CN112723986A - Preparation method of p-chloromethyl styrene - Google Patents

Preparation method of p-chloromethyl styrene Download PDF

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CN112723986A
CN112723986A CN202011552228.3A CN202011552228A CN112723986A CN 112723986 A CN112723986 A CN 112723986A CN 202011552228 A CN202011552228 A CN 202011552228A CN 112723986 A CN112723986 A CN 112723986A
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reaction
chloromethyl
chloromethylation
chloromethylstyrene
chloro
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杨东
曾原
吕高昂
孙元健
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Quzhou Kangpeng Chemical Co ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention relates to the field of organic chemistry, in particular to a preparation method of p-chloromethyl styrene. The invention provides a preparation method of p-chloromethyl styrene, which comprises the following steps: 1- (2-chloroethyl) -4- (chloromethyl) benzene was subjected to elimination reaction under alkaline conditions to provide p-chloromethylstyrene. The preparation method of p-chloromethyl styrene provided by the invention utilizes reaction raw materials with relatively low price, reduces the manufacturing cost, has simple and safe manufacturing process, less side reactions, high product conversion rate and high purity, and thus has good industrialization prospect.

Description

Preparation method of p-chloromethyl styrene
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of p-chloromethyl styrene.
Background
P-chloromethyl styrene (p-CMS) contains two functional groups with high reactivity and is an organic intermediate with wide application. Particularly, the material has good application prospect in the fields of rubber, ion exchange membranes, adhesives and other materials.
The synthesis of p-CMS mainly comprises two methods, wherein the synthesis of styrene methyl bridged cyclopentadienyl rare earth compounds reports that styrene is used as a raw material and is directly prepared by chloromethylation under the catalysis of tin chloride, in the reaction process, vinyl is easy to have addition and polymerization reactions, and the yield and the purity of the product are not high; ethyl benzene is used as raw material and is prepared through chloromethylation and then bromination or bromination and then chloromethylation to generate p-chloromethyl bromoethyl benzene compound, and dehydrohalogenation, for example CN 11045208. However, the method has the disadvantages of high toxicity of raw materials, high production cost and low economy due to introduction of bromine atoms into intermediates, poor reaction selectivity, more side reactions, low yield and the like, and influences the practical production application of the raw materials.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a process for preparing p-chloromethylstyrene, which solves the problems of the prior art.
To achieve the above and other related objects, the present invention provides a method for preparing p-chloromethyl styrene, comprising: 1- (2-chloroethyl) -4- (chloromethyl) benzene was subjected to elimination reaction under alkaline conditions to provide p-chloromethylstyrene.
In some embodiments of the invention, the elimination reaction is carried out with a base comprising an organic base and/or an inorganic base, preferably a combination comprising one or more of a hydroxide of an alkali metal, an alkoxide of an alkali metal, a hydroxide of an alkaline earth metal;
and/or, in the elimination reaction, the molar ratio of 1- (2-chloroethyl) -4- (chloromethyl) benzene to base is 1: 1.05-1: 5, preferably 1: 1.1 to 3.
In some embodiments of the invention, the elimination reaction is carried out in the presence of a polymerization inhibitor.
In some embodiments of the invention, the polymerization inhibitor comprises a combination of one or more of 4-tert-butylcatechol, p-hydroxyanisole, hydroquinone, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-amylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, and wood tar;
and/or the mass of the polymerization inhibitor is 0.1-5%, preferably 0.5-2% of the mass of the 1- (2-chloroethyl) -4- (chloromethyl) benzene.
In some embodiments of the invention, the elimination reaction is carried out in the presence of a solvent, and the solvent used in the elimination reaction comprises an aprotic polar solvent.
In some embodiments of the present invention, in the elimination reaction, the reaction temperature in the elimination reaction is a temperature condition between room temperature and 100 ℃, preferably a temperature condition between 20 ℃ and 50 ℃;
and/or, in the elimination reaction, the reaction is carried out under the condition of gas protection;
and/or in the elimination reaction, the post-treatment of the reaction comprises: and (5) solid-liquid separation and purification.
In some embodiments of the invention, the method for preparing 1- (2-chloroethyl) -4- (chloromethyl) benzene comprises: chloromethylation of 1-chloro-2-phenylethane with formaldehyde and hydrogen chloride in the presence of a lewis acid provides 1- (2-chloroethyl) -4- (chloromethyl) benzene.
In some embodiments of the invention, the chloromethylation reaction is conducted in a 1-chloro-2-phenylethane to formaldehyde molar ratio of 1: 1-10, preferably 1: 2-5;
and/or the formaldehyde is derived from paraformaldehyde;
and/or, in the chloromethylation reaction, the amount of hydrogen chloride is in excess relative to 1-chloro-2-phenylethane;
and/or, in the chloromethylation reaction, the Lewis acid comprises one or more of zinc chloride, ferric chloride, copper chloride, cobalt chloride and nickel chloride;
and/or in the chloromethylation reaction, the mass ratio of the 1-chloro-2-phenylethane to the Lewis acid is 1: 4-20, preferably 1: 5-10;
and/or, in the chloromethylation reaction, the reaction is carried out in the presence of a solvent, and the reaction solvent in the chloromethylation reaction comprises an aqueous solution of sulfuric acid;
and/or in the chloromethylation reaction, the reaction temperature is between room temperature and 100 ℃, and is preferably 80-95 ℃;
and/or, in the chloromethylation reaction, the post-treatment of the reaction comprises: extracting and concentrating the organic phase.
In some embodiments of the invention, the process for the preparation of 1-chloro-2-phenylethane comprises: 2-phenylethyl alcohol is chlorinated with a chlorinating agent to provide 1-chloro-2-phenylethane.
In some embodiments of the invention, the chlorinating reagent is used in an excess amount relative to 2-phenylethyl alcohol in the chlorination reaction;
and/or, in the chlorination reaction, the chlorination reagent comprises hydrogen chloride;
and/or in the chlorination reaction, the reaction temperature is between room temperature and 160 ℃, and preferably 90-120 ℃;
and/or, in the chlorination reaction, the post-treatment of the reaction comprises: extracting and concentrating the organic phase.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, and other advantages and effects of the present invention will be apparent to those skilled in the art from the disclosure of the present specification.
The inventor of the invention provides a preparation method of p-chloromethyl styrene through a great deal of practical research, and compared with the prior art, the preparation method has the advantages of less reaction byproducts, high yield and the like, thereby being more suitable for the industrial scale-up production of the p-chloromethyl styrene and completing the invention on the basis.
The invention provides a preparation method of p-chloromethyl styrene, which comprises the following steps: 1- (2-chloroethyl) -4- (chloromethyl) benzene was subjected to elimination reaction under alkaline conditions to provide p-chloromethylstyrene, the reaction equation is as follows:
Figure BDA0002858333420000031
in the elimination reaction, the reaction is usually carried out in the presence of a base. Eliminating inverseThe base applicable to the reaction may generally include an organic base and/or an inorganic base, and the like, and preferably may include one or a combination of more of alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like), alkali metal alkoxides (for example, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium n-propoxide, sodium isopropoxide, sodium n-butoxide, sodium t-butoxide, potassium t-butoxide, sodium dodecyl alkoxide, and the like), alkaline earth metal hydroxides (for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, and the like), and the like. In one embodiment of the present invention, the base used in the elimination reaction may include NaOH, KOH, LiOH, sodium n-propoxide, sodium isopropoxide,tBuONa、tBuOK, etc., and preferably, the base used in the elimination reaction may include one or more of sodium n-propoxide, sodium isopropoxide, tBuONa, tBuOK, etc. The base is generally used in an amount substantially equivalent to or in excess of 1- (2-chloroethyl) -4- (chloromethyl) benzene, so as to ensure that the reaction proceeds sufficiently in the forward direction. For example, the molar ratio of 1- (2-chloroethyl) -4- (chloromethyl) benzene to base may be 1: 1.05-5, 1: 1.05-1.1, 1: 1.1-1.2, 1: 1.2-1.3, 1: 1.3-1.5, 1: 1.5-2, 1: 2-3, 1: 3-4, or 1: 4 to 5, preferably 1: 1.1 to 3.
In the elimination reaction, the reaction is usually carried out in the presence of a polymerization inhibitor. The polymerization inhibitor applicable in the elimination reaction may include one or a combination of more of 4-t-butylcatechol (TBC), p-hydroxyanisole (MEHQ), Hydroquinone (HQ), 2, 6-di-t-Butylparacresol (BHT), 2, 5-di-t-amylhydroquinone, 2, 5-di-t-butylhydroquinone, 2-t-butylhydroquinone (MTBHQ), p-benzoquinone (PBQ), wood tar, and the like. In one embodiment of the present invention, the polymerization inhibitor may comprise one or more of 4-tert-butylcatechol (TBC), 2, 6-di-tert-butyl-p-cresol (BHT), Hydroquinone (HQ), and the like. The amount of the polymerization inhibitor used in the elimination reaction can be adjusted by those skilled in the art, and can be, for example, 0.1 to 5%, 0.1 to 0.3%, 0.3 to 0.5%, 0.5 to 1%, 1 to 2%, 2 to 3%, 3 to 4%, or 4 to 5% by mass of 1- (2-chloroethyl) -4- (chloromethyl) benzene, and preferably 0.5 to 2%.
In the elimination reaction, the reaction may be carried out in the presence of a solvent. The solvent used in the elimination reaction may generally include an aprotic polar solvent. For example, one or a combination of more of an ether solvent (e.g., tetrahydrofuran, methyltetrahydrofuran, methylcyclopentyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc.), an ester solvent (e.g., dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, etc.), an amide solvent (e.g., N-dimethylformamide, N-dimethylacetamide), and the like may be included. In one embodiment of the present invention, the solvent used in the elimination reaction may include one or a combination of more of tetrahydrofuran, methyltetrahydrofuran, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, N-methylpyrrolidone, and the like. The amount of the solvent used in the elimination reaction can be adjusted by those skilled in the art, for example, the mass of the solvent used may be 1 to 10 times, 1 to 2 times, 2 to 3 times, 3 to 5 times, or 5 to 10 times, preferably 1 to 3 times the mass of 1- (2-chloroethyl) -4- (chloromethyl) benzene.
In the elimination reaction, the reaction may be carried out generally under a temperature condition of from room temperature to the boiling point of the solvent. For example, the reaction temperature in the elimination reaction may be a temperature condition of room temperature to 100 ℃, and preferably a temperature condition of 20 to 50 ℃, 20 to 30 ℃, 30 to 40 ℃, or 40 to 50 ℃. The reaction time can be adjusted by those skilled in the art according to the reaction progress, for example, in the elimination reaction, the reaction progress of the addition reaction can be judged by TLC, chromatography and the like, and for example, the reaction time of the elimination reaction can be 0.5-5 h, 0.5-1 h, 1-2 h, 2-3 h, or 3-5 h.
In the elimination reaction, the reaction may be carried out under a gas blanket. Suitable methods of providing gas shielding will be known to those skilled in the art. For example, the gas shielding conditions may be provided by nitrogen, inert gases (e.g., helium, neon, argon, krypton, etc.), and the like.
In the elimination reaction, the skilled person can select a suitable method to carry out the post-treatment of the product obtained from the reaction, and for example, the method may include: and (5) solid-liquid separation and purification. After the reaction is finished, the product can be subjected to solid-liquid separation, the obtained liquid phase substance can be properly subjected to solvent removal, and p-chloromethyl styrene can be provided after further purification. Suitable purification methods will be known to those skilled in the art and may be, for example, distillation or the like.
The preparation method of p-chloromethyl styrene provided by the invention can also comprise the following steps: chloromethylating 1-chloro-2-phenylethane with formaldehyde and hydrogen chloride in the presence of a lewis acid to provide 1- (2-chloroethyl) -4- (chloromethyl) benzene according to the following equation:
Figure BDA0002858333420000041
in the chloromethylation reaction, the amount of formaldehyde is usually in excess relative to 1-chloro-2-phenylethane, so as to ensure that the reaction is carried out fully in the forward direction. Suitable methods for introducing formaldehyde into the reaction system should be known to those skilled in the art. For example, formaldehyde can be derived from paraformaldehyde, which can be introduced into the reaction system and released by appropriate temperature of the reaction system. For another example, the molar ratio of 1-chloro-2-phenylethane to formaldehyde may be 1: 1-10, 1: 1-2 and 1: 2-3, 1: 3-4, 1: 4-5, 1: 5-6, 1: 6-8, or 1: 8-10, preferably 1: 2 to 5.
In the chloromethylation reaction, the amount of hydrogen chloride is usually in excess relative to 1-chloro-2-phenylethane, so as to ensure that the reaction proceeds fully in the forward direction. Suitable methods for introducing hydrogen chloride into the reaction system should be known to those skilled in the art. For example, hydrogen chloride gas may be continuously introduced into the reaction system so that hydrogen chloride gas is always maintained at a constant concentration in the reaction system.
In the chloromethylation reaction, the reaction can be carried out in the presence of a Lewis acid. One skilled in the art can select the appropriate type and amount of catalyst to use in the chloromethylation reaction. For example, in the chloromethylation reaction, the lewis acid may include a combination of one or more of zinc chloride, ferric chloride, cupric chloride, cobalt chloride, nickel chloride, and the like. For another example, in the chloromethylation reaction, the mass ratio of 1-chloro-2-phenylethane to lewis acid may be 1: 4-20, 1: 4-5, 1: 5-6, 1: 6-8, 1: 8-10, 1: 10-15, or 1: 15-20, preferably 1: 5 to 10.
In the chloromethylation reaction, the reaction can be carried out usually in the presence of a solvent. The solvent used in the chloromethylation reaction can generally be aqueous sulfuric acid. The amount and concentration of solvent in the chloromethylation reaction can generally be adjusted by the person skilled in the art. For example, the concentration of the aqueous sulfuric acid solution may be 40 to 90 wt%, 40 to 45 wt%, 45 to 50 wt%, 50 to 55 wt%, 55 to 60 wt%, 60 to 65 wt%, 65 to 70 wt%, 70 to 75 wt%, 75 to 80 wt%, 80 to 85 wt%, or 85 to 90 wt%, and preferably may be 55 to 75 wt%. For another example, the mass ratio of 1-chloro-2-phenylethane to aqueous sulfuric acid may be 1: 2-10, 1: 2-4, 1: 4-6, 1: 6-8, or 1: 8-10, preferably 1: 3-1: 6.
in the chloromethylation reaction, the reaction can be carried out generally at a temperature ranging from room temperature to the boiling point of the solvent. For example, the reaction temperature in the chloromethylation reaction may be in the range of room temperature to 100 ℃, and preferably may be in the range of 80 to 95 ℃, 80 to 85 ℃, 85 to 90 ℃, or 90 to 95 ℃. The skilled person can adjust the reaction time according to the reaction progress, for example, in the chloromethylation reaction, the reaction progress of the addition reaction can be judged by methods such as TLC and chromatography, and for example, the reaction time of the chloromethylation reaction can be 4-20 h, 4-5 h, 5-6 h, 6-8 h, 8-12 h, or 12-20 h.
In the above chloromethylation reaction, the skilled person can select a suitable method for post-treating the reaction product, and for example, the method may include: and (4) extracting and organic phase desolventizing. After the reaction is completed, the reaction system may be cooled, layered, extracted with an organic solvent (e.g., hexane, etc.), and the organic phase may be freed of the solvent to provide 1- (2-chloroethyl) -4- (chloromethyl) benzene. The resulting product may be further purified (e.g., recrystallized, etc.) to provide 1- (2-chloroethyl) -4- (chloromethyl) benzene in a higher purity.
The preparation method of p-chloromethyl styrene provided by the invention can also comprise the following steps: chlorinating 2-phenylethyl alcohol with a chlorinating agent to provide 1-chloro-2-phenylethyl alcohol according to the following equation:
Figure BDA0002858333420000051
in the chlorination reaction, the amount of the chlorinating agent used is usually in excess relative to 2-phenylethyl alcohol, so that the reaction can be ensured to be fully carried out in the forward direction. For example, the molar ratio of 2-phenylethyl alcohol to chlorinating agent may be 1: 2-20, 1: 2-3, 1: 3-4, 1: 4-5, 1: 5-6, 1: 6-8, 1: 8-10, 1: 10-12, 1: 12-16, or 1: 16 to 20, preferably 1: 5 to 12. Specific applicable chlorinating agents may include hydrogen chloride (hydrochloric acid) and the like. Suitable methods for introducing hydrogen chloride into the reaction system should be known to those skilled in the art. For example, hydrogen chloride gas may be continuously introduced into the reaction system so that hydrogen chloride gas is always maintained at a constant concentration in the reaction system.
In the above chlorination reaction, the reaction may be carried out usually under a temperature condition of from room temperature to the boiling point of the solvent. For example, the reaction temperature in the chlorination reaction may be a temperature of room temperature to 160 ℃, and preferably may be 90 to 120 ℃, 90 to 100 ℃, 100 to 110 ℃, or 110 to 120 ℃. The reaction time can be adjusted by those skilled in the art according to the reaction progress, for example, in the chlorination reaction, the reaction progress of the addition reaction can be judged by methods such as TLC and chromatography, and for example, the reaction time of the chlorination reaction can be 5-48 h, 5-6 h, 6-8 h, 8-12 h, 12-16 h, 16-24 h, 24-36 h, or 36-48 h.
In the above chlorination reaction, the skilled person can select a suitable method to carry out the post-treatment of the reaction product, and for example, the method may include: and (4) extracting and organic phase desolventizing. After the reaction is finished, the reaction system can be cooled and layered, an organic solvent (such as dichloromethane and the like) is used for extraction, and the organic phase is removed from the solvent, so that the 1-chloro-2-phenylethane can be provided.
The preparation method of p-chloromethyl styrene provided by the invention utilizes reaction raw materials with relatively low price, reduces the manufacturing cost, has simple and safe manufacturing process, less side reactions, high product conversion rate and high purity, and thus has good industrialization prospect.
The present application is further illustrated by the following examples, which are not intended to limit the scope of the present application.
Example 1
Synthesis of 1-chloro-2-phenylethane
80g of 2-phenethyl alcohol and 664g of 36% concentrated hydrochloric acid are sequentially added into a 1L reaction bottle, stirred and reacted for 24 hours under the temperature controlled at 100 ℃. The temperature is reduced to room temperature, the mixture is kept stand and layered, an acid layer is extracted once by 100g of dichloromethane, and organic phases are combined. The solvent was recovered by distillation under normal pressure, and 81g of 1-chloro-2-phenylethane was obtained by distillation under reduced pressure. (yield 88%)
Example 2
Synthesis of 1-chloro-2-phenylethane
40g of 2-phenethyl alcohol and 402g of 30% concentrated hydrochloric acid are sequentially added into a 500mL reaction bottle, stirring is started, and the temperature is controlled at 100 ℃ for reaction for 30 hours. The temperature is reduced to room temperature, the mixture is kept stand and layered, an acid layer is extracted once by 100g of dichloromethane, and organic phases are combined. The solvent was recovered by distillation under normal pressure, and then distilled under reduced pressure to obtain 37g of 1-chloro-2-phenylethane. (yield 80%)
Example 3
Synthesis of 1-chloro-2-phenylethane
400g of 2-phenethyl alcohol and 1992g of 36% concentrated hydrochloric acid are sequentially put into a 5L reaction flask, stirred and reacted at the temperature of 100 ℃, hydrogen chloride gas is synchronously introduced during the reaction, and the reaction is carried out for 16 hours. The temperature is reduced to room temperature, the mixture is kept stand and layered, an acid layer is extracted once by 800g of dichloromethane, and organic phases are combined. The solvent was recovered by atmospheric distillation and then distilled under reduced pressure to obtain 428g of 1-chloro-2-phenylethane.
(yield 93%)
Example 4
Synthesis of 1-chloro-2-phenylethane
40g of 2-phenethyl alcohol and 332g of 36% concentrated hydrochloric acid are sequentially added into a 500mL pressure-resistant reaction kettle, stirred and reacted for 8 hours at the temperature of 120 ℃. The temperature is reduced to room temperature, the mixture is kept stand and layered, an acid layer is extracted once by 100g of dichloromethane, and organic phases are combined. The solvent was recovered by distillation under atmospheric pressure, and 44g of 1-chloro-2-phenylethane was obtained by distillation under reduced pressure. (yield 96%)
Example 5
Synthesis of 1- (2-chloroethyl) -4- (chloromethyl) benzene
1000g of a 65% sulfuric acid solution, 134g of paraformaldehyde and 28.8g of zinc chloride were sequentially charged in a 2L four-necked flask. Firstly introducing hydrogen chloride gas for 20 minutes, then heating the system to 90 ℃, dropwise adding 250g of 1-chloro-2-phenylethane while keeping introducing the hydrogen chloride gas, and continuing the heat preservation and aeration reaction for 5 hours after completing the dropwise addition. The temperature is reduced to room temperature, the layers are separated, the aqueous layer is extracted with 1000g of hexane, the combined organic phases are freed from the solvent by evaporation under reduced pressure, and the residue is recrystallized from 840g of methanol to give 263g of 1- (2-chloroethyl) -4- (chloromethyl) benzene.1H NMR(400MHz,(D3C)2δ 3.03(t, J ═ 7.2,2H),3.85(t, J ═ 7.2,2H),4.74(s,2H),7.29(d, J ═ 8,2H),7.38(d, J ═ 8,2H) (yield 78%)
Example 6
Synthesis of 1- (2-chloroethyl) -4- (chloromethyl) benzene
250g of 50% sulfuric acid solution, 34g of paraformaldehyde and 7.2g of zinc chloride were sequentially added to a 500mL four-necked flask. Introducing hydrogen chloride gas for 20 minutes, heating the system to 90 ℃, dropwise adding 1-chloro-2-phenylethane of 62.5g while keeping introducing the hydrogen chloride gas, and continuing the heat preservation and aeration reaction for 5 hours after completing dripping. The temperature is reduced to room temperature, the layers are separated, the aqueous layer is extracted with 200g of hexane, the combined organic phases are evaporated under reduced pressure, and the residue is recrystallized from 200g of methanol to give 58g of 1- (2-chloroethyl) -4- (chloromethyl) benzene. (yield 69%)
Example 7
Synthesis of 1- (2-chloroethyl) -4- (chloromethyl) benzene
250g of 80% sulfuric acid solution, 34g of paraformaldehyde and 7.2g of zinc chloride were sequentially added to a 500mL four-necked flask. Introducing hydrogen chloride gas for 20 minutes, heating the system to 90 ℃, dropwise adding 1-chloro-2-phenylethane of 62.5g while keeping introducing the hydrogen chloride gas, and continuing the heat preservation and aeration reaction for 5 hours after completing dripping. The temperature is reduced to room temperature, the layers are separated, the aqueous layer is extracted with 200g of hexane, the combined organic phases are evaporated under reduced pressure, and the residue is recrystallized from 200g of methanol to give 55g of 1- (2-chloroethyl) -4- (chloromethyl) benzene. (yield 65%)
Example 8
Synthesis of p-chloromethyl styrene
200g of 1- (2-chloroethyl) -4- (chloromethyl) benzene, 300g of tetrahydrofuran and 1g of TBC are sequentially added into a 1L reaction bottle, the temperature of the system is controlled to be 30 ℃, and 122g of sodium tert-butoxide is added in batches under the protection of nitrogen. After the feeding is finished, the stirring is continued for 1 hour under the condition of heat preservation. And GC detection of the reaction solution: 88.7% of p-chloromethylstyrene and 0.4% of 1-tert-butoxymethyl-4-vinylbenzene. Filtering, distilling the filtrate at normal pressure to recover the solvent, and then distilling under reduced pressure to obtain 134g of p-chloromethyl styrene, colorless transparent liquid with the GC purity of 99.7 percent.1H NMR(400MHz,CDCl3) δ 4.56(s,2H),5.26(d, J ═ 10.8,1H),5.75(d, J ═ 17.6,1H),6.70(dd, J ═ 10.8,17.6,1H),7.32(d, J ═ 8,2H),7.38(d, J ═ 8,2H) (yield 83%)
Example 9
Synthesis of p-chloromethyl styrene
100g of 1- (2-chloroethyl) -4- (chloromethyl) benzene, 150g of tetrahydrofuran and 0.5g of TBC are sequentially added into a 500L reaction bottle, the temperature of the system is controlled at 30 ℃, and 74g of KOH is added in batches under the protection of nitrogen. After the feeding is finished, the temperature is increased to reflux and the reaction is stirred for 2.5 hours. And GC detection of the reaction solution: p-chloromethyl styrene 70.7% to yield 1-hydroxymethyl-4-vinylbenzene 9.4%. Filtering, distilling the filtrate at normal pressure to recover the solvent, and then distilling under reduced pressure to obtain 51g of p-chloromethyl styrene with GC purity of 98.9%. (yield 63%)
Example 10
Synthesis of p-chloromethyl styrene
A500L reaction flask was charged with 100g of 1- (2-chloroethyl) -4- (chloromethyl) benzene, 150g of tetrahydrofuran, and 0.5g of TBC in this order, and 43g of sodium methoxide was added in portions while controlling the system temperature at 30 ℃ and under nitrogen protection. After the feeding is finished, the stirring is continued for 1 hour under the condition of heat preservation. And GC detection of the reaction solution: p-chloromethyl styrene 75.8% yielded 1-methoxymethyl-4-vinylbenzene 5.7%. Filtering, distilling the filtrate at normal pressure to recover the solvent, and then distilling under reduced pressure to obtain 57g of p-chloromethyl styrene with the GC purity of 98.5%. (yield 71%)
Example 11
Synthesis of p-chloromethyl styrene
150g of 1- (2-chloroethyl) -4- (chloromethyl) benzene, 250g of N-methylpyrrolidone and 1g of BHT are sequentially added into a 1L reaction bottle, the temperature of the system is controlled to be 30 ℃, and 92g of sodium tert-butoxide is added in batches under the protection of nitrogen. After the feeding is finished, the stirring is continued for 1 hour under the condition of heat preservation. And GC detection of the reaction solution: 88.2% of p-chloromethyl styrene and 0.5% of 1-tert-butoxymethyl-4-vinylbenzene. 200g of water is added into the reaction system, dichloroethane is used for extraction, the organic layer is distilled at normal pressure to recover the solvent, and then is distilled at reduced pressure to obtain 97g of p-chloromethyl styrene, colorless transparent liquid with the GC purity of 99.5 percent. (yield 80%)
Example 12
Synthesis of p-chloromethyl styrene
200g of 1- (2-chloroethyl) -4- (chloromethyl) benzene, 300g of tetrahydrofuran and 1g of hydroquinone are sequentially added into a 1L reaction bottle, the temperature of the system is controlled at 30 ℃, and 145g of potassium tert-butoxide is added in batches under the protection of nitrogen. After the feeding is finished, the stirring is continued for 1 hour under the condition of heat preservation. And GC detection of the reaction solution: 88.9% of p-chloromethylstyrene and 0.4% of 1-tert-butoxymethyl-4-vinylbenzene. Filtering, distilling the filtrate at normal pressure to recover the solvent, and then distilling under reduced pressure to obtain 123g of p-chloromethyl styrene, colorless transparent liquid with GC purity of 99.5%. (yield 83%)
In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. A method for preparing p-chloromethyl styrene comprises the following steps: 1- (2-chloroethyl) -4- (chloromethyl) benzene was subjected to elimination reaction under alkaline conditions to provide p-chloromethylstyrene.
2. The method for preparing p-chloromethylstyrene as claimed in claim 1, wherein the elimination reaction is carried out by using an organic base and/or an inorganic base, preferably one or more selected from alkali metal hydroxide, alkali metal alkoxide, and alkaline earth metal hydroxide;
and/or, in the elimination reaction, the molar ratio of 1- (2-chloroethyl) -4- (chloromethyl) benzene to base is 1: 1.05-1: 5, preferably 1: 1.1 to 3.
3. The process for producing p-chloromethylstyrene as claimed in claim 1, wherein the elimination reaction is carried out in the presence of a polymerization inhibitor.
4. The process for producing p-chloromethylstyrene as claimed in claim 3, wherein the polymerization inhibitor comprises one or more selected from 4-tert-butylcatechol, p-hydroxyanisole, hydroquinone, 2, 6-di-tert-butylp-cresol, 2, 5-di-tert-amylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, and wood tar;
and/or the mass of the polymerization inhibitor is 0.1-5%, preferably 0.5-2% of the mass of the 1- (2-chloroethyl) -4- (chloromethyl) benzene.
5. The process for producing p-chloromethylstyrene as claimed in claim 1, wherein the elimination reaction is carried out in the presence of a solvent, and the solvent used in the elimination reaction comprises an aprotic polar solvent.
6. The method for producing p-chloromethylstyrene according to claim 1, wherein the elimination reaction is carried out at a temperature of from room temperature to 100 ℃, preferably from 20 ℃ to 50 ℃;
and/or, in the elimination reaction, the reaction is carried out under the condition of gas protection;
and/or in the elimination reaction, the post-treatment of the reaction comprises: and (5) solid-liquid separation and purification.
7. The method according to claim 1, wherein the method for producing 1- (2-chloroethyl) -4- (chloromethyl) benzene comprises: chloromethylation of 1-chloro-2-phenylethane with formaldehyde and hydrogen chloride in the presence of a lewis acid provides 1- (2-chloroethyl) -4- (chloromethyl) benzene.
8. The process for preparing p-chloromethylstyrene according to claim 7, wherein the molar ratio of 1-chloro-2-phenylethane to formaldehyde in the chloromethylation reaction is 1: 1-10, preferably 1: 2-5;
and/or the formaldehyde is derived from paraformaldehyde;
and/or, in the chloromethylation reaction, the amount of hydrogen chloride is in excess relative to 1-chloro-2-phenylethane;
and/or, in the chloromethylation reaction, the Lewis acid comprises one or more of zinc chloride, ferric chloride, copper chloride, cobalt chloride and nickel chloride;
and/or in the chloromethylation reaction, the mass ratio of the 1-chloro-2-phenylethane to the Lewis acid is 1: 4-20, preferably 1: 5-10;
and/or, in the chloromethylation reaction, the reaction is carried out in the presence of a solvent, and the reaction solvent in the chloromethylation reaction comprises an aqueous solution of sulfuric acid;
and/or in the chloromethylation reaction, the reaction temperature is between room temperature and 100 ℃, and is preferably 80-95 ℃;
and/or, in the chloromethylation reaction, the post-treatment of the reaction comprises: extracting and concentrating the organic phase.
9. The method of producing p-chloromethylstyrene according to claim 7, wherein the 1-chloro-2-phenylethane comprises: 2-phenylethyl alcohol is chlorinated with a chlorinating agent to provide 1-chloro-2-phenylethane.
10. The process for producing p-chloromethylstyrene as claimed in claim 9, wherein the chlorinating agent is used in an excess amount relative to 2-phenylethyl alcohol in the chlorination reaction;
and/or, in the chlorination reaction, the chlorination reagent comprises hydrogen chloride;
and/or in the chlorination reaction, the reaction temperature is between room temperature and 160 ℃, and preferably 90-120 ℃;
and/or, in the chlorination reaction, the post-treatment of the reaction comprises: extracting and concentrating the organic phase.
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