CN107602364A - A kind of method that acetone high selectivity chlorination prepares 1,1,3 trichloroacetones - Google Patents
A kind of method that acetone high selectivity chlorination prepares 1,1,3 trichloroacetones Download PDFInfo
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Abstract
The present invention relates to folic acid intermediate synthesis technical field, and in particular to a kind of method that acetone high selectivity chlorination prepares 1,1,3 trichloroacetone, its processing step are as follows：First using acetone as raw material, through chlorine catalytic chlorination stage by stage, first using aminated compounds as catalyst by acetone chlorination to dichloroacetone stage, alcohol compound is added as solvent, water regulation reaction process is added simultaneously, and depth chlorination prepares 1,1,3 trichloroacetones, this method yield is up to more than 90%；The defects of technical scheme provided by the invention can make up existing 1 to a certain extent, and the synthetic technology level present in the preparation method of 1,3 trichloroacetone is relatively poor, and preparation efficiency is low, obtained product is selectively low, operating process is cumbersome.
Description
Technical field
The present invention relates to folic acid intermediate synthesis technical field, and in particular to and a kind of acetone high selectivity chlorination prepares 1,1,
The method of 3- trichloroacetones.
Background technology
1,1,3- trichloroacetone is the liquid that a kind of water white transparency has intense stimulus stink, is in a kind of important chemical industry
Mesosome, it is widely used in organic synthesis, medicine, insecticide, spices and dyestuff etc., most important application is to be used to synthesize
Folic acid.
The main method for preparing 1,1,3- trichloroacetones at present has acetone direct chlorination method, acetone indirected chlorination method, acetone
Catalytic chlorination process and method for refining.Acetone direct chlorination method chlorinated with chlorine, reaction time length, 1,1,3- trichloroacetone selectivity
Difference and be difficult to separate.
For obtaining one kind using acetone as raw material in patent application CN106542979A disclosed in China, first and 2- alkyl
Aniline acts on forming imines, then chlorination obtains 1,1,3- trichloroacetone, yield 80%, but course of reaction needs to use substantial amounts of hydrogen
Sodium oxide molybdena adjusts pH, and step is more numerous, and Atom economy is poor.Invented in patent application CN105461529A disclosed in China
1,3-dichloroacetone dimethanol is deprotected a kind of acetone again, depth chlorination obtains 1,1,3- trichlorines for chlorination generation in methyl alcohol
Acetone, yield 73.9%, but processing step is more.It is proposed one kind with three second in patent application CN1047853A disclosed in China
The method that amine, the chlorinated with chlorine of diethylamine catalysis acetone prepare 1,1,3- trichloroacetone, reacts duration 10-20 hours, reaction week
Phase is longer, and 1,1,3- trichloroacetone content is only 40-50% in product.In patent application CN101768066A disclosed in China
A kind of process for purification of 1,1,3- trichloroacetone has been invented, the trichloroacetone that purity is 50% or so has been respectively adopted by two steps
Different solvent carries out solvent refining and obtains that the 1 of higher degree, 1,3- trichloroacetone, but quantity of solvent are big and yield is low.In China
Disclosed in disclosed patent application CN105130780A a kind of using water and petroleum ether as the refined 1,1,3- trichlorines of solvent recrystallization
The method of acetone, but 1 is required, 1,3- trichloroacetone content is more than 42%
The preparation 1,1 that currently available technology is provided, although the method for 3- trichloroacetones can reach certain yield, also
The defects of synthetic technology level is relatively poor, and preparation efficiency is low, obtained product is selectively low, operating process is cumbersome be present.
The content of the invention
For above-mentioned problem, the present invention proposes a kind of acetone high selectivity chlorination and prepares 1,1,3- trichloroacetone
Method.Technical scheme provided by the invention can make up the preparation method institute of existing 1,1,3- trichloroacetones to a certain extent
The defects of existing synthetic technology level is relatively poor, and preparation efficiency is low, obtained product is selectively low, operating process is cumbersome.
The technical problems to be solved by the invention be to provide it is a kind of in high yield, high selectivity, 1,1,3- tri- simple to operate
Chlroacetone synthetic method.
The technical solution adopted for the present invention to solve the technical problems, it is characterised in that its processing step is as follows：
The acetone first chlorination under the catalysis of the aminated compounds such as diethylamine, triethylamine, reaction generation monochloroacetone, continues chlorination
Generate dichloroacetone.Wherein in monochloroacetone chlorizate, 1,1- dichloroacetone is predominant product, with 1,3-DCA ratio
About 2：1.Reaction process is regulated and controled using water, because free radical can be quenched in water, so reaction is hardly produced trichloroacetone, to secondary anti-
Should also there is good inhibiting effect.When monochloroacetone run out of it is full-time, in crude reaction liquid almost all be 1,1- dichloroacetones and
1,3- dichloroacetones.Because the regulation and control of water can suppress side reaction, so reaction temperature can bring up to 60 DEG C, but temperature is too high
When, have a small amount of acetone dichloride hydrolysis generation alcohol.
The trichloroacetone that dichloroacetone continues chlorination generation has two kinds of isomers, and 1,3-DCA chlorizate is almost complete
For 1,1,3- trichloroacetones；1,1- dichloroacetone chlorination predominant product is 1,1,3- trichloroacetone, but has part 1,1 simultaneously,
1- trichloroacetones generate.Because alcohol compound can form unstable ketal or hemiketal compound, Ke Yixian with acetone
Write and improve reaction rate, regulation 1,1- dichloroacetones chlorination selectivity, chlorizate is completely converted into 1,1,3- trichloroacetone.
But monochloroacetone 1,3-DCA dimethyl acetal easily relatively stable with methanol effect generation under chlorine effect, so this hair
It is bright monochloroacetone conversion close to it is complete when add alcohol compound as reaction dissolvent, depth chlorination 1,1,3- trichlorine of synthesis
Acetone.Due to the presence of water, the 1 of generation, 1,3- trichloroacetone hardly continues reaction and generates more acetone dichloride accessory substances.With
Rotary Evaporators desolvation, obtain the 1 of content more than 90%, 1,3- trichloroacetone.
In order to realize above-mentioned purpose, the present invention uses following technical scheme：
A kind of method that acetone high selectivity chlorination prepares 1,1,3- trichloroacetone, the preparation method include following several steps
Suddenly：
(1) 90-105g acetone is added in a reservoir, and 1-3g triethylamine is added under conditions of stirring, is then added
Temperature control is passed through chlorine and carries out the first chlorination stage by 0.5-5% within the specific limits in the water of acetone quality；
(2) when monochloroacetone content is less than 1% in reaction solution, alcohol compound is added, control temperature carries out the second chlorine
The change stage；
(3) when in reaction solution dichloroacetone run out of it is full-time, stop reaction, blast Air blowing residual chlorine, decompression
Desolvation is distilled, obtains 1,1,3- trichloroacetone.
Preferably, the temperature of the first chlorination stage is 30-60 DEG C in step (1).
Preferably, the alcohol compound in step (2) is the one or more in methanol, ethanol, isopropanol.
Preferably, the mass ratio of the addition of alcohol compound and acetone is 1 in step (2):3-1:0.5.
Preferably, 30-50 DEG C of the temperature of the second chlorination stage in step (2).
Preferably, reaction process is monitored using gas-chromatography in the first chlorination stage and second chlorination stage.
It is as follows using above-mentioned technical scheme, beneficial effects of the present invention：
(1) water of catalytic amount is added, reaction process can be regulated and controled, avoids the accessory substances such as more acetone dichlorides from generating, first
In stage chlorination process, reaction can be rested on to the dichloroacetone stage, due to the effect of alcohol compound in second stage,
Reaction is easier to make for, and the presence of water can rest on reaction the trichloroacetone stage.
(2) when monochloroacetone content is higher than 1% in reaction solution, add methanol and easily form stable 1,3-DCA
Easily under chlorine effect a variety of side reactions occur for dimethyl acetal, the material.
When the reaction temperature of (3) first chlorination stages is higher than 70 DEG C, intermolecular condensation, accessory substance easily occur for acetone dichloride
Increase, reduce reaction yield, when reaction temperature is less than 30 DEG C, reaction rate is slower, is unfavorable for the preparation of target product；Cause
This, 30-60 DEG C is set in the present invention by the temperature of the first chlorination stage.
(4) 1,1- dichloroacetones chlorination selectivity can be significantly improved, makes its chlorination as solvent using alcohol compound
1,1,3- trichloroacetone is comprised only in product, suppresses the generation of 1,1,1- trichloroacetones.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described.Based on embodiments of the invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
Embodiment 1：
A kind of method that acetone high selectivity chlorination prepares 1,1,3- trichloroacetone, its preparation method include following several steps
Suddenly：
(1) 90g acetone is added in a reservoir, 1g triethylamine is added under conditions of stirring, then adds 0.5g's
Water, temperature control is passed through chlorine under the conditions of 30 DEG C and carries out the first chlorination stage；
(2) when monochloroacetone content is less than 1% in reaction solution, alcohol compound is added, controls temperature as 30 DEG C of progress
Second chlorination stage；
(3) when in reaction solution dichloroacetone run out of it is full-time, stop reaction, blast Air blowing residual chlorine, decompression
Desolvation is distilled, obtains 1,1,3- trichloroacetone.
Embodiment 2：
A kind of method that acetone high selectivity chlorination prepares 1,1,3- trichloroacetone, its preparation method include following several steps
Suddenly：
(1) 105g acetone is added in a reservoir, 3g triethylamine is added under conditions of stirring, then adds 3g's
Water, temperature control is passed through chlorine under the conditions of 60 DEG C and carries out the first chlorination stage；
(2) when monochloroacetone content is less than 1% in reaction solution, alcohol compound is added, controls temperature as 50 DEG C of progress
Second chlorination stage；
(3) when in reaction solution dichloroacetone run out of it is full-time, stop reaction, blast Air blowing residual chlorine, decompression
Desolvation is distilled, obtains 1,1,3- trichloroacetone.
Embodiment 3：
A kind of method that acetone high selectivity chlorination prepares 1,1,3- trichloroacetone, its preparation method include following several steps
Suddenly：
(1) 100g acetone is added in a reservoir, 1g triethylamine is added under conditions of stirring, then adds 2g's
Water, temperature control is passed through chlorine under the conditions of 40 DEG C and carries out the first chlorination stage；
(2) when monochloroacetone content is less than 1% in reaction solution, alcohol compound is added, controls temperature as 35 DEG C of progress
Second chlorination stage；
(3) when in reaction solution dichloroacetone run out of it is full-time, stop reaction, blast Air blowing residual chlorine, decompression
Desolvation is distilled, obtains 1,1,3- trichloroacetone.
Embodiment 4：
A kind of method that acetone high selectivity chlorination prepares 1,1,3- trichloroacetone, its preparation method include following several steps
Suddenly：
(1) 100g acetone is added in a reservoir, and 1g triethylamine is added under conditions of stirring, then adds 1.5g matter
The water of amount, temperature control is passed through chlorine under the conditions of 50 DEG C and carries out the first chlorination stage；
(2) when monochloroacetone content is less than 1% in reaction solution, alcohol compound is added, controls temperature as 40 DEG C of progress
Second chlorination stage；
(3) when in reaction solution dichloroacetone run out of it is full-time, stop reaction, blast Air blowing residual chlorine, decompression
Desolvation is distilled, obtains 1,1,3- trichloroacetone.
Embodiment 5：
A kind of method that acetone high selectivity chlorination prepares 1,1,3- trichloroacetone, its preparation method include following several steps
Suddenly：
(1) 100g acetone is added in a reservoir, 1g triethylamine is added under conditions of stirring, then adds 1g's
Water, temperature control is passed through chlorine under the conditions of 55 DEG C and carries out the first chlorination stage；
(2) when monochloroacetone content is less than 1% in reaction solution, alcohol compound is added, controls temperature as 45 DEG C of progress
Second chlorination stage；
(3) when in reaction solution dichloroacetone run out of it is full-time, stop reaction, blast Air blowing residual chlorine, decompression
Desolvation is distilled, obtains 1,1,3- trichloroacetone.
Regulate and control the additional proportion of water, control other compositions dosage is identical, detects first stage and second stage crude reaction liquid
Middle depth chlorinated secondary product and unconverted material are as follows in all acetone dichloride percentages, test result：
As can be seen from the above table, when the addition of water and acetone is within 0.5-5%, the trichloroacetone in the first stage
Reduce with the increase of water addition, monochloroacetone increases with the increase of water content；In second stage, more acetone dichlorides contain
Amount reduces with the increase of water content, and the content of dichloroacetone increases with the increase of water content.
According to monochloroacetone content different in reaction solution, identical alcohol compound is added, its dependent variable all same, is surveyed
The content of accessory substance 1,3-DCA dimethyl acetal in reaction solution is tried, test result is as follows：
As can be seen from the above table, when the content difference of monochloroacetone in reaction solution, when its content is less than 1%, production
The content of accessory substance 1,3-DCA dimethyl acetal is considerably less in thing, can be ignored, when the content of monochloroacetone is more than
When 1%, the content increase of accessory substance 1,3-DCA dimethyl acetal is fierce, have impact on the content of target product.
Control the temperature of the first chlorination stage, other conditions all same, test the content of chloro propyl alcohol in product, its result
It is as follows：
| Temperature/DEG C | 30 | 40 | 50 | 60 | 65 | 70 |
| Yield/% | 91 | 95 | 94 | 93 | 92 | 80 |
As can be seen from the above table when the temperature of the first chlorination stage is less than 60 DEG C, target product yield is stablized 90%
More than, when temperature is super more 60 DEG C, the yield of target product has declined.
The yield of 1,1,3- trichloroacetones prepared by technical scheme provided by the present invention is provided with prior art
The yield of 1,1,3- trichloroacetone prepared by technical scheme compares, and its result is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Reference examples | |
| Yield/% | 90 | 94 | 93 | 92 | 91 | 60 |
As can be seen from the above table, the middle yield for preparing 1,1,3- trichloroacetone provided by the present invention is significantly larger than prior art
Yield obtained by the scheme of offer.
Above example is only to illustrate the technical scheme of type of the present invention, rather than its limitations；Although with reference to foregoing implementation
Type of the present invention is described in detail example, it will be understood by those within the art that：It still can be to foregoing each
Technical scheme described in embodiment is modified, or carries out equivalent substitution to which part technical characteristic；And these are changed
Or replace, the essence of appropriate technical solution is departed from the spirit and scope of each embodiment technical scheme of type of the present invention.
Claims (6)
1. a kind of method that acetone high selectivity chlorination prepares 1,1,3- trichloroacetone, it is characterised in that preparation method is included such as
Under several steps：
(1) 90-105g acetone is added in a reservoir, and 1-3g triethylamine is added under conditions of stirring, then adds 0.5-
5%, in the water of acetone quality, temperature control is passed through within the specific limits chlorine and carries out the first chlorination stage；
(2) when monochloroacetone content is less than 1% in reaction solution, alcohol compound is added, control temperature carries out the second chlorination rank
Section；
(3) when in reaction solution dichloroacetone run out of it is full-time, stop reaction, blast Air blowing residual chlorine, be evaporated under reduced pressure
Desolvation, obtain 1,1,3- trichloroacetone.
2. the method that acetone high selectivity chlorination according to claim 1 prepares 1,1,3- trichloroacetone, it is characterised in that
The temperature of the first chlorination stage is 30-60 DEG C in the step (1).
3. the method that acetone high selectivity chlorination according to claim 1 prepares 1,1,3- trichloroacetone, it is characterised in that
Alcohol compound in the step (2) is methanol, the one or more in ethanol, isopropanol.
4. the method that acetone high selectivity chlorination according to claim 1 prepares 1,1,3- trichloroacetone, it is characterised in that
The mass ratio of the addition of alcohol compound and acetone is 1 in the step (2):3-1:0.5.
5. the method that acetone high selectivity chlorination according to claim 1 prepares 1,1,3- trichloroacetone, it is characterised in that
30-50 DEG C of the temperature of the second chlorination stage in the step (2).
6. the method that acetone high selectivity chlorination according to claim 1 prepares 1,1,3- trichloroacetone, it is characterised in that
Using gas-chromatography monitoring reaction process in first chlorination stage and second chlorination stage.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329199A (en) * | 2018-03-28 | 2018-07-27 | 戚文 | A kind of preparation method of 1,1,3- trichloroacetones |
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|---|---|---|---|---|
| US2635118A (en) * | 1949-05-12 | 1953-04-14 | Allied Chem & Dye Corp | Preparation of di-and trichloroacetones |
| SU251565A1 (en) * | 1967-08-15 | 1977-04-05 | Е. В. Сергеев, Е. В. Агапова, Е. Потак, М. С. Бел кова, А. Ф. Автономова, Н. Г. Рум нцева , Л. А. Виноходова | Method for isolating 1,1,3-trichloroacetone |
| CN1047853A (en) * | 1990-07-10 | 1990-12-19 | 中国科学院成都有机化学研究所 | 1,1,3-trichloroacetone preparation method |
| CN105461529A (en) * | 2015-12-29 | 2016-04-06 | 东南大学 | Preparing method for 1,1,3-trichloroacetone |
-
2017
- 2017-09-26 CN CN201710882012.5A patent/CN107602364B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635118A (en) * | 1949-05-12 | 1953-04-14 | Allied Chem & Dye Corp | Preparation of di-and trichloroacetones |
| SU251565A1 (en) * | 1967-08-15 | 1977-04-05 | Е. В. Сергеев, Е. В. Агапова, Е. Потак, М. С. Бел кова, А. Ф. Автономова, Н. Г. Рум нцева , Л. А. Виноходова | Method for isolating 1,1,3-trichloroacetone |
| CN1047853A (en) * | 1990-07-10 | 1990-12-19 | 中国科学院成都有机化学研究所 | 1,1,3-trichloroacetone preparation method |
| CN105461529A (en) * | 2015-12-29 | 2016-04-06 | 东南大学 | Preparing method for 1,1,3-trichloroacetone |
Non-Patent Citations (1)
| Title |
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| 王佳: "氯化反应区域选择性研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329199A (en) * | 2018-03-28 | 2018-07-27 | 戚文 | A kind of preparation method of 1,1,3- trichloroacetones |
| CN108329199B (en) * | 2018-03-28 | 2021-06-18 | 戚一文 | Preparation method of 1,1, 3-trichloroacetone |
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