JP5224262B2 - Process for producing branched alkenylphosphine oxide compounds - Google Patents

Description

  The present invention relates to a method for producing a branched alkenyl phosphine oxide compound.

  The branched alkenyl phosphine oxide compound is a useful compound as a raw material for synthesizing phosphines used as a ligand of a complex catalyst, an additive for imparting flame retardancy to a polymer, a polymerizable vinyl monomer, and the like. For example, Patent Document 1 discloses a technique for producing a polymer compound having high thermal stability by polymerizing a branched alkenyl phosphine oxide compound with a magnesium reagent. Non-Patent Document 1 discloses that a polymer compound obtained by polymerization of alkenyl phosphine oxide is transparent and non-flammable. In Non-Patent Document 2, it is obtained by homopolymerization or copolymerization of a metal complex of alkenyl phosphine oxide. It is disclosed that the obtained polymer compound is soluble in a solvent and has flame retardancy.

An alkenyl phosphine oxide compound can be generally produced by an addition reaction of a secondary phosphine oxide to an acetylene compound. For example, Non-Patent Document 3 discloses that the above addition reaction is Pd (PPh ₃ ) ₄ , cis-PdMe ₂ (PPh ₃ ) ₂ , cis-PdMe ₂ (PPhMe ₂ ) ₂ , PdMe ₂ (PMe ₃ ) ₂ or PdMe. ₂ (PEt ₃ ) ₂ is disclosed in the presence of a palladium complex catalyst. However, in the method described in Non-Patent Document 3, the main product of the reaction with the terminal acetylene compound is generally a linear alkenyl phosphine oxide compound, and the selectivity of the production of a branched alkenyl phosphine oxide compound. However, it is not an industrially advantageous method because of its extremely low point. Non-Patent Document 4 discloses a method of using a nickel complex as a catalyst, but has basically the same problems as the case of using a palladium complex. Non-patent document 4 discloses a method of adding an additive such as phosphinic acid as a method for solving such problems related to regioselectivity, but the addition of phosphinic acid complicates the reaction system. In addition, it is not an industrially advantageous method because it requires not only a side reaction but also a treatment in consideration of the removal of additives when separating the product. Moreover, since an alkenylphosphine is obtained by adding a secondary phosphine to a terminal acetylene compound, a method of oxidizing it with hydrogen peroxide is also possible, but as shown in Non-Patent Documents 5 and 6 The position selectivity is very low. As described above, any of the known methods including the step of adding a P—H bond to a terminal acetylene compound is extremely disadvantageous industrially.
US3519607 Journal of Polymer Science, Part A, 1965, Volume 3, pp. 3439-3449 Journal of Polymer Science, Part A, 1965, Volume 3, pp. 3427-3437 Organometallics, 1996, 15 pp .. 3259-3261 Journal of the American Chemical Society, 2004, 126, pp. 5080-5081 Journal of Alloys and Compounds, 2006, 408-412, pp. 432-436 Journal of Organic Chemistry, 2003, 68, pp. 6554-6565

  An object of the present invention is to provide a method capable of producing a branched alkenylphosphine oxide compound with high selectivity by reacting a secondary phosphine oxide compound with a terminal acetylene compound.

  The inventors of the present invention have made extensive studies on the addition reaction between a secondary phosphine oxide compound and a terminal acetylene compound. As a result, the coordinating ability is too high, so that in the many reactions, the catalyst is deactivated or the catalytic activity is greatly reduced, such as 1,2-bis (diphenylphosphino) ethane, which has been conventionally believed to be the following general A palladium complex having a specific bidentate phosphine represented by the formula (1) as a ligand efficiently proceeds the addition reaction of a secondary phosphine oxide compound and a terminal acetylene compound, and has high selectivity. Thus, it has been found that an exceptionally remarkable effect that can be produced by a person skilled in the art that a branched alkenylphosphine oxide compound can be produced. The present invention has been completed based on such findings.

That is, the present invention relates to the general formula (1)
R ¹ R ² P-A-PR ³ R ⁴ (1)
[Wherein R ¹ is
An aryl group having 12 or less carbon atoms or an aralkyl group having 12 or less carbon atoms is represented.
R ² , R ³ and R ⁴ are the same or different,
An alkyl group having 12 or less carbon atoms,
An aryl group having 12 or less carbon atoms or an aralkyl group having 12 or less carbon atoms is represented.
In R ¹ and R ² , residues obtained by removing one hydrogen atom from each group may be bonded to each other in the molecule to form a ring containing a phosphorus atom.
In R ³ and R ⁴ , residues obtained by removing one hydrogen atom from each group may be bonded to each other in the molecule to form a ring containing a phosphorus atom.
A represents a linear, branched or cyclic divalent organic group having 1 to 15 carbon atoms.
The aromatic ring constituting the aryl group and aralkyl group in R ¹ , R ² , R ³ and R ⁴ may be a heteroaromatic ring, and R ¹ , R ² , R ³ and R ⁴ are functional groups. May be substituted. ]
In the presence of a palladium complex of a chelate-coordinating phosphine represented by the formula ( excluding the chelate-coordinating phosphine where A is a trimethylene group )

[Wherein R ⁵ is
An alkyl group having 12 or less carbon atoms,
An aryl group having 12 or less carbon atoms,
An aralkyl group having 12 or less carbon atoms,
A silyl group substituted with three groups selected from the group consisting of an alkyl group having 6 or less carbon atoms and an aryl group having 12 or less carbon atoms,
Represents a ferrocenyl group.
The aromatic ring constituting the aryl group and aralkyl group in R ⁵ may be a heteroaromatic ring, and R ⁵ may be substituted with a functional group. ]
A terminal acetylene compound represented by the general formula (3)

[Wherein R ⁶ and R ⁷ are the same or different,
An alkyl group having 6 or less carbon atoms,
An aryl group having 12 or less carbon atoms,
An aralkyl group having 12 or less carbon atoms is represented.
Aryl groups in R ⁶ and R ^7, the aromatic ring constituting the aralkyl group may be a heterocyclic aromatic ring, R ⁶ and R ⁷ may be substituted with a functional group. ]
Is reacted with a secondary phosphine oxide compound represented by the general formula (4):

[Wherein R ⁵ , R ⁶ and R ⁷ represent the same meaning as described above. ]
A branched alkenylphosphine oxide compound represented by the formula:

  Each group shown in this specification is specifically as follows.

  Examples of the alkyl group having 12 or less carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, 1 carbon number such as t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. Examples of -12 linear or branched alkyl groups can be exemplified.

  Examples of the aryl group having 12 or less carbon atoms include aryl groups having 6 to 12 carbon atoms such as a phenyl group, a p-tolyl group, a 1- or 2-naphthyl group, an o-biphenyl group, an m-biphenyl group, and a p-biphenyl group. Can be illustrated.

  Examples of the aralkyl group having 12 or less carbon atoms include a phenyl lower alkyl group and a naphthyl lower alkyl group.

  As the phenyl lower alkyl group, an alkyl moiety such as a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, or a 3-phenylpropyl group is a linear or branched alkyl group having 1 to 6 carbon atoms. A phenylalkyl group can be exemplified.

  Examples of the naphthyl lower alkyl group include naphthylalkyl groups in which an alkyl moiety such as a 1-naphthylmethyl group and a 2-naphthylmethyl group is a methyl group or an ethyl group.

In the chelate-coordinating phosphine represented by the general formula (1) used in the present invention, a ring containing a phosphorus atom formed by bonding residues obtained by removing one hydrogen atom from each of R ¹ and R ² groups Examples of the structure include a phosphacyclopentane ring, a phosphacyclohexane ring, and a dibenzophosphacyclopentane ring.

In the chelate-coordinating phosphine represented by the general formula (1) used in the present invention, a ring containing a phosphorus atom formed by bonding residues obtained by removing one hydrogen atom from each of R ³ and R ⁴ groups Examples of the structure include a phosphacyclopentane ring, a phosphacyclohexane ring, and a dibenzophosphacyclopentane ring.

  In the chelate-coordinating phosphine represented by the general formula (1) used in the present invention, the linear, branched or cyclic divalent organic group having 1 to 15 carbon atoms represented by A includes carbon. A linear or branched alkylene group having 1 to 15 carbon atoms; a linear or branched alkenylene group having 2 to 15 carbon atoms; an arylene group having 6 to 14 carbon atoms; a ferrocenylene group; a xanthenediyl group. Etc.

Here, examples of the linear or branched alkylene group having 1 to 15 carbon atoms include a methylene group, a dimethylene group , a 2 -methyltrimethylene group, a tetramethylene group, a decamethylene group, a dodecamethylene group, A tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, etc. can be mentioned.

  Examples of the linear or branched alkenylene group having 2 to 15 carbon atoms include vinylene group, 2-butene-1,4-diyl group, 1-octene-1,2-diyl group, 1- Examples include dodecene-1,2-diyl group.

  Examples of the arylene group having 6 to 14 carbon atoms include an o-phenylene group, a biphenylene group, a binaphthylene group, and an anthracenylene group.

Specific examples of the chelate-coordinating phosphine represented by the general formula (1) include bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (phenylmethylphosphino) Ethane, 1,2-bis (phenylcyclohexylphosphino) ethane , 1,4-bis (diphenylphosphino) butane, 1,2-bis (diphenylphosphino) ethylene, 1,2-bis (diphenylphosphino) benzene 1,1′-bis (diphenylphosphino) ferrocene, 1,2-bis (9-phosphafluoren-9-yl) ethane, 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (Binap), 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane (DIOP) ), 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene (Xanthophos) and the like.

Examples of the chelate-coordinating phosphine represented by the general formula (1) include an alkylene group having 1 to 15 carbon atoms (preferably 1 to 4 carbon atoms) or 6 to 14 carbon atoms in the general formula (1). R ¹ , R ² , R ³ and R ⁴ are aryl groups (preferably phenyl groups) having 12 or less carbon atoms, or R ¹ and R ² , R ^3. And a chelate-coordinating phosphine in which residues obtained by removing one hydrogen atom from R ⁴ are bonded to each other to form a phosphacyclopentane ring.

  Examples of the alkyl group having 6 or less carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, Examples thereof include straight-chain or branched alkyl groups having 1 to 6 carbon atoms such as t-pentyl group, n-hexyl group and isohexyl group.

  Examples of the silyl group substituted with three groups selected from the group consisting of an alkyl group having 6 or less carbon atoms and an aryl group having 12 or less carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, t-butyldimethylsilyl group and the like And a silyl group in which three groups selected from the group consisting of a linear or branched alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are substituted. The three substituents on the silyl group may be the same or different.

The aromatic ring constituting the aryl group and the aralkyl group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be a heteroaromatic ring. A ring, a thiophene ring, a benzothiophene ring, etc. can be illustrated.

R ¹ , R ² , R ³ and R ⁴ may be substituted with, for example, 1 to 2, preferably 1 functional group. Here, when R ¹ , R ² , R ³ and R ⁴ are substituted by two functional groups, these functional groups may be the same or different.

Examples of the functional group in the case where R ¹ , R ² , R ^3, and R ⁴ are substituted with a functional group include an N group having an alkoxy group having 6 or less carbon atoms and an alkyl portion having the above 6 or less carbon group. , N-dialkylamino group (the two alkyl groups on the amino group may be the same or different), a halogen atom, and the like.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. can be mentioned, for example.

  Examples of the alkoxy group having 6 or less carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentyloxy, iso Examples thereof include linear or branched alkoxy groups having 1 to 6 carbon atoms such as a pentyloxy group, a t-pentyloxy group, an n-hexyloxy group, and an isohexyloxy group.

R ⁵ , R ⁶ and R ⁷ may be substituted with, for example, 1 to 3, preferably 1 to 2 functional groups. Here, when R ⁵ , R ⁶ and R ⁷ are substituted with two or more functional groups, these functional groups may be the same or different.

Examples of the functional group in the case where R ⁵ , R ⁶ and R ⁷ are substituted with a functional group include an alkoxy group having 6 or less carbon atoms; an amino group; -An alkylamino group; an N, N-dialkylamino group in which the alkyl part is an alkyl group having 6 or less carbon atoms (the two alkyl groups on the amino group may be the same or different); An alkoxycarbonyl group which is an alkoxy group having 6 or less carbon atoms; an N-alkylaminocarbonyl group whose alkyl portion is the alkyl group having 6 or less carbon atoms (the two alkyl groups on the amino group may be the same or different) Good); N, N-dialkylaminocarbonyl group in which the alkyl part is the alkyl group having 6 or less carbon atoms (the two alkyl groups on the amino group are the same) A halogen atom; a cyano group; a hydroxy group; an alkylcarbonyl group in which the alkyl portion is an alkyl group having 6 or less carbon atoms; an alkylcarbonyloxy in which the alkyl portion is an alkyl group having 6 or less carbon atoms. An aroyl group in which the aryl moiety is an aryl group having 10 or less carbon atoms; an aroyloxy group in which the aryl moiety is an aryl group having 10 or less carbon atoms; a group consisting of an alkyl group having 6 or less carbon atoms and an aryl group having 12 or less carbon atoms A silyl group substituted with three groups selected from: an oxygen atom formed by a silyl group substituted with three groups selected from the group consisting of an alkyl group having 6 or less carbon atoms and an aryl group having 12 or less carbon atoms And a siloxy group formed by bonding with.

  Examples of the aryl group having 10 or less carbon atoms include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a p-tolyl group, a 1- or 2-naphthyl group.

  Hereinafter, the production method of the present invention will be described in detail.

  Formula (4) which is a compound of the present invention

[Wherein R ⁵ , R ⁶ and R ⁷ represent the same meaning as described above. ]
A branched alkenylphosphine oxide compound represented by (hereinafter, this compound may be simply referred to as compound (4))
General formula (1)
R ¹ R ² P-A-PR ³ R ⁴ (1)
[Wherein, R ¹ , R ² , R ³ , R ⁴ , and A represent the same meaning as described above. ]
In the presence of a palladium complex of a chelate-coordinating phosphine represented by the general formula (2)

[Wherein R ⁵ represents the same meaning as described above. ]
A terminal acetylene compound represented by the general formula (3)

[Wherein R ⁶ and R ⁷ represent the same meaning as described above. ]
It is manufactured by making it react with the secondary phosphine oxide compound shown by these.

Examples of the palladium complex include various zero-valent or divalent palladium complexes prepared in advance. Specific examples thereof include PdCl ₂ L (wherein L represents a chelate-coordinating phosphine), PdL. (PEt ₃ ) ₂ (wherein L represents a chelate-coordinating phosphine), Pd (OAc) ₂ L (wherein L represents a chelate-coordinating phosphine), PdClPhL (wherein L is a chelate coordination) PdCl (COPh) L (wherein L represents a chelate-coordinating phosphine), PdMe ₂ L (wherein L represents a chelate-coordinating phosphine), Pd (PhCH═CH ₂ ) L (wherein L represents a chelate-coordinating phosphine), PdL ₂ (wherein L represents a chelate-coordinating phosphine), and the like. In the present specification, Et represents an ethyl group, Ac represents an acetyl group, Me represents a methyl group, and Ph represents a phenyl group (hereinafter the same).

  The usage-amount of a palladium complex is 0.00001-15 mol% normally with respect to the secondary phosphine oxide compound of General formula (3) per palladium atom, Preferably it is 0.0005-10 mol%.

The palladium complex used in the present invention may be generated by mixing a chelate-coordinating phosphine and a palladium compound as a precursor in the reaction system without preparing in advance. As the palladium compound as a precursor preferably used, various zero-valent or divalent palladium compounds can be used, and specific examples thereof include PdCl ₂ , K ₂ PdCl ₄ , Na ₂ PdCl ₄ , PdCl ₂ (PhCN ) ₂ , PdCl ₂ (cod) (cod represents 1,5-cyclooctadiene), Pd (OAc) ₂ , Pd ₂ (dba) ₃ .CHCl ₃ (dba represents dibenzylideneacetone), Pd (PPh ₃ ) Zero-valent or divalent palladium compounds such as ₄ can be suitably used. The usage-amount of a palladium compound is 0.00001-15 mol% normally with respect to the secondary phosphine oxide compound of General formula (3) per palladium atom, Preferably it is 0.0005-10 mol%. The amount of chelate-coordinating phosphine mixed with the palladium compound as a precursor is such that the phosphorus atom in the phosphine is in the range of 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the palladium atom. Selected.

  The terminal acetylene compound represented by the general formula (2) used in the reaction of the present invention is a known compound or a compound that can be easily produced according to a known method.

  Specific examples of the terminal acetylene compound represented by the general formula (2) include propyne, 1-butyne, 1-hexyne, t-butylacetylene, 1-octyne, 1-dodecyne, phenylacetylene, 1- or 2-naphthylacetylene. , P-ethynylbiphenyl, propargylbenzene, (7-octyn-1-yl) benzene, 1-ethynylthiophene, ethynylferrocene, trimethylsilylacetylene, dimethylphenylsilylacetylene, propargylmethyl ether, 4-t-butyldimethylsiloxy-1- Butyne, 5-chloro-1-pentyne, 5-cyano-1-pentyne, methyl 5-hexynoate, p-fluorophenylacetylene, p-chlorophenylacetylene, p-methoxyphenylacetylene, p-trifluoromethylphenylacetylene, 4 It can be exemplified acryloyloxy-1-butyne and the like.

Among the terminal acetylene compounds represented by the general formula (2), for example, corresponding R ⁵ represents a terminal acetylene in which the aryl group having 12 or less carbon atoms or an alkyl group having 12 or less carbon atoms (preferably 1 to 6 carbon atoms) is shown. Compounds are preferred.

  The secondary phosphine oxide compound represented by the general formula (3) is a known compound or can be easily produced according to a known method.

  Specific examples of the secondary phosphine oxide compound represented by the general formula (3) include diphenylphosphine oxide, di (α- or β-naphthyl) phosphine oxide, dibiphenylphosphine oxide, di (2-furyl) phosphine oxide, Examples include di (p-, m-, or o-anisyl) phosphine oxide, di (p-, m-, or o-tolyl) phosphine oxide, phenyl (p-tolyl) phosphine oxide, and the like.

Among the secondary phosphine oxide compounds represented by the general formula (3), for example, the corresponding R ⁶ and R ⁷ are the same or different and each represents an aryl group having 12 or less carbon atoms (preferably a phenyl group). Secondary phosphine oxide compounds are preferred.

  The use ratio of the terminal acetylene compound represented by the general formula (2) and the secondary phosphine oxide compound represented by the general formula (3) is generally 0.5 to 2 mol with respect to 1 mol of the former, Preferably it is 0.8-1.5 mol.

  The reaction of the present invention does not particularly require the use of a solvent, but can also be carried out in a solvent if necessary. Solvents include hydrocarbon solvents such as n-hexane, cyclohexane, benzene, toluene and ethylbenzene; halogenated hydrocarbon solvents such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene; diethyl ether, diisopropyl ether and dimethoxyethane. Ether solvents such as tetrahydrofuran, dioxane, diglyme, dibutyl ether, cyclopentyl methyl ether and anisole; ester solvents such as methyl acetate and ethyl acetate; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; acetone, methyl ethyl ketone, Various solvents such as ketone solvents such as methyl isobutyl ketone and acetophenone can be used. Moreover, these are used individually or in mixture of 2 or more types.

  The above reaction may be carried out under cooling, at room temperature, or under heating. Specifically, it is selected from the range of usually 0 ° C. to 250 ° C., preferably 50 ° C. to 170 ° C.

  The reaction time is usually 30 minutes to several tens of hours, preferably 1 to 10 hours.

  Separation and purification of the purified product from the reaction mixture can be easily achieved by various commonly used separation means and purification means such as chromatography, distillation or recrystallization.

  According to the production method of the present invention, the branched alkenylphosphine oxide compound represented by the general formula (4) can be produced from the terminal acetylene compound and the secondary phosphine oxide compound with high selectivity.

  In addition, according to the production method of the present invention, the branched alkenylphosphine oxide compound represented by the general formula (4) can be produced easily and in high yield from the terminal acetylene compound and the secondary phosphine oxide compound. It can be easily isolated and purified, and is extremely useful industrially.

  The branched alkenylphosphine oxide compound represented by the general formula (4) of the present invention produced by the method of the present invention is a pharmaceutical / agrochemical production intermediate, a flame retardant for polymer addition, and coordination of a complex catalyst. It is useful as a child or a synthetic raw material thereof.

  The branched alkenyl phosphine oxide compound represented by the general formula (4) is, for example, a corresponding phosphine useful as a ligand of a metal complex by easily deoxygenating a P═O bond in the compound (1). Can be easily converted. In this deoxygenation reaction, for example, the method of Fritzche et al. (Chemische Berichte, 1964, 97, p. 1988), the method of Imamoto (Organic Letters, 2001, 3, p. 87), etc. The reaction conditions used in the methods generally used for the reduction reaction of phosphine oxide can be applied.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Example 1 Reaction of p-tolylacetylene with diphenylphosphine oxide (1)
Under a nitrogen atmosphere, 0.067 mmol of palladium acetate and 0.10 mmol of 1,2-bis (diphenylphosphino) ethane (that is, the ratio of phosphorus atom to palladium in 1,2-bis (diphenylphosphino) ethane was 3 1), 1.33 mmol of diphenylphosphine oxide and 1.39 mmol of p-tolylacetylene were added to 2.5 mL of toluene, and the mixture was stirred at 100 ° C. for 3 hours. As a result of analyzing the obtained reaction liquid by 1H NMR, in compound (4), [ ^6- (p-tolyl) ethen-1-yl, wherein R ⁶ and R ⁷ are phenyl groups, and R ⁵ is a p-tolyl group, It was found that diphenylphosphine oxide was produced with a yield of 68% based on the amount of diphenylphosphine oxide charged. The production amount of the linear isomer [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide is only 2%, and the branched chain occupies the entire branched and linear product. The selectivity of the product was 97%.

Comparative Example 1 Reaction of p-tolylacetylene with diphenylphosphine oxide Instead of 1,2-bis (diphenylphosphino) ethane, 0.20 mmol of triphenylphosphine (that is, the ratio of phosphorus atom to palladium in triphenylphosphine) 3: 1) The reaction was carried out in the same manner as in Example 1 except that [1- (p-tolyl) ethen-1-yl] diphenylphosphine oxide was obtained in a yield of 27 with respect to the charged amount of diphenylphosphine oxide. % Was found to be produced. The production amount of the linear isomer [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide also reaches 17%, and the branched chain formation in the entire branched and linear product. The selectivity of the product was only 61%.

Example 2 Reaction of p-tolylacetylene with diphenylphosphine oxide (2)
[1- (p-Tolyl) ethen-1-yl] diphenylphosphine was reacted in the same manner as in Example 1 except that the amount of 1,2-bis (diphenylphosphino) ethane used was 0.067 mmol. It was found that the oxide was produced in a yield of 53% with respect to the charged amount of diphenylphosphine oxide. The production amount of the linear isomer [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide is only 2%, and the branched chain occupies the entire branched and linear product. The selectivity of the product was 96%.

Reference Example 3 Reaction of p-tolylacetylene with diphenylphosphine oxide (3)
The reaction was conducted in the same manner as in Example 1 except that 1,3-bis (diphenylphosphino) propane was used in place of 1,2-bis (diphenylphosphino) ethane. As a result, [1- (p-tolyl) ethene was obtained. It was found that -1-yl] diphenylphosphine oxide was produced in a yield of 54% with respect to the charged amount of diphenylphosphine oxide. The production amount of the linear isomer [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide is only 3%, and the branched chain and the branched chain account for the entire linear product. The selectivity of the product was 95%.

Example 4 Reaction of p-tolylacetylene with diphenylphosphine oxide (4)
The reaction was conducted in the same manner as in Example 1 except that 1,4-bis (diphenylphosphino) butane was used in place of 1,2-bis (diphenylphosphino) ethane. As a result, [1- (p-tolyl) ethene was obtained. It was found that -1-yl] diphenylphosphine oxide was produced in a yield of 49% with respect to the amount of diphenylphosphine oxide charged. The production amount of the linear isomer [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide is only 2%, and the branched chain occupies the entire branched and linear product. The selectivity of the product was 96%.

Example 5 Reaction of p-tolylacetylene with diphenylphosphine oxide (5)
As a result of reacting in the same manner as in Example 1 except that 1,2-bis (9-phosphafluoren-9-yl) ethane was used instead of 1,2-bis (diphenylphosphino) ethane, [1- It was found that (p-tolyl) ethen-1-yl] diphenylphosphine oxide was produced in a yield of 21% with respect to the charged amount of diphenylphosphine oxide. The amount of [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide, which is the linear isomer, is only 7%, and it is branched and accounts for the entire linear product. The selectivity of the product was 75%.

Example 6 Reaction of p-tolylacetylene with diphenylphosphine oxide (6)
The reaction was conducted in the same manner as in Example 1 except that 1,2-bis (diphenylphosphino) benzene was used instead of 1,2-bis (diphenylphosphino) ethane. As a result, [1- (p-tolyl) ethene was obtained. It was found that -1-yl] diphenylphosphine oxide was produced in a yield of 56% with respect to the charged amount of diphenylphosphine oxide. The production amount of the linear isomer [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide is only 4%, and the branched chain occupies the entire branched and linear product. The selectivity of the product was 93%.

Example 7 Reaction of 1-octyne with diphenylphosphine oxide (1)
The reaction was conducted in the same manner as in Example 1 except that 1-octyne was used instead of p-tolylacetylene. As a result, [1-octen-2-yl] diphenylphosphine oxide was obtained in a yield with respect to the amount of diphenylphosphine oxide charged. It was found that 68% was produced. The production amount of the linear isomer [1-octen-1-yl] diphenylphosphine oxide is only 1%, and the selectivity of the branched product in the entire branched and linear product. Was 99%.

Example 8 Reaction of 1-octyne with diphenylphosphine oxide (2)
As a result of carrying out the reaction in the same manner as in Example 7 except that propionitrile was used instead of toluene, the yield of [1-octen-2-yl] diphenylphosphine oxide was 81% with respect to the charged amount of diphenylphosphine oxide. It was found that it was generated. The production amount of the linear isomer [1-octen-1-yl] diphenylphosphine oxide is only 1%, and the selectivity of the branched product in the entire branched and linear product. Was 99%.

Example 9 Reaction of 1-octyne with diphenylphosphine oxide (3)
The reaction was conducted in the same manner as in Example 7 except that methyl isobutyl ketone was used instead of toluene. As a result, [1-octen-2-yl] diphenylphosphine oxide was obtained in a yield of 77% with respect to the charged amount of diphenylphosphine oxide. It was found that it was generated. The production amount of the linear isomer [1-octen-1-yl] diphenylphosphine oxide is only 1%, and the selectivity of the branched product in the entire branched and linear product. Was 99%.

Example 10 Reaction of p-tolylacetylene with diphenylphosphine oxide (7)
The reaction was carried out in the same manner as in Example 1 except that propionitrile was used instead of toluene. As a result, [1- (p-tolyl) ethen-1-yl] diphenylphosphine oxide was compared with the charged amount of diphenylphosphine oxide. It was found that the product was produced with a yield of 88%. The production amount of the linear isomer [2- (p-tolyl) ethen-1-yl] diphenylphosphine oxide is only 2%, and the branched chain occupies the entire branched and linear product. The selectivity of the product was 98%.

Example 11 Reaction of Phenylacetylene and Diphenylphosphine Oxide [1-Phenylethen-1-yl] diphenylphosphine oxide was reacted in the same manner as in Example 10 except that phenylacetylene was used instead of p-tolylacetylene. Was found to be produced at a yield of 77% with respect to the charged amount of diphenylphosphine oxide. The production amount of the linear isomer [2-phenylethen-1-yl] diphenylphosphine oxide is only 4%, and the selection of the branched product in the entire branched and linear product is selected. The sex was 95%.

Example 12 Reaction of p -fluorophenylacetylene and diphenylphosphine oxide The reaction was carried out in the same manner as in Example 10 except that p-fluorophenylacetylene was used instead of p-tolylacetylene. As a result, [1- (p-fluoro It was found that (phenyl) ethen-1-yl] diphenylphosphine oxide was produced in a yield of 67% with respect to the charged amount of diphenylphosphine oxide. The production of [2- (p-fluorophenyl) ethen-1-yl] diphenylphosphine oxide, which is the linear isomer, was not observed, and the branched product occupying the entire branched and linear product The selectivity of was 100%.

Example 13 Reaction of t-butylacetylene with diphenylphosphine oxide The reaction was conducted in the same manner as in Example 10 except that t-butylacetylene was used instead of p-tolylacetylene. As a result, (3,3-dimethyl-1- It was found that buten-2-yl) diphenylphosphine oxide was produced in a yield of 76% with respect to the charged amount of diphenylphosphine oxide. The amount of the linear isomer (3,3-dimethyl-1-buten-1-yl) diphenylphosphine oxide produced is only 2%, and the branched chain accounts for all the branched and linear products. The selectivity of the gaseous product was 97%.

Claims (1)

General formula (1)
R ¹ R ² P-A-PR ³ R ⁴ (1)
[Wherein R ¹ is
An aryl group having 12 or less carbon atoms or an aralkyl group having 12 or less carbon atoms is represented.
R ² , R ³ and R ⁴ are the same or different,
An alkyl group having 12 or less carbon atoms,
An aryl group having 12 or less carbon atoms or an aralkyl group having 12 or less carbon atoms is represented.
In R ¹ and R ² , residues obtained by removing one hydrogen atom from each group may be bonded to each other in the molecule to form a ring containing a phosphorus atom.
In R ³ and R ⁴ , residues obtained by removing one hydrogen atom from each group may be bonded to each other in the molecule to form a ring containing a phosphorus atom.
A represents a linear, branched or cyclic divalent organic group having 1 to 15 carbon atoms.
The aromatic ring constituting the aryl group and aralkyl group in R ¹ , R ² , R ³ and R ⁴ may be a heteroaromatic ring, and R ¹ , R ² , R ³ and R ⁴ are functional groups. May be substituted. ]
In the presence of a palladium complex of a chelate-coordinating phosphine represented by the formula (excluding the chelate-coordinating phosphine where A is a trimethylene group)

[Wherein R ⁵ is
An alkyl group having 12 or less carbon atoms;
An aryl group having 12 or less carbon atoms;
An aralkyl group having 12 or less carbon atoms;
A silyl group substituted with three groups selected from the group consisting of an alkyl group having 6 or less carbon atoms and an aryl group having 12 or less carbon atoms; or a ferrocenyl group.
The aromatic ring constituting the aryl group and aralkyl group in R ⁵ may be a heteroaromatic ring, and R ⁵ may be substituted with a functional group. ]
A terminal acetylene compound represented by the general formula (3)

[Wherein R ⁶ and R ⁷ are the same or different,
An alkyl group having 6 or less carbon atoms,
An aryl group having 12 or less carbon atoms or an aralkyl group having 12 or less carbon atoms is represented.
Aromatic ring constituting the aryl group and aralkyl group in R ⁶ and R ⁷ may be a heterocyclic aromatic ring, R ⁶ and R ⁷ may be substituted with a functional group. ]
Is reacted with a secondary phosphine oxide compound represented by the general formula (4) without substantially adding phosphinic acid to the reaction system.

[Wherein R ⁵ , R ⁶ and R ⁷ represent the same meaning as described above. ]
A method for producing a branched alkenylphosphine oxide compound represented by the formula: