CN110452089A - The synthetic method of p-chloromethyl styrene - Google Patents
The synthetic method of p-chloromethyl styrene Download PDFInfo
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- 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
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- chloromethyl
- chloromethyl styrene
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- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 63
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 chloromethyl-α-bromo ethyl Chemical group 0.000 claims description 23
- 238000005352 clarification Methods 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940057874 phenyl trimethicone Drugs 0.000 claims description 2
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 claims description 2
- LINXHFKHZLOLEI-UHFFFAOYSA-N trimethyl-[phenyl-bis(trimethylsilyloxy)silyl]oxysilane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C1=CC=CC=C1 LINXHFKHZLOLEI-UHFFFAOYSA-N 0.000 claims description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- FTTRLNOPHKYTED-UHFFFAOYSA-M [F-].[NH4+].C(C1=CC=CC=C1)[N+](CC)(CC)CC.[F-] Chemical compound [F-].[NH4+].C(C1=CC=CC=C1)[N+](CC)(CC)CC.[F-] FTTRLNOPHKYTED-UHFFFAOYSA-M 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052794 bromium Inorganic materials 0.000 abstract description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000003408 phase transfer catalysis Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 18
- 238000009835 boiling Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- JNRKYYMRTLBUNR-UHFFFAOYSA-N 1-(2-bromoethyl)-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1CCBr JNRKYYMRTLBUNR-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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.
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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 |
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