CN106496018B - The isobutyric preparation method of alpha-chloro - Google Patents
The isobutyric preparation method of alpha-chloro Download PDFInfo
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- CN106496018B CN106496018B CN201610841408.0A CN201610841408A CN106496018B CN 106496018 B CN106496018 B CN 106496018B CN 201610841408 A CN201610841408 A CN 201610841408A CN 106496018 B CN106496018 B CN 106496018B
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- isobutyric
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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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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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
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of isobutyric preparation methods of alpha-chloro, it the steps include: that (1) adds isobutyric acid in reaction kettle, it is warming up to 45~55 DEG C, it is added dropwise to phosphorus trichloride again, 45 ~ 55 DEG C of dropping temperature of control, after being added dropwise after 50 ± 2 DEG C keep the temperature 3.5 ~ 4.5 hours, stand 2 hours or more, divide and remove inorganic layer, obtains isobutyryl chloride；(2) isobutyric acid and catalyst isobutyryl chloride are added in reaction kettle, are warming up to 70 ~ 85 DEG C, are slowly introducing chlorine, it is carried out with reaction, temperature slowly increases, and increases logical chlorine dose, finally control reaction steams to the essence that cools down after reaction between 120 DEG C ~ 130 DEG C and obtains alpha-chloro isobutyl acid crude；(3) alpha-chloro isobutyl acid crude is put into rectifying still, under decompression, rectifying product collects fraction, obtains alpha-chloro isobutyric acid fine work.Compared with prior art, technique of the present invention is generated without tar, and products obtained therefrom yield is up to 90%.
Description
Technical field
The present invention relates to a kind of synthesis of organic chemical industry's intermediate, and in particular to a kind of alpha-chloro isobutyric acid preparation.
Background technique
Prior art preparation alpha-chloro isobutyric acid synthesis technology is main are as follows: isobutyric acid is with phosphorus trichloride or phosphorus oxychloride
It is reacted under catalyst through chlorinated with chlorine, then divides sub-cloud tar layer, upper layer is through being evaporated under reduced pressure.During its defect is generation
A large amount of lower layer's tar is generated, which is difficult to handle, and the chloro isobutyl for being also dissolved with certain product in tar, and generating
Acid content is low, and product yield is more low.
Summary of the invention
The object of the present invention is to provide a kind of isobutyric preparation methods of alpha-chloro.
The technical problem to be solved by the present invention is to what is realized by technical solution below:
A kind of isobutyric preparation method of alpha-chloro, includes the following steps:
(1) acylated: isobutyric acid is added in reaction kettle, is warming up to 45~55 DEG C, then be added dropwise to phosphorus trichloride, control drop
45 ~ 55 DEG C of heating degree, after being added dropwise after 50 ± 2 DEG C keep the temperature 3.5 ~ 4.5 hours, stand 2 hours or more, divide and remove inorganic layer,
Obtain isobutyryl chloride；
(2) chlorination: isobutyric acid and catalyst isobutyryl chloride are added in reaction kettle, are warming up to 70 ~ 85 DEG C, are slowly introducing
Chlorine is carried out with reaction, and temperature slowly increases, and increases logical chlorine dose, and finally control reaction is between 120 DEG C ~ 130 DEG C, wait react
After cool down essence steam obtain alpha-chloro isobutyl acid crude；
(3) essence is steamed: alpha-chloro isobutyl acid crude being put into rectifying still, under decompression, rectifying product is collected fraction, obtained
Alpha-chloro isobutyric acid fine work；
(4) front-end volatiles are applied: it is steamed in the front-end volatiles generated by essence and contains isobutyric anhydride, the recovery set in next batch reaction
With it is 10% ~ 15% that the isobutyryl chloride and isobutyric anhydride being added when applying, which account for overall reaction liquid mass fraction,.
Further, in step (1), the weight ratio of raw material isobutyric acid and phosphorus trichloride is 120:84.
Further, starting logical chlorine dose is 20 ~ 30kg/h, and increasing is 50kg/h after leading to chlorine dose.
Further, it in step (2), counts in mass ratio, isobutyric acid: isobutyryl chloride=10:1 ~ 1.5.
Compared with prior art, technique of the present invention is generated without tar, and products obtained therefrom yield is up to 90%.
Specific embodiment
In order to which the specific technical solution of the present invention is further described, in order to which those skilled in the art is further geographical
The solution present invention, without constituting the limitation to its right, however, the present invention is not limited to these examples.
1. reaction principle
(1) it is acylated
(2) chlorination
Embodiment 1
It is pumped into 1200kg isobutyric acid in 2000L reaction kettle, is warming up to 45 to 55 DEG C, then be added dropwise to phosphorus trichloride 840kg,
45~55 DEG C of dropping temperature of control stands 2 hours, divides sub-cloud inorganic layer after being added dropwise after 50 ± 2 DEG C keep the temperature 4 hours,
Upper organic layer 200kg barreled bucket, obtains isobutyryl chloride.
It is lengthened in 2000L and isobutyric acid 2000kg, isobutyryl chloride 200kg is added in reaction kettle.Opening stirring is heating, works as temperature
Degree stops heating when being raised to 75 DEG C, is slowly introducing chlorine, is passed through temperature with chlorine and slowly rises, opens when temperature rises to 120 DEG C
Chlorine dose logical greatly controls logical chlorine temperature at 125 DEG C~130 DEG C, and GC cools down after the completion of detecting logical chlorine.It is again that product alpha-chloro isobutyric acid is thick
Product are transferred to rectifying still rectifying.Obtain alpha-chloro isobutyric acid 2480kg, content 99.12%.Yield 89%.
Embodiment 2
It is pumped into 1200kg isobutyric acid in 2000L reaction kettle, is warming up to 45 to 55 DEG C, then be added dropwise to phosphorus trichloride 840kg,
45~55 DEG C of dropping temperature of control stands 2 hours, divides sub-cloud inorganic layer after being added dropwise after 50 ± 2 DEG C keep the temperature 4 hours,
Upper organic layer 200kg barreled bucket, obtains isobutyryl chloride.
It is lengthened in 2000L and isobutyric acid 2000kg, isobutyryl chloride 300kg is added in reaction kettle.Opening stirring is heating, works as temperature
Degree stops heating when being raised to 80 DEG C, is slowly introducing chlorine, is passed through temperature with chlorine and slowly rises, opens when temperature rises to 120 DEG C
Chlorine dose logical greatly controls logical chlorine temperature at 125 DEG C~130 DEG C, and GC cools down after the completion of detecting logical chlorine.It is again that product alpha-chloro isobutyric acid is thick
Product are transferred to rectifying still rectifying.Obtain alpha-chloro isobutyric acid 2550kg, content 99.08%.Yield 91.5%.
Claims (4)
1. a kind of isobutyric preparation method of alpha-chloro, which comprises the steps of:
(1) acylated: isobutyric acid being added in reaction kettle, is warming up to 45-55 DEG C, then be added dropwise to phosphorus trichloride, temperature is added dropwise in control
45-55 DEG C of degree after being added dropwise at 50 ± 2 DEG C after heat preservation 3.5-4.5 hour, standing 2 hours or more, divides and removes inorganic layer, obtain different
Butyl chloride；
(2) chlorination: isobutyric acid and catalyst isobutyryl chloride are added in reaction kettle, are warming up to 70-85 DEG C, is slowly introducing chlorine
Gas is carried out with reaction, and temperature slowly increases, and increases logical chlorine dose, and finally control reaction is between 120 DEG C -130 DEG C, wait react knot
The essence that cools down after beam, which is steamed, obtains alpha-chloro isobutyl acid crude；
(3) essence is steamed: alpha-chloro isobutyl acid crude being put into rectifying still, under decompression, rectifying product collects fraction, obtains α-chlorine
For isobutyric acid fine work；
(4) front-end volatiles are applied: it is steamed in the front-end volatiles generated by essence and contains isobutyric anhydride, the recovery in next batch reaction,
It is 10% -15% that the isobutyryl chloride and isobutyric anhydride being added when applying, which account for overall reaction liquid mass fraction,.
2. the isobutyric preparation method of alpha-chloro as described in claim 1, which is characterized in that in step (1), raw material isobutyric acid
Weight ratio with phosphorus trichloride is 120: 84.
3. the isobutyric preparation method of alpha-chloro as described in claim 1, which is characterized in that starting logical chlorine dose is 20-30 kg
/ h, increasing is 50 kg/ h after leading to chlorine dose.
4. the isobutyric preparation method of alpha-chloro as described in claim 1, which is characterized in that in step (2), in mass ratio
Meter, isobutyric acid: isobutyryl chloride=10:1-1.5.
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| CN201610841408.0A CN106496018B (en) | 2016-09-23 | 2016-09-23 | The isobutyric preparation method of alpha-chloro |
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| CN106496018B true CN106496018B (en) | 2019-04-26 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157609A (en) * | 2007-11-27 | 2008-04-09 | 浙江启明药业有限公司 | Method for preparing alpha, alpha-dimethylphenylacetic acid |
| CN102304033A (en) * | 2011-07-18 | 2012-01-04 | 连云港升南化学有限公司 | Process for synthesizing 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
-
2016
- 2016-09-23 CN CN201610841408.0A patent/CN106496018B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157609A (en) * | 2007-11-27 | 2008-04-09 | 浙江启明药业有限公司 | Method for preparing alpha, alpha-dimethylphenylacetic acid |
| CN102304033A (en) * | 2011-07-18 | 2012-01-04 | 连云港升南化学有限公司 | Process for synthesizing 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
Non-Patent Citations (1)
| Title |
|---|
| α-氯代异丁酸的合成研究;张国安 等;《精细化工》;19911231;第8卷(第3期);40-41 |
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