Patent Description:
An organophosphorus compound is a chemical substance widely used in various products such as a flame-retardant, a plasticizer, an insecticide, medical and agrochemical agents, a ligand of a metallic complex. Recently, organophosphorus compounds have been drawing attention industrially in the fields of constituting materials and electronic materials such as a metal surface treatment agent and a flame-retardant resin as functional materials.

Among the organophosphorus compounds, a phosphonic acid derivative is a useful precursor substance for the various chemicals described above, and therefore, various manufacturing methods have been studied conventionally. For example, a phosphonic acid derivative has been manufactured by addition reaction of P(O)-H bond of phosphonic acid to alkynes using a catalyst (hereinafter referred to as hydrophosphorylation reaction). For example, in Patent Document <NUM>, it is proposed to manufacture a phosphonic acid derivative by using a phosphonic acid diester compound of which a part had been hydrolyzed beforehand as a raw material. Further, in Non-Patent Document <NUM>, it is proposed that a phosphonic acid derivative is produced by using various zero valent nickel catalysts.

However, there were problems that under the reaction conditions described in Patent Document <NUM>, hydrolysis reaction must be carried out as a pretreatment and one additional step is required, or that on one hand the reaction has to be carried out at a low temperature, a large amount of reaction heat is generated so it is difficult to control the temperature in order to produce in a large amount. In addition, the catalyst used for the hydrophosphorylation reaction is expensive, unstable, flammable, and has malodor, and a safe and inexpensive catalyst had been desired. On the other hand, although Non-Patent Document <NUM> discloses that the hydrophosphorylation reaction was carried out with a nickel complex using inexpensive triphenylphosphine, the reactivity was low, and the phosphonic acid derivative was only obtained with a low yield even with a large amount of catalyst. Further, there was a problem that the option of the raw materials was narrow because many of the phosphine compounds and nickel compounds are not easily obtainable in the industry.

Therefore, the problem of the present invention is to provide a method for manufacturing an alkenyl phosphorus compound which allows to proceed the hydrophosphorylation reaction efficiently at room temperature to mild heating by using a divalent nickel compound which is a raw material easily obtained in the industry, stable in the air, and inexpensive, and phosphine which is stable in the air and inexpensive, and adjusting the catalyst in the reaction system.

As a result of intensive studies to solve the above problem, the present inventors have found that an alkenylphosphorus compound can be efficiently manufactured by performing a hydrophosphorylation reaction between a specific phosphorus compound and a specific alkynyl compound in the presence of a transition metal complex and a Lewis acid, and have thus completed the present invention as claimed in claim <NUM>.

That is, according to the present invention, the following inventions are provided.

According to the present invention, an alkenyl phosphorus compound can be efficiently produced by performing a hydrophosphorylation reaction of a specific phosphorus compound and a specific alkynyl compound in the presence of the transition metal complex and the Lewis acid. In particular, the hydrophosphorylation reaction can be efficiently performed under a heating temperature condition of equal to or higher than room temperature.

The method for producing an alkenyl phosphorus compound of the present invention is a method in which an alkenyl phosphorus compound is produced by a hydrophosphorylation reaction of a phosphorus compound and an alkynyl compound as raw materials in the presence of the transition metal complex and the Lewis acid as catalysts. According to the method for producing an alkenyl phosphorus compound of the present invention, the alkenyl phosphorus compound can be efficiently synthesized under the heating temperature condition of equal to or higher than the room temperature.

A phosphorus compound represented by the following general formula (<NUM>) can be used as a raw material for the hydrophosphorylation reaction. <CHM>
wherein R<NUM> and R<NUM> 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. In addition, R<NUM> and R<NUM> may be bonded to each other to form a cyclic structure.

In general formula (<NUM>), the number of carbons of the alkyl group, alkoxy group, cycloalkyl group, aralkyl group, aryl group, and aryloxy group of R<NUM> and R<NUM> is preferably <NUM> to <NUM>. The number of carbons above does not include the number of carbons of the substituent. Examples of R<NUM> and R<NUM> include alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, and hexyl group; alkoxy groups such as a methoxy group, ethoxy group, and butoxy group; cycloalkyl groups such as a cyclohexyl group; aralkyl groups such as a benzyl group and phenethyl group; aryl groups such as a phenyl group, tolyl group, xylyl group, and naphthyl group; and aryloxy groups such as a phenoxy group. Among these, R<NUM> and R<NUM> are each independently preferably a substituted or unsubstituted alkoxy group.

In general formula (<NUM>), examples of the substituent which R<NUM> and R<NUM> may have include an alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, heterocyclic group, alkylidene group, silyl group, acyl group, acyloxy group, carboxyl group, cyano group, nitro group, hydroxy group, mercapto group, and oxo group. The number of carbons contained in the substituent is preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>, and further preferably from <NUM> to <NUM>.

Alkynyl compounds represented by the following general formula (<NUM>) can be used as the raw material for the hydrophosphorylation reaction.

In general formula (<NUM>), R<NUM> and R<NUM> 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.

In general formula (<NUM>), the alkyl group, cycloalkyl group, aralkyl group, aryl group, heteroaryl group, alkenyl group, alkoxy group, and aryloxy group of R<NUM> and R<NUM> preferably have <NUM> to <NUM> carbons. The number of carbons above does not include the number of carbons of the substituent. Examples of R<NUM> and R<NUM> include an alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group; cycloalkyl group such as a cyclohexyl group; an aralkyl group such as a benzyl group and phenethyl group; an aryl group such as a phenyl group, tolyl group, xylyl group, and naphthyl group; an alkenyl group such as a <NUM>-butenyl group, <NUM>-butenyl group, <NUM>,<NUM>-butadienyl group, pentenyl group, and hexenyl group; an alkoxy group such as a methoxy group, ethoxy group, and butoxy group; and an aryloxy group such as a phenoxy group. Among these, R<NUM> and R<NUM> are each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group having <NUM> to <NUM> carbons.

In general formula (<NUM>), examples of the substituent which R<NUM> and R<NUM> may include an alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, heterocyclic group, alkylidene group, silyl group, acyl group, acyloxy group, carboxyl group, cyano group, nitro group, hydroxy group, mercapto group, and oxo group. The number of carbons contained in the substituent is preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>, and further preferably from <NUM> to <NUM>.

The mass ratio of the phosphorus compound represented by general formula (<NUM>) to the alkynyl compound represented by general formula (<NUM>) as the raw materials for the hydrophosphorylation reaction is preferably <NUM>:<NUM> to <NUM>:<NUM>, more preferably <NUM>:<NUM> to <NUM>:<NUM>, and further preferably <NUM>:<NUM> to <NUM>:<NUM>.

A transition metal complex is used as a catalyst for the hydrophosphorylation reaction. The transition metal complex is a zero valent nickel complex.

The nickel complex as above is a nickel complex of nickel and phosphines. As the phosphine, a phosphine having an aromatic substituent is preferable. Examples of the phosphine having an aromatic substituent include triphenylphosphine, <NUM>,<NUM>-diphenylphosphinoethane, <NUM>,<NUM>-diphenylphosphinopropane, <NUM>,<NUM>-diphenylphosphinobutane, diphenylmethylphosphine, tri(<NUM>-methylphenyl)phosphine, tri(<NUM>-methylphenyl)phosphine, tri(<NUM>-methylphenyl)phosphine, and the like. The phosphine having an aromatic substituent is inexpensive, can be easily handled in the air, and thus the manufacturing cost can be reduced and the manufacturing efficiency can be improved.

A metal compound is used as the Lewis acid used for the hydrophosphorylation reaction. The metal compound is selected from the group consisting of zinc chloride, zinc bromide and iron (II) chloride. Addition of the Lewis acid to the hydrophosphorylation reaction can exhibit catalytic activity near room temperature, improve the reaction rate and the conversion ratio of the phosphorus compound as the raw material to the alkenyl phosphorus compound.

The amount of transition metal complex (catalyst) used in the hydrophosphorylation reaction is not particularly limited as long as the reaction proceeds sufficiently, and is preferably <NUM> to <NUM> mol, more preferably <NUM> to <NUM> mol, and further preferably <NUM> to <NUM> mol per <NUM> mol of the phosphorus compound as the raw material.

The amount of Lewis acid used in the hydrophosphorylation reaction is not particularly limited as long as the reaction proceeds sufficiently, and is preferably <NUM> to <NUM> mol, more preferably <NUM> to <NUM> mol, and further preferably <NUM> to <NUM> mol per <NUM> mol of the transition metal complex. The amount of Lewis acid being within the above ranges can increase the activation temperature of the catalysts in the hydrophosphorylation reaction and improve the reaction rate greatly, so that the conversion ratio of the raw material, phosphorus compound to the alkenyl phosphorus compound can be improved.

The reaction temperature of the hydrophosphorylation reaction is not particularly limited, and is preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>, and further preferably <NUM> to <NUM>, taking into consideration of reaction efficiency, reaction rate, and by-products. The reaction temperature being within the above ranges can improve the reaction rate of the hydrophosphorylation reaction and the conversion ratio of the phosphorus compound as the raw material to the alkenyl phosphorus compound.

The reaction time of the hydrophosphorylation reaction is not particularly limited, and is preferably from <NUM> minutes to <NUM> hours, more preferably from <NUM> minutes to <NUM> hours, and further preferably from <NUM> to <NUM> hours, taking into consideration of reaction efficiency, reaction rate, and by-products. The reaction time being within the above-described ranges can make the hydrophosphorylation reaction proceed sufficiently, and improve the conversion ratio of the phosphorus compound as the raw material to the alkenyl phosphorus compound.

The hydrophosphorylation reaction may be carried out either in the presence or absence of an organic solvent; however, it is preferably carried out in the absence of a solvent. The hydrophosphorylation reaction can proceed by mild heating using the solvent-free method. The solvent-free method eliminates the solvent removal step after the reaction has completed, thereby reducing the manufacturing cost. The organic solvent is not particularly limited, and examples thereof include alcohols, ethers, hydrocarbons, ketones, esters, aromatic hydrocarbons, and the like.

The hydrophosphorylation reaction is preferably carried out under an inert gas atmosphere, taking into consideration of reaction efficiency, reaction rate, and by-products. Preferred for use as the inert gas are use nitrogen, argon, and the like.

The conversion of the phosphorus compound to the alkenyl phosphorus compound by the hydrophosphorylation reaction is preferably <NUM>% or more, more preferably <NUM>% or more, further preferably at least <NUM>% or more, and furthermore preferably <NUM>% or more. The conversion of the phosphorus compound to the alkenyl phosphorus compound being equal to or higher than the above-mentioned values can make the raw materials be efficiently utilized, reduce the manufacturing cost, and improve the manufacturing efficiency.

In the present invention, an alkenyl phosphorus compound represented by the following general formula (<NUM>) can be obtained by the hydrophosphorylation reaction.

In general formula (<NUM>), R<NUM> and R<NUM> are synonymous with R<NUM> and R<NUM> in general formula (<NUM>), and R<NUM> and R<NUM> are synonymous with R<NUM> and R<NUM> in general formula (<NUM>).

The present invention shall be described in details below with reference to the Examples and Comparative Examples.

<NUM> mmol of bis(triphenylphosphine)nickel (II) dichloride, <NUM> mmol of zinc powder, and <NUM> mmol of triphenylphosphine were metered in a glass Schlenk tube and the container was substituted with nitrogen. To this was added <NUM> of acetone, and the mixture was heated and stirred at <NUM> for <NUM> hours to obtain an orange precipitate. The pressure in the flask was reduced, acetone was removed from the precipitate, and subsequently <NUM> mol of a phosphorus compound ((MeO)<NUM>P(O)H) and <NUM> mmol of zinc chloride were added, and the mixture was stirred at <NUM> for <NUM> hours in an acetylene gas atmosphere to obtain an alkenyl compound (MeO)<NUM>P(O)CH = CH<NUM>. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that the reaction time was changed to <NUM> hours. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that <NUM> mmol of zinc chloride was used as the Lewis acid. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that only <NUM> mmol of zinc chloride precipitated as a by-product in the preparation of the zero valent nickel complex was used as the Lewis acid and the reaction time was changed to <NUM> hours. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that the reaction temperature was changed to <NUM>. The conversion rate from the phosphorus compound to the alkenylphosphorus compound was <NUM>%.

<NUM> mmol of <NUM>,<NUM>-bis(cyclooctadiene)nickel (<NUM>), <NUM> mmol of triphenylphosphine, and <NUM> of acetone were added to a glass Schlenk tube, and the mixture was heated and stirred at <NUM> for <NUM> hours to obtain an orange precipitate. The pressure in the flask was reduced, acetone was removed from the precipitate, then <NUM> mol of a phosphorus compound ((MeO)<NUM>P(O)H) was added, and the mixture was stirred at <NUM> for <NUM> hours in an acetylene gas atmosphere, thereby obtaining an alkenyl compound (MeO)<NUM>P(O)CH = CH<NUM>. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

When the reaction time in Comparative Example <NUM> was changed to <NUM> hours, the conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

The results of Examples <NUM>-<NUM> and Comparative Examples <NUM> and <NUM> are listed in Table <NUM>.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that <NUM> mmol of nickel chloride was used instead of bis(triphenylphosphine)nickel (II) dichloride, and the amount of triphenylphosphine used was changed to <NUM> mmol. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that <NUM> mmol of <NUM>,<NUM>-diphenylphosphinobutane (dppb) was used instead of triphenylphosphine. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that <NUM> mmol of diphenylmethylphosphine was used in place of triphenylphosphine. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM>, except that <NUM> mmol of iron (II) chloride (FeCl<NUM>) was used as a Lewis acid. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl phosphorus compound ((MeO)<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that <NUM> mmol of zinc bromide (ZnBr<NUM>) was used as the Lewis acid. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

A list of the results of Examples <NUM> to <NUM> are listed in Table <NUM>.

An alkenyl phosphorus compound (Ph<NUM>P(O)CH = CH<NUM>) was obtained in the same manner as in Example <NUM> except that <NUM> mmol of diphenylphosphine oxide (Ph<NUM>P(O)H) as the phosphorus compound and <NUM> of tetrahydrofuran (THF) were used. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

<NUM> mmol of nickel chloride, <NUM> mmol of zinc powder, and <NUM> mmol of methyldiphenylphosphine were metered in a glass Schlenk tube, and the container was substituted with nitrogen. To this, <NUM> of acetone was added, and the mixture was heated and stirred at <NUM> for <NUM> hours to obtain an orange precipitate. The pressure in the flask was reduced, acetone was distilled off from the precipitate, then <NUM> mol of a phosphorus compound ((MeO)<NUM>P(O)H), <NUM> mmol of zinc chloride, and <NUM> mmol of <NUM>-octyne were added, and the mixture was stirred at <NUM> for <NUM> hours to obtain an alkenyl compound (a mixture of (MeO)<NUM>P(O)C(C<NUM>H<NUM>) = CH<NUM> and (MeO)<NUM>P(O)CH = CHC<NUM>H<NUM>). The conversion of the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

An alkenyl compound (a mixture of Ph<NUM>P(O)C(C<NUM>H<NUM>) = CH<NUM> and Ph<NUM>P(O)CH = CHC<NUM>H<NUM>) was obtained in the same manner as in Example <NUM>, except that <NUM> mmol of diphenylphosphine oxide (Ph<NUM>P(O)H) was used as a phosphorus compound, <NUM> mmol of triphenylphosphine was used as a phosphine, and <NUM> of THF was used as a solvent. The conversion of the phosphorus compound to the alkenyl compound was <NUM>%.

<NUM> mmol of bis (<NUM>,<NUM>-cyclopentadiene)nickel and <NUM> mmol of triphenylphosphine were metered in a glass Schlenk tube under a nitrogen atmosphere, <NUM> of THF was added, and the mixture was stirred at room temperature for <NUM> hours to obtain an orange precipitate. The precipitate was washed with <NUM> of n-hexane three times, dried under reduced pressure, and a catalyst was prepared. The entire amount of this catalyst, <NUM> mmol of diphenylphosphine oxide (Ph<NUM>P(O)H), 15mmol of <NUM>-octyne and <NUM> of THF were added and the mixture was stirred at <NUM> for <NUM> hours to give an alkenyl compound (a mixture of Ph<NUM>P(O)C(C<NUM>H<NUM>) = CH<NUM> and Ph<NUM>P(O)CH = CHC<NUM>H<NUM>). The conversion of the phosphorus compound to the alkenyl phosphorus compound was <NUM>%.

The results of Examples <NUM>-<NUM> and Comparative Example <NUM> are listed in Table <NUM>.

Claim 1:
A method for manufacturing an alkenyl phosphorus compound by reacting a phosphorus compound represented by the following general formula (<NUM>):
<CHM>
wherein
R<NUM> and R<NUM> 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; and R<NUM> and R<NUM> may be bonded to each other to form a cyclic structure;
and an alkynyl compound represented by the following general formula (<NUM>):
<CHM>
wherein
R<NUM> and R<NUM> 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,
in the presence of a transition metal complex and a Lewis acid, wherein the transition metal complex is a zero valent nickel complex of nickel and phosphines,
wherein the Lewis acid is a least one metal compound selected from the group consisting of zinc chloride, zinc bromide, and iron (II) chloride,
wherein the alkenyl phosphorus compound is represented by the following general formula (<NUM>):
<CHM>
wherein, R<NUM> and R<NUM> are synonymous with R<NUM> and R<NUM> in general formula (<NUM>), and R<NUM> and R<NUM> are synonymous with R<NUM> and R<NUM> in general formula (<NUM>).