CN1064671C - Synthetic method for gamma halogenated butyric ester - Google Patents
Synthetic method for gamma halogenated butyric ester Download PDFInfo
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- CN1064671C CN1064671C CN96116451A CN96116451A CN1064671C CN 1064671 C CN1064671 C CN 1064671C CN 96116451 A CN96116451 A CN 96116451A CN 96116451 A CN96116451 A CN 96116451A CN 1064671 C CN1064671 C CN 1064671C
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- butyrolactone
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Abstract
The present invention relates to a synthetic method for gamma-halogenated butyric ester. The present invention uses gamma-butyrolactone, halogenated sulfoxide and alcohol comprising 1 to 4 carbon atoms as raw materials. The raw materials are reacted under reaction pressure of -0.03MPa to normal pressure and at a reaction temperature of -5 to 130 DEG C to obtain gamma-halogenated butyric ester, wherein after the gamma-butyrolactone enters a reactor, the halogenated sulfoxide and the alcohol are simultaneously added to the reactor. The synthetic method has the advantages that the reaction yield of the gamma-halogenated butyric ester is high, the operation is simple, etc. The synthetic method can be used in the industrial production of gamma-halogenated butyric ester.
Description
The present invention relates to the synthetic method of gamma halogenated butyric ester, particularly about being the synthetic method of the gamma halogenated butyric ester of raw material with gamma-butyrolactone, halogenation sulfoxide.
Gamma halogenated butyric ester, especially γ-chloro butyric ester is the important intermediate of synthetic drugs and agricultural chemicals, also is simultaneously the important source material of producing cyclopropylamine.Document US 3711549 has been introduced with gamma-butyrolactone and hydrogen halide at ZnCl
2Exist down, pressurized catalysis synthesizes γ-halo butyric acid, and then makes the technology of gamma halogenated butyric ester with alcohol reflux.Shortcomings such as this technology exists that step is many, side reaction is many in the troublesome poeration, processing condition harshness, esterification process, its product yield only about 87%.It is raw material that document US 3927074 has been introduced with gamma-butyrolactone, halogenation sulfoxide, the alcohol that contains 1～4 carbon atom, the technology of synthetic gamma halogenated butyric ester.Though this synthetic technology has overcome the troublesome poeration that exists in the document US 3711549, the shortcoming that reactions steps is many, owing to drive system HCl and SO with nitrogen in the reaction process
2, cause part raw polyol loss, on the one hand owing to drip the halogenation sulfoxide again and add pure technology after adopting moles adding reaction systems such as reaction raw materials gamma-butyrolactone and alcohol, make by product still more in addition, product gamma halogenated butyric ester yield only about 95%.Because the halogenation sulfoxide has certain corrodibility to equipment, therefore drip the halogenation sulfoxide service life of equipment is shortened in addition.
In order to overcome the shortcoming that above-mentioned document exists, the purpose of this invention is to provide a kind of both simple to operate, and the high synthetic method of product yield.
The objective of the invention is to realize: a kind of synthetic method of gamma halogenated butyric ester by following technical scheme, with gamma-butyrolactone, halogenation sulfoxide, the alcohol that contains 1～4 carbon atom is raw material, gamma-butyrolactone: halogenation sulfoxide: the mol ratio that contains 1～4 carbon atom alcohol is 1: 1～2.5: 1～3.5, after wherein the raw material gamma-butyrolactone enters reactor, the halogenation sulfoxide is to add simultaneously in the reactor with the raw polyol that contains 1～4 carbon atom, its reaction pressure is-0.03MPa～normal pressure that temperature of reaction is-5～130 ℃.
Purpose of the present invention also can be achieved through the following technical solutions: a kind of synthetic method of gamma halogenated butyric ester, with γ～butyrolactone, halogenation sulfoxide, the alcohol that contains 1～4 carbon atom is raw material, wherein with the molar ratio computing gamma-butyrolactone: the halogenation sulfoxide: the mol ratio that contains 1～4 carbon atom alcohol is 1: 1～2.5: 1～3.5, in reaction pressure be-0.03MPa～normal pressure, temperature of reaction makes for reacting under-5～130 ℃ of conditions, after wherein the raw material gamma-butyrolactone enters reactor, add the halogenation sulfoxide earlier, add the raw polyol that contains 1～4 carbon atom afterwards again.
For overcoming the corrosive nature of halogenation sulfoxide to equipment pipe, technical purpose can realize by following scheme: a kind of synthetic method of gamma halogenated butyric ester, with gamma-butyrolactone, the halogenation sulfoxide, the alcohol that contains 1～4 carbon atom is raw material, wherein with the molar ratio computing gamma-butyrolactone: the halogenation sulfoxide: the mol ratio that contains 1～4 carbon atom alcohol is 1: 1～2.5: 1～3.5, in reaction pressure be-0.03MPa～normal pressure, temperature of reaction makes for reacting under-5～130 ℃ of conditions, after wherein raw material halogenation sulfoxide enters reactor, add gamma-butyrolactone earlier, add the raw polyol that contains 1～4 carbon atom afterwards again.
The halogenation sulfoxide can be sulfur oxychloride, thionyl bromide, fluoridize sulfoxide, iodate sulfoxide in the technique scheme.The raw polyol that contains 1～4 carbon atom can be methyl alcohol, ethanol.Gamma-butyrolactone: halogenation sulfoxide: the mol ratio preferable range that contains 1～4 carbon atom alcohol is 1: 1～1.6: 1～2.0.The temperature of reaction preferable range is 10～℃.
The technical program is owing to the HCl and the SO that drive without nitrogen in the system
2, thereby do not have pure loss problem, and adopt halogenation sulfoxide, alcohol, gamma-butyrolactone technological line simultaneously, open loop in the reaction, esterification are integrated, all in a step, to finish, operating process is simplified.The mode that adopts halogenation sulfoxide and raw polyol to add simultaneously in reaction has improved the reaction yield of gamma halogenated butyric ester, has obtained result preferably.
(embodiment 1)
Embodiment 1 adds gamma-butyrolactone 172.0g in 1000 milliliters of glass there-necked flasks, 147 milliliters of sulfur oxychlorides, methyl alcohol are loaded on respectively in two dropping funnels for 105 milliliters, start stirring, under 15～25 ℃ of conditions, drip off sulfur oxychloride and methyl alcohol simultaneously in 1.0 hours.The hydrogenchloride that produces in the process, sulfur dioxide gas body and function buck absorb, and are warming up to 90 ℃ after dripping off, the insulation 90 minutes that refluxes, and reaction finishes, and it is pending to be cooled to room temperature.
Above-mentioned reactant is neutralized to neutrality with aqueous sodium hydroxide solution, leaves standstill to tell organic layer, and water merges organic layer with dichloromethane extraction for several times.Fractionation by distillation goes out methylene dichloride, gets γ-chloro methyl-butyrate 280.2 grams, content 95.0%, and γ-chloro methyl-butyrate yield is 97.6%.
(embodiment 2)
In 1000 milliliters of glass there-necked flasks, add 220 gram gamma-butyrolactones, take by weighing 350 gram sulfur oxychlorides in the dropping funnel, start stirring, drip off sulfur oxychloride at 25～30 ℃ in following 1 hour, drip 100.0 gram methyl alcohol afterwards, in 1.5 hours, drip off, be warming up to 90 ℃, be incubated 50 minutes, reaction stops, cooling.
Above-mentioned reaction solution is neutralized to neutrality with 33% sodium hydroxide solution, through distill γ-chloro methyl-butyrate 358.1 grams, content 94.0%, γ-chloro methyl-butyrate yield is 96.5%.
(embodiment 3)
In 1000 milliliters of glass there-necked flasks, add sulfur oxychloride 165.0 grams, begin to stir, be cooled to 25～30 ℃, in 1 hour, drip 100.0 gram gamma-butyrolactones, continue agitation and dropping 49.0 gram methyl alcohol, in 1.5 hours, drip off, be warming up to 90 ℃, be incubated 30 minutes, reaction finishes.Analyzing γ-chloro methyl-butyrate yield is 95.0%.
(embodiment 4)
Each step according to embodiment 1: 174 milliliters of gamma-butyrolactone 200.0 grams, sulfur oxychloride 329.3 grams, ethanol, through reaction, separate γ-chloro ethyl butyrate 354.0 grams, content 96.0%, γ-chloro ethyl butyrate yield is 97.3%.
(embodiment 5)
Each step according to embodiment 2: gamma-butyrolactone 220.0 restrains, sulfur oxychloride 400.0 restrains, ethanol 150.0 grams, through reaction, neutralization, separates to such an extent that γ-chloro ethyl butyrate 385.4 restrains, content 95%, and γ-chloro ethyl butyrate yield is 95.2%.
(embodiment 6)
According to embodiment 3 steps: gamma-butyrolactone 100.0 grams, sulfur oxychloride 170.0 grams, ethanol 75.0 grams, γ-chloro ethyl butyrate yield be 92.5%.
Claims (7)
1. the synthetic method of a gamma halogenated butyric ester, with gamma-butyrolactone, halogenation sulfoxide, the alcohol that contains 1～4 carbon atom is raw material, wherein with the molar ratio computing gamma-butyrolactone: the halogenation sulfoxide: the alcohol that contains 1～4 carbon atom is 1: 1～2.5: 1～3.5, react under for-5～130 ℃ of conditions for-0.03MPa～normal pressure, temperature of reaction in reaction pressure and to make, after it is characterized in that the raw material gamma-butyrolactone enters reactor, the halogenation sulfoxide is to add in the reactor simultaneously with the raw polyol that contains 1～4 carbon atom.
2. according to the synthetic method of the described halo butyric ester of claim 1, it is characterized in that the halogenation sulfoxide is sulfur oxychloride, thionyl bromide, fluoridizes sulfoxide, iodate sulfoxide.
3. according to the synthetic method of the described gamma halogenated butyric ester of claim 1, the raw polyol that it is characterized in that containing 1～4 carbon atom is methyl alcohol, ethanol.
4. according to the synthetic method of the described gamma halogenated butyric ester of claim 1, it is characterized in that gamma-butyrolactone: the halogenation sulfoxide: the mol ratio that contains the alcohol of 1～4 carbon atom is 1: 1～1.6: 1～2.0.
5. according to the synthetic method of the described gamma halogenated butyric ester of claim 1, it is characterized in that temperature of reaction is 10～100 ℃.
6. the synthetic method of a gamma halogenated butyric ester, with gamma-butyrolactone, halogenation sulfoxide, the alcohol that contains 1～4 carbon atom is raw material, wherein with the molar ratio computing gamma-butyrolactone: the halogenation sulfoxide: the alcohol that contains 1～4 carbon atom is 1: 1～2.5: 1～3.5, in reaction pressure be-0.03MPa～normal pressure, temperature of reaction makes for reacting under-5～130 ℃ of conditions, after it is characterized in that the raw material gamma-butyrolactone enters reactor, add the halogenation sulfoxide earlier, adding the alcohol that contains 1～4 carbon atom more afterwards is raw material.
7. the synthetic method of a gamma halogenated butyric ester, with gamma-butyrolactone, halogenation sulfoxide, the alcohol that contains 1～4 carbon atom is raw material, wherein with the molar ratio computing gamma-butyrolactone: the halogenation sulfoxide: the alcohol that contains 1～4 carbon atom is 1: 1～2.5: 1～3.5, in reaction pressure be-0.03MPa～normal pressure, temperature of reaction makes for reacting under-5～130 ℃ of conditions, after it is characterized in that raw material halogenation sulfoxide enters reactor, add gamma-butyrolactone earlier, adding the alcohol that contains 1～4 carbon atom more afterwards is raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116451A CN1064671C (en) | 1996-08-06 | 1996-08-06 | Synthetic method for gamma halogenated butyric ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116451A CN1064671C (en) | 1996-08-06 | 1996-08-06 | Synthetic method for gamma halogenated butyric ester |
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| Publication Number | Publication Date |
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| CN1172798A CN1172798A (en) | 1998-02-11 |
| CN1064671C true CN1064671C (en) | 2001-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96116451A Expired - Fee Related CN1064671C (en) | 1996-08-06 | 1996-08-06 | Synthetic method for gamma halogenated butyric ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130815A (en) * | 2015-10-22 | 2015-12-09 | 山东国邦药业股份有限公司 | Preparation method and preparation device for gamma-chloro-methyl butyrate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898307B (en) * | 2012-09-18 | 2014-11-26 | 浙江大学 | Synthetic method of methyl 4-chlorobutyrate |
| CN109265336B (en) * | 2018-09-26 | 2021-05-07 | 大丰跃龙化学有限公司 | Method for synthesizing gamma-chlorobutyric acid |
| CN109369432B (en) * | 2018-11-02 | 2021-06-25 | 永农生物科学有限公司 | Preparation method of (S) -4-chloro-2-aminobutyrate |
| CN114736119B (en) * | 2022-05-09 | 2024-02-06 | 迈奇化学股份有限公司 | One-step preparation method of ethyl 4-bromobutyrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB104667A (en) * | 1917-02-02 | 1917-03-15 | Sam Willie Moorhouse | An Improved "Picking Plate Block" for Whip Pick Picking Motion of a Loom. |
| US3927074A (en) * | 1974-06-19 | 1975-12-16 | Olin Corp | Preparation of halobutyrate esters |
-
1996
- 1996-08-06 CN CN96116451A patent/CN1064671C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB104667A (en) * | 1917-02-02 | 1917-03-15 | Sam Willie Moorhouse | An Improved "Picking Plate Block" for Whip Pick Picking Motion of a Loom. |
| US3927074A (en) * | 1974-06-19 | 1975-12-16 | Olin Corp | Preparation of halobutyrate esters |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130815A (en) * | 2015-10-22 | 2015-12-09 | 山东国邦药业股份有限公司 | Preparation method and preparation device for gamma-chloro-methyl butyrate |
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| CN1172798A (en) | 1998-02-11 |
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