JP2002332290A - Method of production for alkenylphosphinates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of production for alkenylphosphinates by using a hydrogenated phosphinate as raw material. SOLUTION: This method of production for alkenylphosphinates comprises reacting a hydrogenated phosphinate with acetylenic compound in the presence of a catalyst comprising a metal of the group IX or X of the periodic table.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an alkenyl phosphinate compound.
It is known that alkenyl phosphinates have a basic skeleton found naturally and act themselves with enzymes and the like to exhibit physiological activities themselves. This compound is also a very useful compound that can be easily converted to tertiary phosphine, which is widely used as an auxiliary ligand for various catalytic reactions. Further, the compound is a group of compounds having high utility in the synthesis of fine chemicals, such that nucleophiles and radical species easily react and can be used for the Horner-Wittig reaction.

[0002]

2. Description of the Related Art As a method of synthesizing such alkenyl phosphinates with formation of a carbon-phosphorus bond, generally, a method of replacing a corresponding alkenyl halide compound with a hydrogenated phosphinate is considered. Can be 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. Further, the alkenyl halide compound as the starting material is not always easily available industrially and generally has toxicity. For this reason, this method can not be said hardly to be industrially advantageous method.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel process for producing alkenyl phosphinates by using a hydrogenated phosphinate as a starting material.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on the reaction between an easily available hydrogenated phosphinic ester and an acetylene compound, and as a result, this addition reaction has progressed in the presence of a specific catalyst. The present inventors have found that alkenyl phosphinates can be easily provided, and have completed the present invention based on these facts.

That is, according to the present invention, the ninth periodic table
Using a catalyst comprising a Group 10 or Group 10 metal, a general formula [1] R ¹ (C≡CR ² ) _n [1] (wherein n is 1 or 2, and R ¹ and R ² when n is ¹ and R ² when n is ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl R ¹ represents an alkylene group, a cycloalkylene group, an arylene group, an aralkylene group, an aralkyl group, a heteroaryl group, a ferrocenyl group, an alkenyl group, an alkoxy group, an aryloxy group or a silyl group. Group, heteroarylene group, ferrosenylene group, alkenylene group,
It represents an alkylenedioxy group, an arylenedioxy group or a silylenedioxy group. To the acetylene compound represented by the general formula [2] HP (O) (OR ³ ) R ⁴ [2] (wherein R ³ and R ⁴ are each independently an alkyl group, a cycloalkyl group, R ¹ホ ス CH ＝ CR ² [P (O) (OR ³ ) R ⁴ , characterized by reacting a hydrogenated phosphinic ester represented by an aralkyl group or an aryl group. ] _N [3] and / or general formula [4] R ¹ {C [P (O) (OR ³ ) R ⁴ ] = CHR ² } _n [4] (R ¹ , R ² , R ³ and R ⁴ Is the same as described above).

In the production method of the present invention,
The acetylene compound used is represented by the general formula [1].
R when n is 1¹And R², And when n is 2
R ²Is a hydrogen atom, an alkyl group, a cycloalkyl group,
Aryl group, aralkyl group, heteroaryl group, ferro
Cenyl, alkenyl, alkoxy, aryloxy
R represents a silyl group or a silyl group;¹Is al
Cylene, cycloalkylene, arylene, aral
Alkylene group, heteroarylene group, ferrosenylene group,
Lucenylene group, alkylenedioxy group, arylenedio
It represents a xy group or a silylenedioxy group.

In the general formulas [1], [3] and [4], when R ¹ and / or R ² is an alkyl group, the alkyl group may for example have 1 to 18 carbon atoms, preferably 1 10 to 10 linear or branched alkyl groups,
Specific examples thereof include a methyl group, an ethyl group, n- or i
so-propyl group, n-, iso-, sec- or te
rt-butyl group, n-, iso-, sec-, tert
-Or neo-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1-methylheptyl group, n-
Examples include a nonyl group and an n-decyl group. Examples of the cycloalkyl group in the case of the cycloalkyl group include a cycloalkyl group having 5 to 18 carbon atoms, preferably 5 to 12 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group. And the like. The aryl group in the case of 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 a phenyl group and a naphthyl group. (Tolyl group, xylyl group, benzylphenyl group, etc.). Examples of the heteroaryl group in the case of the heteroaryl group include various heteroaromatic ring groups containing a hetero atom such as oxygen, nitrogen, and sulfur, and the number of carbon atoms contained therein is generally 4 to 12, preferably 4 to 8 carbon atoms. is there. Specific examples thereof include a thienyl group, a furyl group, a pyridyl group, and a pyrrolyl group. The aralkyl group in the case of the aralkyl group includes, for example, 7 to 13 carbon atoms, preferably 7 carbon atoms.
To 9 aralkyl groups, and specific examples thereof include:
Examples include a benzyl group, a phenethyl group, a phenylbenzyl group, and a naphthylmethyl group. Examples of the alkenyl group in the case of the alkenyl group include an alkenyl group having 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, a 3-butenyl group, and a cyclohexenyl group. Examples of the alkoxy group in the case of the alkoxy group include an alkoxy group having 1 to 8, preferably 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, and a butoxy group. In the case of an aryloxy group, examples of the aryloxy group include an aryloxy group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, and specific examples thereof include a phenoxy group and a naphthoxy group. In the case of a silyl group, examples of the silyl group include those substituted with, for example, 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, and a t-butyldimethylsilyl group.

When n is 2, the alkylene group, cycloalkylene group, arylene group, aralkylene group, heteroarylene group, ferrosenylene group, alkenylene group, alkylenedioxy group, arylenedioxy group or silylenedioxy group represented by R ¹ is represented by R ^1. The group is a group represented by R when n is 1
^{It is selected} from divalent residues obtained by removing one hydrogen atom from 1 or divalent residues obtained by replacing one hydrogen atom with one oxygen atom, and specific examples thereof include a methylene group, a pentamethylene group, and a cyclohexyl group. Examples thereof include a silene group, a phenylene group, a naphthylene group, a furandiyl group, a ferrocenylene group, a 2-butenediyl group, a tetramethylenedioxy group, a phenylenedioxy group, and a dimethylsilylene group.

Regardless of n, R ¹ and R ² in the general formulas [1], [3] and [4] represent a functional group inert to the reaction, for example, a methoxy group, a methoxy group. It may be substituted with a carbonyl group, a cyano group, a dimethylamino group, a fluoro group, a chloro group, a hydroxy group, or the like.

Examples of the acetylene compound preferably used in the production method of the present invention include, for example, unsubstituted acetylene, methylacetylene, butyne, octyne, phenylacetylene, trimethylsilylacetylene, ethynylthiophene, hexinonitrile, cyclohexenylacetylene, 1,4-pentadiyne, Examples include, but are not limited to, 1,8-nonadiyne, diethynylbenzene, and the like.

In the production method of the present invention, the hydrogenated phosphinic ester used as a raw material is represented by the general formula [2]. Here, R ³ and R ⁴ each independently represent an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.

When R ³ and / or R ⁴ is an alkyl group, examples of the alkyl group include a linear or branched alkyl group having 1 to 8, preferably 1 to 6 carbon atoms. Examples are methyl, ethyl, n- or is
o-propyl group, n-, iso-, sec- or ter
t-butyl group, n-, iso-, sec-, tert-
Or a neo-pentyl group, an n-hexyl group, or the like. Examples of the cycloalkyl group in the case of the cycloalkyl group include a cycloalkyl group having 3 to 12 carbon atoms, preferably 5 to 12 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group,
Examples thereof include a cyclododecyl group. The aralkyl group in the case of the aralkyl group includes, for example, an aralkyl group having 7 to 13 carbon atoms, preferably 7 to 11 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a phenylbenzyl group, and a naphthylmethyl group. No. As the aryl group in the case of the aryl group, for example, the aryl group may have
4, preferably 6 to 10 aryl groups, specific examples of which include a phenyl group, a naphthyl group and the like, and further substituted substances thereof (tolyl group, xylyl group, benzylphenyl group and the like). You.

R ³ and R ⁴ in the general formulas [2], [3] and [4] are functional groups inert to the reaction, for example, methoxy, methoxycarbonyl, cyano,
It may be substituted with a dimethylamino group, a fluoro group, a chloro group, a hydroxy group, or the like.

Specific examples of suitable hydrogenated phosphinic esters include, but are not limited to, ethyl phenylphosphinate and cyclohexyl phenylphosphinate.

In general, the molar ratio of the acetylene compound to the hydrogenated phosphinic ester compound is preferably 1: 1. However, even if the molar ratio is larger or smaller, it does not inhibit the occurrence of the reaction.

In order for the reaction of the present invention to occur efficiently,
It is preferable to use a catalyst containing a metal of Group 9 or 10 of the periodic table, and a complex catalyst containing rhodium or palladium is particularly preferable. These complex catalysts may have various structures, but preferred ones are those having a low valence, and those having tertiary phosphine or tertiary phosphite as a ligand are particularly preferable. It is also a preferred embodiment to use a precursor which is easily converted to a low valence in the reaction system. Further, a tertiary phosphine or a complex containing no tertiary phosphite as a ligand is mixed with a tertiary phosphine or a phosphite in the reaction system.
A method of forming a low-valent complex having a primary phosphine or a phosphite as a ligand is also a preferred embodiment. Examples of ligands that exhibit advantageous performance by any of these methods include various tertiary phosphines and tertiary phosphites.

In the present invention, ligands which can be suitably used include, for example, triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,4-bis (diphenylphosphino) butane,
1,3-bis (diphenylphosphino) propane, 1,
2-bis (diphenylphosphino) ethane, 1,1′-
Bis (diphenylphosphino) ferrocene, trimethyl phosphite, triphenyl phosphite and the like can be mentioned.

Complexes which do not contain tertiary phosphine or tertiary phosphite as a coordinator used in combination therewith include acetylacetonatobis (ethylene) rhodium, chlorobis (ethylene) rhodium dimer, dicarbonyl (acetylacetonato ) Rhodium, hexarhodium hexadecacarbonyl, chloro (1,5-cyclooctadiene) rhodium dimer, chloro (norbornadiene) rhodium dimer, bis (dibenzylideneacetone) palladium, palladium acetate, etc.
It is not limited to these.

In addition, preferably used phosphine or phosphine is used.
As the phyllite complex, chlorocarbonyl bis (tri
Phenylphosphine) rhodium, hydridecarbonyl
Lis (triphenylphosphine) rhodium, chlorotri
(Triphenylphosphine) rhodium, bromotris
(Triphenylphosphine) rhodium [Rh (PPh ₃)
₃Br], chlorocarbonylbis (trimethylphospha
Ito) rhodium, dimethylbis (triphenylphosphite)
Palladium, dimethylbis (diphenylmethylphos)
Fin) palladium, dimethylbis (dimethylphenyl)
Phosphine) palladium [Me₂Pd (PPhM
e₂)₂], Dimethyl bis (triethylphosphine)
Radium, (ethylene) bis (triphenylphosphite)
Palladium, tetrakis (triphenylphosphine)
Palladium, dichlorobis (triphenylphosphine)
N) palladium and the like.

In addition to these complexes, it is also possible to use a simple substance of palladium or rhodium, or a catalyst in which these metals are supported on activated carbon or silica.

The amount of these catalysts used may be a so-called catalytic amount, and is generally sufficient to be 20 mol% or less based on the acetylene compound.

A palladium catalyst, a rhodium catalyst or the like exhibits activity alone, but can be used together with a phosphinic acid additive. In particular, in reactions where regioisomers occur,
Recombinant use of a phosphinic acid additive enhances regioselectivity. In such a case, it is desirable to use the phosphinic acid additive in combination. These phosphinic acids are, for example, represented by the general formula [5] HO-P (O) (R ⁵ ) ₂ [5] (In the formula, R ⁵ represents an alkyl group, a cycloalkyl group or an aryl group.)

In the general formula [5], when R ⁵ is an alkyl group, examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl and the like. Examples of the cycloalkyl group in the case of the cycloalkyl group include cycloalkyl groups having 3 to 12 carbon atoms, preferably 5 to 6 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group. As the aryl group in the case of the aryl group, for example, the aryl group may have
4, preferably 6 to 10 aryl groups, specific examples of which include a phenyl group, a naphthyl group and the like, and further substituted substances thereof (tolyl group, xylyl group, benzylphenyl group and the like). You.

The alkyl group, cycloalkyl group or aryl group represented by R ⁵ is a functional group 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.

Specific examples of the phosphinic acid used in the present invention include, for example, diphenylphosphinic acid and dimethylphosphinic acid. The amount of the phosphinic acid ester to be used is equal to or less than equimolar, preferably 0.1 to 10 mol%, based on the hydrogenated phosphinic ester used.

The reaction does not need to use a solvent, but can be carried out in a solvent if necessary. As the solvent, hydrocarbons, halogenated hydrocarbons, ethers,
Various substances such as ketones, nitriles, and esters can be used. These may 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 at room temperature to 300 ° C., because 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 performed in the range of 150 ° C.

The catalyst used in this reaction is sensitive to oxygen, and the reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon, or methane. Separation of the product from the reaction mixture is easily achieved by chromatography, distillation or recrystallization and the like.

[0029]

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

Example 1 In 2 ml of toluene, 1 mmol of ethyl phenylphosphinate, 1 mmol of 1-octyne, and Me ₂ Pd (PPhMe ₂ ) ₂ (5 mol%) as a catalyst were used. 10 mol%) and reacted at 80 ° C. for 5 hours. As a result, a mixture of ethyl phenyl [(E) -1-octen-1-yl] phosphinate and ethyl phenyl (1-octen-2-yl) phosphinate was obtained. (Ratio = 4: 96) was obtained with a yield of 96%. This compound is a novel compound not listed in the literature,
The spectral data of ethyl phenyl (1-octen-2-yl) phosphinate are as follows. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.6
9 to 7.73 (m, 2H), 7.45 to 7.46 (m,
1H), 7.39-7.41 (m, 2H), 5.91.
(Dd, 1H, J _HP = 21.4 Hz, J = 1.2H
z), 5.71 (dd, 1H, J _HP = 44.0 Hz,
1.2 Hz), 3.93 to 4.04 (m, 2H), 2.
10 to 2.13 (m, 2H), 1.34 to 1.36
(M, 2H), 1.28 (t, 3H, J = 7.0H
z), 1.13 to 1.19 (m, 4H), 0.77
(T, 3H, J = 7.0 Hz). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
42.78 (J _CP = 121.9 Hz), 132.1
2,131.83,130.73 (J _CP = 131.2
Hz), 128.47, 128.08, 60.80, 3
1.56, 31.43, 28.80, 27.91,2
2.54, 16.51, 14.04. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
3.26. HRMS as C ₁₆ H ₂₅ O ₂ P, calculated: 28
0.1592, found: 280.1581.

Example 2 To 2 ml of toluene, 1 mmol of cyclohexyl phenylphosphinate, 1 mmol of 1-octyne,
When Rh (PPh ₃ ) ₃ Br (3 mol%) was used as a catalyst and reacted at 100 ° C. for 20 hours under a nitrogen atmosphere, cyclohexyl phenyl [(E) -1-octen-1-yl] phosphinate was 98%. % Yield.

Example 3 The reaction of Example 1 was carried out without adding diphenylphosphinic acid. As a result, ethyl phenyl [(E) -1-octen-1-yl] phosphinate and phenyl (1-octene-2) were added.
-Yl) ethyl phosphinate mixture (ratio = 44: 5)
6) was obtained in a yield of 71%.

Examples 4 to 13 In the same manner as in Example 1, various alkenyl phosphinates were synthesized using various acetylene compounds. The results are summarized in Table 1.

[0034]

[Table 1]

The spectral data of these products are as follows.

[Product of Example 4] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.70
To 7.78 (m, 2H), 7.26 to 7.50 (m, 1
H), 7.39 to 7.43 (m, 2H), 6.01 to
6.30 (m, 3H), 3.99 to 4.07 (m, 1
H), 3.89-3.97 (m, 1H), 7.39-
7.43 (m, 2H), 6.01 to 6.30 (m, 3
H), 3.99-4.07 (m, 1H), 3.89-
3.97 (m, 1H), 1.27 (t, 3H, J = 7.
0 Hz). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
34.59, 132.25, 131.48, 130.6
1 (J _CP = 135.4 Hz), 129.79 (J _CP
= 133.3 Hz), 128.52, 60.80, 1
6.42. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
0.07. HRMS as C ₁₀ H ₁₃ O ₂ P, calculated: 19
6.0653, found: 196.0644.

[Product of Example 5] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.62
To 7.67 (m, 2H), 7.40 to 7.43 (m, 1
H), 7.28 to 7.34 (m, 4H), 7.17 to
7.22 (m, 3H), 6.19 (dd, 1H, J _HP
= 19.8 Hz, J = 2.5 Hz), 6.05 (dd,
3. 1H, J _HP = 40.8 Hz, J = 2.5 Hz);
11 to 3.95 (m, 2H), 1.25 (t, 3H, J
= 7.0 Hz). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
43.17 (J _CP = 124.0 Hz), 137.1
2,132.10,131.77,131.33,13
0.53 (J _CP = 135.3 Hz), 128.30,
128.23, 128.12, 127.84, 61.1
1, 16.37. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
0.74. HRMS as C ₁₆ H ₁₇ O ₂ P, calculated: 27
2.0960, found: 272.0970.

[Product of Example 6] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.68
-7.72 (m, 2H), 7.51-7.47 (m, 1
H), 7.39-7.43 (m, 2H), 5.91.
_{(D, 1H, J HP =} 20.8Hz), 5.75 (d
d, 1H, J _HP = 43.0 Hz, J = 1.2 Hz),
4.01 to 4.08 (m, 1H), 3.86 to 3.95
(M, 1H), 2.23 to 2.32 (m, 4H), 1.
76 to 1.81 (m, 2H), 1.27 (t, 3H, J
= 7.0 Hz). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
49.1, 140.7 (J _CP = 125.0 Hz), 1
32.3, 131.7, 129.8 (J _CP = 130.
99.5), 129.5, 128.5, 60.9, 30.
70, 23.9, 16.3, 16.2. . ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
2.51. HRMS as C ₁₄ H ₁₈ NO ₂ P, calculated: 26
3.1075, found: 263.1067.

[Product of Example 7] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.70
To 7.75 (m, 2H), 7.49 to 7.53 (m, 1
H), 7.39-7.45 (m, 2H), 5.79.
(D, 1H, J _HP = 44.4 Hz), 5.82 (d,
1H, J _HP = 23.45 Hz), 4.04 to 4.11.
(M, 1H), 3.88 to 4.03 (m, 1H), 3.
69 (t, 2H, J = 5.90 Hz), 3.46 (b
r, 1H), 2.55-2.36 (m, 2H), 1.2
9 (t, 3H, J = 7.0 Hz). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
40.33 (J _CP = 125.0 Hz), 132.5
0, 131.98, 130.43, 129.36 (J
_CP = 132.2 Hz), 128.58, 61.79,
61.32, 36.25, 16.38. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
5.04. HRMS as C ₁₂ H ₁₇ O ₃ P, Calculated: 24
0.0915, found: 240.0952.

[Product of Example 8] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.69
To 7.73 (m, 2H), 7.48 to 7.47 (m, 1
H), 7.42 to 7.39 (m, 2H), 5.91.
_{(D, 1H, J HP =} 21.4Hz), 5.75 (d
d, 1H, J _HP = 43.3 Hz, J = 1.2 Hz),
3.92 to 4.05 (m, 2H), 3.41 to 3.44
(M, 2H), 2.20 to 2.45 (m, 2H), 1.
85 to 1.89 (m, 2H), 1.28 (t, 3H, J
= 7.0 Hz). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
_{41.7 (J CP = 123.6Hz),} 132.2,1
31.8, 130.1 (J _CP = 131.3 Hz), 1
29.1, 128.5, 60.9, 44.0, 30.8
2,28.9,16.4. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
2.75. HRMS as C ₁₃ H ₁₈ ClO ₂ P, Calculated: 2
72.733, found: 272.0759.

[Product of Example 9] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.22
-7.32 (m, 2H), 6.90-7.03 (m, 3
H), 5.74-5.72 (m, 1H), 5.43
_{(D, 1H, J HP =} 21.2Hz), 5.39 (d,
1H, J _HP = 47.3 Hz), 3.43 to 3.95
(M, 2H), 1.61-1.53 (m, 4H), 1.
11 to 1.14 (m, 2H), 1.05 to 0.98
(M, 2H), 1.26 (t, 3H, J = 7.0H
z). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
43.3, 132.2, 131.9, 131.5, 13
1.1, 130.3, 128.3, 126.6, 27.
0, 25.8, 22.6, 21.7, 21.6, 16.
5. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ3
7.35. HRMS for C ₁₆ H ₂₁ O ₂ P, Calculated: 27
6.1279, found: 276.1274.

[Product of Example 10] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.54
To 7.47 (m, 2H), 7.25 to 7.21 (m, 1
H), 7.16 to 7.12 (m, 2H), 6.98 (d
d, 1H, J = 3.4, 0.9 Hz), 6.91 (d
d, 1H, J = 5.4, 0.9 Hz), 664 (dd,
1H, J = 3.4, 5.4 Hz), 5.99 (d, 1
H, J _HP = 38.9 Hz), 5.91 (d, 1H, J
_HP = 19.2 Hz), 3.94 to 3.84 (m, 2
H), 1.10, (t, 3H, J = 7.0 Hz). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
40.13, 138.97, 135.73, 132.2
4,131.47,129.08,128.38,12
7.59, 127.24, 125.63, 61.38,
16.38. ³¹ P NMR (201.9 MHz, CD
Cl ₃₎ δ 29.31.

[Product of Example 11] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.81
~ 7.86 (m, 2H), 7.46 to 7.62 (m, 3
H), 7.22 (dd, 1H, J _HP = 37.7 Hz,
J = 20.7 Hz), 6.55 (dd, 1H, J _HP =
29.5 Hz, J = 20.7 Hz), 4.08-4.1.
5 (m, 1H), 3.96 to 4.04 (m, 1H),
1.37 (t, 3H, J = 7.0 Hz), 0.15
(S, 9H). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
58.58, 139.50, 135.85, 135.3
5,134.60,132.23,64.49,20.
19, 1.68. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 2
9.38.

[Product of Example 12] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.67
To 7.71 (m, 4H), 7.44 to 7.47 (m, 2
H), 7.36-7.39 (m, 4H), 5.88.
_{(D, 2H, J HP =} 21.3Hz), 5.66 (d,
2H, J _HP = 43.8 Hz), 3.98-4.03.
(M, 2H), 3.89-3.94 (m, 2H), 2.
03-2.10 (m, 4H), 1.24-1.36
(M, 4H), 1.26 (t, 6H, J = 7.0H
z), 1.10-1.20 (m, 2H). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
52.50, 142.42 (J _CP = 124.0H)
z), 131.98, 131.64, 128.32, 1
27.91, 60.63, 31.16, 28.44, 2
7.52, 16.35. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
3.09. C ₂₅ H ₃₄ O ₄ HRMS as P _2, Calculated: 46
0.1932, found: 460.1869.

[Product of Example 13] ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.63
_{(D, 1H, J HP =} 21.9Hz), 7.48~7.
52 (m, 2H), 7.34 to 7.38 (m, 1H),
7.23 to 7.27 (m, 2H), 7.17 to 7.20
(M, 3H), 7.00 to 7.08 (m, 3H), 6.
94-6.96 (m, 2H), 6.88-6.90
(M, 2H), 3.97-4.11 (m, 2H), 1.
25 (t, J = 7.0 Hz, 3H). ¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 1
42.55, 135.47, 134.67, 133.9
0, 131.95, 131.83, 130.67, 13
0.18, 129.42, 128.82, 128.5
3,128.03,127.93,127.52,6
0.83, 16.34. ³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 3
0.65. HRMS as C ₂₂ H ₂₁ O ₂ P, calculated: 34
8.1279, found: 348.1273.

[0046]

Industrial Applicability The present invention provides a process for producing alkenyl phosphinic esters useful as synthetic intermediates for physiologically active substances such as pharmaceuticals and agricultural chemicals and ligands for preparing catalysts in high yield and high practicability. According to the production method of the present invention, only by reacting a hydrogenated phosphinic acid ester with acetylenes, a simple, safe, and efficient alkenyl phosphinic acid ester can be synthesized, The separation and purification of the product is also easy. Therefore, the present invention has a great effect industrially.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor, Han Li Biao 1-1-1, Higashi, Tsukuba, Ibaraki Pref. National Institute of Advanced Industrial Science and Technology Tsukuba Center −19−12 303 (72) Inventor Masato Tanaka 1-1-1 Higashi, Tsukuba City, Ibaraki Prefecture Independent Administrative Law National Institute of Advanced Industrial Science and Technology Tsukuba Center F-term (reference)

Claims (8)

[Claims] 1. A catalyst comprising a metal belonging to Group 9 or Group 10 of the periodic table, and a general formula [1] R ¹ (C≡CR ² ) _n [1] (in the formula, n is 1 or 2, and R ¹ and R ² when n is ¹ and R ² when n is ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group , Aralkyl groups,
A heteroaryl group, a ferrocenyl group, an alkenyl group, an alkoxy group, an aryloxy group or a silyl group. Further, when n is 2, R ¹ represents an alkylene group, a cycloalkylene group, an arylene group, an aralkylene group, a heteroarylene group, a ferrosenylene group, an alkenylene group, an alkylenedioxy group, an arylenedioxy group or a silylenedioxy group. Show. To the acetylene compound represented by the general formula [2] HP (O) (OR ³ ) R ⁴ [2] (wherein R ³ and R ⁴ are each independently an alkyl group, a cycloalkyl group, R ¹基 CH ＝ CR ² [P (O) (OR ³ ) R ⁴ , characterized by reacting a hydrogenated phosphinic ester represented by an aralkyl group or an aryl group. ] _N [3] and / or general formula [4] R ¹ {C [P (O) (OR ³ ) R ⁴ ] = CHR ² } _n [4] (R ¹ , R ² , R ³ and R ⁴ Is the same as described above). 2. The group 9 metal is rhodium.
The production method described in 1. 3. The method according to claim 1, wherein the Group 10 metal is palladium. 4. A catalyst comprising a metal belonging to Group 9 or 10 of the periodic table is a low-valent complex catalyst.
The production method according to any one of the above. 5. The catalyst comprising a metal of Group 9 or 10 of the periodic table is a low-valent complex having a tertiary phosphine or a tertiary phosphite as a ligand. The production method according to any one of the above. 6. The catalyst according to claim 1, wherein the catalyst comprising a metal belonging to Group 9 or 10 of the periodic table is a precursor complex that can be easily converted to a low-valent complex in a reaction system. The production method described in Crab. 7. A catalyst comprising a metal of Group 9 or 10 of the Periodic Table, wherein the catalyst comprises a tertiary phosphine or a tertiary phosphite as a ligand and a tertiary phosphine or / and / or The production according to any one of claims 1 to 3, wherein the tertiary phosphite and / or a low valence complex having a tertiary phosphite as a ligand is used in combination with a tertiary phosphite. Method. 8. The reaction represented by the general formula [5] HO—P (O) (R ⁵ ) ₂ [5] The production method according to any one of claims 1 to 7, wherein the production is performed in the presence of a phosphinic acid represented by the formula (wherein, R ⁵ represents an alkyl group, a cycloalkyl group, or an aryl group).