CN110483224A - The synthetic method of 1,2- bis- (4- ethenylphenyl) ethane - Google Patents
The synthetic method of 1,2- bis- (4- ethenylphenyl) ethane Download PDFInfo
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- CN110483224A CN110483224A CN201910704814.6A CN201910704814A CN110483224A CN 110483224 A CN110483224 A CN 110483224A CN 201910704814 A CN201910704814 A CN 201910704814A CN 110483224 A CN110483224 A CN 110483224A
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- ethenylphenyl
- toluene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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Abstract
The present invention relates to a kind of synthetic methods of organic intermediate, the especially synthetic method of one kind 1,2- bis- (4- ethenylphenyl) ethane.Using phase transfer catalysis process, using p-chloromethyl styrene, copper powder and iron powder as raw material, water and toluene are solvent, and phase transfer catalyst is added and synthesizes 1,2- bis- (4- ethenylphenyl) ethane.Danger of production process is low, improves yield using this method, reduces side reaction, obtain the product of high-quality.
Description
Technical field
The present invention relates to a kind of synthetic methods of organic intermediate, especially one kind 1,2- bis- (4- ethenylphenyl) ethane
Synthetic method.
Background technique
As a kind of organic intermediate, purposes is growing 1,2- bis- (4- ethenylphenyl) ethane, and upstream raw material is under
It is abundant to swim product category, is widely used in the industrial productions such as pesticide, dyestuff.Currently used synthetic method are as follows: to chlorine
Methyl styrene, tetrahydrofuran and magnesium chips are raw material, and nitrogen makees protective gas, n-hexane extraction, and recrystallizing methanol obtains product.
Wherein, tetrahydrofuran has toxicity, and reaction process risk is high, explosive substance easily generated.
Summary of the invention
It is an object of the invention to overcome prior art there are the shortcomings that, one kind 1,2- bis- (4- ethenylphenyl) second is provided
The synthetic method of alkane reduces the risk of production using phase transfer catalyst, 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, is with p-chloromethyl styrene, copper powder and iron powder
Raw material, water and toluene are solvent, and phase transfer catalyst is added and synthesizes 1,2- bis- (4- ethenylphenyl) ethane, including following step
It is rapid:
A. p-chloromethyl styrene, toluene, copper powder, iron powder, phase transfer catalyst and water are mixed, it is anti-at 30-40 DEG C
It answers 3-5 hours,
B. toluene stirring, stratification are added after reacting, upper layer is organic phase, and lower layer is that water phase and remaining unreacted are solid
Body,
C. it takes upper solution to distill, removes toluene, surplus solution pours into precipitation finished product 1, (the 4- vinyl benzene of 2- bis- in methanol
Base) ethane；
The amount ratio of p-chloromethyl styrene, toluene, copper powder, iron powder, phase transfer catalyst and water in the step a is
0.1mol:20g:(5-10) g:(20-30) g:1g:50g.
The molar ratio of toluene is 1:5 in the step a and step b；Toluene is as reaction dissolvent in step a, first in step b
Benzene does not react as extractant.
Include (4- ethenylphenyl) ethane of 1,2- bis- and toluene in the organic phase, includes copper chloride, chlorine in water phase
Change iron, phase transfer catalyst and water, remaining unreacted solid is copper powder and iron powder.Copper powder and iron powder excessively make to chloromethane in reaction
Base styrene fully reacting, recycling is recovered by filtration in copper powder and iron powder some residual, remaining solid after reaction.
Phase transfer catalyst in the step a includes benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl three
Ethyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, phenyl trimethicone ammonium chloride, phenyltrimethylammonium bromide, 18- crown-
One of 6 and 15- crown- 5 or a variety of mixtures.
In the step a, it is preferable that reaction temperature is 40 DEG C, and the reaction time is 5 hours.
Water phase in the step b is reused as reaction solution；The toluene that organic phase in step c is distilled,
It is reused as reaction dissolvent.
The present invention has the advantage that danger of production process is low compared with prior art, improves yield using this method, subtracts
Few side reaction, obtains the product of high-quality.
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
50g water, 15.25g p-chloromethyl styrene, 20g toluene, 5g copper powder, 20g iron are added in 500ml four-hole boiling flask
Powder, 6,40 DEG C of 1g18- crown- are reacted 5 hours.Reaction terminates, and 100g toluene is added, and stirs 30 minutes, stratification.Take upper layer molten
The distillation of liquid precipitation, removes toluene, surplus solution, which pours into methanol, is precipitated to obtain finished product 1,2- bis- (4- ethenylphenyl) ethane
11.75g, yield 50.2%.
Embodiment 2
50g water, 15.25g p-chloromethyl styrene, 20g toluene, 5g copper powder, 30g iron are added in 500ml four-hole boiling flask
Powder, 6,40 DEG C of 1g18- crown- are reacted 5 hours.Reaction terminates, and 100g toluene is added, and stirs 30 minutes, stratification.Take upper layer molten
The distillation of liquid precipitation, removes toluene, surplus solution, which pours into methanol, is precipitated to obtain finished product 1,2- bis- (4- ethenylphenyl) ethane
12.69g, yield 54.2%.
Embodiment 3
50g water, 15.25g p-chloromethyl styrene, 20g toluene, 5g copper powder, 20g iron are added in 500ml four-hole boiling flask
Powder, 1g tetrabutylammonium bromide, 40 DEG C are reacted 8 hours.Reaction terminates, and 100g toluene is added, and stirs 30 minutes, stratification.It takes
The distillation of upper solution precipitation, removes toluene, surplus solution, which pours into methanol, is precipitated to obtain finished product 1,2- bis- (4- ethenylphenyl) second
Alkane 7.05g, yield 30.1%.
Embodiment 4
50g water, 15.25g p-chloromethyl styrene, 20g toluene, 10g copper powder, 20g iron are added in 500ml four-hole boiling flask
Powder, 1g tetrabutylammonium bromide, 40 DEG C are reacted 8 hours.Reaction terminates, and 100g toluene is added, and stirs 30 minutes, stratification.It takes
The distillation of upper solution precipitation, removes toluene, surplus solution, which pours into methanol, is precipitated to obtain finished product 1,2- bis- (4- ethenylphenyl) second
Alkane 8.23g, yield 35.1%.
Embodiment 5
50g water, 15.25g p-chloromethyl styrene, 20g toluene, 10g copper powder, 20g iron are added in 500ml four-hole boiling flask
Powder, 6,40 DEG C of 1g18- crown- are reacted 5 hours.Reaction terminates, and 100g toluene is added, and stirs 30 minutes, stratification.Take upper layer molten
The distillation of liquid precipitation, removes toluene, and surplus solution, which pours into methanol, is precipitated to obtain finished product 1,2- bis- (4- ethenylphenyl) ethane 12g,
Yield is 51.2%.
Comparative example 1
Tetrahydrofuran 150ml, the magnesium chips 2.0085g for passing through Non-aqueous processing are added in 250ml three-neck flask, is protected in nitrogen
Under shield and magnetic agitation, 0 DEG C is slowly added into p-chloromethyl styrene, the reaction was continued at 0 DEG C 20h.Decompression rotation after reaction
Evaporation of solvent is extracted with 75ml water and 75ml n-hexane mixed solution, and water phase discards after being washed with HCl solution, and oil is mutually used
100ml washing discards water phase three times, and decompression rotary evaporation obtains faint yellow solid after anhydrous magnesium sulfate is dry.Recrystallizing methanol,
Product 1,2- bis- (4- ethenylphenyl) ethane 9.2626g, yield 66.3% are obtained after 40 DEG C of dry 2h.
Claims (5)
1. one kind 1, the synthetic method of 2- bis- (4- ethenylphenyl) ethane, it is characterised in that: the following steps are included:
A. p-chloromethyl styrene, toluene, copper powder, iron powder, phase transfer catalyst and water are mixed, reacts 3-5 at 30-40 DEG C
Hour,
B. toluene stirring is added after reacting, stratification, upper layer is organic phase, and lower layer is water phase and remaining unreacted solid,
C. it takes upper solution to distill, removes toluene, surplus solution pours into precipitation finished product 1,2- bis- (4- ethenylphenyl) in methanol
Ethane；
The amount ratio of p-chloromethyl styrene, toluene, copper powder, iron powder, phase transfer catalyst and water in the step a is
0.1mol:20g:(5-10) g:(20-30) g:1g:50g；
The molar ratio of toluene is 1:5 in the step a and step b；
Include (4- ethenylphenyl) ethane of 1,2- bis- and toluene in the organic phase, include in water phase copper chloride, iron chloride,
Phase transfer catalyst and water, remaining unreacted solid are copper powder and iron powder.
2. the synthetic method of 1,2- bis- (4- ethenylphenyl) ethane according to claim 1, it is characterised in that: the step
Phase transfer catalyst in rapid a includes benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium fluoride, four
In butyl ammonium chloride, tetrabutylammonium bromide, phenyl trimethicone ammonium chloride, phenyltrimethylammonium bromide, 18- crown- 6 and 15- crown- 5
One or more mixtures.
3. the synthetic method of 1,2- bis- (4- ethenylphenyl) ethane according to claim 1, it is characterised in that: described
Step a reaction temperature is 40 DEG C, and the reaction time is 5 hours.
4. the synthetic method of 1,2- bis- (4- ethenylphenyl) ethane according to claim 1, it is characterised in that: the step
Water phase in rapid b, reuses as reaction solution.
5. the synthetic method of 1,2- bis- (4- ethenylphenyl) ethane according to claim 1, it is characterised in that: the step
The toluene that organic phase in rapid c is distilled, reuses as reaction dissolvent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372187A (en) * | 2021-06-02 | 2021-09-10 | 西安瑞联新材料股份有限公司 | Industrial synthesis method of BVPE |
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| US20050010068A1 (en) * | 2001-12-01 | 2005-01-13 | Holmes Andrew Bruce | Use of microencapsulated transition metal reagents for reactions in supercritical fluids |
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| US4665246A (en) * | 1984-03-09 | 1987-05-12 | Chem Biochem Research, Inc. | Method of producing ethynyl aromatic compounds |
| US4929785A (en) * | 1989-03-20 | 1990-05-29 | Ethyl Corporation | Process for preparing diphenylalkane |
| US20050010068A1 (en) * | 2001-12-01 | 2005-01-13 | Holmes Andrew Bruce | Use of microencapsulated transition metal reagents for reactions in supercritical fluids |
| WO2005003068A1 (en) * | 2003-07-04 | 2005-01-13 | Matsushita Electric Industrial Co., Ltd. | Process for producing divinylbiphenyl and divinylbiphenyl |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372187A (en) * | 2021-06-02 | 2021-09-10 | 西安瑞联新材料股份有限公司 | Industrial synthesis method of BVPE |
| CN113372187B (en) * | 2021-06-02 | 2022-12-30 | 西安瑞联新材料股份有限公司 | Industrial synthesis method of BVPE |
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