CN109503354A - A kind of preparation method of alpha-brominated aliphatic ester - Google Patents
A kind of preparation method of alpha-brominated aliphatic ester Download PDFInfo
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- CN109503354A CN109503354A CN201811453250.5A CN201811453250A CN109503354A CN 109503354 A CN109503354 A CN 109503354A CN 201811453250 A CN201811453250 A CN 201811453250A CN 109503354 A CN109503354 A CN 109503354A
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- brominated
- aliphatic ester
- fatty acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
- Y02P20/584—Recycling of catalysts
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation methods of alpha-brominated aliphatic ester, including bromination and esterification, bromination: using bromo-succinimide as catalyst, fatty acid and bromine generate alpha-brominated fatty acid through bromination reaction, esterification: using disulfate as catalyst, the bromo fatty acid and lower alcohol generate alpha-brominated aliphatic ester through esterification.The phenomenon that the method for the present invention uses disulfate as catalyst in esterification, avoids red phosphorus inflammable and that the smell that feeds intake is big, and entire reaction process is environmental-friendly, and there is no equipment to corrode, and portioned product is carbonized, catalyst can recycle, and yield is higher, up to 98%.
Description
Technical field
The invention belongs to the synthesis of organic chemical industry's intermediate, are more particularly to a kind of preparation side of alpha-brominated aliphatic ester
Method.
Background technique
Prior art preparation bromo aliphatic ester synthesis technology is main are as follows: fatty acid and phosphorus trichloride or red phosphorus, tribromo
Changing phosphorus, polyphosphoric acids etc. is under catalyst through bromine gas bromination reaction, then with lower alcohol in sulfuric acid, chlorosulfonic acid etc. is under catalyst
Esterification, through being evaporated under reduced pressure.Its defect is that bromination environment is unfriendly during generating, since phosphorus trichloride, phosphorus tribromide are raw
At part acyl chlorides, cause bromination yield low, red phosphorus is again inflammable, and the smell that feeds intake is big etc., esterification sulfuric acid, the catalyst such as chlorosulfonic acid are set
Standby seriously corroded, portioned product carbonization, product colour is deeper, catalyst sulfuric acid, and chlorosulfonic acid is difficult to recycle again, becomes solid
It is useless, increase cost, the disadvantages such as yield is low.
Summary of the invention
The present invention provides a kind of preparation methods of environment amenable alpha-brominated aliphatic ester.
According to an aspect of the invention, there is provided a kind of preparation method of alpha-brominated aliphatic ester, comprising:
Bromination: using bromo-succinimide as catalyst, fatty acid and bromine generate alpha-brominated fat through bromination reaction
Acid, synthetic route are as follows:
Esterification: using disulfate as catalyst, the bromo fatty acid and lower alcohol generate alpha-brominated through esterification
Aliphatic ester, synthetic route are as follows:
Wherein, middle R is C0~C30Saturation, linear chain or branched chain alkyl.
In some embodiments, it is pumped into fatty acid in bromination reaction kettle, catalyst bromo-succinimide is added, rises
Temperature is to 80 to 120 DEG C, then is added dropwise to bromine, and after being added dropwise after 80 to 120 DEG C keep the temperature 4 hours, negative pressure sloughs extra bromine
Element and hydrogen bromide, are made alpha-brominated fatty acid.
In some embodiments, the mass ratio of the fatty acid and bromine is 40~60:100.
In some embodiments, the mass ratio of the fatty acid and bromo-succinimide is 100:0.5-5.
In some embodiments, alpha-brominated fatty acid, lower alcohol and catalyst sulfuric acid hydrogen salt are added in reaction kettle,
Be warming up to 70 DEG C~120 DEG C, slowly start to flow back, carried out with reaction, temperature slowly increases, control back flow reaction 80 DEG C~
Between 130 DEG C, to filter off catalyst lower batch use after reaction, in filtrate and rectifying, fraction is collected, bromo fatty acid is obtained
Ester.
In some embodiments, the disulfate is anhydrous slufuric acid hydrogen sodium or anhydrous slufuric acid hydrogen potassium.
In some embodiments, the mass ratio of the alpha-brominated fatty acid and disulfate is 10:0.2~1.
In some embodiments, the molar ratio of the alpha-brominated fatty acid and the lower alcohol is 1:1.5~3.
In some embodiments, contain lower alcohol in the front-end volatiles generated in rectifying, the recovery set in lower batch reaction
With.
It has the advantage that: the method for the present invention uses disulfate as catalyst in esterification, avoids inflammable and feed intake
The phenomenon that big red phosphorus of smell, entire reaction process is environmental-friendly, and there is no equipment to corrode, and portioned product is carbonized, catalyst can
To recycle, yield is higher, up to 98%.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
In 2000L bromination reaction kettle be pumped into 1000kg butyric acid, catalyst bromo-succinimide 5kg, be warming up to 90 to
100 DEG C, then it is added dropwise to bromine 2000kg, 90~100 DEG C of dropping temperature are controlled, keeps the temperature 4 hours at 100 ± 2 DEG C after being added dropwise
Afterwards, butyric acid end of reaction is detected, vacuum is slowly opened, negative pressure dehydrobromination 2 hours, after hydrogen bromide removing, turns to expect esterifying kettle.
2- bromo-butyric acid 1000kg, ethyl alcohol 600kg are added in 2000L reaction kettle of the esterification, anhydrous slufuric acid hydrogen sodium is added
100kg.Opening stirring is heating, stops heating when temperature is raised to 70 DEG C or so, slowly has reflux to generate, increases with temperature,
Reflux is gradually increased, and is flowed back 2 hours, and when temperature rises to 85~90 DEG C, GC detects raw material 2- bromo-butyric acid after the reaction was completed, slowly
Ethyl alcohol is distilled out, ethyl alcohol has been distilled, cooling filters out lower batch, anhydrous slufuric acid hydrogen sodium reuse, recovers down and criticize after ethyl alcohol is dry.
The 2- bromobutyrate filtered out is neutralized with soda ash again, then is transferred to rectifying still rectifying.Under injecting type water punching pump and lobe pump decompression,
Rectifying product collects fraction, obtains bromo aliphatic ester 1145kg, content 99.12%, yield 98%.
Embodiment 2
In 2000L bromination reaction kettle be pumped into 1000kg butyric acid, catalyst bromo-succinimide 10kg, be warming up to 90 to
100 DEG C, then it is added dropwise to bromine 2000kg, 90~100 DEG C of dropping temperature are controlled, keeps the temperature 2 hours at 100 ± 2 DEG C after being added dropwise
Afterwards, butyric acid end of reaction is detected, vacuum is slowly opened, negative pressure dehydrobromination 2 hours, after hydrogen bromide removing, turns to expect esterifying kettle.
2- bromo-butyric acid 1000kg, ethyl alcohol 800kg are added in 2000L reaction kettle of the esterification, anhydrous slufuric acid hydrogen potassium is added
100kg.Opening stirring is heating, stops heating when temperature is raised to 70 DEG C or so, slowly has reflux to generate, increases with temperature,
Reflux is gradually increased, and is flowed back 2 hours, and when temperature rises to 85~90 DEG C, GC detects raw material 2- bromo-butyric acid after the reaction was completed, slowly
Ethyl alcohol is distilled out, ethyl alcohol has been distilled, cooling filters out lower batch, anhydrous slufuric acid hydrogen potassium reuse, recovers down and criticize after ethyl alcohol is dry.
The 2- bromobutyrate filtered out is neutralized with soda ash again, then is transferred to rectifying still rectifying.Under injecting type water punching pump and lobe pump decompression,
Rectifying product collects fraction, obtains bromo aliphatic ester 1150kg, content 99.08%, yield 98.5%.
Above-described is only some embodiments of the present invention.For those of ordinary skill in the art, it is not taking off
Under the premise of from concept of the invention, various modifications and improvements can be made, these belong to protection model of the invention
It encloses.
Claims (10)
1. a kind of preparation method of alpha-brominated aliphatic ester characterized by comprising
Bromination: using bromo-succinimide as catalyst, fatty acid and bromine generate alpha-brominated fatty acid through bromination reaction, close
It is as follows at route:
Esterification: using disulfate as catalyst, the bromo fatty acid and lower alcohol generate alpha-brominated fat through esterification
Acid esters, synthetic route are as follows:
Wherein, middle R is C0~C30Saturation, linear chain or branched chain alkyl.
2. the preparation method of alpha-brominated aliphatic ester according to claim 1, which is characterized in that
It is pumped into fatty acid in bromination reaction kettle, catalyst bromo-succinimide is added, is warming up to 80 to 120 DEG C, then be added dropwise
Enter bromine, after being added dropwise after 80 to 120 DEG C keep the temperature 4 hours, negative pressure sloughs extra bromine and hydrogen bromide, is made alpha-brominated
Fatty acid.
3. the preparation method of alpha-brominated aliphatic ester according to claim 2, which is characterized in that the fatty acid and bromine
Mass ratio be 40~60:100.
4. the preparation method of alpha-brominated aliphatic ester according to claim 2, which is characterized in that the fatty acid and bromo
The mass ratio of succimide is 100:0.5-5.
5. the preparation method of alpha-brominated aliphatic ester according to claim 2, which is characterized in that
Alpha-brominated fatty acid, lower alcohol and catalyst sulfuric acid hydrogen salt are added in reaction kettle, are warming up to 70 DEG C~120 DEG C, is delayed
Slowly starting to flow back, be carried out with reaction, temperature slowly increases, back flow reaction is controlled between 80 DEG C~130 DEG C, to the end of reacting
The catalyst lower batch use of filter gained.
6. the preparation method of alpha-brominated aliphatic ester according to claim 5, which is characterized in that the disulfate is nothing
Water sodium bisulfate or anhydrous slufuric acid hydrogen potassium.
7. the preparation method of alpha-brominated aliphatic ester according to claim 5, which is characterized in that the alpha-brominated fatty acid
Mass ratio with disulfate is 10:0.2~1.
8. the preparation method of alpha-brominated aliphatic ester according to claim 5, which is characterized in that the alpha-brominated fatty acid
Molar ratio with the lower alcohol is 1:1.5~3.
9. the preparation method of alpha-brominated aliphatic ester according to claim 5, which is characterized in that
The bromo fat acid crude of filtering is neutralized with soda ash, then is transferred to rectifying still rectifying, rushes pump and lobe pump in injecting type water
Under decompression, rectifying product collects fraction, obtains alpha-brominated aliphatic ester.
10. the preparation method of alpha-brominated aliphatic ester according to claim 10, which is characterized in that generated in rectifying
Contain lower alcohol in front-end volatiles, the recovery in lower batch reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110803989A (en) * | 2019-11-26 | 2020-02-18 | 江西盛伟科技股份有限公司 | Synthesis method of ethyl 3-hydroxycaproate |
| CN117105769A (en) * | 2023-10-24 | 2023-11-24 | 山东顺成化学有限公司 | Preparation method of ethyl 2-bromopropionate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627560A (en) * | 2012-03-21 | 2012-08-08 | 山东润鑫精细化工有限公司 | Preparation method of alpha-bromoalkyl carboxylate |
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2018
- 2018-11-30 CN CN201811453250.5A patent/CN109503354A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627560A (en) * | 2012-03-21 | 2012-08-08 | 山东润鑫精细化工有限公司 | Preparation method of alpha-bromoalkyl carboxylate |
Non-Patent Citations (4)
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| 吴警等: "N-溴代丁二酰亚胺在有机反应中的研究进展", 《广州化工》 * |
| 庄美华: "α-溴代物的合成", 《江苏农学院学报》 * |
| 徐凤杰: "溴代反应试剂在化工合成中的应用", 《广东化工》 * |
| 隋晓锋等: "N-溴代丁二酰亚胺在有机反应中的应用进展", 《有机化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110803989A (en) * | 2019-11-26 | 2020-02-18 | 江西盛伟科技股份有限公司 | Synthesis method of ethyl 3-hydroxycaproate |
| CN117105769A (en) * | 2023-10-24 | 2023-11-24 | 山东顺成化学有限公司 | Preparation method of ethyl 2-bromopropionate |
| CN117105769B (en) * | 2023-10-24 | 2024-01-05 | 山东顺成化学有限公司 | Preparation method of ethyl 2-bromopropionate |
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Application publication date: 20190322 |