CN114805052A - Method for synthesizing p-vinylbenzoic acid - Google Patents
Method for synthesizing p-vinylbenzoic acid Download PDFInfo
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- CN114805052A CN114805052A CN202210636805.XA CN202210636805A CN114805052A CN 114805052 A CN114805052 A CN 114805052A CN 202210636805 A CN202210636805 A CN 202210636805A CN 114805052 A CN114805052 A CN 114805052A
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- vinylbenzoic
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- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- HHRKFGMMAHZWIM-UHFFFAOYSA-N ethenoxyboronic acid Chemical compound OB(O)OC=C HHRKFGMMAHZWIM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 239000011630 iodine Substances 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- -1 vinyl Grignard reagent Chemical class 0.000 claims abstract description 4
- 239000004327 boric acid Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 229950000688 phenothiazine Drugs 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- QHFAXRHEKNHTDH-UHFFFAOYSA-N (2-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=C QHFAXRHEKNHTDH-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical group CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- MXZQOTDQZBUTHH-UHFFFAOYSA-M [I-].[Mg+]C=C Chemical compound [I-].[Mg+]C=C MXZQOTDQZBUTHH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012267 brine Substances 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 5
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- YFXCNIVBAVFOBX-UHFFFAOYSA-N ethenylboronic acid Chemical compound OB(O)C=C YFXCNIVBAVFOBX-UHFFFAOYSA-N 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OOAPBGPLZAFZSO-UHFFFAOYSA-N 4-(2-chloroethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CCCl)C=C1 OOAPBGPLZAFZSO-UHFFFAOYSA-N 0.000 description 1
- FUWHCTSQIAULAK-UHFFFAOYSA-N 4-(2-hydroxyethyl)benzoic acid Chemical compound OCCC1=CC=C(C(O)=O)C=C1 FUWHCTSQIAULAK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of synthesizing p-vinylbenzoic acid, comprising: s1, synthesizing p-vinyl boric acid; adding alkyl ester triborate and a small amount of iodine into a first solvent as an initiator, and dropwise adding a vinyl Grignard reagent dissolved in the first solvent at-20 to-30 ℃; continuously stirring and reacting at the temperature of minus 20 ℃ to minus 30 ℃, and carrying out aftertreatment after complete reaction to obtain vinyl boric acid; s2, synthesizing p-vinyl benzoic acid; and under the inert gas atmosphere, adding vinyl boric acid and a substrate into a second solvent, adding a catalyst, alkali and a polymerization inhibitor, heating and refluxing, and carrying out aftertreatment after complete reaction to obtain p-vinylbenzoic acid. The method has the advantages of mild reaction conditions, simple operation and high comprehensive yield; the raw materials are easy to obtain and low in price, and the method is suitable for industrial production of p-vinylbenzoic acid and has potential application prospect.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing p-vinylbenzoic acid.
Background
P-vinylbenzoic acid is an important organic synthesis intermediate, and is widely used in the synthesis of medical intermediates and photosensitive materials.
The existing synthesis methods mainly comprise the following steps: (1) double bonds are generated by dehydrating hydroxyl of p-hydroxyethyl benzoic acid under concentrated sulfuric acid, and a large amount of concentrated sulfuric acid is used in the method, so that very large acid waste is generated; (2) carrying out witting reaction on p-chloroethylbenzoic acid and formaldehyde to generate a double bond; triphenylphosphine is needed in the reaction, and the generated triphenyl phosphine oxide is difficult to treat; (3) the reaction of p-bromobenzoic acid and carbon dioxide has higher requirements on reaction equipment due to the use of gas.
For the above reasons, the present invention provides a method for synthesizing p-vinylbenzoic acid.
Disclosure of Invention
The invention provides a method for synthesizing p-vinylbenzoic acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of synthesizing p-vinylbenzoic acid, comprising:
s1, synthesizing p-vinyl boric acid; adding alkyl ester triborate and a small amount of iodine into a first solvent as an initiator, and dropwise adding a vinyl Grignard reagent dissolved in the first solvent at-20 to-30 ℃; continuously stirring and reacting at the temperature of minus 20 ℃ to minus 30 ℃, and carrying out aftertreatment after complete reaction to obtain vinyl boric acid;
s2, synthesizing p-vinyl benzoic acid; under the inert gas atmosphere, adding vinyl boric acid and a substrate into a second solvent, adding a catalyst, alkali and a polymerization inhibitor, heating and refluxing, and carrying out post-treatment after complete reaction to obtain p-vinylbenzoic acid;
wherein the substrate has the structural formula:
x is halogen.
Preferably, the first solvent is tetrahydrofuran, diethyl ether, acetonitrile, DMF or DMSO.
Preferably, the alkyl triborate is methyl triborate, ethyl triborate or isopropyl triborate.
Preferably, the Grignard reagent for vinyl is vinyl magnesium chloride, vinyl magnesium bromide or vinyl magnesium iodide.
Preferably, the molar ratio of the alkyl triborate to the Grignard reagent of vinyl is 1:1 to 1.2.
Further, the post-processing of step S1 includes: the reaction was quenched by adding dilute hydrochloric acid, the quenched mixture was extracted with ethyl acetate, the extract was washed with dilute hydrochloric acid and brine, and the organic phase was dried over anhydrous sodium sulfate or anhydrous magnesium sulfate, concentrated by vacuum filtration, and used as the reactant of step S2 without purification after concentration.
Preferably, the inert gas is nitrogen or argon.
Preferably, the molar ratio of the vinylphenylboronic acid to the substrate is 1.05-1.1: 1.
The second solvent is dioxane, dichloromethane, dichloroethane, tetrahydrofuran, ethylene glycol dimethyl ether, DMF or acetonitrile.
Preferably, the catalyst is Pd (PPh) 3 ) 4 、Pd(dppf)Cl 2 Or Pd (PPh) 3 ) 2 Cl 2 。
Preferably, the base is sodium carbonate, potassium carbonate, sodium acetate, sodium tert-butoxide, potassium phosphate or cesium carbonate. Preferably, the polymerization inhibitor is p-tert-butyl catechol, p-hydroxyanisole, phenothiazine or 4-hydroxy TEMPO.
Further, the post-processing of step S2 includes: cooling to room temperature, filtering and washing the filter cake with ethyl acetate; concentrating the filtrate, and purifying by column chromatography to obtain eluent of petroleum ether and ethyl acetate 5: 1.
The method has the advantages of mild reaction conditions, simple operation and high comprehensive yield; the raw materials are easy to obtain and low in price, and the method is suitable for industrial production of p-vinylbenzoic acid and has potential application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1
S1, adding 50g of methyl triborate and a small amount of iodine into 500mL of anhydrous tetrahydrofuran to be used as an initiator, cooling the mixture to-20 to-30 ℃ in a dry ice acetone bath, and dropwise adding 505mL of tetrahydrofuran solution of vinyl magnesium bromide (1 mol/L); continuously stirring and reacting at the temperature of minus 20 ℃ to minus 30 ℃ for 40min, quenching the reaction by using 500mL of hydrochloric acid (2mol/L), extracting the mixture by using 1L of ethyl acetate, washing the extract by using 500mL of hydrochloric acid (2mol/L) and saturated saline (500mL), drying an organic phase by using anhydrous sodium sulfate, and then carrying out vacuum filtration and concentration to obtain 33.2g of a crude product of the vinyl boric acid;
s2 Nitrogen gasUnder the atmosphere, 30g of crude vinylboronic acid and 79.9g of p-bromobenzoic acid are added to 1L of dioxane, and 1.5g of Pd (dppf) Cl is added 2 42g of sodium carbonate and 0.5g of phenothiazine, heating and refluxing, cooling to room temperature, filtering, and washing a filter cake by using 1L of ethyl acetate; concentrating the filtrate, and purifying by column chromatography to obtain eluent containing petroleum ether and ethyl acetate 5: 1. 55g of p-vinylbenzoic acid was obtained in a yield of 93.4%.
Example 2
S1, adding 50g of ethyl triborate and a small amount of iodine into 500mL of anhydrous tetrahydrofuran to be used as an initiator, cooling the mixture to the temperature of minus 20 to minus 30 ℃ in a dry ice acetone bath, and dropwise adding 360mL of tetrahydrofuran solution of vinyl magnesium chloride (1 mol/L); continuously stirring and reacting at the temperature of minus 20 ℃ to minus 30 ℃ for 40min, quenching the reaction by using 500mL of hydrochloric acid (2mol/L), extracting the mixture by using 1L of ethyl acetate, washing the extract by using 500mL of hydrochloric acid (2mol/L) and saturated saline (500mL), drying the organic phase by using anhydrous sodium sulfate, and then carrying out vacuum filtration and concentration to obtain 23g of crude vinyl boric acid;
s2 adding 20g of crude vinylboronic acid and 53.3g of p-bromobenzoic acid into 800mL of dioxane under nitrogen atmosphere, and then adding 1g of Pd (PPh) 3 ) 4 28.1g of sodium carbonate and 0.3g of phenothiazine, heating and refluxing, cooling to room temperature, filtering, and washing a filter cake by 1L of ethyl acetate; concentrating the filtrate, and purifying by column chromatography to obtain eluent containing petroleum ether and ethyl acetate 5: 1. 36g of p-vinylbenzoic acid was obtained in a yield of 91.7%.
Example 3
S1, adding 50g of isopropyl triborate and a small amount of iodine as an initiator into 500mL of anhydrous tetrahydrofuran, cooling the mixture to-20 to-30 ℃ in a dry ice acetone bath, and dropwise adding 280mL of tetrahydrofuran solution of vinyl magnesium bromide (1 mol/L); continuously stirring and reacting at the temperature of minus 20 ℃ to minus 30 ℃ for 40min, quenching the reaction by using 500mL of hydrochloric acid (2mol/L), extracting the mixture by using 1L of ethyl acetate, washing the extract by using 500mL of hydrochloric acid (2mol/L) and saturated saline (500mL), drying an organic phase by using anhydrous sodium sulfate, and then carrying out vacuum filtration and concentration to obtain 17.8g of a crude product of the vinyl boric acid;
s2 adding 15g of crude vinylboronic acid and 40g of p-bromobenzoic acid into 500mL of dioxane under nitrogen atmosphere, and then adding 1g of Pd (PPh) 3 ) 4 Carbon, carbonHeating and refluxing 21g of sodium and 0.2g of phenothiazine, cooling to room temperature, filtering, and washing a filter cake by using 1L of ethyl acetate; concentrating the filtrate, and purifying by column chromatography to obtain eluent containing petroleum ether and ethyl acetate 5: 1. 27.3g of p-vinylbenzoic acid was obtained in a yield of 92.7%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for synthesizing p-vinylbenzoic acid is characterized by comprising the following steps:
s1, synthesizing p-vinyl boric acid; adding alkyl ester triborate and a small amount of iodine into a first solvent as an initiator, and dropwise adding a vinyl Grignard reagent dissolved in the first solvent at-20 to-30 ℃; continuously stirring and reacting at the temperature of minus 20 ℃ to minus 30 ℃, and carrying out aftertreatment after complete reaction to obtain vinyl boric acid;
s2, synthesizing p-vinyl benzoic acid; under the inert gas atmosphere, adding vinyl boric acid and a substrate into a second solvent, adding a catalyst, alkali and a polymerization inhibitor, heating and refluxing, and carrying out post-treatment after complete reaction to obtain p-vinylbenzoic acid;
wherein the substrate has the structural formula:
x is halogen.
2. The method for synthesizing p-vinylbenzoic acid according to claim 1, which comprises at least one of the following technical features:
a1) the first solvent is tetrahydrofuran, diethyl ether, acetonitrile, DMF or DMSO;
a2) the alkyl ester of the triboric acid is methyl ester of triboric acid, ethyl ester of triboric acid or isopropyl ester of triboric acid;
a3) the Grignard reagent of the vinyl is vinyl magnesium chloride, vinyl magnesium bromide or vinyl magnesium iodide.
3. The method for synthesizing p-vinylbenzoic acid according to claim 2, wherein the molar ratio of the alkyl triborate to the Grignard reagent for vinyl is 1:1 to 1.2.
4. The method for synthesizing p-vinylbenzoic acid according to claim 3, wherein the post-treatment of step S1 comprises: the reaction was quenched by adding dilute hydrochloric acid, the quenched mixture was extracted with ethyl acetate, the extract was washed with dilute hydrochloric acid and brine, and the organic phase was dried over anhydrous sodium sulfate or anhydrous magnesium sulfate, concentrated by vacuum filtration, and used as the reactant of step S2 without purification after concentration.
5. The method for synthesizing p-vinylbenzoic acid according to claim 4, further comprising at least one of the following technical features:
b1) the inert gas is nitrogen or argon;
b2) the second solvent is dioxane, dichloromethane, dichloroethane, tetrahydrofuran, ethylene glycol dimethyl ether, DMF or acetonitrile;
b3) the catalyst is Pd (PPh) 3 ) 4 、Pd(dppf)Cl 2 Or Pd (PPh) 3 ) 2 Cl 2 ；
b4) The alkali is sodium carbonate, potassium carbonate, sodium acetate, sodium tert-butoxide, potassium phosphate or cesium carbonate;
b5) the polymerization inhibitor is p-tert-butyl catechol, p-hydroxyanisole, phenothiazine or 4-hydroxy TEMPO.
6. The method for synthesizing p-vinylbenzoic acid according to claim 5, wherein the molar ratio of vinylphenylboronic acid to substrate is 1.05-1.1: 1.
7. The method of claim 6, wherein the post-processing of step S2 includes: cooling to room temperature, filtering and washing the filter cake with ethyl acetate; concentrating the filtrate, and purifying by column chromatography to obtain eluent containing petroleum ether and ethyl acetate 5: 1.
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| WO2013000994A1 (en) * | 2011-06-30 | 2013-01-03 | Abbott Gmbh & Co. Kg | Novel inhibitor compounds of phosphodiesterase type 10a |
| KR20150033493A (en) * | 2013-09-24 | 2015-04-01 | 도레이케미칼 주식회사 | Manufacturing method of vinylphthalate and vinylphthalate for manufacturing aminocarbonylstyrene |
| CN112409176A (en) * | 2020-11-20 | 2021-02-26 | 惠泽化学科技(濮阳)有限公司 | Synthesis method of p-acetoxystyrene |
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| WO2013000994A1 (en) * | 2011-06-30 | 2013-01-03 | Abbott Gmbh & Co. Kg | Novel inhibitor compounds of phosphodiesterase type 10a |
| KR20150033493A (en) * | 2013-09-24 | 2015-04-01 | 도레이케미칼 주식회사 | Manufacturing method of vinylphthalate and vinylphthalate for manufacturing aminocarbonylstyrene |
| CN112409176A (en) * | 2020-11-20 | 2021-02-26 | 惠泽化学科技(濮阳)有限公司 | Synthesis method of p-acetoxystyrene |
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