JP3836395B2 - Process for producing alkenyl phosphorus compound - Google Patents

Description

[0001]
The present invention relates to a method for producing an alkenyl phosphorus compound such as an alkenyl phosphinic acid ester and an alkenyl phosphine oxide compound. It is known that an alkenyl phosphorus compound has its basic skeleton found in nature and exhibits physiological activity by acting with an enzyme or the like. This compound is also an extremely useful compound that can be easily converted into tertiary phosphine and the like widely used as an auxiliary ligand for various catalytic reactions. Furthermore, these compounds are a group of compounds that are highly useful in the synthesis of fine chemicals, such as easily reacting with nucleophiles and radical species, and can be used in Horner-Wittig reactions.
[0002]
As a method for synthesizing such an alkenyl phosphorus compound with the formation of a carbon-phosphorus bond, generally, the corresponding alkenyl halide compound is synthesized from a hydrogenated phosphinic acid ester and a disubstituted phosphine oxide (hereinafter, these phosphorus compounds). Are generally referred to as P—H compounds). However, in this method, it is necessary to add a base for capturing the hydrogen halide generated simultaneously with the reaction, thereby producing a large amount of a hydrogen halide salt. Moreover, the alkenyl halide compound which is the starting material is not always easily available industrially and generally has toxicity. For this reason, this method is not considered to be an industrially advantageous method. On the other hand, although a method for producing an alkenyl phosphorus compound by addition of a P—H compound to acetylene using a catalyst has recently been reported (Japanese Patent Nos. 2775426, 2777985, 2849712, 3007984, No. 3041396, etc.), all of which use expensive palladium or rhodium catalysts, and none of these methods has a high product selectivity.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing an alkenyl phosphorus compound using a P—H compound as a starting material and using an inexpensive catalyst.
[0004]
[Means for Solving the Problems]
As a result of intensive studies on the reaction between an easily available PH compound and an acetylene compound, the present inventors proceeded with this addition reaction in the presence of an inexpensive nickel catalyst. And the present invention has been completed.
[0005]
That is, the present invention provides a general formula [1] in the presence of a catalyst comprising nickel.
R ¹ (C≡CR ² ) _n [1]
(Wherein, n is 1 or 2, R ² in the case of R ¹ and R ² when n is ^1, and n is 2 are each independently a hydrogen atom, substituted Alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, heteroaryl groups, alkoxy groups, cycloalkoxy groups, aralkyloxy groups, aryloxy groups, The same silyl group or ferrocenyl group, and when n is 2, R ¹ is an alkylene group, the same cycloalkylene group, the same alkenylene group, the same cycloalkenylene group, the same arylene which may have a substituent. Group, the same aralkylene group, the same heteroarylene group, the same alkylene dioxy group, the same cycloalkylene dioxy group, the same aralkylene dioxy group, the same arylene oxy group, The silylene group, or ferrocenylene a group.) Acetylene compound represented by the general formula [2]
HP (O) X ¹ X ² [2]
[Wherein, X ¹ represents OR ³ or R ³ and X ² represents R ⁴ (provided that R ³ and R ⁴ each independently represents an alkyl group which may have a substituent, A cycloalkyl group, the same aralkyl group or the same aryl group, and bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself from each of R ³ and R ⁴ to form a cyclic structure You may do it.) And a phosphorus compound represented by the general formula [3]
R ¹ {CH = CR ² [P (O) X ¹ X ² ]} _n [3]
Or / and general formula [4]
R ¹ {C [P (O) X ¹ X ² ] = CHR ² } _n [4]
(Wherein, n, R ¹ , R ² , X ¹ and X ² are the same as described above).
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The above-mentioned general formula [1], in [3] and [4], n is ^{R 1} and ^{R 2} in the case of 1, and n is represented by ^{R 2} in the case of two may have a substituent Examples of the alkyl group of the alkyl group include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and more specifically, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, and a hexyl group.
The cycloalkyl group of the cycloalkyl group which may have a substituent is, for example, a monocyclic, polycyclic or condensed ring having 3 to 30, preferably 3 to 20, more preferably 3 to 12 carbon atoms. A cycloalkyl group of the formula, and more specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and the like.
Examples of the alkenyl group of the alkenyl group which may have a substituent include those having one or more double bonds in the aforementioned alkyl group having 2 or more carbon atoms, and more specifically, allyl Group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group and the like.
Examples of the cycloalkenyl group of the cycloalkenyl group which may have a substituent include those having one or more double bonds in the aforementioned cycloalkyl group, and more specifically, a cyclopropenyl group, a cycloalkenyl group, A pentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. are mentioned.
[0007]
As the aryl group of the aryl group which may have a substituent, for example, a monocyclic, polycyclic or condensed cyclic aromatic having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms. More specifically, examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.
The aralkyl group of the aralkyl group which may have a substituent is, for example, a monocyclic, polycyclic or condensed cyclic aralkyl group having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms. More specifically, for example, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group and the like can be mentioned.
Examples of the heteroaryl group of the heteroaryl group which may have a substituent include various heteroaromatic ring groups containing heteroatoms such as oxygen, nitrogen and sulfur, and the number of carbons contained therein is usually 4 to 12 , Preferably 4-8. Specific examples thereof include a thienyl group, a furyl group, a pyridyl group, and a pyrrolyl group.
Examples of the alkoxy group that may have a substituent include an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, and a butoxy group. Etc.
The cycloalkoxy group of the cycloalkoxy group which may have a substituent is, for example, a monocyclic, polycyclic or condensed cyclic group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. A cycloalkoxy group is mentioned, More specifically, a cyclopropyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cyclooctyloxy group, a cyclododecyloxy group, etc. are mentioned.
Examples of the aralkyloxy group which may have a substituent include a monocyclic, polycyclic or condensed cyclic aralkyloxy group having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms. More specifically, examples include benzyloxy group, phenethyloxy group, naphthylmethyloxy group, naphthylethyloxy group, and the like.
The aryloxy group of the aryloxy group which may have a substituent is, for example, a monocyclic, polycyclic or condensed cyclic group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms. An aryloxy group having an aromatic hydrocarbon group can be mentioned, and more specifically, for example, phenoxy group, tolyloxy group, xylyloxy group, naphthoxy group, methylnaphthyloxy group, anthryloxy group, phenanthryloxy group, And biphenyloxy group.
[0008]
Substituents for these alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, heteroaryl groups, alkoxy groups, cycloalkoxy groups, aralkyloxy groups and aryloxy groups include, for example, methyl groups, ethyl groups Alkyl groups such as propyl group, hydroxyl groups such as alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, halogen atoms such as chlorine, bromine and fluorine, cyano groups such as dimethylamino group and diethylamino group Dialkylamino groups such as alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group and the like substituted silyl groups such as t-butyldi Such siloxy group such Chirushirokishi group.
[0009]
Examples of the silyl group that may have a substituent include those substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and the like. Specific examples thereof include trimethylsilyl group, triethylsilyl group, triphenylsilyl group, phenyldimethylsilyl group, trimethoxysilyl group, t-butyldimethylsilyl group and the like.
[0010]
an alkylene group which may have a substituent represented by R ¹ when n is 2, a cycloalkylene group which may have a substituent, an alkenylene group which may have a substituent, a substituent A cycloalkenylene group which may have a substituent, an arylene group which may have a substituent, an aralkylene group which may have a substituent, a heteroarylene group which may have a substituent, a substituent An alkylenedioxy group which may have a cycloalkylenedioxy group which may have a substituent, an aryleneoxy group which may have a substituent, and a substituent which may have a substituent The silylene group or ferrocenylene group is selected from the divalent residues obtained by removing one hydrogen atom from R ¹ when n is 1, or the divalent residue obtained by replacing one hydrogen atom with one oxygen atom. As a specific example Are methylene, ethylene, trimethylene, methylethylene, tetramethylene, 1,2-dimethylethylene, pentamethylene, hexamethylene, cyclohexylene, phenylene, naphthylene, phenylmethylene, flange Yl group, 2-butenediyl group, tetramethylenedioxy group, tetralindiyloxy group, phenylenedioxy group, dimethylsilylene group, ferrocenylene group and the like.
[0011]
Examples of the acetylene compound represented by the above general formula [1] preferably used in the production method of the present invention include unsubstituted acetylene, methylacetylene, butyne, 1-hexyne, 2-hexyne, 1-octyne, 4-octyne, 1-butyn-4-ol, 2-butyn-1-ol, 3-butyn-1-ol, 5-hexyn-1-ol, 1-octin-3-ol, 5-chloro-1-pentyne, phenylacetylene , Trimethylsilylacetylene, ethynylthiophene, hexinonitrile, cyclohexenylacetylene, ethynylferrocene, 1,4-pentadiyne, 1,8-nonadiyne, diethynylbenzene, and the like, but are not limited thereto.
[0013]
In the general formula [2], when X ¹ is OR ³ and X ² is R ⁴ , the phosphorus compound (PH compound) represented by the general formula [2] is represented by the following general formula [2b]
HP (O) (OR ³ ) R ⁴ [2b]
(Wherein R ³ and R ⁴ each independently represents an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent. R ³ and R ⁴ Each group may be bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself to form a cyclic structure). The alkenyl phosphorus compound represented by the general formula [3] or / and the general formula [4] is represented by the following general formula [3b] or / and the general formula [4b].
R ¹ {CH = CR ² [P (O) (OR ³ ) R ⁴ ]} _n [3b]
R ¹ {C [P (O) (OR ³ ) R ⁴ ] = CHR ² } _n [4b]
(Wherein n, R ¹ , R ² , R ^3, and R ⁴ are the same as described above).
[0014]
In the general formula [2], when X ¹ is R ³ and X ² is R ⁴ , the phosphorus compound (PH compound) represented by the general formula [2] is represented by the following general formula [2c]
HP (O) R ³ R ⁴ [2c]
(Wherein R ³ and R ⁴ each independently represents an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent. R ³ and R ⁴ Each group may be bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself to form a cyclic structure. The alkenyl phosphorus compound represented by the general formula [3] or / and the general formula [4] is represented by the following general formula [3c] or / and the general formula [4c].
R ¹ {CH = CR ² [P (O) R ³ R ⁴ ]} _n [3c]
R ¹ {C [P (O) R ³ R ⁴ ] = CHR ² } _n [4c]
(Wherein n, R ¹ , R ² , R ^3, and R ⁴ are the same as described above).
[0015]
Substituents represented by R ³ and R ⁴ in the general formulas [2a], [3a], [4a], [2b], [3b], [4b], [2c], [3c] and [4c] Examples of the alkyl group, cycloalkyl group, aralkyl group, and aryl group in the alkyl group, cycloalkyl group, aralkyl group, and aryl group that may have an alkyl group, cycloalkyl groups, aralkyl groups, and aryl groups, and specific examples thereof include the above R ¹ and R ^2. The same ones as mentioned above can be mentioned. In addition, these substituents may be the same as those mentioned for R ¹ and R ² above. In addition, specific examples of the case where each of R ³ and R ⁴ are bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself to form a cyclic structure include, for example, an ethylene group , Tetramethylethylene group, trimethylene group, tetramethylene group, orthophenylene group, orthoxylylene group and the like, but are not limited thereto.
[0016]
Specific examples of suitable P—H compounds used in the production method of the present invention include 4,4,5,5-tetramethyl-1,3,2-dioxaphosphorane-2-oxide, phenylphosphinic acid. Examples include, but are not limited to, ethyl, cyclohexyl phenylphosphinate, and diphenylphosphine oxide.
In general, the ratio of the acetylene compound and the P—H compound compound used is preferably 1: 1 in terms of a molar ratio. However, even if it is larger or smaller than this, it does not inhibit the occurrence of the reaction.
[0018]
The reaction according to the present invention proceeds at a preferred rate in the presence of a catalyst comprising nickel, especially a nickel complex catalyst.
As the nickel complex catalyst, those having various structures can be used, but a preferable one is a so-called low valence nickel complex catalyst.
A low-valence nickel complex having a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand can also be preferably used.
Furthermore, it is also a preferred embodiment to use a precursor complex that can be easily converted into a low-valence complex in the reaction system, and to form a low-valent nickel complex in the reaction system for reaction. Furthermore, the same metal complex not containing a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand and a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite are used in combination. A method in which a low-valent complex having a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand is formed and used in the reaction system, or a trivalent such as tertiary phosphine or tertiary phosphite. A method in which a trivalent phosphorus compound such as a tertiary phosphine or tertiary phosphite of the same or different type is further added to a low valence complex having the above phosphorus compound as a ligand is also a preferred embodiment.
Examples of ligands that exhibit advantageous performance by any of these methods include various trivalent phosphorus compounds such as tertiary phosphines and tertiary phosphites.
[0019]
Examples of ligands that can be suitably used include, for example, triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, triethylphosphine, tricyclohexylphosphine, 1,4-bis (diphenylphosphino) butane, 1,3- Bis (diphenylphosphino) propane, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino) ferrocene, 1,2-bis (diphenylphosphino) benzene, trans-1,2 -Bis (diphenylphosphino) cyclopentane, triethylphosphine, trimethylphosphine, trimethylphosphite, triphenylphosphite and the like.
[0020]
Examples of the complex not containing tertiary phosphine or tertiary phosphite used as a ligand in combination with these ligands include bis (acrylonitrile) nickel and bis (1,5-cyclooctadiene). ) Nickel [Ni (cod) ₂ ], bis (π-allyl) nickel, nickelocene, nickel carbonyl, (π-cyclopentadienyl) (π-allyl) nickel, nickel acetate, nickel bromide and the like.
[0021]
As a complex comprising tertiary phosphine or phosphite as a ligand,
For example, bis (tricyclohexylphosphine) nickel, dichlorobis (triphenylphosphine) nickel, dimethylbis (diphenylmethylphosphine) nickel, (ethylene) bis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel [Ni (PPh _{3 4} ], tetrakis (diphenylmethylphosphine) nickel, tetrakis (dimethylphenylphosphine) nickel, tetrakis (triethylphosphine) nickel, dicarbonylbistriphenylphosphinenickel, (tricarbonyl) (triphenylphosphine) nickel [Ni (CO) ₃ (PPh _3)], include tetrakis (triphenyl phosphite) nickel, and examples of the phosphine or phosphite complex is particularly preferably used, Tet Tetrakis (triphenylphosphine) nickel, tetrakis (diphenylmethyl phosphine) nickel, tetrakis (dimethylphenylphosphine) nickel, tetrakis (triethylphosphine) nickel, tetrakis (triphenyl phosphite) nickel.
[0022]
In the method of generating a low-valence nickel complex in a reaction system using a precursor complex, it is preferable to use a treatment agent for reducing the valence depending on the structure of the precursor nickel complex. Examples of the treating agent used at that time include reducing agents and Grignard reagents. More specifically, for example, hydrides such as sodium borohydride, lithium aluminum hydride, sodium hydride, triethylaluminum, phenyl Examples include lithium, butyllithium, metallic lithium, metallic sodium, sodium amalgam, metallic zinc, methylmagnesium bromide, phenylmagnesium iodide, isopropylmagnesium bromide and the like.
Specific examples of the precursor nickel complex include, for example, dichlorobis (triphenylphosphine) nickel, dichlorobis (diphenylmethylphosphine) nickel, dichlorobis (dimethylphenylphosphine) nickel, chlorophenylbis (triphenylphosphine) nickel, etc. It is not limited to.
[0023]
As the above-mentioned catalyst used in the reaction of the present invention, one or two or more suitable catalysts are appropriately selected depending on the reaction.
The amount of nickel catalyst used in the reaction of the present invention may be a so-called catalytic amount, which is 20 mol% or less with respect to the acetylene compound, but usually 10 mol% or less is sufficient.
Note that the amount of these trivalent phosphorus compounds used as a ligand is not particularly strict, but if the atomic ratio of phosphorus to nickel is excessive, the catalyst activity tends to decrease. Generally, the atomic ratio is preferably set to 50 or less, preferably 10 or less.
[0024]
A catalyst comprising nickel is active alone, but can also be used with a phosphinic acid additive. In particular, in a reaction in which a regioisomer is formed, regioselectivity is enhanced by using a phosphinic acid additive in combination.
These phosphinic acids are represented, for example, by the general formula [5].
^{HO-P (O) (R} 5) 2 [5]
(Wherein R ⁵ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group).
[0025]
In general formula [5], examples of the alkyl group when R ⁵ is an alkyl group include an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples thereof include, for example, a methyl group, Examples include an ethyl group, n- or iso-propyl group, n-, iso-, sec- or tert-butyl group, n-pentyl group, n-hexyl group and the like.
Examples of the cycloalkyl group when R ⁵ is a cycloalkyl group include a cycloalkyl group having 3 to 12 carbon atoms, preferably 5 to 12 carbon atoms, and specific examples thereof include, for example, a cyclopentyl group, a cyclohexyl group, a cyclo An octyl group, a cyclododecyl group, etc. are mentioned.
Examples of the aryl group when R ⁵ is an aryl group include an aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. Furthermore, those substitution products (tolyl group, xylyl group, benzylphenyl group, etc.) are also included.
Examples of the aralkyl group when R ⁵ is an aralkyl group include aralkyl groups having 7 to 15 carbon atoms, preferably 7 to 11 carbon atoms, and specific examples thereof include benzyl group, phenethyl group, naphthylmethyl group and the like. Can be mentioned.
The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by R ⁵ is a substituent inert to the reaction, for example, methoxy group, methoxycarbonyl group, cyano group, dimethylamino group, fluoro group, chloro group, hydroxy group. It may be substituted with a group or the like.
[0026]
Specific examples of the phosphinic acid used in the present invention include diphenylphosphinic acid and dimethylphosphinic acid. The amount used is equimolar or less, preferably 0.1 to 10 mol% with respect to the P—H compound used.
[0027]
The reaction is not particularly required to use a solvent, but can be carried out in a solvent if necessary. Solvents include hydrocarbon solvents such as toluene and xylene, ether solvents such as dioxane, tetrahydrofuran (THF), diisopropyl ether and dimethoxyethane, ester solvents such as ethyl acetate and butyl acetate, and ketones such as acetone and methyl ethyl ketone. Various solvents such as nitrile solvents such as acetonitrile and propiononitrile and amide solvents such as N, N-dimethylformamide (DMF) can be used. Moreover, these can also be used individually or in mixture of 2 or more types.
[0028]
The reaction temperature is generally selected from the range of −20 ° C. to 300 ° C., preferably 0 ° C. to 150 ° C., because the reaction does not proceed at an advantageous rate at too low temperature and the catalyst decomposes at too high temperature. It is carried out in the range. The reaction time varies depending on the kind of acetylene compound and P—H compound to be used, reaction temperature and other reaction conditions, but is usually about several hours to several tens of hours.
[0029]
Although this reaction proceeds even in the presence of oxygen, such as in the air, the catalytically active species that act in this reaction system are sensitive to oxygen, so the reaction should be carried out in an inert gas atmosphere such as nitrogen, argon, or methane. preferable. Separation of the product from the reaction mixture is readily accomplished by chromatography, distillation, recrystallization and the like.
[0030]
【Example】
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
[0041]
Example 1
1 milliliter of THF was added with 1 mmol of HP (O) (OEt) Ph, 1 mmol of phenylacetylene, and Ni (PPhMe ₂ ) ₄ (5 mol%) as a catalyst, and reacted at room temperature for 0.5 hours under a nitrogen atmosphere. However, a mixture (ratio = 29: 71) of ethyl [(E) -2-phenylethenyl] phenylphosphinate and ethyl (1-phenylethenyl) phenylphosphinate was obtained in a yield of 56%.
[0042]
Example 2
When the reaction of Example 1 was carried out in the presence of diphenylphosphinic acid (10 mol%), ethyl (1-phenylethenyl) phenylphosphinate was selectively produced in a yield of 98%.
[0043]
Example 3
Under the same reaction conditions as in Example 2, the reaction was carried out using 1-octyne instead of phenylacetylene. CH ₂ ═C (n—C ₆ H ₁₃ ) [P (O) Ph (OEt)] Was selectively produced in 88% yield.
[0044]
Example 4
When the reaction was carried out using trimethylsilylacetylene instead of phenylacetylene under the same reaction conditions as in Example 2, (E) —CH (SiMe ₃ ) ═CH [P (O) Ph (OEt)] was 92. Selectively produced in a yield of%.
[0045]
Example 5
Under the same reaction conditions as in Example 2, the reaction was carried out using 2-ethynylthiophene instead of phenylacetylene. As a result, ethyl [1- (2-thienyl) ethenyl] phenylphosphinate was obtained in a yield of 63%. Selectively generated.
[0046]
Reference example 1
When reaction was performed using HP (O) Ph ₂ instead of HP (O) (OEt) Ph under the same reaction conditions as in Example 1, CH ₂ = C (Ph) [P (O) Ph ₂ ] And (E) -CH (Ph) = CH [P (O) Ph ₂ ] (ratio = 56: 44) were obtained in a yield of 93%.
[0047]
Reference example 2
When the reaction of Example 6 was carried out in the presence of diphenylphosphinic acid (10 mol%), CH ₂ ═C (Ph) [P (O) Ph ₂ ] was selectively produced in a yield of 98%.
[0048]
【The invention's effect】
The present invention provides a high yield and practical use of alkenyl phosphorus compounds (alkenyl phosphinic acid esters and alkenyl phosphine oxide compounds) useful as synthetic intermediates for physiologically active substances such as pharmaceuticals and agricultural chemicals and ligands for catalyst preparation. It provides a high manufacturing method. The method for synthesizing an alkenyl phosphorus compound of the present invention uses a relatively inexpensive nickel complex catalyst as a catalyst, and converts a P—H compound (hydrogenated phosphonate, hydrogenated phosphinate, and disubstituted phosphine oxide) to acetylene. It can be synthesized simply, safely and efficiently simply by reacting, and the product can be easily separated and purified. Therefore, the present invention has a great industrial effect.

Claims (2)

In the presence of a catalyst comprising nickel, the general formula [1]
R ¹ (C≡CR ² ) _n [1]
(Wherein, n is 1 or 2, R ² in the case of R ¹ and R ² when n is ^1, and n is 2 are each independently a hydrogen atom, substituted Alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, heteroaryl groups, alkoxy groups, cycloalkoxy groups, aralkyloxy groups, aryloxy groups, The same silyl group or ferrocenyl group, and when n is 2, R ¹ is an alkylene group, the same cycloalkylene group, the same alkenylene group, the same cycloalkenylene group, the same arylene which may have a substituent. Group, the same aralkylene group, the same heteroarylene group, the same alkylene dioxy group, the same cycloalkylene dioxy group, the same aralkylene dioxy group, the same arylene oxy group, Shows a silylene group, or a ferrocenylene group.)
An acetylene compound represented by the general formula [2b]
HP (O) (OR ³ ) R ⁴ [2b]
(Wherein R ³ and R ⁴ each independently represents an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent. R ³ and R ⁴ (It may be bonded to each other by a residue or a bond obtained by removing one hydrogen atom or the group itself from each group to form a cyclic structure.)
The following general formula [3b] or / and general formula [4b], wherein the reaction is carried out at a reaction temperature of 0 ° C. to 150 ° C.
R ¹ {CH = CR ² [P (O) (OR ³ ) R ⁴ ]} n [3b]
R ¹ {C [P (O) (OR ³ ) R ⁴ ] = CHR ² } n [4b]
(In the formula, n, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
The manufacturing method of the alkenyl phosphorus compound represented by these.   The process according to claim 1, wherein the catalyst comprising nickel is a low-valence nickel complex catalyst having a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand.