CN116462569A - Process for producing aromatic olefin compound and process for purifying the same - Google Patents

Process for producing aromatic olefin compound and process for purifying the same Download PDF

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Publication number
CN116462569A
CN116462569A CN202310486400.7A CN202310486400A CN116462569A CN 116462569 A CN116462569 A CN 116462569A CN 202310486400 A CN202310486400 A CN 202310486400A CN 116462569 A CN116462569 A CN 116462569A
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compound
reaction
sodium carbonate
aromatic olefin
steps
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陆茜
匡逸
徐松根
钟景
罗德智
赵濬宇
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Shanghai Linkchem Technology Co ltd
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Shanghai Linkchem Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/42—Use of additives, e.g. for stabilisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the field of organic synthesis, in particular to a preparation method and a purification method of an aromatic olefin compound. The reaction formula is as follows:wherein R is 1 、R 2 Independently of one another selected from H, C C1-C10 alkyl or C1-C10 haloalkyl. The preparation method comprises the following steps: forming a reaction stock solution containing at least the compound 1 and the pyridinium paratoluenesulfonate, treating the reaction stock solution under the condition of converting the compound 1 into the compound 2 to obtain a reaction solution, and performing post-treatment to obtain the compound 2, wherein the post-treatment at least comprisesThe method comprises the following steps: washing with aqueous sodium carbonate solution. According to the method for producing an olefin-based aromatic halogenated compound of the present invention, since the aqueous sodium carbonate solution is used for washing during the post-treatment, the present invention can reduce the generation of polymer during the distillation, thereby improving the recovery rate of the target product.

Description

Process for producing aromatic olefin compound and process for purifying the same
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method and a purification method of an aromatic olefin compound.
Background
Aromatic olefin compounds are widely used as a polymerizable monomer in the field of resins.
For example, AChemically Inert Hydrophilic Resin for Solid Phase Organic Synthesis (Tetrahedron Letters,1998, vol.39, #47, p.8695-8698), in which it is pointed out that 4- (3-chloropropyl) styrene can be used as a monomer for preparing the inert hydrophilic resin.
In the prior art, taiwan patent TW 202219048A discloses a preparation method of 4- (3-chloropropyl) styrene, which comprises preparing corresponding grignard reagent from 4-vinylbenzyl chloride, and using p-toluenesulfonyl-OCH 2 CH 2 Cl reacts with it to produce 4- (3-chloropropyl) styrene.
The preparation method has the advantages of harsh reaction conditions, high mass production cost and low yield which is only 81 percent, and needs to be carried out under anhydrous conditions.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing and purifying an aromatic olefin compound under simple reaction conditions and with a high yield.
In one aspect, the invention provides a method for preparing an aromatic olefin compound, wherein the reaction formula is as follows:
wherein R is 1 、R 2 Independently of one another selected from H, C C1-C10 alkyl, or C1-C10 haloalkyl;
the preparation method comprises the following steps:
forming a reaction stock solution containing at least the compound 1 and the pyridinium paratoluenesulfonate, treating the reaction stock solution under the condition of converting the compound 1 into the compound 2 to obtain a reaction solution, carrying out post treatment to obtain the compound 2,
wherein the post-treatment at least comprises the following steps:
washing with aqueous sodium carbonate solution.
In another aspect, the present invention provides a method for purifying an aromatic olefin compound, for separating compound 2 from a mixture containing both compound 2 and pyridinium p-toluenesulfonate;
wherein R is 1 、R 2 Independently of one another selected from H, C C1-C10 alkyl, or C1-C10 haloalkyl;
the method comprises the following steps:
washing with sodium carbonate aqueous solution;
distillation gave compound 2.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for producing an olefin-based aromatic halogenated compound of the present invention, since the aqueous sodium carbonate solution is used for washing during the post-treatment, the present invention can reduce the generation of polymer during the distillation, thereby improving the recovery rate of the target product. The yield of the olefin aromatic halogenated compound prepared by the invention can reach 94.0 percent, and the purity can reach 99.7 percent.
Drawings
FIG. 1 is an HPLC chart of the product of example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of the product of example 1 of the present invention.
Detailed Description
Embodiments of a method for producing and purifying an aromatic olefin compound specifically disclosed are described in detail below.
Definition of terms
The following words, phrases and symbols used in the present specification have the meanings as described below in general unless otherwise indicated.
Generally, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including those used in cell culture, organic chemistry, analytical chemistry, pharmacology, and the like) are those well known and commonly employed in the art. Unless defined otherwise, all scientific and technical terms used herein in connection with the disclosure described herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, in the claims and/or the specification, the terms "a" or "an" when used in conjunction with the term "comprising" or noun may have the meaning of "one" but are also consistent with the meaning of "one or more", "at least one", and "one or more". Similarly, the term "another" or "other" may mean at least a second or more.
It will be understood that whenever aspects are described herein by the terms "comprising" or "including," other similar aspects are provided as described by "consisting of …" and/or "consisting essentially of ….
The term "alkyl" used herein, alone or in combination, may be straight or branched and the number of carbon atoms may be, for example, C1 to C10, C1 to C8, C1 to C6, C1 to C5, C1 to C4, C1 to C3, C1 to C2, etc. By way of example, alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, and the like.
The term "haloalkyl" as used herein, alone or in combination, refers to an alkyl group wherein one or more hydrogen atoms are each replaced by a halogen. Wherein "halogen" refers to fluorine, chlorine, bromine or iodine. As an illustration, "haloalkyl" includes, but is not limited to, -CCl 3 、-CHCl 2 、-CH 2 Cl、-CH 2 -CCl 3 、-CH 2 -CHCl 2 、-CH 2 -CH 2 Cl、-CH 2 -CH 2 -CCl 3 、-CH 2 -CH 2 -CHCl 2 、-CH 2 -CH 2 -CH 2 Cl、-CH 2 -CH 2 -CH 2 -CCl 3 、-CH 2 -CH 2 -CH 2 -CHCl 2 、-CH 2 -CH 2 -CH 2 -CH 2 Cl、-CH 2 -CH 2
-CH 2 -CH 2 -CCl 3 、-CH 2 -CH 2 -CH 2 -CH 2 -CHCl 2 、-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 Cl、-CF 3 、-CHF 2 、-CH 2 F、-CH 2 -CF 3 、-CH 2 -CHF 2 、-CH 2 -CH 2 F、-CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 -CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 F, etc. Here, the alkyl group is as defined above.
Preparation method
The invention provides a preparation method of an aromatic olefin compound, which has the following reaction formula:
wherein R is 1 、R 2 Independently of one another selected from H, C C1-C10 alkyl or C1-C10 haloalkyl,
the preparation method comprises the following steps:
forming a reaction stock solution containing at least the compound 1 and the pyridinium paratoluenesulfonate, treating the reaction stock solution under the condition of converting the compound 1 into the compound 2 to obtain a reaction solution, and performing post-treatment to obtain the compound 2.
In this application, the post-processing may be implemented by various embodiments:
in a first embodiment, the post-treatment comprises at least the steps of: washing with aqueous sodium carbonate solution.
In a second embodiment, the post-processing includes the steps of: washing with sodium carbonate aqueous solution; distillation gave compound 2.
In a third embodiment, the reaction stock solution further includes a reaction solvent. When the reaction stock solution contains a reaction solvent, the post-treatment comprises the following steps: displacing the reaction solvent; washing with sodium carbonate aqueous solution; distillation gave compound 2.
Wherein the reaction solvent is selected from any one or more of xylene, trimethylbenzene, ethylbenzene, chlorobenzene, nitrobenzene, nitrotoluene, and the like, for example.
Displacing the reaction solvent includes removing the reaction solvent and adding an organic medium. In some embodiments, the organic medium is selected from one or both of n-heptane, n-hexane.
In some embodiments, the volume ratio of the reaction solvent to the organic medium is (1-2): 1-2.
In the preparation method of the aromatic olefin compound, the reaction liquid contains a polymerization inhibitor or the polymerization inhibitor is added in the post-treatment process. Wherein the polymerization inhibitor is selected from one or more of para-tertiary butyl catechol, 2, 6-dinitro-p-cresol, 2, 5-dihydroxytoluene and the like. Preferably, the polymerization inhibitor is selected from para-tert-butylcatechol and/or 2, 6-dinitro-p-cresol.
Wherein when the polymerization inhibitor is added during the post-treatment, the polymerization inhibitor may be applied to the second embodiment and the third embodiment, respectively, to form the fourth embodiment and the fifth embodiment, respectively.
In a fourth embodiment, the method comprises the following steps: adding a polymerization inhibitor; washing with sodium carbonate aqueous solution; distillation gave compound 2. Preferably, the order of the two steps of adding the polymerization inhibitor and washing with the sodium carbonate aqueous solution is not limited, and the step of adding the polymerization inhibitor is completed before the step of distilling to obtain the compound 2 is performed, so that the technical scheme can be realized.
In a fifth embodiment, the method comprises the following steps: displacing the reaction solvent; adding a polymerization inhibitor; washing with sodium carbonate aqueous solution; distillation gave compound 2. Preferably, the specific timing of performing the step of adding the polymerization inhibitor is not limited here, and the present technical scheme may be realized by performing the step at any timing before the step of distilling to obtain the compound 2. Wherein the step of displacing the reaction solvent comprises removing the reaction solvent and adding an organic medium.
In the method for preparing an aromatic olefin compound according to the present invention, in the above five embodiments, the concentration of the aqueous sodium carbonate solution is 5wt% to 10wt%. In some embodiments, the concentration of the aqueous sodium carbonate solution may be, for example, 5wt% to 8wt%, or 8wt% to 10wt%, or the like.
In the method for producing an aromatic olefin compound, the molar ratio of the compound 1 to the pyridine p-toluenesulfonate is 1 (0.1 to 0.2). In some embodiments, the molar ratio of compound 1 to pyridine p-toluenesulfonate may also be 1 (0.1-0.15), or 1 (0.15-0.2), etc.
In the preparation method of the aromatic olefin compound provided by the invention, R 1 、R 2 Independently of one another selected from H, C C1-C6 alkyl or C1-C6 haloalkyl. Further alternatively, R 1 、R 2 Independently of one another selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, -CH 2 -CH 2 Cl、-CH 2 -CH 2 -CH 2 Cl、-CH 2 -CH 2 -CH 2 -CH 2 Cl, and the like.
In the method for producing an aromatic olefin compound according to the present invention, the compound 1 may be, for exampleCompound 2 can be, for example +.>
Purification method
The invention also provides a purification method of the aromatic olefin compound, which is used for separating the compound 2 from a mixture containing the compound 2 and the pyridinium p-toluenesulfonate.
Wherein R is 1 、R 2 Independently of one another selected from H, C C1-C10 alkyl or C1-C10 haloalkyl.
In a first embodiment, the purification method comprises the steps of: washing with sodium carbonate aqueous solution; distillation gave compound 2.
In a second embodiment, the mixture further comprises a solvent, and the purification method comprises the following steps:
displacing the solvent;
washing with sodium carbonate aqueous solution;
distillation gave compound 2.
Wherein the displacing the solvent comprises removing the solvent and adding an organic medium.
In the purification method of the aromatic olefin compound, the purification method also comprises the step of adding a polymerization inhibitor, wherein the polymerization inhibitor is added before the distillation step. The specific explanation is as follows: the specific timing of the step of adding the polymerization inhibitor is not limited here, and the step may be performed at any timing before the step of distilling to obtain the compound 2. In a specific embodiment, a polymerization inhibitor is incorporated into the first embodiment to form a third embodiment. The polymerization inhibitor is incorporated into the second embodiment to form the fourth embodiment.
In a third embodiment, the purification method comprises the steps of: adding a polymerization inhibitor; washing with sodium carbonate aqueous solution; distillation gave compound 2. Preferably, the order of the two steps of adding the polymerization inhibitor and washing with the sodium carbonate aqueous solution is not limited, and the step of adding the polymerization inhibitor is completed before the step of distilling to obtain the compound 2 is performed, so that the technical scheme can be realized.
In a fourth embodiment, the purification method comprises the steps of: displacing the solvent; adding a polymerization inhibitor; washing with sodium carbonate aqueous solution; distillation gave compound 2. Wherein displacing the solvent comprises removing the solvent and adding an organic medium. Preferably, the specific timing of performing the step of adding the polymerization inhibitor is not limited here, and the present technical scheme may be realized by performing the step at any timing before the step of distilling to obtain the compound 2.
The purification method of an olefin-based aromatic halogenated compound provided by the present invention may further have the following features: the solvent is selected from any one or more of xylene, trimethylbenzene, ethylbenzene, chlorobenzene, nitrobenzene, nitrotoluene, and the like.
The purification method of an olefin-based aromatic halogenated compound provided by the present invention may further have the following features: the organic medium is selected from one or two of n-heptane and n-hexane.
The purification method of an olefin-based aromatic halogenated compound provided by the present invention may further have the following features: the polymerization inhibitor is selected from one or more of para-tertiary butyl catechol, 2, 6-dinitro-p-cresol, 2, 5-dihydroxytoluene and the like. Preferably, the polymerization inhibitor is selected from para-tert-butylcatechol and/or 2, 6-dinitro-p-cresol.
The purification method of an olefin-based aromatic halogenated compound provided by the present invention may further have the following features: the volume ratio of the solvent to the organic medium is (1-2) 1-2.
The purification method of an olefin-based aromatic halogenated compound provided by the present invention may further have the following features: the concentration of the sodium carbonate aqueous solution is 5wt% to 10wt%. In some embodiments, the concentration of the aqueous sodium carbonate solution may be, for example, 5wt% to 8wt%, or 8wt% to 10wt%, or the like.
In the method for purifying an aromatic olefin compound provided by the present invention, R in the compound 2 1 、R 2 Independently of one another selected from H, C C1-C6 alkyl or C1-C6 haloalkyl. Further alternatively, R 1 、R 2 Independently of one another selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, -CH 2 -CH 2 Cl、-CH 2 -CH 2 -CH 2 Cl、-CH 2 -CH 2 -CH 2 -CH 2 Cl, and the like.
The technical solutions of the present application are clearly and completely described below in connection with the embodiments of the present invention. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In the examples described below, reagents, materials and apparatus used are commercially available unless otherwise specified.
In an embodiment of the present invention, in the present invention,the yield was calculated by: yield= (mass of actual product/mass of theoretical product) Amount) 100%。
Example 1 ]
Preparation method of compound 2a
This example provides a method for preparing compound 2a, which has the following reaction formula:
the method comprises the following steps:
5g of compound 1a (0.025 mol,1.0 eq), 0.5g of pyridine p-toluenesulfonate (2.5 mmol,0.1 eq) and 0.05g of p-tert-butylcatechol (1 wt%) are added into 25mL of xylene, the temperature is raised to 140 ℃ for reaction for 12h, the filtrate is taken to obtain a reaction stock solution, the xylene is distilled off, 25mL of n-heptane is added, 25mL of 5wt% sodium carbonate aqueous solution is added for washing, the distillation is carried out under reduced pressure, and a fraction at 60-80 ℃ is taken, thus obtaining 4.07g of compound 2a with the yield of 90.4% and the purity of 99.7%.
Wherein the yield= [4.07 g/(0.025 mol×180) ], 100% = 90.4%. Other example calculations refer to example 1.
The HPLC profile of the product is shown in FIG. 1.
1 H NMR(400MHz,Chloroform-d)δ7.35(d,J＝8.1Hz,2H),7.17(d,J＝8.0Hz,2H),6.70(dd,J＝17.6,10.9Hz,1H),5.72(dd,J＝17.6,1.0Hz,1H),5.22(dd,J＝10.9,1.0Hz,1H),3.53(t,J＝6.5Hz,2H),2.78(t,J＝7.4Hz,2H),2.08(tt,J＝8.3,6.5Hz,2H).
Example 2 ]
Screening of acid reagents
This example uses the following experimental procedure to screen for acid reagents based on example 1, and the reaction scheme is as follows:
the method comprises the following steps:
5g of compound 1a (0.01 mol,1.0 eq), an acid reagent and 0.05g of p-tert-butylcatechol (1 wt%) are added into 25mL of dimethylbenzene, the temperature is raised to 140 ℃ for reaction for 12h, the filtration is carried out, a filtrate is taken to obtain a reaction stock solution, the dimethylbenzene is distilled off, 25mL of n-heptane is added, 25mL of 5wt% sodium carbonate aqueous solution is added for washing, and the target product 2a is obtained through reduced pressure distillation.
The screening results are shown in Table 1.
TABLE 1 screening of acid reagents
As is clear from Table 1, when p-toluenesulfonic acid was used as the acid reagent, the product was mainly dimer even if 0.06 equivalent was used in the reaction system, and the target product was not detected. When 75wt% sulfuric acid water solution is used as acid reagent, the main product in the reaction system is the ether compound formed by condensation of the raw material, and the yield of the target product olefin is only 16.3%. When pyridine p-toluenesulfonate is used as an acid reagent, the main product of the reaction system is olefin, and good yield can be obtained when the amount of pyridine p-toluenesulfonate is between 0.1eq and 0.2 eq.
Example 3 ]
Screening of polymerization inhibitor
This example uses the following experimental procedure to screen for inhibitors on the basis of example 1.
The method comprises the following steps:
5g of compound 1a (0.025 mol,1.0 eq), 0.5g of pyridine p-toluenesulfonate (2.5 mmol,0.1 eq) and a polymerization inhibitor are added into 25mL of dimethylbenzene, the temperature is raised to 140 ℃ for reaction for 12 hours, the filtration is carried out, filtrate is taken to obtain reaction stock solution, dimethylbenzene is distilled off, 25mL of n-heptane is added, 25mL of 5wt% sodium carbonate aqueous solution is added for washing, reduced pressure distillation is carried out, and 60-80 ℃ fraction is taken to obtain compound 2a.
The screening results are shown in Table 2.
TABLE 2 screening of polymerization inhibitors
As is clear from Table 2, when p-tert-butylcatechol and 2, 6-dinitro-p-cresol are used as polymerization inhibitors, higher yields can be obtained, while 2, 5-dimethylbenzene and polymerization inhibitor ZJ-701 have poor polymerization inhibition effect in the reaction system, and a large amount of target products are still converted into dimeric or multimeric compounds during the reaction or post-treatment.
Example 4 ]
Screening of washing solutions
In this example, the washing solution was screened using the following experimental procedure.
The method comprises the following steps:
5g of compound 1a (0.025 mol,1.0 eq), 0.5g of pyridine p-toluenesulfonate (2.5 mmol,0.1 eq) and 0.05g of p-tert-butylcatechol (1 wt%) are added into 25mL of xylene, the temperature is raised to 140 ℃ for reaction for 12h, the filtrate is taken to obtain a reaction stock solution, the xylene is distilled off, 25mL of n-heptane is added, 25mL of washing solution is added for washing, and the distillation under reduced pressure is carried out, and a fraction at 60-80 ℃ is taken to obtain compound 2a.
The screening results are shown in Table 3.
TABLE 3 screening of washing solutions
Sequence number Washing liquid Yield is good
1 Not washing 68.0％
2 5wt% sodium bicarbonate aqueous solution The system becomes viscous and cannot be distilled
3 5wt% aqueous sodium hydroxide solution 71.9％
4 After washing with 5wt% sodium carbonate, the mixture was washed with 25mL of water 94.0％
As is clear from Table 3, the target product was obtained in a high yield only when the product washed with sodium carbonate was distilled again.
Example 5 ]
Without adding polymerization inhibitor
This example provides a method for preparing compound 2a, which has the following reaction formula:
the method comprises the following steps:
5g of compound 1a (0.025 mol,1.0 eq) and 0.5g of pyridine p-toluenesulfonate (2.5 mmol,0.1 eq) were added to 25mL of xylene, the temperature was raised to 140 ℃ and the mixture was reacted for 3 hours, the mixture was filtered, the filtrate was taken to obtain a reaction stock solution, the xylene was distilled off, 25mL of n-heptane was added, 25mL of 5wt% sodium carbonate aqueous solution was added for washing, and the mixture was distilled under reduced pressure to obtain 3.14g of compound 2a with a yield of 69.5%.
Comparative example 1 ]
Without displacing solvent
This example provides a method for preparing compound 2a, which has the following reaction formula:
the method comprises the following steps:
5g of Compound 1a (0.025 mol,1.0 eq), 0.5g of pyridine p-toluenesulfonate (2.5 mmol,0.1 eq) and 0.05g of p-tert-butylcatechol (0.25 mmol,0.01 eq) were added to 25mL of xylene, the temperature was raised to 140℃for reaction for 12h, the filtrate was filtered, the reaction stock solution was obtained, 25mL of 5wt% aqueous sodium carbonate solution was added for washing, the system was emulsified, and further separation was not possible without demulsification.
Effects and effects of the examples
According to the method for producing an olefin-based aromatic halogenated compound according to the above-described embodiment, since washing is performed with an aqueous sodium carbonate solution in the post-reaction treatment, the above-described embodiment can reduce dimerization of the product to thereby improve the yield of the target product.
Further, p-t-butylcatechol and 2, 6-dinitro-p-cresol are used as polymerization inhibitors in the above examples, so that the above examples can reduce the generation of dimerization or multimerization in the process of producing the objective product.
Further, in the above examples, n-heptane was used as a system solvent instead of xylene during the post-treatment, so that emulsification in the subsequent washing step was not generated, which is advantageous for accelerating the process flow.
The applicant states that the present invention is described by way of the above examples as a method for producing an aromatic olefin compound according to the present invention, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention. However, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.

Claims (10)

1. A process for producing an aromatic olefin compound, characterized by comprising the following steps:
wherein R is 1 、R 2 Independently of one another selected from H, C C1-C10 alkyl, or C1-C10 haloalkyl;
the preparation method comprises the following steps:
forming a reaction stock solution containing at least the compound 1 and the pyridinium paratoluenesulfonate, treating the reaction stock solution under the condition of converting the compound 1 into the compound 2 to obtain a reaction solution, carrying out post treatment to obtain the compound 2,
wherein the post-treatment at least comprises the following steps:
washing with aqueous sodium carbonate solution.
2. The method for producing an aromatic olefin compound according to claim 1, wherein the post-treatment comprises the steps of: washing with sodium carbonate aqueous solution;
distillation gave compound 2.
3. The method for producing an aromatic olefin compound according to claim 1, wherein the reaction solution further comprises a reaction solvent.
4. A method for producing an aromatic olefin compound according to claim 3, wherein the post-treatment comprises the steps of:
displacing the reaction solvent;
washing with sodium carbonate aqueous solution;
distillation gave compound 2.
5. The method for producing an aromatic olefin compound according to claim 4, wherein the reaction solvent is one or more selected from the group consisting of xylene, trimethylbenzene, ethylbenzene, chlorobenzene, nitrobenzene, and nitrotoluene;
and/or, the displacing the reaction solvent comprises removing the reaction solvent and adding an organic medium; the organic medium is selected from one or two of n-heptane and n-hexane.
6. The method for producing an aromatic olefin compound according to claim 1, wherein the reaction liquid contains a polymerization inhibitor or a polymerization inhibitor is added during the post-treatment; wherein the polymerization inhibitor is selected from any one or more of para-tertiary butyl catechol, 2, 6-dinitro-p-cresol and 2, 5-dihydroxytoluene;
and/or the concentration of the sodium carbonate aqueous solution is 5wt% to 10wt%;
and/or the molar ratio of the compound 1 to the pyridine p-toluenesulfonate is 1 (0.1-0.2);
and/or R 1 、R 2 Independently of one another, from C1-C6 alkyl, C1-C6 haloalkyl or absent.
7. A purification method of an aromatic olefin compound, characterized by comprising separating compound 2 from a mixture containing both compound 2 and pyridinium p-toluenesulfonate;
wherein R is 1 、R 2 Independently of one another selected from H, C C1-C10 alkyl, or C1-C10 haloalkyl;
the method comprises the following steps:
washing with sodium carbonate aqueous solution;
distillation gave compound 2.
8. The method for purifying an aromatic olefin compound according to claim 7, wherein the mixture further comprises a solvent, the method comprising the steps of:
displacing the solvent;
washing with sodium carbonate aqueous solution;
distillation gave compound 2.
9. The method for purifying an aromatic olefin compound according to claim 8, wherein the displacement solvent comprises removing the solvent and adding an organic medium.
10. The method for purifying an aromatic olefin compound according to claim 7 or 8, wherein the method further comprises adding a polymerization inhibitor, the polymerization inhibitor being added before the distillation step.
CN202310486400.7A 2023-04-28 2023-04-28 Process for producing aromatic olefin compound and process for purifying the same Pending CN116462569A (en)

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