CN110452089A - The synthetic method of p-chloromethyl styrene - Google Patents
The synthetic method of p-chloromethyl styrene Download PDFInfo
- Publication number
- CN110452089A CN110452089A CN201910704828.8A CN201910704828A CN110452089A CN 110452089 A CN110452089 A CN 110452089A CN 201910704828 A CN201910704828 A CN 201910704828A CN 110452089 A CN110452089 A CN 110452089A
- Authority
- CN
- China
- Prior art keywords
- chloromethyl
- chloromethyl styrene
- added
- synthetic method
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Abstract
The present invention relates to a kind of synthetic methods of organic intermediate, especially a kind of synthetic method of p-chloromethyl styrene, using phase transfer catalysis process, using to chloromethyl-α-bromine ethylbenzene and potassium hydroxide as raw material, toluene is solvent, and phase transfer catalyst is added and synthesizes p-chloromethyl styrene；Synthetic method reaction is mild, energy consumption is low, and high temperature and pressure is not needed in reaction process；Reactant and solvent and phase transfer catalyst do not react, and improve yield using this method, reduce side reaction, obtain the product of high-quality.
Description
Technical field
The present invention relates to a kind of synthetic method of organic intermediate, especially a kind of synthesis side of p-chloromethyl styrene
Method.
Background technique
P-chloromethyl styrene is growing as a kind of organic intermediate, purposes, upstream raw material and downstream product type
It is abundant, it is widely used in rubber, amberplex, adhesive and pesticide etc..The method for synthesizing p-chloromethyl styrene
It is varied, including phase transfer catalysis process, the direct null method of highly basic and high temperature gas-phase chlorination etc., but in practice,
Because low yield, complex synthetic route, side reaction are mostly and the reasons such as difficult to control, many methods may not apply to actual production.
Chinese patent application CN100560550C uses gas-phase chlorination, using p-methylstyrene as reaction raw materials, chlorine
For halide reagent, nitrogen is recycling-guard gas, and hydroquinone is polymerization inhibitor, and carbon tetrachloride is that solvent has synthesized purpose product,
In the synthesis process: p-methylstyrene flow velocity is 0.035-0.092mol/min, and p-methylstyrene and chlorine molar ratio are
10: 3-10: 9.5, reaction temperature is 180-220 DEG C.
The advantages of above-mentioned gas-phase chlorination is that the conversion per pass of p-methylstyrene is improved, and product qualities are preferable,
But reaction needs high temperature and pressure, equipment requirement height, energy consumption big.
Summary of the invention
It is an object of the invention to overcome prior art there are the shortcomings that, provide that a kind of reaction is mild, energy consumption is low to chlorine
The synthetic method of methyl styrene improves yield using this method, reduces side reaction, obtain the product of high-quality.
The technical solution adopted by the present invention is that: phase transfer catalysis process is used, to chloromethyl-α-bromine ethylbenzene and potassium hydroxide
For raw material, toluene is solvent, and phase transfer catalyst is added and synthesizes p-chloromethyl styrene.
The following steps are included:
A. chloromethyl-α-bromo ethyl phenenyl and toluene are uniformly mixed, stirring and dissolving clarification,
B. potassium hydroxide and phase transfer catalyst are added in clear solution, is reacted 3-5 hours at 30-40 DEG C,
C. cooling after reacting, water stirring and dissolving is added, stratification, upper layer is organic phase, and lower layer is water phase,
D. it takes upper organic phase to distill, obtains finished product p-chloromethyl styrene.
The molar ratio to chloromethyl-α-bromo ethyl phenenyl, toluene and potassium hydroxide is 1:1:(1.2-1.5), toluene
It does not react, without by-product.
The amount ratio to chloromethyl-α-bromo ethyl phenenyl, phase transfer catalyst and water is 0.1mol:2g:100g.
Include p-chloromethyl styrene, toluene in the organic phase, include in water phase potassium bromide, phase transfer catalyst,
Potassium hydroxide and water.Potassium hydroxide excessively makes to chloromethyl-α-bromo ethyl phenenyl fully reacting in reaction process, after the reaction was completed hydrogen
Potassium oxide some residual.
The phase transfer catalyst includes benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium fluorine
Change ammonium, tetrabutylammonium chloride, tetrabutylammonium bromide, phenyl trimethicone ammonium chloride, phenyltrimethylammonium bromide, 18- crown- 6 and 15-
One of crown- 5 or a variety of mixtures.
In the step b, it is preferable that reaction temperature is 40 DEG C, and the reaction time is 4 hours.
After water phase filtering in the step c, reused as reaction solution.
The toluene that organic phase in the step d is distilled is reused as reaction dissolvent.
The present invention has the advantage that synthetic method reaction is mild, energy consumption is low, pollution is small compared with prior art, reacts
High temperature and pressure is not needed in journey；Reactant and solvent and phase transfer catalyst do not react, and improve yield using this method,
Side reaction is reduced, the product of high-quality is obtained.Mature technology is stablized, and is suitble to industrialized production, has a extensive future.
Specific embodiment
It elaborates below to the embodiment of the present invention, embodiment carries out reality under the premise of the technical scheme of the present invention
It applies, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
6.72g potassium hydroxide is added, 2g18- crown- 6 reacts 4 hours at 40 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, it is quiet
Set layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 12.5g, yield 81.9%.
Embodiment 2
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
8.4g potassium hydroxide is added, 2g18- crown- 6 reacts 4 hours at 40 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, has been stood
Layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 12.98g, yield 85%.
Embodiment 3
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
11.2g potassium hydroxide is added, 2g18- crown- 6 reacts 4 hours at 40 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, it is quiet
Set layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 14.5g, yield 95%.
Embodiment 4
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
6.72g potassium hydroxide is added, 2g18- crown- 6 reacts 4 hours at 30 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, it is quiet
Set layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 11.45g, yield 75.1%.
Embodiment 5
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
6.72g potassium hydroxide is added, 2g18- crown- 6 reacts 4 hours at 50 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, it is quiet
Set layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 10.98g, yield 71.9%.
Embodiment 6
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
6.72g potassium hydroxide is added, 2g18- crown- 6 reacts 3 hours at 40 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, it is quiet
Set layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 11.75g, yield 77%.
Embodiment 7
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
6.72g potassium hydroxide is added, 2g18- crown- 6 reacts 5 hours at 40 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, it is quiet
Set layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 12.67g, yield 83%.
Embodiment 8
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
6.72g potassium hydroxide is added, 2g18- crown- 6 reacts 6 hours at 40 DEG C.Cooling has been reacted, 100g water stirring and dissolving is added, it is quiet
Set layering.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 12.67g, yield 83%.
Embodiment 9
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
6.72g potassium hydroxide is added, 2g tetrabutylammonium bromide is reacted 4 hours at 40 DEG C.Cooling has been reacted, it is molten that the stirring of 100g water is added
Solution, stratification.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 10.68g, yield 69.9%.
Embodiment 10
23.4g is added in 500ml four-hole boiling flask to chloromethyl-α-bromo ethyl phenenyl, 92g toluene, after stirring and dissolving clarification
8.4g potassium hydroxide is added, 2g benzyltriethylammoinium chloride reacts 4 hours at 40 DEG C.Cooling has been reacted, the stirring of 100g water is added
Dissolution, stratification.Upper solution precipitation is taken to distill to obtain finished product p-chloromethyl styrene 10.82g, yield 70.1%.
Reactant dosage, reaction temperature, reaction time, catalyst and the final product quality of 1 embodiment 1-10 of table
Comparative example 1
48.8g2- benzyl carbinol is added in the 400ml four-hole boiling flask equipped with mechanical agitator and reflux condenser,
64.8g50% hydrobromic acid, 2g zinc chloride.Heating, 80~90 DEG C keep the temperature 6 hours, stop reaction, cooling, stratification.Organic layer
It is evaporated under reduced pressure after washing, anhydrous calcium chloride are dry, collects the fraction 2 bromoethyl benzene 64g of 110~115 DEG C/5mmHg.
Aforementioned fraction 37g2- bromoethyl is added in the 400ml four-hole boiling flask equipped with mechanical agitator and reflux condenser
Benzene, 18g paraformaldehyde, 8g zinc chloride.It is passed through dry hydrogen chloride gas, is reacted 18 hours at 30 DEG C, reaction is stopped, standing and divides
Layer, organic layer is added 100g petroleum ether after washing, aqueous sodium carbonate washing, anhydrous calcium chloride are dry, dissolves by heating, cooling
It is filtered to 10 DEG C, obtains white crystal, dry to chloromethyl -2 bromoethyl benzene 32g.
23.4g is added in 100ml three-necked flask to chloromethyl -2 bromoethyl benzene, 7g potassium hydroxide, 3.5gTBAB and
The 40g tert-butyl alcohol reacts 4 hours at 30 DEG C.It has reacted cooling to pour into 100g water, has extracted 3 times (each 50ml) with ether.Merge
Extract liquor, revolving remove solvent, and the fraction p-chloromethyl styrene 13g of 110~120 DEG C/5mmHg is collected in decompression, and yield is
50.1%.
Comparative example 2
In the 100ml four-hole boiling flask equipped with mechanical agitator and reflux condenser, the dried curing of 40ml is added
Carbon, 10.4g styrene, 11.5g chloromethyl ether, 5g anhydrous zinc chloride, 40 DEG C keep the temperature 5 hours.Stop reaction, cooling, organic layer warp
Washing, aqueous sodium carbonate washing, anhydrous calcium chloride are dry, and revolving removes solvent carbon disulfide.110~120 DEG C of decompression collection/
The fraction of 5mmHg obtains product p-chloromethyl styrene 2g, yield 13%.
Comparative example 3
In the 400ml four-hole boiling flask equipped with mechanical agitator and reflux condenser, the ethylo benzene of 42.4g is added, heats
To reflux, 64g bromine is slowly added dropwise in illumination, is dripped, then is kept the temperature illumination reaction 1 hour within about 2 hours.It is cooling, nitrogen purging
Remaining bromine and hydrogen bromide in reaction system.Reaction solution is through washing, and sodium bicarbonate aqueous solution washing, anhydrous calcium chloride is dry, mistake
Fraction α-bromo ethyl phenenyl 56g of 100~104 DEG C/5mmHg is collected in decompression after filter.
In the 400ml four-hole boiling flask equipped with mechanical agitator and reflux condenser, aforementioned fraction 55.5g α-bromine second is added
Base benzene, 13.5g paraformaldehyde, 7.5g anhydrous zinc chloride.It is passed through dry hydrogen chloride gas, after 40 DEG C are reacted 20 hours, is stopped
Reaction, stratification, organic layer are washed through washing, aqueous sodium carbonate, and anhydrous calcium chloride is dry.150g petroleum is added after filtering
Ether recrystallization, 10 DEG C of suction filtrations, obtains white crystal, dries to chloromethyl-α-bromo ethyl phenenyl 30g.
23.4g is added in 100ml three-necked flask to chloromethyl-α-bromo ethyl phenenyl, 7g potassium hydroxide, 3.5gTBAB and
The 40g tert-butyl alcohol reacts 4 hours at 30 DEG C.It has reacted cooling to pour into 100g water, has extracted 3 times (each 50ml) with ether.Merge
Extract liquor, revolving remove solvent, and decompression collects the fraction of 110~120 DEG C/5mmHg, obtains product p-chloromethyl styrene 8g, produce
Rate is 17.1%.
Claims (5)
1. a kind of synthetic method of p-chloromethyl styrene, it is characterised in that: the following steps are included:
A. chloromethyl-α-bromo ethyl phenenyl and toluene are uniformly mixed, stirring and dissolving clarification,
B. potassium hydroxide and phase transfer catalyst are added in clear solution, is reacted 3-5 hours at 30-40 DEG C,
C. cooling after reacting, water stirring and dissolving is added, stratification, upper layer is organic phase, and lower layer is water phase,
D. it takes upper organic phase to distill, obtains finished product p-chloromethyl styrene；
The molar ratio to chloromethyl-α-bromo ethyl phenenyl, toluene and potassium hydroxide is 1:1:(1.2-1.5)；
The amount ratio to chloromethyl-α-bromo ethyl phenenyl, phase transfer catalyst and water is 0.1mol:2g:100g；
Include p-chloromethyl styrene and toluene in the organic phase, includes potassium bromide, phase transfer catalyst, hydrogen-oxygen in water phase
Change potassium and water.
2. the synthetic method of p-chloromethyl styrene according to claim 1, it is characterised in that: the phase in the step b
Transfer catalyst includes benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium fluoride, tetrabutyl chlorination
One of ammonium, tetrabutylammonium bromide, phenyl trimethicone ammonium chloride, phenyltrimethylammonium bromide, 18- crown- 6 and 15- crown- 5 or
A variety of mixtures.
3. the synthetic method of p-chloromethyl styrene according to claim 1, it is characterised in that: the step b reaction
Temperature is 40 DEG C, and the reaction time is 4 hours.
4. the synthetic method of p-chloromethyl styrene according to claim 1, it is characterised in that: the water in the step c
After mutually filtering, reused as reaction solution.
5. the synthetic method of p-chloromethyl styrene according to claim 1, it is characterised in that: having in the step d
The toluene that machine mutually distills is reused as reaction dissolvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910704828.8A CN110452089A (en) | 2019-08-01 | 2019-08-01 | The synthetic method of p-chloromethyl styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910704828.8A CN110452089A (en) | 2019-08-01 | 2019-08-01 | The synthetic method of p-chloromethyl styrene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110452089A true CN110452089A (en) | 2019-11-15 |
Family
ID=68484388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910704828.8A Pending CN110452089A (en) | 2019-08-01 | 2019-08-01 | The synthetic method of p-chloromethyl styrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110452089A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112723986A (en) * | 2020-12-24 | 2021-04-30 | 衢州康鹏化学有限公司 | Preparation method of p-chloromethyl styrene |
| CN113121317A (en) * | 2019-12-31 | 2021-07-16 | 江苏中旗科技股份有限公司 | Synthesis method of 1, 4-dichloro-2- (chloromethyl) -5-ethoxybenzene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072621A (en) * | 1999-09-02 | 2001-03-21 | Nippon Light Metal Co Ltd | Production of chloromethylstyrenes |
| US20140058126A1 (en) * | 2012-01-31 | 2014-02-27 | F.I.S. - Fabrica Italiana Sintetici S.P.A. | New process for the preparation of 2,4,5- trifluorophenylacetic acid" |
| CN106892794A (en) * | 2016-12-28 | 2017-06-27 | 西安近代化学研究所 | A kind of method for preparing trans 1,3,3,3 tetrafluoropropene |
-
2019
- 2019-08-01 CN CN201910704828.8A patent/CN110452089A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072621A (en) * | 1999-09-02 | 2001-03-21 | Nippon Light Metal Co Ltd | Production of chloromethylstyrenes |
| US20140058126A1 (en) * | 2012-01-31 | 2014-02-27 | F.I.S. - Fabrica Italiana Sintetici S.P.A. | New process for the preparation of 2,4,5- trifluorophenylacetic acid" |
| CN106892794A (en) * | 2016-12-28 | 2017-06-27 | 西安近代化学研究所 | A kind of method for preparing trans 1,3,3,3 tetrafluoropropene |
Non-Patent Citations (3)
| Title |
|---|
| NISHIKUBO, TADATOMI ET AL.: "Facile synthesis of p-chloromethylated styrene by elimination reaction of p-(2-bromoethyl)benzyl chloride using potassium hydroxide as a base under phase-transfer catalysis", 《TETRAHEDRON LETTERS》 * |
| 李江: "对氯甲基苯乙烯合成研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
| 王心如 主编: "《毒理学》", 31 March 2019, 中国协和医科大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121317A (en) * | 2019-12-31 | 2021-07-16 | 江苏中旗科技股份有限公司 | Synthesis method of 1, 4-dichloro-2- (chloromethyl) -5-ethoxybenzene |
| CN112723986A (en) * | 2020-12-24 | 2021-04-30 | 衢州康鹏化学有限公司 | Preparation method of p-chloromethyl styrene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110452089A (en) | The synthetic method of p-chloromethyl styrene | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| CN108440409B (en) | Green and efficient preparation method of rebamipide | |
| CN102786427B (en) | Synthetic method of bis-(2-dimethylaminoethyl)ether | |
| CN108530301A (en) | A kind of synthetic method of tri- fluorin benzyl amines of 2,4,6- | |
| CN1432556A (en) | Prepn process of 2,2,2-trifluoroethyl acetate | |
| CN102491951B (en) | Production process of triallyl cyanurate | |
| CN106831857B (en) | A kind of production technology of acid-sensitive phosphite ester | |
| CN101665407A (en) | Preparation method of 2,4,5-trifluorobenzyl chloride | |
| CN108147950A (en) | A kind of preparation method of dipropylene glycol monomethyl mono allyl ether | |
| CN109438194A (en) | A kind of synthetic method of 1,3- bis- (2- chloro-trifluoromethyl phenoxy) benzene | |
| CN113233972B (en) | Synthesis method of (R) -2-benzyloxy propionic acid and intermediate thereof | |
| CN108129251A (en) | A kind of synthesis technology of 2- ethyl styrenes | |
| CN109438158A (en) | A method of synthesis 1,1,3,4,4,6- hexamethyl tetrahydronaphthalene | |
| CN101941930B (en) | Preparation method of 3-mercaptopropionic acid | |
| CN103288641A (en) | Synthetic method of hydroxypropyl methacrylate | |
| CN101607871A (en) | Method for preparing 4, 4' -dimethylolbiphenyl | |
| CN101880216A (en) | Method for producing chloropentyl alcohol by combination of n-pentylene and hypochlorous acid | |
| CN103408438A (en) | 2-hydroxyl-3-butene-1-amine separation and purification method | |
| CN101973855B (en) | Novel 4,4'-di(alkoxy/aryloxy methyl) biphenyl and preparation thereof | |
| CN115536548B (en) | Environment-friendly synthesis method of intermediate | |
| JP2815071B2 (en) | Method for producing dichlorodiphenyl sulfone | |
| CN104387259A (en) | Method for preparing 2,4,5-trifluorophenylacetic acid | |
| CN1182100C (en) | Method for preparing diglycol double carbonyl diallyls | |
| CN106117022B (en) | A method of it recycles sevoflurane impurity F (1) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211123 Address after: 274100 east section of Luhua East Road, Dingtao District, Heze City, Shandong Province (obliquely across Luhua oil factory) Applicant after: Shandong Xingshun New Material Co.,Ltd. Address before: 213000 No. 3, building 28, Huayuan new village, HUTANG Town, Wujin District, Changzhou City, Jiangsu Province Applicant before: Gu Xiaoxing |
|
| TA01 | Transfer of patent application right |