未反応原料を留去し、油分Ｑ．９１ｆを得た。After irradiation, unreacted raw materials are distilled off and oil Q. I got 91f.
これより４・５・５−トリクロロー４−ペンテン−３−
オール０．２２１（収率４．６％）およびｂｐ７９．ｏ
〜８３，Ｏ℃／ ８ｍｍＨｇ （ ｄ２０１． ２ ９
５ ５、弓１．４７８５）の３−アセトキシー４・５
・５−トリクロロー４−ペンテン０．３７１（収率５．
９％）を得た。From this, 4,5,5-trichloro-4-pentene-3-
All 0.221 (yield 4.6%) and bp 79. o
~83,O℃/8mmHg (d201.29
5 5, bow 1.4785) 3-acetoxy 4.5
・5-Trichloro-4-pentene 0.371 (yield 5.
9%).
実施例 ５
酢酸イソプロビル１０．２１１ｉ’（０．１０モル）と
テトラクロロエチレン４．１４ｆ（０．０２５モル）の
混合物を実施例４と同様にして封じ、コバルト６０をγ
線源として、線量率Ｉ Ｘ １ ０５Ｒ／ｈｒで、２５
℃で１９６時間闇射した。Example 5 A mixture of isoprobyl acetate 10.211i' (0.10 mol) and tetrachloroethylene 4.14f (0.025 mol) was sealed in the same manner as in Example 4, and cobalt 60 was γ
As a radiation source, at a dose rate of I X 105R/hr, 25
It was irradiated for 196 hours at ℃.
照射後未反応原料を留去し、油分０．４５Ｐを得た。After irradiation, unreacted raw materials were distilled off to obtain 0.45P of oil.
これより２メチル−３・４・４−トリクロロ−３−ブテ
ン２−オール０．０８１（収率１．７％）および２アセ
トキシー２−メチル−３・４・４−トリクロロー３−フ
テン（ｂｐ６６．０〜６７．０℃／９ｍｍＨｇ，ｎ”ａ
１．５０５４）０．１４Ｐ（収率３．０％）を得た。From this, 2-methyl-3,4,4-trichloro-3-buten-2-ol 0.081 (yield 1.7%) and 2-acetoxy-2-methyl-3,4,4-trichloro-3-phthene (bp66. 0-67.0℃/9mmHg, n”a
1.5054) 0.14P (yield 3.0%) was obtained.
実施例 ６
酢酸ブチル１１．６１Ｐ（０．１０モル）とテトラクロ
ロエチレン４．１４Ｐ（０．０２５モル）の混合物を減
圧下に封管中に封じ、コバルト−６０をγ線源として、
線量率ＩＸ１０５Ｒ／ｈｒ で、２５℃で２００時間照
射した。Example 6 A mixture of butyl acetate 11.61P (0.10 mol) and tetrachloroethylene 4.14P (0.025 mol) was sealed in a sealed tube under reduced pressure, and cobalt-60 was used as a γ-ray source.
Irradiation was carried out at 25° C. for 200 hours at a dose rate of IX105R/hr.
照射後、未反応原料を留去し、油分１．４４Ｐを得た。After irradiation, unreacted raw materials were distilled off to obtain 1.44P of oil.
これより５・６・６−トリクロロ−５−ヘキセン−４−
オール０．１４１（収率１．３％）およびｂｐ９６．５
〜９８，５℃／７ｍｍＨｇ （ ｄ２０１． ２ ７
１ ４、ｎ２ＤＩ１．４８３６）の４
４−アセトキシー５・６・６ − ｝ ＩＪクロロー５
ヘキセン０．８７ｙ′（収率１４．２％）を得た。From this, 5,6,6-trichloro-5-hexene-4-
All 0.141 (yield 1.3%) and bp 96.5
~98,5℃/7mmHg (d201.27
1 4, n2DI1.4836) of 4 4-acetoxy 5, 6, 6 -} IJ Chlor 5
0.87y' of hexene (yield 14.2%) was obtained.
Claims (1)
ある）で表わされるハロゲン化エチレンを反応させて、 一般式 （上記各式中のＲ１、Ｒ２、Ｒ３、Ｘ１、Ｘ２およびＸ
３は前記と同じ意味をもつ） で表わされるハロゲン化不飽和エステルとの混合物を製
造するに当たり、イオン化放射線を照射して反応を行わ
せることを特徴とする、ハロゲン化不飽和アルコールと
ハロゲン化不飽和エステルの混合物を製造する方法。[Scope of Claims] 1 An aliphatic monocarboxylic acid ester (which is a hydrogen atom or an alkyl group of the general formula) and a fatty acid represented by the general formula (X1, X2, X3 and X4 are halogen atoms) of the general formula (R1, R2, R3, X1, X2 and
3 has the same meaning as above) In producing a mixture of halogenated unsaturated alcohol and halogenated unsaturated ester represented by A method of producing a mixture of saturated esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54100574A JPS5849529B2 (en) | 1979-08-07 | 1979-08-07 | Method for producing halogenated alcohol and halogenated ester from ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54100574A JPS5849529B2 (en) | 1979-08-07 | 1979-08-07 | Method for producing halogenated alcohol and halogenated ester from ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5625119A JPS5625119A (en) | 1981-03-10 |
| JPS5849529B2 true JPS5849529B2 (en) | 1983-11-05 |
Family
ID=14277663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54100574A Expired JPS5849529B2 (en) | 1979-08-07 | 1979-08-07 | Method for producing halogenated alcohol and halogenated ester from ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5849529B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832812A (en) * | 1971-08-24 | 1973-05-02 |
-
1979
- 1979-08-07 JP JP54100574A patent/JPS5849529B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832812A (en) * | 1971-08-24 | 1973-05-02 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5625119A (en) | 1981-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH05112482A (en) | Method for suppressing and decomposing peroxide in dialkyl ether | |
| JPS5849529B2 (en) | Method for producing halogenated alcohol and halogenated ester from ester | |
| SU515465A3 (en) | Photopolymerizable composition | |
| JPS60158136A (en) | Method for preventing polymerization of fluorine-containing acrylic acid or derivative thereof | |
| US3217032A (en) | Preparation of vinyl esters | |
| JP3003890B2 (en) | 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane | |
| JPS58140041A (en) | Preparation of halogenovinyl-substituted carboxylic ester | |
| JP2001192346A (en) | Method for producing perfluoroalkadiene | |
| US2488336A (en) | Production of nu-alkyl pyrroles | |
| JPS584738A (en) | Preparation of 2-halogenated vinylcyclohexanol | |
| JPH04173752A (en) | Production of perfluoroalkyl bromide | |
| US3647893A (en) | Process for the preparation of alkyl and aryl iodine | |
| JPS6127943A (en) | Bisphenol derivative, its preparation, and crosslinkable composition comprising same | |
| US3661743A (en) | Photochemical process for preparing beta-thiolactones | |
| JPS6293258A (en) | Compound | |
| US2502507A (en) | Dithiocyanogen adducts of esters of 4-hydroxybutadiene-1, 2, and process of making same | |
| JPS61172849A (en) | Production of halogenated unsaturated ester | |
| JPS5944307B2 (en) | Method for producing a fluorine-containing α-amino acid derivative having an acyl group | |
| JP2565977B2 (en) | Photochemical production method of α-allylpropionic acid | |
| US3491006A (en) | Process for preparing cyclobutane-1,2-dinitrile from acrylonitrile | |
| US3236625A (en) | Method of inhibiting plant growth | |
| JPS63110241A (en) | Vinyl chloride resin composition highly resistant to gammarays | |
| Lynn et al. | Synthesis and Epoxidation of Bis (2-cyclopentenyl) Carbonate. | |
| JPS63211242A (en) | Production of carbinol derivative | |
| JP2946698B2 (en) | Method for producing α, β-substituted cycloalkanone |