CN110903318B - Preparation method of alkenyl phosphonate compound - Google Patents

Preparation method of alkenyl phosphonate compound Download PDF

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CN110903318B
CN110903318B CN201911335353.6A CN201911335353A CN110903318B CN 110903318 B CN110903318 B CN 110903318B CN 201911335353 A CN201911335353 A CN 201911335353A CN 110903318 B CN110903318 B CN 110903318B
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phosphite
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trifluoromethanesulfonate
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solvent
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CN110903318A (en
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魏小红
曾亮
张平
陈丽华
王彦斌
赵连彪
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Northwest Minzu University
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4018—Esters of cycloaliphatic acids
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4056—Esters of arylalkanephosphonic acids
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4084—Esters with hydroxyaryl compounds
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4087—Esters with arylalkanols

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Abstract

The invention discloses a preparation method of an alkenyl phosphonate compound, which comprises the following steps: mixing ketone, phosphite ester, catalyst, additive and solvent, stirring for 8-36 hr at 40-120 deg.c to complete ketone reaction, and column chromatographic separation of the reaction liquid to obtain alkenyl phosphonate compound. The method has mild reaction conditions and high reaction efficiency 1 H NMR detection shows that the yield is 5% -94%; compared with the prior art, the method takes the cheap ketone as the raw material, the byproduct in the reaction is water, the catalyst and the additive do not contain heavy metal, the problems of heavy metal pollution and the like do not exist, and the method is green and environment-friendly and has better atom economy.

Description

Preparation method of alkenyl phosphonate compound
Technical Field
The invention belongs to the technical field of organic medicine synthesis, and particularly relates to a preparation method of an alkenyl phosphonate compound.
Background
The organic phosphonate and the derivatives thereof have unique biological activity and play an important role in the fields of medicine, organic synthesis, agricultural chemistry, material chemistry and the like. These organophosphonate compounds also have a wide range of applications in organic chemistry, synthesizing important biologically active intermediates containing phosphoryl groups, such as inhibitors and semi-antibiotics. The synthesis method mainly comprises the following steps:
1) The classical synthesis method is an alkenyl phosphonate compound obtained by taking alkyne and phosphite compounds as raw materials and adding the alkyne in the presence of transition metal catalyst, but the regioselectivity or stereoselectivity of the product olefin is difficult to control by the method, and particularly the method is non-terminal alkyne or asymmetric alkyne.
2) Transition metal catalyzed olefins and phosphite compounds are used as raw materials, and although regioselectivity or stereoselectivity of the product olefin can be solved through the C-C coupling reaction, the olefins contain leaving groups, such as boron ester, organometallic reagent, halogen, phosphonate and the like. And the synthesis method has poor atom economy and is not friendly to the environment.
The methods usually adopt transition metal as a catalyst, and have the disadvantages of high price, harsh reaction conditions and high equipment requirement.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of an alkenyl phosphonate compound, which takes cheap ketone as a raw material and water as a byproduct in the reaction, and is environment-friendly and has better atom economy.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing an alkenyl phosphonate compound, comprising the steps of: mixing ketone, phosphite ester, catalyst, additive and solvent, stirring for 8-36 hours at 40-120 ℃ to completely convert ketone reaction, and then carrying out column chromatography separation on reaction liquid to obtain alkenyl phosphonate compound;
the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1;
the catalyst is trifluoromethanesulfonic acid metal salt;
the additive is trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, acetic acid, p-toluenesulfonic acid, pivalic acid or trifluoroacetic acid;
the solvent is dichloroethane, toluene, tetrahydrofuran, chloroform or trifluoroethanol.
The function of selecting the trifluoromethane sulfonic acid metal salt as the catalyst is as follows: is a Lewis acid which may coordinate to the carbonyl group on the ketone, causing the nucleophile phosphite to undergo an addition reaction.
The additive has the following functions: acidic conditions are provided. The reasons for the above additives are as follows: acidic conditions can be provided.
Preferably, the metal trifluoromethanesulfonate is silver trifluoromethanesulfonate, nickel trifluoromethanesulfonate, iron trifluoromethanesulfonate, ferrous trifluoromethanesulfonate, copper trifluoromethanesulfonate, zinc trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, scandium trifluoromethanesulfonate or aluminum trifluoromethanesulfonate.
Preferably, the metal trifluoromethanesulfonate is silver trifluoromethanesulfonate.
When the catalyst is silver trifluoromethanesulfonate, the product yield is highest.
Preferably, during the column chromatography, the eluent is petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 3.
Preferably, the additive is trifluoromethanesulfonic acid.
When the additive is trifluoromethanesulfonic acid, the product yield is highest.
Preferably, the solvent is dichloroethane.
The highest product yield is obtained when the solvent is dichloroethane.
Preferably, the molar ratio of the ketone to phosphite, catalyst, additive and solvent is 1.
Preferably, the molar ratio of the ketone to phosphite, catalyst, additive and solvent is 1.
Preferably, the reaction is carried out under stirring at 110 ℃ for 15 hours.
Preferably, the ketone is acetophenone or C 1 ～C 4 Alkyl-substituted acetophenones, C 1 ～C 4 Alkoxy-substituted acetophenones, halogenated acetophenones, naphthylethanones, indanones, tetralones, chroman-4-ones, phenylaliphatic ketones or phenylacetophenones.
Preferably, the phosphite is dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-tert-butyl phosphite, dibutyl phosphite, diphenyl phosphite, dibenzyl phosphite, ethyl phenylphosphonate, or bis (2, 2-trifluoroethyl) phosphite.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention takes the cheap ketone compound as the raw material to prepare the alkenyl phosphonate compound, and has the advantages of easily obtained raw material, simple operation and low production cost.
2) The preparation method has the advantages of no generation of pollution intermediates or products, water as the only byproduct, environmental friendliness, good atom economy, environmental friendliness, realization of large-scale production and good industrial application prospect.
3) The catalyst and the additive do not contain heavy metals, the problems of heavy metal pollution and the like do not exist, and the yield of the product is 5-94%.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified.
Example 1
Adding p-methoxyacetophenone, silver trifluoromethanesulfonate, dimethyl phosphite, dichloroethane as organic solvent and trifluoromethanesulfonic acid as additive into a reaction tube in sequence, and stirring at 110 deg.C for 15 hr to complete the reaction and conversion of p-methoxyacetophenone. The reaction solution is subjected to direct use of an eluent (V) Petroleum ether :V Acetic acid ethyl ester = 3) is obtained by column chromatography silica gel separation. Warp beam 1 The yield of dimethyl (1- (4-methoxyphenyl) vinyl) phosphonate as determined by H NMR was 84%. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 2
This example differs from example 1 in that the dimethyl phosphite used was replaced with an equimolar amount of diethyl phosphite and the other procedure was the same as example 1, the product being diethyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 80% by H NMR.
Example 3
This example differs from example 1 in that the dimethyl phosphite used was replaced with equimolar dibutyl phosphite and the other procedure was the same as example 1, the product being dibutyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 82% by H NMR.
Example 4
This example differs from example 1 in that the dimethyl phosphite used is replaced by an equimolar amount of bis (2, 2-trifluoroethyl) phosphite and the procedure is otherwise the same as in example 1, the product being bis (2, 2-trifluoroethyl) bis (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 86% by H NMR.
Example 5
This example differs from example 1 in that the dimethyl phosphite used was replaced with an equimolar amount of dibenzyl phosphite and the procedure was the same as in example 1, the product being dibenzyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 60% by H NMR.
Example 6
This example differs from example 1 in that the dimethyl phosphite used was replaced with an equimolar amount of diphenyl phosphite and the other procedure was the same as example 1, the product being diphenyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 66% by H NMR.
Example 7
This example differs from example 1 in that the dimethyl phosphite used was replaced with an equimolar amount of ethyl phenylphosphonate and the other procedure was the same as example 1, the product being ethyl (1- (4-methoxyphenyl) vinyl) phenylphosphonate. Warp beam 1 The yield was 76% by H NMR.
Example 8
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by an equimolar amount of acetophenone, the other steps were the same as in example 1, and the product was bis (2, 2-trifluoroethyl) 1- (phenyl) vinyl) phosphonate. Warp beam 1 The yield was 52% by H NMR.
Example 9
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar p-fluoroacetophenone and the procedure was the same as in example 1, the product being bis (2, 2-trifluoroethyl) bis (1- (4-fluorophenyl) vinyl) phosphonate. Warp beam 1 The yield was 60% by H NMR.
Example 10
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar p-chloroacetophenone and the procedure was otherwise the same as in example 1, the product being bis (2, 2-trifluoroethyl) bis (1- (4-chlorophenyl) vinyl) phosphonate. Warp beam 1 The yield was 55% by H NMR.
Example 11
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar p-bromoacetophenone, the other procedure was the same as in example 1, and the product was bis (2, 2-trifluoroethyl) 1- (4-bromophenyl) vinyl) phosphonate. Warp beam 1 The yield was 45% by H NMR.
Example 12
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar p-methylacetophenone and the other procedure was the same as in example 1, the product being bis (2, 2-trifluoroethyl) 1- (4-methylphenyl) vinyl) phosphonate. Warp beam 1 The yield was 64% by H NMR.
Example 13
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar 3-methylacetophenone and the other procedure was the same as in example 1, the product being bis (2, 2-trifluoroethyl) 1- (3-methylphenyl) vinyl) phosphonate. Warp beam 1 The yield was 43% by H NMR.
Example 14
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by an equimolar amount of 2-methylacetophenone and the other procedure was the same as in example 1, the product being bis (2, 2-trifluoroethyl) 1- (2-methylphenyl) vinyl) phosphonate. Warp beam 1 The yield was 50% by H NMR.
Example 15
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by an equimolar amount of 1-acetonaphthone and the other steps were the same as in example 1, the product being bis (2, 2-trifluoroethyl) bis (1- (1-naphthyl) vinyl) phosphonate. Warp beam 1 The yield was 67% by H NMR.
Example 16
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar 1-tetralone and the other procedure was the same as in example 1, the product being bis (2, 2-trifluoroethyl) 3, 4-dihydronaphthalen-1-ylphosphonate. Warp beam 1 The yield was 80% by H NMR.
Example 17
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar amounts of the chroman 4-one and the other steps were the same as in example 1, the product being bis (2, 2-trifluoroethyl) 2H-chromium-4-ylphosphonate. Warp beam 1 The yield was 94% by H NMR.
Example 18
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by an equimolar amount of 1-indanone, the other steps are the same as in example 1, and the product is bis (2, 2-trifluoroethyl) 1H-inden-3-ylphosphonate. Warp beam 1 The yield was 80% by H NMR.
Example 19
This example differs from example 1 in that p-methoxyacetophenone was replaced by equimolar p-methoxypropiophenone, the procedure was otherwise the same as in example 1, and the product was bis (2, 2-trifluoroethyl) bis (1- (4-methoxyphenyl) propenyl) phosphonate. Warp beam 1 The yield was 80% by H NMR.
Example 20
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar phenylacetophenone, the other procedure was the same as in example 1, and the product was (1, 2-diphenylvinyl) phosphonic acid bis (2, 2-trifluoro-phenyl-vinyl) ethyl acetateEthyl) ester. Warp beam 1 The yield was 60% by H NMR.
Example 21
This example differs from example 1 in that the molar ratio of ketone to phosphite, catalyst, additive and solvent is 1. Warp beam 1 The yield was 84% by H NMR.
Example 22
This example differs from example 1 in that the catalyst used was replaced by an equimolar amount of nickel trifluoromethanesulfonate and the other steps were the same as in example 1. Warp beam 1 The yield was 80% by H NMR.
Example 23
This example differs from example 1 in that the catalyst used was replaced by an equimolar amount of ferric trifluoromethanesulfonate and the other steps were the same as in example 1. Warp beam 1 The yield was 78% by H NMR.
Example 24
This example differs from example 1 in that the catalyst used was replaced with an equimolar amount of ferrous trifluoromethanesulfonate and the other steps were the same as in example 1. Warp beam 1 The yield was 77% by H NMR.
Example 25
This example differs from example 1 in that the catalyst used was replaced by equimolar amounts of copper trifluoromethanesulfonate and the procedure was otherwise the same as in example 1. Warp beam 1 The yield was 60% by H NMR.
Example 26
This example differs from example 1 in that the catalyst used is replaced by an equimolar amount of zinc trifluoromethanesulfonate and the other steps are the same as in example 1. Warp beam 1 The yield was 68% by H NMR.
Example 27
This example differs from example 1 in that the catalyst used is replaced by an equimolar amount of magnesium trifluoromethanesulfonate and the procedure is otherwise the same as in example 1. Warp beam 1 The yield was 74% by H NMR.
Example 28
This example differs from example 1 in that the catalyst used was replaced by an equimolar amount of scandium trifluoromethanesulfonate and the other steps were the same as in example 1. Warp beam 1 The yield was 79% by H NMR.
Example 29
This example differs from example 1 in that the catalyst used was replaced with an equimolar amount of aluminum trifluoromethanesulfonate and the other steps were the same as in example 1. Warp beam 1 The yield was 71% by H NMR.
Example 30
This example differs from example 1 in that the molar ratio of ketone to phosphite, catalyst, additive and solvent is 1. Warp beam 1 The yield was 40% by H NMR.
Example 31
This example differs from example 1 in that the molar ratio of ketone to phosphite, catalyst, additive and solvent is 1. Warp beam 1 The yield was 84% by H NMR.
Example 32
This example differs from example 1 in that the molar ratio of ketone to phosphite, catalyst, additive and solvent is 1.5. Warp beam 1 The yield was 85% by H NMR.
Example 33
This example differs from example 1 in that the additive used was replaced with equimolar trifluoromethanesulfonic anhydride and the procedure was otherwise the same as in example 1. Warp beam 1 The yield was 70% by H NMR.
Example 34
This example differs from example 1 in that the additive used was replaced with equimolar acetic acid and the other procedure was the same as in example 1. Warp beam 1 The yield was 60% by H NMR.
Example 35
The difference between this embodiment and embodiment 1In that the additive used was replaced by equimolar p-toluenesulfonic acid and the other steps were the same as in example 1. Warp beam 1 The yield was 40% by H NMR.
Example 36
This example differs from example 1 in that the additive used was replaced by an equimolar amount of pivalic acid and the other procedure was the same as in example 1. Warp beam 1 The yield was 60% by H NMR.
Example 37
This example differs from example 1 in that the additive used is replaced by an equimolar amount of trifluoroacetic acid and the procedure is otherwise the same as in example 1. Warp beam 1 The yield was 60% by H NMR.
Example 38
This example is different from example 1 in that the solvent used is replaced by an equimolar amount of toluene and the other steps are the same as example 1. Warp beam 1 The yield was 32% by H NMR.
Example 39
This example differs from example 1 in that the solvent used was replaced by an equimolar amount of tetrahydrofuran and the other steps were the same as in example 1. Warp beam 1 The yield was 10% by H NMR.
Example 40
This example is different from example 1 in that the solvent used was replaced with equimolar chloroform, and the other steps are the same as example 1. Warp beam 1 The yield was 15% by H NMR.
EXAMPLE 41
This example differs from example 1 in that the solvent used was replaced by an equimolar amount of trifluoroethanol and the other steps were the same as in example 1. Warp beam 1 The yield was 10% by H NMR.
Example 42
This example differs from example 1 in that the dimethyl phosphite used was replaced with equimolar diethyl phosphite, no catalyst was used, and the solvent was chloroform. Then stirred at 100 ℃ for 15 hours, and the other steps were the same as in example 1.The product is diethyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 40% by H NMR. Wherein the molar ratio of the ketone to the phosphite, additive and solvent is 1.
Example 43
This example differs from example 1 in that the dimethyl phosphite used was replaced with equimolar dibutyl phosphite, the catalyst was ferric trifluoromethanesulfonate, the solvent was toluene, and no additives were used. The other steps were the same as in example 1. The product was dibutyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 30% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst and solvent is 1.
Example 44
This example differs from example 1 in that the dimethyl phosphite used is replaced by an equimolar amount of bis (2, 2-trifluoroethyl) phosphite, no catalyst is used and the solvent is tetrahydrofuran. Then stirred at 120 ℃ for 8 hours, and the other steps were the same as in example 1. The product is (1- (4-methoxyphenyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 48% by H NMR. Wherein the molar ratio of the ketone to the phosphite, additive and solvent is 1.
Example 45
This example differs from example 1 in that the dimethyl phosphite used was replaced with equimolar dibenzyl phosphite, the catalyst was copper trifluoromethanesulfonate, and the solvent was chloroform. Then stirred at 90 ℃ for 18 hours, and the other steps were the same as in example 1. The product is dibenzyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 10% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 46
This example differs from example 1 in that the dimethyl phosphite used is replaced by an equimolar amount of diphenyl phosphite, no catalyst is used and the solvent is the same as that used in the previous exampleIs trifluoroethanol. The other steps are the same as in example 1. The product is diphenyl (1- (4-methoxyphenyl) vinyl) phosphonate. Warp beam 1 The yield was 6% by H NMR. Wherein the molar ratio of the ketone to the phosphite, additive and solvent is 1.
Example 47
This example differs from example 1 in that the dimethyl phosphite used is replaced by an equimolar amount of ethyl phenylphosphonate, no catalyst is used and the additive is acetic acid. Then stirred at 70 ℃ for 24 hours, and the other steps were the same as in example 1. The product is (1- (4-methoxyphenyl) vinyl) ethyl phenylphosphonate. Warp beam 1 The yield was 46% by H NMR. Wherein the molar ratio of the ketone to the phosphite, additive and solvent is 1.
Example 48
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar acetophenone, the catalyst was scandium trifluoromethanesulfonate, no additive was used, and the solvent was chloroform. Then stirred at 95 ℃ for 16 hours, and the other steps were the same as in example 1. The product is (1- (phenyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 42% by H NMR. Wherein the molar ratio of ketone to phosphite, catalyst and solvent is 1.
Example 49
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar p-fluoroacetophenone, the catalyst was aluminium trifluoromethanesulfonate, the solvent was trifluoroethanol and no additive was used. Then stirred at 40 ℃ for 34 hours, and the other steps were the same as in example 1. The product is (1- (4-fluorophenyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 39% by H NMR. Wherein the molar ratio of ketone to phosphite, catalyst and solvent is 1.
Example 50
This example differs from example 1 in that the p-methoxyphenylethyl usedThe ketone is replaced by equimolar p-chloroacetophenone, and the solvent is tetrahydrofuran. Then stirred at 65 ℃ for 30 hours, and the other steps were the same as in example 1. The product is (1- (4-chlorophenyl) ethenyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 5% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 51
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by equimolar amounts of p-bromoacetophenone, and the solvent is trifluoroethanol. Then, the mixture was stirred at 50 ℃ for 33 hours, and the other steps were the same as in example 1. The product was (1- (4-bromophenyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 9% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 52
This example is different from example 1 in that p-methoxyacetophenone used was replaced with equimolar p-methylacetophenone, no catalyst was used, and then stirring was carried out at 105 ℃ for 10 hours, and the other steps were the same as in example 1. The product is (1- (4-methylphenyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 34% by H NMR. Wherein the molar ratio of the ketone to the phosphite, additive and solvent is 1.
Example 53
This example is different from example 1 in that dimethyl phosphite used was replaced with diethyl phosphite in an equimolar amount, p-methoxyacetophenone used was replaced with p-methylacetophenone in an equimolar amount, and stirring was carried out at 70 ℃ for 24 hours, and the other steps were the same as example 1. The product is (1- (4-methylphenyl) vinyl) phosphonic acid ethyl ester. Warp beam 1 The yield was 44% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 54
This example is different from example 1Characterized in that the p-methoxyacetophenone used is replaced by equimolar 3-methylacetophenone and the additive is trifluoroacetic acid. Then stirred at 75 ℃ for 24 hours, and the other steps were the same as in example 1. The product is (1- (3-methylphenyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 43% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 55
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by an equimolar amount of 2-methylacetophenone and the additive is pivalic acid. Then, the mixture was stirred at 45 ℃ for 35 hours, and the other steps were the same as in example 1. The product is (1- (2-methylphenyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 30% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 56
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by an equimolar amount of 1-acetonaphthone and the additive is trifluoroacetic acid. Then, the mixture was stirred at 115 ℃ for 9 hours, and the other steps were the same as in example 1. The product is (1- (1-naphthyl) vinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 57% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 57
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by equimolar 1-tetralone, the additive is trifluoromethanesulfonic anhydride, and the solvent is toluene. Then, the mixture was stirred at 65 ℃ for 30 hours, and the other steps were the same as in example 1. The product is 3, 4-dihydronaphthalene-1-yl phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 50% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 58
This example differs from example 1 in that the p-methoxyacetophenone used was replaced by equimolar amounts of the chroman 4-one and then stirred at 110 ℃ for 16 hours, the other procedure being the same as in example 1 and the product being bis (2, 2-trifluoroethyl) 2H-chromium-4-ylphosphonate. Warp beam 1 The yield was 94% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 59
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by equimolar 1-indanone and the solvent is trifluoroethanol. Then stirred at 120 ℃ for 19 hours, and the other steps were the same as in example 1. The product was bis (2, 2-trifluoroethyl) 1H-inden-3-ylphosphonate. Warp beam 1 The yield was 60% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1.
Example 60
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by equimolar p-methoxypropiophenone and the additive is acetic acid. Then stirred at 100 ℃ for 32 hours, and the other steps were the same as in example 1. The product is (1- (4-methoxyphenyl) propenyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 60% by H NMR. Wherein the molar ratio of ketone to phosphite, catalyst, additive and solvent is 1.
Example 61
This example differs from example 1 in that the p-methoxyacetophenone used is replaced by equimolar phenylacetophenone, the solvent is chloroform and the additive is trifluoromethanesulfonic anhydride. Then stirred at 85 ℃ for 36 hours, and the other steps were the same as in example 1. The product is (1, 2-diphenylvinyl) phosphonic acid bis (2, 2-trifluoroethyl) ester. Warp beam 1 The yield was 8% by H NMR. Wherein the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1:2:40。
finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (12)

1. A method for preparing an alkenyl phosphonate compound, which is characterized by comprising the following steps: the method comprises the following steps: mixing ketone, phosphite ester, catalyst, additive and solvent, stirring for 8-36 hours at 40-120 ℃ to completely convert ketone reaction, and then carrying out column chromatography separation on reaction liquid to obtain alkenyl phosphonate compound;
the molar ratio of the ketone to the phosphite, catalyst, additive and solvent is 1;
the catalyst is trifluoromethanesulfonic acid metal salt;
the additive is trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, acetic acid, p-toluenesulfonic acid, pivalic acid or trifluoroacetic acid;
the solvent is dichloroethane or toluene;
the ketone is acetophenone, indanone, tetralone, 4-ketone of benzodihydrofuran, phenyl aliphatic ketone or phenyl acetophenone;
the phosphite ester is dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-tert-butyl phosphite, dibutyl phosphite, diphenyl phosphite, dibenzyl phosphite, ethyl phenylphosphonate or bis (2, 2-trifluoroethyl) phosphite ester.
2. The method of producing an alkenylphosphonate compound according to claim 1, characterized in that: the phenyl aliphatic ketone is acetophenone, C l ～C 4 Alkyl-substituted acetophenones, C l ～C 4 Alkoxy-substituted acetophenones or halogenated acetophenones.
3. The method for producing an alkenylphosphonate compound according to claim 1 or 2, characterized in that: the metal trifluoromethanesulfonate is silver trifluoromethanesulfonate, nickel trifluoromethanesulfonate, iron trifluoromethanesulfonate, ferrous trifluoromethanesulfonate, copper trifluoromethanesulfonate, zinc trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, scandium trifluoromethanesulfonate or aluminum trifluoromethanesulfonate.
4. The method for producing an alkenylphosphonate compound according to claim 3, characterized in that: the metal trifluoromethanesulfonate is silver trifluoromethanesulfonate.
5. The method of producing an alkenylphosphonate ester compound according to claim 3, characterized in that: during column chromatography, the eluent is petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 3.
6. The method of producing an alkenylphosphonate compound according to claim 1 or 2, characterized in that: the additive is trifluoromethanesulfonic acid.
7. The method for producing an alkenylphosphonate compound according to claim 3, characterized in that: the additive is trifluoromethanesulfonic acid.
8. The method of producing an alkenylphosphonate compound according to claim 1 or 2, characterized in that: the solvent is dichloroethane.
9. The method for producing an alkenylphosphonate compound according to claim 3, characterized in that: the solvent is dichloroethane.
10. The method for producing an alkenylphosphonate compound according to claim 1 or 2, characterized in that: the molar ratio of the ketone to phosphite, catalyst, additive and solvent is 1.
11. The method for producing an alkenylphosphonate compound according to claim 10, characterized in that: the molar ratio of the ketone to phosphite, catalyst, additive and solvent is 1.
12. The method for producing an alkenylphosphonate compound according to claim 1 or 2, characterized in that: the reaction was carried out under stirring at 110 ℃ for 15 hours.
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