JP2004075688A - Method for producing alkenylphosphonic ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for production of an alkenylphosphorus compound (alkenylphosphonic ester) by using a hydrogenated phosphonic ester as a starting material and using an inexpensive catalyst. <P>SOLUTION: The method for production of the alkenylphosphonic ester expressed by formula (3), (4) comprises a process reacting a hydrogenated phosphonic ester expressed by formula (2) to an acetylenic compound of formula (1) in the presence of a nickel complex with lower valency comprising a tertiary phosphorus compound such as a tertiary phosphine or a tertiary phosphite or the like, as a ligand [excluding nickel complexes with lower valency using a phosphine containing two or more tertiary phosphorus atoms, triphenylphosphine, tri(hydroxymethyl)phosphine, tri(n-butyl)phosphine or triphenyl phosphite as ligand]. And the method for production of the alkenylphosphonic ester with improved position-selectivity carries out the reaction in the presence of a phosphinic acid. R<SP>1</SP>(C≡CR<SP>2</SP>)<SB>n</SB>[1], HP(O)(OR<SP>3</SP>)(OR<SP>4</SP>) [2], R<SP>1</SP>äCH=CR<SP>2</SP>[P(O)(OR<SP>3</SP>)(OR<SP>4</SP>)]}<SB>n</SB>[3], R<SP>1</SP>äC[P(O)(OR<SP>3</SP>)(OR<SP>4</SP>)]=CHR<SP>2</SP>}<SB>n</SB>[4], (in the formulas n is 1 or 2, R<SP>1</SP>-R<SP>4</SP>are each an alkylene group or the like). <P>COPYRIGHT: (C)2004,JPO

Description

<< The present invention relates to a method for producing an alkenyl phosphorus compound such as an alkenyl phosphonic acid ester. It is known that alkenyl phosphorus compounds themselves show physiological activity when their basic skeleton is found in nature and act with enzymes and the like. The compound is also a very useful compound that can be easily converted to tertiary phosphine or the like widely used as an auxiliary ligand or the like in various catalytic reactions. Further, the compound is a group of compounds having high utility also in synthesizing fine chemicals, for example, easily reacting with a nucleophile or a radical species, and can be used for the Horner-Wittig reaction.

As a method of synthesizing such an alkenyl phosphorus compound with generation of a carbon-phosphorus bond, generally, a corresponding alkenyl halide compound is converted to a hydrogenated phosphonic acid ester, a hydrogenated phosphinic acid ester and a disubstituted phosphine oxide ( Hereinafter, these phosphorus compounds are collectively referred to as a PH compound.). However, in this method, it is necessary to add a base for capturing the hydrogen halide produced simultaneously with the reaction, thereby producing a large amount of a hydrogen halide salt. Further, the alkenyl halide compound as the starting material is not always easily available industrially, and generally has toxicity. Therefore, this method is not considered to be an industrially advantageous method. On the other hand, a method for producing an alkenyl phosphorus compound by addition of a PH compound to acetylene using a catalyst has also been recently reported (Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5). Etc.), all of which use expensive palladium or rhodium catalysts, and none of these methods has a very high product selectivity.

Japanese Patent No. 2775426 Japanese Patent No. 2777985 Japanese Patent No. 2849712 Japanese Patent No. 3007984 Japanese Patent No. 3041396

An object of the present invention is to provide a method for producing an alkenyl phosphorus compound (alkenyl phosphonate) using a hydrogenated phosphonate as a starting material and using an inexpensive catalyst.

The present inventors have conducted intensive studies on the reaction between an easily available hydrogenated phosphonate and an acetylene compound, and as a result, this addition reaction proceeds in the presence of an inexpensive nickel catalyst, and the corresponding alkenyl phosphorus compound (Alkenyl phosphonate), and completed the present invention.

That is, the present invention relates to a low-valent nickel complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand [provided that a phosphine having two or more trivalent phosphorus atoms or Excludes low-valent nickel complexes having phenylphosphine, tri (hydroxymethyl) phosphine, tri (n-butyl) phosphine or triphenylphosphite as a ligand. ] In the presence of 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 Good alkyl group, the same cycloalkyl group, the same alkenyl group, the same cycloalkenyl group, the same aryl group, the same aralkyl group, the same heteroaryl group, the same alkoxy group, the same cycloalkoxy group, the same aralkyloxy group, the same aryloxy group, R ¹ when n is 2 is an alkylene group, a cycloalkylene group, an alkenylene group, an alkenylene group, an arylene group, or an arylene group, which may have a substituent; Group, the same aralkylene group, the same heteroarylene group, the same alkylenedioxy group, the same cycloalkylenedioxy group, the same aralkylenedioxy group, the same arylenedioxy group, The silylene group, or ferrocenylene a group.) Acetylene compound represented by the general formula [2]
^{HP (O) (OR 3)} (OR 4) [2]
(Wherein, R ³ and R ⁴ each independently represent an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. In addition, R ³ and R ⁴ May be bonded to each other by a residue or a bond formed by removing one hydrogen atom or the group itself from each group to form a cyclic structure.) Characteristic, general formula [3]
R ¹ {CH = CR ² [P (O) (OR ³ ) (OR ⁴ )]} _n [3]
Or / and general formula [4]
R ¹ {C [P (O) (OR ³ ) (OR ⁴ )] = CHR ² } _n [4]
(Wherein, n, R ¹ , R ² , R ³ and R ⁴ are the same as described above).

The present invention provides a process for producing alkenyl phosphonate esters useful as synthetic intermediates such as physiologically active substances such as pharmaceuticals and agricultural chemicals and ligands for preparing catalysts in high yield and high practicability. The method for synthesizing an alkenyl phosphonate according to the present invention provides a simple, safe, and efficient synthesis by simply reacting a hydrogenated phosphonate with an acetylene using a relatively inexpensive nickel complex catalyst as a catalyst. And the separation and purification of the product is easy. Therefore, the present invention has a great effect industrially.

The 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 a linear or branched alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, and more specifically, Examples 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 includes, for example, a monocyclic, polycyclic or condensed ring having 3 to 30, preferably 3 to 20, and more preferably 3 to 12 carbon atoms. Examples include the cycloalkyl group of the formula, 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, for example, those having one or more double bonds in the alkyl group having 2 or more carbon atoms, and more specifically, allyl. Groups, 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 above-described cycloalkyl group, and more specifically, a cyclopropenyl group and a cycloalkyl group Examples include a pentenyl group, a cyclohexenyl group, and a cyclooctenyl group.

Examples of the aryl group of the aryl group which may have a substituent include, for example, a monocyclic, polycyclic or condensed ring aromatic having 6 to 30, preferably 6 to 20, and more preferably 6 to 14 carbon atoms. Examples include a hydrocarbon group, and more specifically, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and the like.
Examples of the aralkyl group of the aralkyl group which may have a substituent include, for example, a monocyclic, polycyclic or condensed aralkyl group having 7 to 30, preferably 7 to 20, and more preferably 7 to 15 carbon atoms. And more specifically, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and the like.
Examples of the heteroaryl group of the heteroaryl group which may have a substituent include various heteroaromatic ring groups containing a hetero atom such as oxygen, nitrogen, and sulfur, and the number of carbon atoms contained therein is usually 4 to 12 , Preferably 4 to 8. Specific examples thereof include a thienyl group, a furyl group, a pyridyl group, and a pyrrolyl group.
Examples of the alkoxy group of the optionally substituted alkoxy group 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. And the like.
Examples of the cycloalkoxy group of the cycloalkoxy group which may have a substituent include, for example, a monocyclic, polycyclic or condensed cyclic compound having 3 to 30, preferably 3 to 20, and more preferably 3 to 12 carbon atoms. A cycloalkoxy group is mentioned, and more specifically, a cyclopropyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cyclooctyloxy group, a cyclododecyloxy group and the like are mentioned.
Examples of the aralkyloxy group which may have a substituent include a monocyclic, polycyclic or fused cyclic aralkyloxy group having 7 to 30, preferably 7 to 20, and more preferably 7 to 15 carbon atoms. More specifically, examples include a benzyloxy group, a phenethyloxy group, a naphthylmethyloxy group, a naphthylethyloxy group, and the like.
Examples of the aryloxy group of the aryloxy group which may have a substituent include, for example, a monocyclic, polycyclic or condensed cyclic one having 6 to 30, preferably 6 to 20, and more preferably 6 to 14 carbon atoms. Examples include an aryloxy group having an aromatic hydrocarbon group, and more specifically, for example, a phenoxy group, a tolyloxy group, a xylyloxy group, a naphthoxy group, a methylnaphthyloxy group, an anthryloxy group, a phenanthryloxy group, And a biphenyloxy group.

Examples of the substituent for the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, aralkyl group, heteroaryl group, alkoxy group, cycloalkoxy group, aralkyloxy group and aryloxy group include, for example, methyl group, ethyl group , An alkyl group such as a propyl group, a hydroxyl group such as a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, such as a halogen atom such as chlorine, bromine and fluorine, a cyano group such as a dimethylamino group and a diethylamino group. Dialkylamino group, for example, methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, silyl group, for example, substituted silyl group such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, for example, t-butyl Such siloxy groups such as methylsiloxy group.

The silyl group which may have a substituent includes, for example, those substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and the like. Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, a trimethoxysilyl group, a t-butyldimethylsilyl group, and the like.

an alkylene group optionally having a substituent, a cycloalkylene group optionally having a substituent, an alkenylene group optionally having a substituent, a substituent represented by R ¹ when n is 2 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, and a substituent May have an alkylenedioxy group, an optionally substituted cycloalkylenedioxy group, an optionally substituted arylenedioxy group, may have a substituent The silylene group or ferrosenylene group is selected from divalent residues obtained by removing one hydrogen atom from R ¹ when n is 1, or divalent residues 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 Examples thereof include an yl group, a 2-butenediyl group, a tetramethylenedioxy group, a tetralindiyloxy group, a phenylenedioxy group, a dimethylsilylene group, and a ferrocenylene group.

Examples of the acetylene compound represented by the 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.

In the general formulas [2], [3] and [4], in the alkyl group optionally having a substituent, the cycloalkyl group, the aralkyl group and the aryl group represented by R ³ and R ⁴ , The definition and specific examples of the alkyl group, cycloalkyl group, aralkyl group and aryl group include the same as those described for R ¹ and R ² above. In addition, the same substituents as those described above for R ¹ and R ² can also be used. Further, specific examples of the case where a ring structure is formed by bonding to each other with a residue or a bond formed by removing one hydrogen atom or a group itself from each of R ³ and R ⁴ to form, for example, an ethylene group , A tetramethylethylene group, a trimethylene group, a tetramethylene group, an orthophenylene group, an orthoxylylene group, and the like, but are not limited thereto.

Specific examples of suitable hydrogenated phosphonates used in the production method of the present invention include dimethyl phosphonate, diethyl phosphonate, dibutyl phosphonate, diphenyl phosphonate, and the like, but are not limited thereto. Absent

The use ratio of the acetylene compound to the hydrogenated phosphonic acid ester is generally preferably 1: 1 in molar ratio, but larger or smaller than this does not inhibit the occurrence of the reaction.

The reaction according to the present invention is a low-valent nickel complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand [however, a phosphine having two or more trivalent phosphorus atoms, or Excludes low-valent nickel complexes having triphenylphosphine, tri (hydroxymethyl) phosphine, tri (n-butyl) phosphine or triphenylphosphite as a ligand. ] At a preferred rate.
Further, a low-valent nickel complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand in the reaction system [however, a phosphine having two or more trivalent phosphorus atoms, Alternatively, a low-valent nickel complex having triphenylphosphine, tri (hydroxymethyl) phosphine, tri (n-butyl) phosphine, or triphenylphosphite as a ligand is excluded. The reaction may be carried out by forming a low-valent nickel complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand in a reaction system using a precursor complex that can be converted to This is a preferred embodiment.
Further, a nickel complex containing no 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 low-valent nickel complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand in the reaction system [however, a phosphine having two or more trivalent phosphorus atoms or a triphenylphosphine] And low-valent nickel complexes having tri (hydroxymethyl) phosphine, tri (n-butyl) phosphine or triphenylphosphite as a ligand. And a low-valent complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand [however, a phosphine having two or more trivalent phosphorus atoms, Alternatively, a low-valent nickel complex having triphenylphosphine, tri (hydroxymethyl) phosphine, tri (n-butyl) phosphine, or triphenylphosphite as a ligand is excluded. In another preferred embodiment, a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite is used.
Examples of ligands that exhibit advantageous performance by any of these methods include various tertiary phosphorus compounds such as tertiary phosphine and tertiary phosphite, and ligands that can be preferably used. Illustrative ligands include, for example, diphenylmethylphosphine, phenyldimethylphosphine and the like.

Examples of the complex which does not contain a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand used in combination with the ligand according to the present invention 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, bromide Nickel and the like can be mentioned.

Examples of the complex containing tertiary phosphine or phosphite as a ligand include dimethylbis (diphenylmethylphosphine) nickel, tetrakis (diphenylmethylphosphine) nickel, and tetrakis (dimethylphenylphosphine) nickel. Particularly preferred examples of the phosphine complex include tetrakis (diphenylmethylphosphine) nickel and tetrakis (dimethylphenylphosphine) nickel.

In the method of generating a low-valent nickel complex in a reaction system using a precursor complex, it is preferable to use a treating agent for lowering the valence depending on the structure of the precursor nickel complex. Examples of the treating agent used at that time include a reducing agent and a Grignard reagent, and more specifically, for example, sodium borohydride, lithium aluminum hydride, hydrides such as sodium hydride, triethylaluminum, phenyl Examples include lithium, butyl lithium, metallic lithium, metallic sodium, sodium amalgam, metallic zinc, methylmagnesium bromide, phenylmagnesium iodide, and isopropylmagnesium bromide.
Specific examples of the precursor nickel complex include, but are not limited to, dichlorobis (diphenylmethylphosphine) nickel, dichlorobis (dimethylphenylphosphine) nickel, and the like.

One or more of the above complexes used in the reaction of the present invention may be suitably selected according to the reaction and used.
The amount of the nickel complex used in the reaction of the present invention may be a so-called catalytic amount, which is sufficient to be 20 mol% or less based on the acetylene compound, but usually 10 mol% or less is sufficient.
When a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite is used as a ligand, the amount of these ligands is not particularly strictly limited, but the atomic ratio of phosphorus to nickel is excessively large. In general, it is preferable to set the atomic ratio to 50 or less, preferably 10 or less.

A low-valent nickel complex having a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand exhibits activity even when used alone, but can be used together with a phosphinic acid additive. Particularly, in a reaction in which a regioisomer is generated, regioselectivity is enhanced by the combined use of a phosphinic acid additive.
These phosphinic acids have, for example, the general formula [5]
^{HO-P (O) (R} 5) 2 [5]
(In the formula, R ⁵ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.)

In the general formula [5], when R ⁵ is an alkyl group, examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples thereof include 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.
When R ⁵ is a cycloalkyl group, examples of the cycloalkyl group include a cycloalkyl group having 3 to 12 carbon atoms, preferably 5 to 12 carbon atoms. Specific examples thereof include, for example, a cyclopentyl group, a cyclohexyl group, and a cycloalkyl group. Examples include an octyl group and a cyclododecyl group.
When R ⁵ is an aryl group, the aryl group includes, for example, an aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, and specific examples thereof include, for example, a phenyl group and a naphthyl group. Further, their substituted products (tolyl group, xylyl group, benzylphenyl group, etc.) are also included.
When R ⁵ is an aralkyl group, the aralkyl group includes, for example, an aralkyl group having 7 to 15 carbon atoms, preferably 7 to 11 carbon atoms, and specific examples thereof include, for example, a benzyl group, a phenethyl group, and a naphthylmethyl group. No.
The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by R ⁵ is a substituent inert to the reaction, for example, a methoxy group, a methoxycarbonyl group, a cyano group, a dimethylamino group, a fluoro group, a chloro group, a hydroxy group. It may be substituted with a group or the like.

具体 Specific examples of the phosphinic acid used in the present invention include, for example, diphenylphosphinic acid and dimethylphosphinic acid. The amount of use is not more than equimolar to the P-H compound used, preferably 0.1 to 10 mol%.

The reaction does not need to use a solvent, but can be carried out in a solvent if necessary. Examples of the solvent 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 can be used, such as a nitrile solvent such as acetic acid, acetonitrile and propiononitrile, and an amide solvent such as N, N-dimethylformamide (DMF). These can be used alone or as a mixture of two or more.

The reaction temperature is generally selected from the range of −20 ° C. to 300 ° C., preferably 0 ° C. to 150 ° C., since the reaction does not proceed at an advantageous rate at a too low temperature and the catalyst decomposes at a too high temperature. It is carried out within the range. The reaction time varies depending on the kind of the acetylene compound and the PH compound used, the reaction temperature and other reaction conditions, but is usually about several hours to several tens of hours.

Although this reaction proceeds even in the presence of oxygen such as in air, the catalytically active species acting in this reaction system is sensitive to oxygen, so the reaction should be performed in an inert gas atmosphere such as nitrogen, argon, or methane. preferable. Separation of the product from the reaction mixture is easily achieved by chromatography, distillation, recrystallization, and the like.

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

Using a nickel complex according to the present invention having phenyldimethylphosphine or diphenylmethylphosphine as a ligand, 1 mmol of HP (O) (OCMe ₂ -Me ₂ CO) and 1 mmol of 1-octyne in 1 ml of a solvent were mixed in a nitrogen atmosphere. When the reaction was carried out at room temperature for each reaction time shown in Table 1, 2- (1-octen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaphospho was obtained. Run 2-oxide was obtained in each of the yields listed in Table 1. These results are summarized in Table 1. Table 1 also shows the results of Reference Examples 1 to 11 using a phosphine having two trivalent phosphorus atoms, triphenylphosphine, or a nickel complex having triphenylphosphite as a ligand.

As is clear from Table 1, the production method of the present invention using the nickel complex of the present invention having phenyldimethylphosphine or diphenylmethylphosphine as a ligand ((1) to (5) of Example 1). For example, as compared with Reference Examples (1) to (11) using a nickel complex having phosphine, triphenylphosphine, or triphenylphosphite having two trivalent phosphorus atoms as a ligand, the reaction time and yield are higher. It can be seen that a very favorable result is obtained in terms of surface.
Reference Example 12
To 1 ml of 1,4-dioxane, 1 mmol of HP (O) (OCMe ₂ -Me ₂ CO), 1 mmol of 1-octyne, and Ni (cod) ₂ (10 mol%) as a catalyst were used under a nitrogen atmosphere at room temperature. For 5 hours, the yield of 2- (1-octen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaphosphorane 2-oxide was 36%. Was obtained.

Reference Example 13
The reaction was carried out under the same reaction conditions as in Reference Example 12 using Ni (cod) ₂ (10 mol%) and Ph ₂ P (CH ₂ ) ₃ PPh ₂ (10 mol%) as catalysts. 1-octen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaphosphorane 2-oxide was obtained with a yield of 72%.

When the reaction was carried out under the same reaction conditions as in (3) of Example 1 using phenylacetylene instead of 1-octyne, CH ₂ ＣC (Ph) [P (O) (OCMe ₂ -Me ₂ CO)] was obtained in a yield of 99%.

The reaction was carried out under the same reaction conditions as in Example 2 using acetylene gas (1 atm), and CH ₂ ＣＨCH [P (O) (OCMe ₂ -Me ₂ CO)] was obtained in a yield of 95%. Obtained.

Using (MeO) ₂ P (O) H instead of HP (O) (OCMe ₂ -Me ₂ CO), the reaction with 1-octyne was carried out under the same reaction conditions as in (3) of Example 1. When _{went, CH 2 = C (n-} C 6 H 13) [P (O) (OMe) 2] and _{(E) -CH (n-C} 6 H 13) = CH [P (O) (OMe) ₂ ] (ratio = 100: 46) was obtained in 97% yield.

When the reaction of Example 4 was carried out in the presence of diphenylphosphinic acid (10 mol%), CH ₂ ＣC (n-C ₆ H ₁₃ ) [P (O) (OMe) ₂ ] was obtained in a yield of 96%. Selectively generated.

The reaction with (MeO) ₂ P (O) H using 1,8-nonadiyne as an acetylene compound under the same reaction conditions as in Example 5 gave CH ₂ ＣＨC [P (O) (OMe ) ₂ ]-(CH ₂ ) _5- [P (O) (OMe) ₂ ] C ＝ CH ₂ was produced in 91% yield.

The reaction was carried out under the same reaction conditions as in Example 4 using acetylene gas (1 atm) in place of 1-octyne. As a result, the yield of CH ₂ ＣＨCH [P (O) (OMe) ₂ ] was 92%. Was obtained.

Claims (5)

Low-valent nickel complex having a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand [however, phosphine having two or more trivalent phosphorus atoms, or triphenylphosphine, tri (hydroxy) Excludes low-valent nickel complexes having methyl) phosphine, tri (n-butyl) phosphine or triphenylphosphite as a ligand. ] In the presence of 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 Good alkyl group, the same cycloalkyl group, the same alkenyl group, the same cycloalkenyl group, the same aryl group, the same aralkyl group, the same heteroaryl group, the same alkoxy group, the same cycloalkoxy group, the same aralkyloxy group, the same aryloxy group, R ¹ when n is 2 is an alkylene group, a cycloalkylene group, an alkenylene group, an alkenylene group, an arylene group, or an arylene group, which may have a substituent; Group, the same aralkylene group, the same heteroarylene group, the same alkylenedioxy group, the same cycloalkylenedioxy group, the same aralkylenedioxy group, the same arylenedioxy group, The silylene group, or ferrocenylene a group.) Acetylene compound represented by the general formula [2]
^{HP (O) (OR 3)} (OR 4) [2]
(Wherein, R ³ and R ⁴ each independently represent an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent. In addition, R ³ and R ⁴ May be bonded to each other by a residue or a bond formed by removing one hydrogen atom or the group itself from each group to form a cyclic structure.) Characteristic, general formula [3]
R ¹ {CH = CR ² [P (O) (OR ³ ) (OR ⁴ )]} _n [3]
Or / and general formula [4]
R ¹ {C [P (O) (OR ³ ) (OR ⁴ )] = CHR ² } _n [4]
(Wherein n, R ¹ , R ² , R ³ and R ⁴ are the same as described above). The low-valent nickel complex having a ligand of a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite is a low-valent nickel complex having a ligand of phenyldimethylphosphine or diphenylmethylphosphine. Item 1. The production method according to Item 1. The reaction is carried out using a precursor complex which can be easily converted to a low-valent nickel complex having a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite as a ligand in the reaction system. 3. The production method according to 2. A low-valent nickel complex having a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand contains a trivalent phosphorus compound such as tertiary phosphine or tertiary phosphite as a ligand. And a trivalent phosphorus compound such as a tertiary phosphine or a tertiary phosphite formed in the reaction system. The production method according to claim 1, wherein the production method is a low-valent complex used as a ligand. The reaction is performed according to 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). The method according to claim 1, wherein the reaction is performed in the presence of a phosphinic acid represented by the formula: