Method for producing alkenyl phosphorus compound

Abstract

[Problem] Provide a method for producing an alkenyl phosphorus compound. [Solution] The method for producing an alkenyl phosphorus compound of the present invention comprises reacting a specific phosphorus compound with a specific alkynyl compound in the presence of a transition metal complex, a Lewis acid, and a low-polarity additive to produce a specific alkenyl phosphorus compound.

Description

Technical Field

[0001] The present invention relates to a method for producing an alkenyl phosphorus compound. More specifically, the present invention relates to a method for producing an alkenyl phosphorus compound by a hydrophosphylation reaction in the presence of a transition metal complex, a Lewis acid, and a low-polarity additive. Background Art

[0002] Organophosphorus compounds are chemical substances used extensively in a variety of products, including flame retardants, plasticizers, pesticides, agricultural chemicals, and ligands for metal complexes. In recent years, organophosphorus compounds have garnered particular industrial attention as functional materials in the fields of metal surface treatment agents, flame-retardant resins, and electronic materials.

[0003] Among organophosphorus compounds, phosphonic acid derivatives are useful precursors for the various chemical substances mentioned above, and therefore various methods for their production have been studied. For example, a process has been implemented in which phosphonic acid derivatives are produced by the addition reaction of the P(O)-H bond of phosphonic acid to alkynes using a catalyst (hereinafter referred to as a hydrophosphylation reaction). For example, Patent Document 1 proposes the production of phosphonic acid derivatives using a partially hydrolyzed phosphonic acid diester compound as a raw material. Furthermore, Non-Patent Document 1 proposes the production of phosphonic acid derivatives using various zero-valent nickel catalysts.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2017 / 043552

[0007] Non-patent literature

[0008] Non-patent document 1: J. AM. CHEM. SOC. 2004, 126, 5080-5081 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] However, under the reaction conditions described in Patent Document 1, there are the following problems: as a pre-treatment, a hydrolysis reaction must be carried out, which requires an additional step; or, in terms of the reaction temperature, it must also be carried out at a low temperature, and on the other hand, a large amount of reaction heat will be generated, and temperature control is difficult for mass production. In addition, the catalyst used in the hydrophosphylation reaction is expensive, unstable, flammable, and has a bad odor, and a safe and inexpensive catalyst is desired. On the other hand, in Non-Patent Document 1, a hydrophosphylation reaction is carried out using a nickel complex using inexpensive triphenylphosphine, but the reactivity is low, and even if a large amount of catalyst is used, phosphonic acid derivatives can only be obtained in low yields. In addition, phosphine compounds and nickel compounds are mostly difficult to obtain industrially, and there is also the problem of a narrow range of raw material selection.

[0011] Therefore, an object of the present invention is to provide a method for producing an alkenyl phosphorus compound, which uses a divalent nickel compound that is easily available as an industrial raw material, stable in air, and inexpensive, and a phosphine having an aromatic substituent that is stable in air and inexpensive, and adjusts the catalyst in the reaction system to enable efficient hydrophosphylation reaction under conditions of room temperature to slight heating.

[0012] Means for solving problems

[0013] The inventors of the present application have conducted intensive studies to solve the above-mentioned problems and have found that alkenyl phosphorus compounds can be efficiently produced by subjecting a specific phosphorus compound to a hydrophosphylation reaction with a specific alkynyl compound in the presence of a transition metal complex, a Lewis acid, and a low-polarity additive, thereby completing the present invention.

[0014] That is, according to the present invention, the following inventions can be provided.

[0015] [1] A method for producing an alkenyl phosphorus compound represented by the following general formula (4), comprising reacting a phosphorus compound represented by the following general formula (1) with an alkynyl compound represented by the following general formula (2) in the presence of a transition metal complex, a Lewis acid, and a low-polarity additive.

[0016] [Chemical Formula 1]

[0017]

[0018] (In general formula (1), R 1 and R 2 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. 1 and R 2 They can bond to each other to form a ring structure.)

[0019] [Chemical Formula 2]

[0020]

[0021] (In general formula (2), R 3 and R 4 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group.

[0022] [Chemical Formula 3]

[0023]

[0024] (In general formula (4), R 13 and R 14 With R in general formula (1) 1 and R 2 Synonymous, R 15 and R 16 and R in general formula (2) 3 and R 4 Synonymous.)

[0025] [2] The production method according to [1], wherein the transition metal complex is a nickel complex.

[0026] [3] The production method according to [2], wherein the transition metal complex is a zero-valent nickel complex formed by nickel and phosphines.

[0027] [4] The production method according to [3], wherein the phosphine is a phosphine having an aromatic substituent.

[0028] [5] The production method according to any one of [1] to [4], wherein the Lewis acid is a metal compound.

[0029] [6] The production method according to [5], wherein the metal compound is at least one selected from the group consisting of zinc chloride, zinc bromide, and iron (II) chloride.

[0030] [7] The production method according to any one of [1] to [6], wherein in the general formula (1), R 1 and R 2 Each independently represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms. In the general formula (4), R 13 and R 14 Each independently represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms.

[0031] [8] The production method according to any one of [1] to [7], wherein in the general formula (2), R 3 and R 4 are all hydrogen atoms. In the general formula (4), R 15 and R 16 All are hydrogen atoms.

[0032] [9] The production method according to any one of [1] to [8], wherein the reaction is carried out at 10 to 60°C.

[0033]

[10] The production method according to any one of [1] to [9], wherein the low-polarity additive is at least one selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons.

[0034]

[11] The production method according to any one of [1] to

[10] , wherein the low-polarity additive is at least one selected from the group consisting of toluene, tetralin, and methylnaphthalene.

[0035]

[12] The production method according to any one of [1] to

[11] , wherein the amount of the low-polarity additive added is 1% by mass or more and 70% by mass or less relative to the total amount of the reaction system excluding the alkynyl compound.

[0036]

[13] The production method according to any one of [1] to

[12] , wherein the generation rate of by-products is 10% or less.

[0037] Effects of the Invention

[0038] According to the present invention, by subjecting a specific phosphorus compound and a specific alkynyl compound to a hydrophosphorylation reaction in the presence of a transition metal complex, a Lewis acid, and a low-polarity additive, an alkenyl phosphorus compound can be efficiently produced. Furthermore, according to the present invention, the amount of the transition metal complex used as a catalyst can be reduced, and the reaction selectivity is high, thereby increasing the yield of the alkenyl phosphorus compound while suppressing the generation of by-products. DETAILED DESCRIPTION

[0039] [Method for producing alkenyl phosphorus compound]

[0040] (Hydrophosphylation reaction)

[0041] The method for producing an alkenyl phosphorus compound of the present invention comprises the following steps: producing the alkenyl phosphorus compound by a hydrophosphylation reaction using a phosphorus compound and an alkynyl compound as starting materials in the presence of a transition metal complex as a catalyst, a Lewis acid, and a low-polarity additive. The method for producing an alkenyl phosphorus compound of the present invention can reduce the amount of the transition metal complex used as a catalyst, and has high reaction selectivity, thereby increasing the yield of the alkenyl phosphorus compound while suppressing the production of by-products.

[0042] (Phosphorus compounds)

[0043] As a raw material for the hydrophosphylation reaction, a phosphorus compound represented by the following general formula (1) can be used.

[0044] [Chemical Formula 4]

[0045]

[0046] (In general formula (1), R 1 and R 2 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. 1 and R 2 They can bond to each other to form a ring structure.)

[0047] In the general formula (1), R 1 and R 2 The number of carbon atoms in the alkyl, alkoxy, cycloalkyl, aralkyl, aryl, and aryloxy groups is preferably 1 to 10. It should be noted that the number of carbon atoms mentioned above does not include the number of carbon atoms in the substituent. For example, as R 1 and R 2 , alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, and hexyl, alkoxy groups such as methoxy, ethoxy, and butoxy, cycloalkyl groups such as cyclohexyl, aralkyl groups such as benzyl and phenethyl, aryl groups such as phenyl, tolyl, xylyl, and naphthyl, and aryloxy groups such as phenoxy. Among them, R 1 and R 2 Each independently is preferably a substituted or unsubstituted alkoxy group.

[0048] In the general formula (1), R 1 and R 2Examples of substituents that may be present include alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, heterocyclic groups, alkylidene groups, silyl groups, acyl groups, acyloxy groups, carboxyl groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, and oxo groups. The number of carbon atoms in the substituents is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.

[0049] (Alkynyl Compounds)

[0050] As a starting material for the hydrophosphylation reaction, an alkynyl compound represented by the following general formula (2) can be used.

[0051] [Chemical Formula 5]

[0052]

[0053] (In general formula (2), R 3 and R 4 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group.

[0054] In the general formula (2), R 3 and R 4 The number of carbon atoms in the alkyl, cycloalkyl, aralkyl, aryl, heteroaryl, alkenyl, alkoxy, and aryloxy groups is preferably 1 to 10. It should be noted that the number of carbon atoms mentioned above does not include the number of carbon atoms in the substituent. For example, as R 3 and R 4 , alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, and hexyl, cycloalkyl groups such as cyclohexyl, aralkyl groups such as benzyl and phenethyl, aryl groups such as phenyl, tolyl, xylyl, and naphthyl, alkenyl groups such as 1-butenyl, 2-butenyl, 1,3-butadienyl, pentenyl, and hexenyl, alkoxy groups such as methoxy, ethoxy, and butoxy, and aryloxy groups such as phenoxy. Among them, R 3 and R 4 Each independently preferably is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group having 1 to 10 carbon atoms.

[0055] In the general formula (2), R 3 and R 4Examples of substituents that may be present include alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, heterocyclic groups, alkylidene groups, silyl groups, acyl groups, acyloxy groups, carboxyl groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, and oxo groups. The number of carbon atoms in the substituents is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.

[0056] In addition, in the general formula (2), R 3 and R 4 All of them may be hydrogen atoms. That is, the alkynyl compound may be acetylene. By using acetylene, the hydrophosphylation reaction can be efficiently carried out under conditions of room temperature to slight heating, thereby increasing the yield of the alkenyl phosphorus compound.

[0057] The molar ratio of the phosphorus compound represented by the general formula (1) to the alkynyl compound represented by the general formula (2) as starting materials for the hydrophosphylation reaction is preferably 10:1 to 0.1:1, more preferably 3:1 to 0.7:1, and even more preferably 1.1:1 to 0.9:1.

[0058] (Transition Metal Complex (Catalyst))

[0059] As a catalyst used in the hydrophosphylation reaction, a transition metal complex can be used. Examples of the transition metal complex include nickel complexes, and zero-valent nickel complexes are preferred.

[0060] The nickel complex is preferably a nickel complex formed by nickel and phosphines. As phosphines, phosphines with aromatic substituents are preferably phosphines. As phosphines with aromatic substituents, for example, triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, diphenylmethylphosphine, tri(2-methylphenyl)phosphine, tri(3-methylphenyl)phosphine, tri(4-methylphenyl)phosphine, tri(4-methoxyphenyl)phosphine, etc. can be cited. Phosphines with aromatic substituents are cheap and easy to handle in the air, so that manufacturing costs can be reduced and manufacturing efficiency can be improved.

[0061] (Lewis acid)

[0062] As the Lewis acid used in the hydrophosphylation reaction, a metal compound can be used. Examples of the metal compound include zinc chloride, zinc bromide, and iron (II) chloride. Adding a Lewis acid to the hydrophosphylation reaction allows for catalytic activity to be exhibited at around room temperature, increasing the reaction rate and improving the conversion rate of the starting phosphorus compound to the alkenyl phosphorus compound.

[0063] (Low polarity additives)

[0064] As low-polarity additives used in the hydrophosphylation reaction, for example, aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons can be mentioned. As aromatic hydrocarbons, for example, toluene, tetralin and methylnaphthalene, xylene, ethylbenzene, styrene, naphthalene, indene, etc. can be mentioned. As aliphatic hydrocarbons, for example, n-hexane, n-heptane, isooctane, n-decane, etc. can be mentioned. As alicyclic hydrocarbons, for example, cyclopentane, cyclopentadiene, cyclohexane, methylcyclohexane, cyclohexene, dicyclopentadiene, decalin, norbornane, etc. can be mentioned. Among them, aromatic hydrocarbons are preferred, and toluene, tetralin and methylnaphthalene are particularly preferred. These low-polarity additives can be used alone or in combination of two or more. By using low-polarity additives in the hydrophosphylation reaction, the amount of transition metal complex used as a catalyst can be reduced, and the reaction selectivity is high, which can improve the yield of the alkenyl phosphorus compound while suppressing the generation of by-products.

[0065] (Reaction Conditions)

[0066] The amount of the transition metal complex (catalyst) used in the hydrophosphylation reaction is not particularly limited as long as the reaction proceeds sufficiently, but is preferably 0.01 to 10 mol, more preferably 0.1 to 5.0 mol, and even more preferably 0.3 to 1.0 mol per 1 mol of the phosphorus compound as a raw material.

[0067] The amount of the Lewis acid used in the hydrophosphylation reaction is not particularly limited as long as the reaction proceeds sufficiently, but is preferably 1 to 30 mol, more preferably 2 to 10 mol, and even more preferably 3 to 5 mol per 1 mol of the transition metal complex. When the amount of the Lewis acid used is within the above range, the activity of the catalyst in the hydrophosphylation reaction increases, significantly improving the reaction rate, thereby increasing the conversion rate of the phosphorus compound as a starting material to the alkenyl phosphorus compound.

[0068] The amount of the low-polarity additive used in the hydrophosphylation reaction is not particularly limited as long as the reaction proceeds sufficiently, but is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, even more preferably 7.5 to 40% by mass, and even more preferably 8 to 30% by mass, relative to the total amount of the reaction system (reaction solution of the mixture) excluding the alkynyl compound. When the amount of the low-polarity additive used is within the above range, the amount of the transition metal complex used as a catalyst can be reduced, and the reaction selectivity is improved, thereby suppressing the formation of by-products and increasing the yield of the alkenyl phosphorus compound.

[0069] The reaction temperature of the hydrophosphylation reaction is not particularly limited, but is preferably 10 to 60° C., more preferably 15 to 50° C., and even more preferably 20 to 35° C., taking into account reaction efficiency, reaction rate, and by-products. When the reaction temperature is within the above range, the reaction rate of the hydrophosphylation reaction can be increased, and the conversion rate of the raw material phosphorus compound to the alkenyl phosphorus compound can be increased.

[0070] The reaction time of the hydrophosphylation reaction is not particularly limited, but considering the reaction efficiency, reaction rate, and by-products, it is preferably 30 minutes to 1000 minutes, more preferably 60 minutes to 900 minutes, and even more preferably 120 minutes to 800 minutes. If the reaction time is within the above range, the hydrophosphylation reaction can be fully carried out, thereby improving the conversion rate of the phosphorus compound of the raw material to the alkenyl phosphorus compound.

[0071] The hydrophosphylation reaction can be carried out under any conditions, either in the presence of an organic solvent or in the absence of a solvent, but is preferably carried out in the absence of a solvent. A solvent-free method can be used to carry out the hydrophosphylation reaction by gentle heating. Since the reaction is solvent-free, the solvent removal step after completion of the reaction can be omitted, thereby reducing manufacturing costs. It should be noted that the organic solvent is not particularly limited, and examples thereof include alcohols, ethers, ketones, and esters.

[0072] The hydrophosphylation reaction is preferably carried out under an inert gas atmosphere in consideration of reaction efficiency, reaction rate, and by-products. As the inert gas, nitrogen, argon, or the like is preferably used.

[0073] The conversion rate from the phosphorus compound to the alkenyl phosphorus compound in the hydrophosphylation reaction is preferably 60% or more, more preferably 70% or more, further preferably 75% or more, and further more preferably 80% or more. It should be noted that the so-called "conversion rate (%)" in the present invention can be obtained by calculating the reduction ratio of the raw material phosphorus compound at the end of the reaction based on the amount of substance of the raw material phosphorus compound at the beginning of the reaction. Here, for the conversion rate of the reaction, GC-FID can be utilized to identify and measure each component. If the conversion rate from the phosphorus compound to the alkenyl phosphorus compound is above the above numerical value, the raw materials can be efficiently utilized, the manufacturing cost can be reduced, and the manufacturing efficiency can be improved.

[0074] The selectivity from the phosphorus compound to the alkenyl phosphorus compound in the hydrophosphating reaction is preferably more than 65%, more preferably more than 70%, further preferably more than 75%. It should be noted that, in the present invention, so-called " selectivity (%) " can be obtained by calculating the ratio of generating the target alkenyl phosphorus compound in the raw material phosphorus compound consumed by the reaction. Herein, for the selectivity of reaction, GC-FID can be utilized to identify and measure each component. If the selectivity from the phosphorus compound to the alkenyl phosphorus compound is more than the above-mentioned numerical value, then raw materials can be efficiently utilized, the amount of waste after the manufacturing can be reduced in manufacturing cost and the reduction can be achieved, and manufacturing efficiency can be improved.

[0075] The yield from phosphorus compound to alkenyl phosphorus compound in the hydrophosphating reaction is preferably more than 60%, more preferably more than 65%.It should be noted that, in the present invention, so-called " yield (%) " can be obtained in the following manner: relative to the theoretical yield of the alkenyl phosphorus compound calculated by the amount of substance of the raw material phosphorus compound used by the reaction, the ratio of the alkenyl phosphorus compound actually generated is calculated.Herein, for the yield of reaction, GC-FID can be utilized to identify and measure each component.If the yield from phosphorus compound to alkenyl phosphorus compound is more than the above-mentioned numerical value, then raw material can be efficiently utilized, the amount of waste after manufacturing can be reduced, manufacturing cost can be reduced, and manufacturing efficiency can be improved.

[0076] The by-product generation rate in the hydrophosphylation reaction is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less. It should be noted that the so-called by-product is a hexatrienyl compound represented by the following general formula (3) produced by the reaction of the raw material phosphorus compound with three equivalents of the alkynyl compound. If the by-product generation rate is below the above value, the raw material can be efficiently utilized, production costs can be reduced, and production efficiency can be improved.

[0077] [Chemical Formula 6]

[0078]

[0079] (In general formula (3), R 5 and R 6 With R in general formula (1) 1 and R 2 Synonymous, R 7 ~R 12 and R in general formula (2) 3 and R 4 Synonymous.)

[0080] About R 5 and R 6 The preferred embodiment is the same as the above R 1 and R 2 The preferred embodiment of R is the same.7 ~R 12 The preferred embodiment is the same as the above R 3 and R 4 The preferred method is the same.

[0081] (Alkenyl Phosphorus Compounds)

[0082] In the present invention, an alkenyl phosphorus compound represented by the following general formula (4) can be obtained by a hydrophosphylation reaction.

[0083] [Chemical Formula 7]

[0084]

[0085] (In general formula (4), R 13 and R 14 With R in general formula (1) 1 and R 2 Synonymous, R 15 and R 16 and R in general formula (2) 3 and R 4 Synonymous.)

[0086] About R 13 and R 14 The preferred embodiment is the same as the above R 1 and R 2 The preferred embodiment of R is the same. 15 and R 16 The preferred embodiment is the same as the above R 3 and R 4 The preferred method is the same.

[0087] Example

[0088] The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0089] <Synthesis of Alkenyl Phosphorus Compounds>

[0090] [Example 1]

[0091] In a 1 L three-necked flask, 3.71 g of nickel chloride, 2.18 g of zinc, and 30.3 g of triphenylphosphine were weighed and purged with nitrogen. 42.0 g of toluene was added and heated and stirred at 95° C. for 6 hours to obtain a mixture of a nickel complex and a low-polarity additive.

[0092] Next, 21.0 g of zinc chloride and the entire amount of the mixture of the nickel complex obtained above and a low-polarity additive as a catalyst were added to 420 g of dimethyl phosphite. Acetylene gas was then introduced. The reaction temperature was varied between 25 and 28°C, and 3.19 mol of gas was absorbed over 660 minutes to produce dimethyl vinylphosphonate. The reaction achieved a conversion of 79.9%, a selectivity of 80.7%, and a yield of 64.4%. The conversion, selectivity, and yield of the reaction were determined by GC-FID analysis of the components. Furthermore, no dimethyl 1,3,5-hexatrienylphosphonate was produced as a byproduct.

[0093] [Example 2]

[0094] The reaction was performed using 4.95 g of nickel chloride, 2.91 g of zinc, and 40.4 g of triphenylphosphine, varying the reaction temperature between 25 and 27°C. Over 660 minutes, 3.72 mol of acetylene gas were absorbed to produce dimethyl vinylphosphonate. The conversion was 90.8%, the selectivity was 76.3%, and the yield was 69.3%. Furthermore, dimethyl 1,3,5-hexatrienylphosphonate was produced as a by-product, comprising 2.4% by mass of the reaction solution.

[0095] [Example 3]

[0096] The same procedures as in Example 2 were repeated except that the amount of toluene used was changed to 200.0 g. 3.61 mol of acetylene gas was absorbed to produce dimethyl vinylphosphonate. The reaction conversion was 79.6%, the selectivity was 77.5%, and the yield was 61.7%. Furthermore, dimethyl 1,3,5-hexatrienylphosphonate was produced as a by-product, accounting for 0.94% by mass of the reaction solution.

[0097] [Comparative Example 1]

[0098] 85.9 mL of acetone, 7.42 g of nickel chloride, 60.6 g of triphenylphosphine, and 4.36 g of zinc were added to a 1L USUS kettle and heated with stirring for 4 hours under a nitrogen atmosphere. The pressure in the flask was then reduced to 1.0 kPa, and the acetone was distilled off. 420 g of dimethyl phosphite and 21.0 g of zinc chloride were added to a 1L three-necked flask and stirred for 30 minutes under a nitrogen atmosphere. The solution was placed in a 1L USUS container, kept warm at 40°C, and acetylene gas was blown in. As a result, 4.14 mol was absorbed in 510 minutes to obtain dimethyl vinylphosphonate. The conversion rate of the reaction was 91.5%, the selectivity was 62%, and the yield was 56.8%. In addition, dimethyl 1,3,5-hexatrienylphosphonate was produced as a by-product, comprising 23.8% by mass in the reaction solution.

[0099] Table 1 shows a summary of the results of Examples 1 to 3 and Comparative Example 1 described above.

[0100] [Table 1]

[0101]

[0102] [Example 4]

[0103] The same procedures as in Example 2 were followed, using 42.0 g of tetralin as a low-polarity additive instead of toluene. Over 720 minutes, 3.81 mol of acetylene gas was absorbed to produce dimethyl vinylphosphonate. The reaction yield was 91.2%, the selectivity was 75.1%, and the yield was 68.5%. In addition, dimethyl 1,3,5-hexatrienylphosphonate was produced, accounting for 1.8% of the reaction mixture.

[0104] [Example 5]

[0105] The same procedures as in Example 2 were followed, using 42.0 g of methylnaphthalene instead of toluene as a low-polarity additive. Over 420 minutes, 3.40 mol of acetylene gas was absorbed to produce dimethyl vinylphosphonate. The reaction yield was 81.3%, the selectivity was 85.3%, and the yield was 69.3%. In addition, dimethyl 1,3,5-hexatrienylphosphonate was produced, accounting for 2.3% of the reaction mixture.

[0106] [Example 6]

[0107] The reaction time was changed to 570 minutes, and the same procedures as in Example 5 were repeated. As a result, 3.89 mol of acetylene gas was absorbed to produce dimethyl vinylphosphonate. The reaction conversion was 91.9%, the selectivity was 73.0%, and the yield was 67.1%. In addition, dimethyl 1,3,5-hexatrienylphosphonate was produced, accounting for 2.2% of the reaction solution.

[0108] Table 2 shows a summary of the results of Examples 4 to 6 described above.

[0109] [Table 2]

[0110]

Claims

1. A method for producing an alkenyl phosphorus compound represented by the following general formula (4), comprising reacting a phosphorus compound represented by the following general formula (1) with an alkynyl compound represented by the following general formula (2) in the presence of a nickel complex, a Lewis acid, and a low-polarity additive, wherein the Lewis acid is a metal compound. The metal compound is at least one selected from the group consisting of zinc chloride, zinc bromide and iron (II) chloride, The low-polarity additive is an aromatic hydrocarbon, In the general formula (1), R 1 and R 2 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group having 1 to 10 carbon atoms; the carbon number does not include the carbon number of the substituent. In addition, R 1 and R 2 Can bond with each other to form a ring structure; R 1 and R 2 The substituents that may be present are selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy, heterocyclic, alkylidene, silyl, acyl, acyloxy, carboxyl, cyano, nitro, hydroxy, mercapto or oxo groups, In the general formula (2), R 3 and R 4 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group; the number of carbon atoms mentioned does not include the number of carbon atoms of the substituent, and R 3 and R 4 The substituents that may be present are selected from alkyl, cycloalkyl, alkoxy, cycloalkoxy, heterocyclic, alkylidene, silyl, acyl, acyloxy, carboxyl, cyano, nitro, hydroxy, mercapto or oxo groups, In the general formula (4), R 13 and R 14 With R in general formula (1) 1 and R 2 Synonymous, R 15 and R 16 and R in general formula (2) 3 and R 4 Synonymous.

2. The manufacturing method according to claim 1, wherein The nickel complex is a zero-valent nickel complex formed by nickel and phosphines.

3. The manufacturing method according to claim 2, wherein: The phosphines are phosphines having an aromatic substituent.

4. The production method according to any one of claims 1 to 3, wherein In the general formula (1), R 1 and R 2 Each independently represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms. In the general formula (4), R 13 and R 14 Each independently represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms.

5. The production method according to any one of claims 1 to 3, wherein In the general formula (2), R 3 and R 4 are all hydrogen atoms. In the general formula (4), R 15 and R 16 All are hydrogen atoms.

6. The production method according to any one of claims 1 to 3, wherein The reaction is carried out at 10-60°C.

7. The production method according to any one of claims 1 to 3, wherein The low-polarity additive is at least one selected from the group consisting of toluene, tetralin, and methylnaphthalene.

8. The production method according to any one of claims 1 to 3, wherein The amount of the low-polarity additive added is 1% by mass or more and 70% by mass or less relative to the total amount of the reaction system excluding the alkynyl compound.

9. The production method according to any one of claims 1 to 3, wherein The generation rate of by-products was 10% or less.

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