CN110294667A - A method of preparing cyclohexyl phenyl ketone - Google Patents
A method of preparing cyclohexyl phenyl ketone Download PDFInfo
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- CN110294667A CN110294667A CN201810244863.1A CN201810244863A CN110294667A CN 110294667 A CN110294667 A CN 110294667A CN 201810244863 A CN201810244863 A CN 201810244863A CN 110294667 A CN110294667 A CN 110294667A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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Abstract
The present invention provides a kind of new method for preparing cyclohexyl phenyl ketone, and this method produces target product under the conditions of alkane solvents, with chlorobenzoyl chloride and hexamethylene alkene reaction, be it is a kind of have it is environmental-friendly, it is at low cost, it is easy to operate, reaction is mild, the preparation method with industrial production value.
Description
Technical field
It is specifically a kind of to prepare hexamethylene the present invention relates to a kind of preparation method of a- alcohol ketone photoinitiator intermediate
The method of base phenyl ketone.
Background technique
Cyclohexyl phenyl ketone is a kind of important chemical intermediate, can be prepared one by chlorination, Basic fluxing raction
The efficient photoinitiator a- hydroxycyclohexyl phenyl ketone of kind.This a- hydroxyl ketone-type photoinitiators being prepared are a kind of efficiently
, the solid photoinitiator for being not likely to produce xanthochromia.Be mainly used in paper, timber, metal surface acrylate varnish paint
Ultraviolet light solidification.
A- hydroxycyclohexyl phenyl ketone
About the synthesis of cyclohexyl phenyl ketone, traditional gram acylation technique of paying industrially is mostly used to prepare greatly at present.
The method is starting material in 1,2- dichloroethane solvent using benzene, passes through the work in lewis acid catalyst aluminum trichloride (anhydrous)
Cyclohexyl phenyl ketone is prepared with lower react with cyclohexanecarbonyl chloride；It is as follows to pay gram process flow:
The characteristics of reaction, is that operating condition is relatively easy, yield is higher, but use is arrived during friedel-crafts reaction
Benzene and 1,2- dichloroethanes have potential carcinogenic toxicity, and cyclohexanecarbonyl chloride due to smell it is very big, be not to environment it is very friendly,
Therefore the requirement of green chemical industry is not met.
Domestic University Of Xiangtan sieve Shao Wei proposes another synthetic method: using benzoic acid and cyclohexanecarboxylic acid as raw material, in MnO
Catalytic condition under, 345 DEG C of progress decarboxylic reactions be made phenylcyclohexyl ketone, yield 56.4%.
The characteristics of reaction, is, environmentally protective, simple process, but the reaction temperature is excessively high, the ratio of the requirement to equipment
It is relatively stringent, and since catalyst circulation is poor, more solid waste can be generated.
Yasuhida Y proposes that under the carbonyls catalysis of ruthenium, benzaldehyde and cyclohexene carry out instead in a kettle
It answers, is passed through CO gas, reaction temperature is 200 DEG C, reaction pressure 2.0Mpa, reaction time 48h, phenylcyclohexyl ketone yield
It is 50%.
Carbonylation route uses rare metal ruthenium, and severe reaction conditions, needs high temperature.High pressure, yield and selectivity
It is not high, it is unfavorable for later purification.
Summary of the invention
The purpose of the present invention is avoid friedel-crafts reaction use with potential carcinogenic toxicity benzene and 1,2- dichloroethanes and
To the disagreeableness cyclohexanecarbonyl chloride of environment, a kind of novel method for preparing cyclohexyl phenyl ketone is provided.The preparation method is first
Secondary to use under the conditions of alkane solvents, in the method that phenylcyclohexyl ketone is made in chlorobenzoyl chloride and hexamethylene alkene reaction, substitution is former
Some carries out friedel-crafts reaction with 1,2- dichloroethanes for solvent, benzene and cyclohexanecarbonyl chloride under Catalyzed by Anhydrous Aluminium Chloride and prepares ring
The method of hexyl phenyl ketone, operating method avoid the use of poisonous and harmful raw material, have environmental-friendly, at low cost, behaviour
The features such as work is simple, and reaction condition is mild can preferably meet the current ever-increasing market demand.
A kind of method of cyclohexyl phenyl ketone of the present invention, specifically includes the following steps:
(1) in reaction flask be added alkane solvents, aluminum trichloride (anhydrous), at 0~20 DEG C stir 0.5~2h, then-
Chlorobenzoyl chloride is added dropwise at 10~20 DEG C, after being added dropwise, cyclohexene is added dropwise under assigned temperature, after drop finishes, insulation reaction 1~
4h is finally warming up to assigned temperature and reacts 4~12h until reaction terminates；
(2) material of previous step after reaction is hydrolyzed at -5~10 DEG C with aqueous hydrochloric acid solution, is divided and is gone water phase, organic
Mutually secondary washing layering, obtains cyclohexyl phenyl ketone after gained organic phase precipitation, dehydration.
Wherein, chemical equation is as follows:
The alkane solvents that starting is added in above-mentioned steps (1) refer to including one of normal heptane, hexamethylene or petroleum ether
Or it is several.
The alkane solvents volumetric usage that starting is added in reaction flask in above-mentioned steps (1) is the 3.0 of chlorobenzoyl chloride quality
~10.0 times.
The cyclohexene dosage that starting is added in reaction flask in above-mentioned steps (1) is the 1.0~2.0 of chlorobenzoyl chloride mole
Times.
The aluminum trichloride (anhydrous) dosage that starting is added in reaction flask in above-mentioned steps (1) is the 1.0 of chlorobenzoyl chloride mole
~3.0 times.
Cyclohexene is added dropwise in above-mentioned steps (1), the specified temperature that is stirred to react is -10~20 DEG C.
Cyclohexene drop finishes in above-mentioned steps (1), and 30~60 DEG C are warming up to after insulation reaction.
The concentration that aqueous hydrochloric acid solution used is hydrolyzed in above-mentioned steps (2) is 5%~10%.
The present invention is used for the first time under the conditions of alkane solvents, and cyclohexyl benzene first is made with chlorobenzoyl chloride and hexamethylene alkene reaction
The method of ketone, substitute it is original with 1,2- dichloroethanes be solvent, benzene and cyclohexanecarbonyl chloride under Catalyzed by Anhydrous Aluminium Chloride into
The method that row friedel-crafts reaction prepares cyclohexyl phenyl ketone, operating method have avoided the use of poisonous and harmful raw material, have had
It is environmental-friendly, it is at low cost, it is easy to operate, the features such as high income, it can preferably meet the current ever-increasing market demand.
Specific embodiment:
It is as follows that example is embodied:
Embodiment one
14ml hexamethylene, 13.3g (0.1mol) aluminum trichloride (anhydrous) are added in reaction flask, stirs 0.5 at 0~20 DEG C
~2h is added dropwise to 14.1g (0.1mol) chlorobenzoyl chloride at -10~20 DEG C, after being added dropwise, in 20 DEG C of dropwise addition 8.2g
(0.1mol) cyclohexene, after drop finishes, 1~4h of insulation reaction then heats to 60 DEG C, 4~12h of insulation reaction.
10% aqueous hydrochloric acid solution of reaction solution after insulation reaction is hydrolyzed, divides and goes water phase, organic phase secondary water
Wash layering, gained organic phase precipitation, dehydration obtain faint yellow solid 16.8g, and 54.0~55.0 DEG C of fusing point, yield 88.0%, purity
98.5%.
Embodiment two
50ml petroleum ether, 40.0g (0.3mol) aluminum trichloride (anhydrous) are added in reaction flask, stirs 0.5 at 0~20 DEG C
~2h is added dropwise to 14.1g (0.1mol) chlorobenzoyl chloride at -10~20 DEG C, after being added dropwise, in 0 DEG C of dropwise addition 16.4g
(0.2mol) cyclohexene, after drop finishes, 1~4h of insulation reaction then heats to 45 DEG C, 4~12h of insulation reaction.
8% aqueous hydrochloric acid solution of reaction solution after insulation reaction is hydrolyzed, divides and goes water phase, the secondary washing of organic phase
Layering, gained organic phase precipitation, dehydration, obtains faint yellow solid 16.5g, and 55.0~56.2 DEG C of fusing point, yield 86.1%, purity
98.1%.
Embodiment three
141ml hexamethylene, 31.2g (0.23mol) aluminum trichloride (anhydrous) are added in reaction flask, is stirred at 0~20 DEG C
0.5~2h is added dropwise to 14.1g (0.1mol) chlorobenzoyl chloride at -10~20 DEG C, after being added dropwise, in -10 DEG C of dropwise addition 13.2g
(0.16mol) cyclohexene, after drop finishes, 1~4h of insulation reaction then heats to 30 DEG C, 4~12h of insulation reaction.
5% aqueous hydrochloric acid solution of reaction solution after insulation reaction is hydrolyzed, divides and goes water phase, the secondary washing of organic phase
Layering, gained organic phase precipitation, dehydration, obtains faint yellow solid 16.6g, and 54.5~56.0 DEG C of fusing point, yield 86.9%, purity
98.4%.
Example IV
70ml normal heptane, 13.3g (0.1mol) aluminum trichloride (anhydrous) are added in reaction flask, stirs 0.5 at 0~20 DEG C
~2h is added dropwise to 14.1g (0.1mol) chlorobenzoyl chloride at -10~20 DEG C, after being added dropwise, in 20 DEG C of dropwise addition 8.2g
(0.1mol) cyclohexene, after drop finishes, 1~4h of insulation reaction then heats to 40 DEG C, 4~12h of insulation reaction.
10% aqueous hydrochloric acid solution of reaction solution after insulation reaction is hydrolyzed, divides and goes water phase, organic phase secondary water
Wash layering, gained organic phase precipitation, dehydration obtain faint yellow solid 16.1g, and 54.8~56.5 DEG C of fusing point, yield 84.0%, purity
98.1%.
Embodiment five
50ml hexamethylene, 70ml normal heptane, 40.0g (0.3mol) aluminum trichloride (anhydrous) are added in reaction flask, 0~20
0.5~2h is stirred at DEG C, 14.1g (0.1mol) chlorobenzoyl chloride is added dropwise at -10~20 DEG C, after being added dropwise, is dripped at 20 DEG C
After adding 16.4g (0.2mol) cyclohexene, drop to finish, 1~4h of insulation reaction then heats to 40 DEG C, 4~12h of insulation reaction.
5% aqueous hydrochloric acid solution of reaction solution after insulation reaction is hydrolyzed, divides and goes water phase, the secondary washing of organic phase
Layering, gained organic phase precipitation, dehydration, obtains faint yellow solid 15.5g, and 54.3~56.3 DEG C of fusing point, yield 81.3%, purity
98.6%.
Embodiment six
50ml hexamethylene, 50ml petroleum ether, 40.0g (0.3mol) aluminum trichloride (anhydrous) are added in reaction flask, 0~20
0.5~2h is stirred at DEG C, 14.1g (0.1mol) chlorobenzoyl chloride is added dropwise at -10~20 DEG C, after being added dropwise, is dripped at 20 DEG C
After adding 16.4g (0.2mol) cyclohexene, drop to finish, 1~4h of insulation reaction then heats to 40 DEG C, 4~12h of insulation reaction.
5% aqueous hydrochloric acid solution of reaction solution after insulation reaction is hydrolyzed, divides and goes water phase, the secondary washing of organic phase
Layering, gained organic phase precipitation, dehydration, obtains faint yellow solid 15.6g, and 54.5~56.2 DEG C of fusing point, yield 82.1%, purity
99.0%.
Embodiment seven
70ml normal heptane, 50ml petroleum ether, 40.0g (0.3mol) aluminum trichloride (anhydrous) are added in reaction flask, 0~20
0.5~2h is stirred at DEG C, 14.1g (0.1mol) chlorobenzoyl chloride is added dropwise at -10~20 DEG C, after being added dropwise, is dripped at 20 DEG C
After adding 16.4g (0.2mol) cyclohexene, drop to finish, 1~4h of insulation reaction then heats to 40 DEG C, 4~12h of insulation reaction.
5% aqueous hydrochloric acid solution of reaction solution after insulation reaction is hydrolyzed, divides and goes water phase, the secondary washing of organic phase
Layering, gained organic phase precipitation, dehydration, obtains faint yellow solid 15.9g, and 54.0~56.0 DEG C of fusing point, yield 83.1%, purity
98.3%.
The above is only the preferred embodiment of the present invention, it is noted that for ordinary skill people in the art
For member, without departing from the principles of the present invention, several improvement and optimization can also be made, these are improved and optimization
It should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of method for preparing cyclohexyl phenyl ketone, it is characterised in that the following steps are included:
(1) alkane solvents, aluminum trichloride (anhydrous) are added in reaction flask, 0.5~2h are stirred at 0~20 DEG C, at -10~20 DEG C
Lower dropwise addition chlorobenzoyl chloride, is stirred to react 0.5~2h, then under assigned temperature, cyclohexene is added dropwise and is warming up to specified after drop finishes
Temperature reacts 4~12h, until reaction terminates；
(2) material after insulation reaction is hydrolyzed at -5~10 DEG C with aqueous hydrochloric acid solution, is divided and is gone water phase, organic phase is secondary
Washing layering, obtains cyclohexyl phenyl ketone after gained organic phase precipitation, dehydration.
2. according to the method described in claim 1, it is characterized by: the alkane solvents that starting is added in reaction flask refer to including just
One of heptane, hexamethylene or petroleum ether are several.
3. according to the method described in claim 1, it is characterized by: the alkane solvents volumetric usage in reaction flask is added in starting
It is 3.0~10.0 times of chlorobenzoyl chloride quality.
4. according to the method described in claim 1, it is characterized by: the cyclohexene dosage that starting is added in reaction flask is benzoyl
1.0~2.0 times of chlorine mole.
5. according to the method described in claim 1, it is characterized by: the aluminum trichloride (anhydrous) dosage that starting is added in reaction flask is
1.0~3.0 times of chlorobenzoyl chloride mole.
6. according to the method described in claim 1, it is characterized by: cyclohexene is added dropwise, it is specified be stirred to react temperature be -10~
20℃。
7. according to the method described in claim 1, be warming up to 30 after insulation reaction it is characterized by: cyclohexene drop finishes~
60℃。
8. according to the method described in claim 1, it is characterized by: the concentration for hydrolyzing aqueous hydrochloric acid solution used is 5%~10%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627152A (en) * | 2018-11-08 | 2019-04-16 | 甘肃金盾化工有限责任公司 | A kind of photocatalytic synthesis method of cyclohexyl-(4-R phenyl) first ketone compounds and its application |
| CN111440053A (en) * | 2020-04-07 | 2020-07-24 | 西安瑞联新材料股份有限公司 | Industrial production method of cyclopropylmethyl cyclohexyl difluorobiphenyl compounds |
| CN116535303A (en) * | 2023-07-07 | 2023-08-04 | 山东齐阳光电科技有限公司 | Method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267887A (en) * | 2011-07-18 | 2011-12-07 | 连云港升南化学有限公司 | Synthesis process for 1-hydroxycyclohexyl phenyl ketone |
-
2018
- 2018-03-23 CN CN201810244863.1A patent/CN110294667A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267887A (en) * | 2011-07-18 | 2011-12-07 | 连云港升南化学有限公司 | Synthesis process for 1-hydroxycyclohexyl phenyl ketone |
Non-Patent Citations (1)
| Title |
|---|
| QIANGYAAN: ""傅克反应"", 《HTTPS://TIEBA.BAIDU.COM/P/2171180820》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627152A (en) * | 2018-11-08 | 2019-04-16 | 甘肃金盾化工有限责任公司 | A kind of photocatalytic synthesis method of cyclohexyl-(4-R phenyl) first ketone compounds and its application |
| CN109627152B (en) * | 2018-11-08 | 2022-01-25 | 甘肃金盾化工有限责任公司 | Photocatalytic synthesis method and application of cyclohexyl- (4-R phenyl) ketone compound |
| CN111440053A (en) * | 2020-04-07 | 2020-07-24 | 西安瑞联新材料股份有限公司 | Industrial production method of cyclopropylmethyl cyclohexyl difluorobiphenyl compounds |
| CN116535303A (en) * | 2023-07-07 | 2023-08-04 | 山东齐阳光电科技有限公司 | Method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane |
| CN116535303B (en) * | 2023-07-07 | 2023-09-05 | 山东齐阳光电科技有限公司 | Method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane |
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Application publication date: 20191001 |