JP2004075650A - Alkenyl phosphorus compound and method for producing the same - Google Patents

Abstract

An alkenyl phosphorus compound that is useful as a synthetic intermediate for a physiologically active substance such as a medicine or an agricultural chemical and that can be synthesized easily, safely, and efficiently.
A compound of the formula (1) obtained by reacting hypoacetyl acid with an acetylene compound.
R ¹ CH = CR ² [P (O) (OH) H] (1)
(In the formula, R ¹ and R ² may be the same or different and represent a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group, or a substituted silyl group.)
[Selection diagram] None

Description

【００３２】
【表２】

【００３３】
実施例２２〜２５
実施例２１の条件下、種々のアセチレンを用いて反応を行った。その結果を表３にまとめた。
【００３４】
これらの化合物は、新規化合物であり、そのスペクトルデータは以下の通りである。
【００３５】
（実施例２２の生成物）
^１ＨＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）δ７．１８（ｄ，Ｊ_{（Ｐ−Ｈ）}＝５６５Ｈｚ，１Ｈ），５．９５（ｄ，Ｊ_{（Ｐ−Ｈ）}＝２６Ｈｚ，１Ｈ），５．８７（ｄ，Ｊ_{（Ｐ−Ｈ）}＝５２Ｈｚ，１Ｈ），２．４７〜２．４１（ｍ，２Ｈ），２．３６（ｔ，Ｊ＝７Ｈｚ，２Ｈ），１．９２〜１．８６（ｍ，２Ｈ）。
^１３ＣＮＭＲ（１２５．４ＭＨｚ，ＣＤＣｌ_３）δ１４０．１（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１２２Ｈｚ），１２９．６（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１４．５Ｈｚ），１１９，２９．４（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１３Ｈｚ），２３．６（ｄ，Ｊ_{（Ｐ−Ｃ）}＝４Ｈｚ），１６．２。
^３１ＰＮＭＲ（２０１．９ＭＨｚ，ＣＤＣｌ_３）δ２６．９。
Ｃ_６Ｈ_１０ＮＯ_２ＰとしてのＨＲＭＳ、計算値：１５９．０４４９、実測値（Ｍ＋１）：１６０．０３７９。
【００３６】
（実施例２３の生成物）
^１ＨＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）δ７．１７（ｄ，Ｊ_{（Ｐ−Ｈ）}＝５６１Ｈｚ，１Ｈ），５．９８（ｄ，Ｊ_{（Ｐ−Ｈ）}＝２９Ｈｚ，１Ｈ），５．８９（ｄ，Ｊ_{（Ｐ−Ｈ）}＝４９Ｈｚ，１Ｈ），３．５７（ｔ，Ｊ＝６．４Ｈｚ，２Ｈ），２．５２〜２．４７（ｍ，２Ｈ），２．０６〜２．０１（ｍ，２Ｈ）。
^１３ＣＮＭＲ（１２５．４ＭＨｚ，ＣＤＣｌ_３）δ１４０．９（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１２２Ｈｚ），１２８．９（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１４Ｈｚ），４４．１，３０．５４（ｄ，Ｊ_{（Ｐ−Ｃ）}＝４Ｈｚ），２７．８（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１３Ｈｚ）。
^３１ＰＮＭＲ（２０１．９ＭＨｚ，ＣＤＣｌ_３）δ２７．１。
Ｃ_５Ｈ_１０ＣｌＯ_２ＰとしてのＨＲＭＳ、計算値：１６８．０１０７、実測値（Ｍ＋１）：１６９．０１７７。
【００３７】
（実施例２４の生成物）
^１ＨＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）δ７．３１〜７．１４（ｍ，５Ｈ），７．０８（ｄ，Ｊ_{（Ｐ−Ｈ）}＝５６５Ｈｚ，１Ｈ），６．００（ｄ，Ｊ_{（Ｐ−Ｈ）}＝２４Ｈｚ，１Ｈ），５．６１（ｄ，Ｊ（Ｐ−Ｈ）＝４７．５Ｈｚ，１Ｈ），３．６２（ｄ，Ｊ＝１１．３Ｈｚ，２Ｈ）。
^１３ＣＮＭＲ（１２５．４ＭＨｚ，ＣＤＣｌ３）δ１４１．９（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１２３Ｈｚ），１３６．８（ｄ，Ｊ_{（Ｐ−Ｃ）}＝７．３Ｈｚ），１２９．３５（２Ｃ），１２９．３，１２８．７（２Ｃ），１２６．７，３６．７（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１３．４Ｈｚ）。
^３１ＰＮＭＲ（２０１．９ＭＨｚ，ＣＤＣｌ３）δ２７．１。
Ｃ_９Ｈ_１１Ｏ_２ＰとしてのＨＲＭＳ，計算値：１８２．０４９７，実測値：１８２．０４９２。
【００３８】
（実施例２５の生成物）
^１ＨＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）δ７．２０（ｄ，Ｊ_{（Ｐ−Ｈ）}＝５６４Ｈｚ，１Ｈ），６．０５（ｄ，Ｊ_{（Ｐ−Ｈ）}＝２５Ｈｚ，１Ｈ），５．６１（ｄ，Ｊ_{（Ｐ−Ｈ）}＝３４Ｈｚ，１Ｈ），４．２５（ｔ，Ｊ＝６．７Ｈｚ，２Ｈ），２．６６（ｄｔ，Ｊ_{（Ｐ−Ｈ）}＝１３．７Ｈｚ，Ｊ＝６．４Ｈｚ，２Ｈ）。
^１３ＣＮＭＲ（１２５．４ＭＨｚ，ＣＤＣｌ３）δ１７８．２，１３８．７（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１２３Ｈｚ），１３０．４（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１２Ｈｚ），６２．０（ｄ，Ｊ_{（Ｐ−Ｃ）}＝４．１Ｈｚ），３８．６，３０．１（ｄ，Ｊ_{（Ｐ−Ｃ）}＝１２．４Ｈｚ），２７．１。
^３１ＰＮＭＲ（２０１．９ＭＨｚ，ＣＤＣｌ_３）δ２５．２。
Ｃ_９Ｈ_１７Ｏ_４ＰとしてのＨＲＭＳ，計算値：２２０．０８６４，実測値（Ｍ＋１）：２２１．０９０１。
【００３９】
【表３】

【００４０】
【発明の効果】
本発明に係る前記一般式（１）及び一般式（２）で表されるアルケニルリン化合物は、医薬・農薬などの生理活性物質の合成中間体として有用である。また、本発明の上記アルケニルリン化合物の合成方法は、アセチレン類に次亜リン酸を反応させるのみで、簡便、安全、かつ効率的に合成することができ、その分離精製も容易である。
従って、本発明は工業的に多大の効果をもたらす。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to alkenyl phosphorus compounds and methods for producing them.
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 easily converted to a tertiary phosphine. Tertiary phosphines are very useful compounds because they are widely used as auxiliary ligands in various catalytic reactions. Further, the compound reacts easily with a nucleophile or a radical species, and can be used for a Horner-Wittig reaction. Therefore, it is a group of compounds having high utility also in synthesizing fine chemicals.
[0002]
[Prior art]
As a method of synthesizing such an alkenyl phosphorus compound with generation of a carbon-phosphorus bond, generally, a method of substituting a corresponding alkenyl halide compound with a hydrogenated phosphinic ester or the like can be considered. 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.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel alkenyl phosphorus compound which can be easily obtained and a method for producing the same.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
[0005]
That is, according to the present invention, there are provided the following alkenyl phosphorus compounds and methods for producing the same.
(1) An alkenyl phosphorus compound represented by the following general formula (1).
Embedded image
R ¹ CH = CR ² [P (O) (OH) H] (1)
(Wherein R ¹ and R ² may be the same or different and represent a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group or a substituted silyl group)
(2) An alkenyl phosphorus compound represented by the following general formula (2).
Embedded image
R ³ {CH = CR ⁴ [P (O) (OH) H]} ₂ (2)
(Wherein, R ³ represents a divalent hydrocarbon group, and R ⁴ represents a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group, or a substituted silyl group)
(3) The following general formula (1)
Embedded image
R ¹ CH = CR ² [P (O) (OH) H] (1)
(Wherein R ¹ and R ² may be the same or different and represent a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group or a substituted silyl group)
In the method for producing an alkenyl phosphorus compound represented by the following general formula (3):
Embedded image
R ¹ C @ CR ² (3)
(Wherein R ¹ and R ² have the same meaning as described above)
Wherein the acetylene compound represented by the formula is reacted with hypophosphorous acid.
(4) The following general formula (2)
Embedded image
R ³ {CH = CR ⁴ [P (O) (OH) H]} ₂ (2)
(Wherein, R ³ represents a divalent hydrocarbon group, and R ⁴ represents a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group, or a substituted silyl group)
In the method for producing an alkenyl phosphorus compound represented by the following general formula (4):
Embedded image
R ³ (C≡CR ⁴ ) ₂ (4)
(Wherein, R ³ and R ⁴ have the same meanings as described above)
Wherein the acetylene compound represented by the formula is reacted with hypophosphorous acid.
(5) The method according to (3) or (4), wherein the reaction is performed in the presence of a metal complex catalyst.
(6) The method according to any one of (3) to (5), wherein the hypophosphorous acid is used as an aqueous solution.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
In the general formulas (1) and (3), R ¹ and R ² may be the same or different, and represent a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group, or a substituted silyl. Represents a group.
[0007]
The hydrocarbon group includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms. The aliphatic hydrocarbon group includes a linear group having 1 to 18 carbon atoms and a cyclic group having 4 to 18 carbon atoms. In the form of a chain, an alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 4 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, preferably 2 to 10, more preferably 2 to 4 carbon atoms Is included. The cyclic one includes a cycloalkyl group and a cycloalkenyl group having 4 to 18, preferably 5 to 10, and more preferably 6 to 8 carbon atoms.
[0008]
The aromatic hydrocarbon group includes an aryl group having 6 to 18, preferably 6 to 14, more preferably 6 to 10 carbon atoms, and an aryl group having 7 to 18, preferably 7 to 14, more preferably 7 to 10 carbon atoms. Alkyl groups are included.
[0009]
Specific examples of the hydrocarbon group include, for example, methyl, ethyl, propyl, hexyl, decyl, vinyl, 3-butenyl, cyclohexyl, cyclooctyl, cyclododecyl, cyclohexenyl, cyclooctynyl, phenyl, tolyl, xylyl, phenethyl, benzyl Examples include phenyl, benzyl, phenethyl, phenylbenzyl, naphthylmethyl and the like.
[0010]
The hydrocarbon group may have a substituent. Such a substituent includes a substituent inert to a reaction capable of bonding to a carbon atom, for example, a halogen atom, a hydroxyl group, a cyano group, an amino group, a substituted amino group (methylamino, dimethylamino and the like), an alkoxy group ( Methoxy, ethoxy, etc.) and alkoxycarbonyl groups (methoxycarbonyl, etc.).
[0011]
The heterocyclic group includes an aromatic heterocyclic group and an aliphatic heterocyclic group containing at least one heteroatom such as oxygen, nitrogen, and sulfur as ring constituent elements. The heterocyclic group includes a monocyclic or condensed polycyclic group. In this heterocyclic group, the number of ring-constituting elements is 4 to 12, preferably 4 to 8. Specific examples thereof include thienyl, furyl, pyridyl, quinolyl, benzothiazonyl, pyrrolinyl, piperidinyl, morphonyl, pyranyl and the like.
[0012]
In the hydrocarbon oxy group, the hydrocarbon group includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 4, and an alkenyl having 2 to 18, preferably 2 to 10, and more preferably 2 to 4 carbon atoms. Groups are included. The cyclic hydrocarbon group includes a cycloalkyl group and a cycloalkenyl group having 4 to 18, preferably 5 to 10, and more preferably 6 to 8 carbon atoms.
The aromatic hydrocarbon group includes an aryl group having 6 to 18, preferably 6 to 14, more preferably 6 to 10 carbon atoms, and an aryl group having 7 to 18, preferably 7 to 14, more preferably 7 to 10 carbon atoms. Alkyl groups are included.
[0013]
Specific examples of the hydrocarbon oxy group include an alkoxy group (methoxy, ethoxy, butoxy, etc.), an aryloxy group (phenoxy, naphthoxy, etc.), and an arylalkyloxy group (benzyloxy, phenethyloxy, naphthylmethoxy, etc.). Can be
[0014]
A substituted silyl group is one in which at least one of the hydrogen atoms bonded to the silyl group is substituted with a substituent inert to a reaction capable of bonding to silicon. The substituent includes a hydrocarbon group, a hydrocarbon oxy group and the like. In this case, the types and specific examples of the hydrocarbon group in the hydrocarbon group and the hydrocarbon oxy group include those described above.
Specific examples of the substituted silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, phenyldimethylsilyl, trimethoxysilyl, t-butyldimethylsilyl and the like.
[0015]
In the general formulas (2) and (4), R ³ represents a divalent hydrocarbon group. In this case, examples of the divalent hydrocarbon group include those obtained by removing one hydrogen atom from the monovalent hydrocarbon group described for R ¹ . Such hydrocarbon groups include alkylene groups such as methylene, tetramethylene, pentamethylene, cycloalkylene groups such as cyclohexylene, arylene groups such as phenylene and naphthylene, and arylene dialkylenes such as phenylene methylene and naphthylene dimethylene. And the like. These hydrocarbon groups may have a substituent that is inert to the reaction capable of binding to carbon.
[0016]
In the general formulas (2) and (4), R ⁴ has the same meaning as R ² shown in the general formulas (1) and (3).
[0017]
Examples of the acetylene compound preferably used in the present invention include, for example, unsubstituted acetylene, methylacetylene, butyne, octyne, phenylacetylene, trimethylsilylacetylene, ethynylthiophene, hexononitrile, cyclohexenylacetylene, 1,4-pentadiyne, 1,8-nonadiyne, Examples include but are not limited to diethynylbenzene.
[0018]
Hypophosphorous acid used as a reaction raw material in the present invention is used in the form of anhydrous or aqueous solution.
[0019]
The alkenyl phosphorus compound of the general formula (1) according to the present invention can be obtained by reacting the acetylene compound of the general formula (3) with hypophosphorous acid (H ₃ PO ₂ ).
[0020]
The alkenyl phosphorus compound of the general formula (2) according to the present invention can be obtained by reacting the acetylene compound of the general formula (4) with hypophosphorous acid (H ₃ PO ₂ ).
[0021]
When carrying out the reaction, it is preferable to use a catalyst. As the catalyst, a metal complex of Group 10 of the periodic table is preferably used. In this case, the metal includes palladium, rhodium, ruthenium, iridium, platinum and the like. As the metal complex, various known structures can be used, but preferred ones are those having a low valence (valence: 0 to 2), such as tertiary phosphine and tertiary phosphite. Is particularly preferable. It is also a preferred embodiment to use an appropriate precursor which is easily converted to a low valence in the reaction system.
[0022]
Further, a tertiary phosphine or phosphite is mixed with a tertiary phosphine or a phosphite in a reaction system, and a tertiary phosphine or a phosphite is mixed in the reaction system. A method for generating a low-valent complex is also a preferred embodiment. Examples of ligands that exhibit advantageous performance by any of these methods include various tertiary phosphines and tertiary phosphites.
[0023]
In the present invention, examples of ligands that can be suitably used include triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,4-bis (diphenylphosphino) butane, and 1,3-bis (diphenylphosphino). ) Propane, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino) ferrocene, trimethylphosphite, triphenylphosphite and the like. Examples of the metal complex containing no tertiary phosphine or tertiary phosphite as a ligand used in combination with the above include bis (dibenzylideneacetone) palladium, palladium chloride, and palladium acetate when palladium is used as the metal. And the like, but are not limited thereto.
[0024]
In addition, as the phosphine or phosphite metal complex suitably used, when palladium is used as the metal, dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, dimethylbis (dimethylphenylphosphine) palladium, Examples thereof include dimethylbis (triethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and dichlorobis (triphenylphosphine) palladium.
[0025]
The amount of these catalysts used may be a so-called catalytic amount, generally 20 mol% or less with respect to the acetylene compound is sufficient, and preferably 0.01 to 5 mol%. In general, the molar ratio of the acetylene compound to the hypophosphorous acid used is preferably 1: 1. However, if it is larger or smaller than this, it does not inhibit the occurrence of the reaction.
The reaction does not particularly require the use of a solvent, but can be carried out in a solvent if necessary. Various solvents such as hydrocarbons, halogenated hydrocarbons, ethers, ketones, nitriles, and esters can be used as the solvent. These are used alone or as a mixture of two or more.
If the reaction temperature is too low, the reaction does not proceed at an advantageous rate, and if the temperature is too high, the catalyst decomposes. Implemented in a range.
[0026]
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.
[0027]
【Example】
The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0028]
Example 1
Using 5 mmol of THF (tetrahydrofuran), 2 mmol of 30% H ₃ PO ₂ , 1 mmol of 1-octyne, and Me ₂ Pd (PPh ₃ ) ₂ (5 mol%) as a catalyst were reacted at room temperature under a nitrogen atmosphere for 24 hours. This gave (1-octen-2-yl) phosphinic acid in a yield of 75%.
This compound is a novel compound, and its spectrum data is as follows.
[0029]
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.15 (d, J _(P−H) = 558 Hz, 1 H), 5.91 (d, J _(P−H) = 25.65 Hz), 5.64 (d, J _(P−H) = 49.7 Hz), 2.33 to 2.27 (m, 2H), 1.57 to 1.51 (m, 2H), 1.36 to 1.25 (m, 6H) , 0.88 (t, J _(P−H) = 7.0 Hz, 3H).
¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 142.7 (d, J ₍ PC) = 121 Hz), 127.4 (d, J ₍ PC) = 14.5 Hz), 31.5, 30. 5 (d, J _(P-C) = 12 Hz), 28.8, 27.7 (d, J _(P-C) = 5 Hz), 22.5, 14.1.
³¹ PNMR (201.9 MHz, CDCl3) [delta] 27.7.
HRMS as C ₈ H ₁₇ O ₂ P, calculated: 176.0966, Found: 176.1000.
[0030]
Examples 2 to 21
The reaction was carried out under the same conditions as in Example 1 using various catalysts. The results are summarized in Tables 1 and 2.
[0031]
[Table 1]

[0032]
[Table 2]

[0033]
Examples 22 to 25
The reaction was carried out under the conditions of Example 21 using various acetylenes. Table 3 summarizes the results.
[0034]
These compounds are novel compounds, and their spectral data are as follows.
[0035]
(Product of Example 22)
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.18 (d, J _(P−H) = 565 Hz, 1 H), 5.95 (d, J _{(P − H)} = 26 Hz, 1 H), 5.87 (d, J _(P−H) = 52 Hz, 1H), 2.47 to 2.41 (m, 2H), 2.36 (t, J = 7 Hz, 2H), 1.92 to 1.86 (m, 2H) .
¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 140.1 (d, J ₍ PC) = 122 Hz), 129.6 (d, J ₍ PC) = 14.5 Hz), 119, 29.4 ( d, J ₍ PC ₎ = 13 Hz), 23.6 (d, J ₍ PC) = 4 Hz), 16.2.
³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 26.9.
HRMS as C ₆ H ₁₀ NO ₂ P, calculated: 159.0449, found (M + 1): 160.0379.
[0036]
(Product of Example 23)
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.17 (d, J _(P−H) = 561 Hz, 1 H), 5.98 (d, J _(P−H) = 29 Hz, 1 H), 5.89 (d, J _(P−H) = 49 Hz, 1H), 3.57 (t, J = 6.4 Hz, 2H), 2.52 to 2.47 (m, 2H), 2.06 to 2.01 (m, 2H).
¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 140.9 (d, J ₍ PC) = 122 Hz), 128.9 (d, J ₍ PC ₎ = 14 Hz), 44.1, 30.54 ( d, J ₍ PC ₎ = 4 Hz), 27.8 (d, J ₍ PC) = 13 Hz).
³¹ P NMR (201.9 MHz, CDCl ₃ ) δ 27.1.
HRMS as C ₅ H ₁₀ ClO ₂ P, calculated: 168.0107, found (M + 1): 169.0177.
[0037]
(Product of Example 24)
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.31 to 7.14 (m, 5H), 7.08 (d, J _(P−H) = 565 Hz, 1 H), 6.00 (d, J _{(P−H) )} = 24 Hz, 1H), 5.61 (d, J (P−H) = 47.5 Hz, 1H), 3.62 (d, J = 11.3 Hz, 2H).
¹³ C NMR (125.4 MHz, CDCl 3) δ 141.9 (d, J ₍ PC) = 123 Hz), 136.8 (d, J ₍ PC) = 7.3 Hz), 129.35 (2C), 129.3, 128.7 (2C), 126.7, 36.7 (d, J ₍ PC) = 13.4 Hz).
³¹ PNMR (201.9 MHz, CDCl3) [delta] 27.1.
HRMS as C ₉ H ₁₁ O ₂ P, calculated: 182.0497, Found: 182.0492.
[0038]
(Product of Example 25)
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.20 (d, J _(P−H) = 564 Hz, 1 H), 6.05 (d, J _(P−H) = 25 Hz, 1 H), 5.61 (d, J _(P−H) = 34 Hz, 1 H), 4.25 (t, J = 6.7 Hz, 2 H), 2.66 (dt, J _(P−H) = 13.7 Hz, J = 6.4 Hz, 2H).
¹³ C NMR (125.4 MHz, CDCl 3) δ 178.2, 138.7 (d, J ₍ PC) = 123 Hz), 130.4 (d, J ₍ PC ₎ = 12 Hz), 62.0 (d , J ₍ PC ₎ = 4.1 Hz), 38.6, 30.1 (d, J ₍ PC) = 12.4 Hz), 27.1.
³¹ PNMR (201.9 MHz, CDCl ₃ ) δ25.2.
HRMS as C ₉ H ₁₇ O ₄ P, calculated: 220.0864, found (M + 1): 221.0901.
[0039]
[Table 3]

[0040]
【The invention's effect】
The alkenyl phosphorus compounds represented by the general formulas (1) and (2) according to the present invention are useful as intermediates for synthesizing physiologically active substances such as medicines and agricultural chemicals. In addition, the method for synthesizing the alkenyl phosphorus compound of the present invention can be simply, safely, and efficiently synthesized only by reacting acetylene with hypophosphorous acid, and the separation and purification thereof are also easy.
Therefore, the present invention has a great effect industrially.

Claims (6)

An alkenyl phosphorus compound represented by the following general formula (1).

(Wherein R ¹ and R ² may be the same or different and represent a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group or a substituted silyl group) An alkenyl phosphorus compound represented by the following general formula (2).

(Wherein, R ³ represents a divalent hydrocarbon group, and R ⁴ represents a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group, or a substituted silyl group) The following general formula (1)

(Wherein R ¹ and R ² may be the same or different and represent a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group or a substituted silyl group)
In the method for producing an alkenyl phosphorus compound represented by the following general formula (3):

(Wherein R ¹ and R ² have the same meaning as described above)
Wherein the acetylene compound represented by the formula is reacted with hypophosphorous acid. The following general formula (2)

(Wherein, R ³ represents a divalent hydrocarbon group, and R ⁴ represents a hydrogen atom, a hydrocarbon group, a heterocyclic group, a ferrocenyl group, a hydrocarbonoxy group, a silyl group, or a substituted silyl group)
In the method for producing an alkenyl phosphorus compound represented by the following general formula (4):

(Wherein, R ³ and R ⁴ have the same meanings as described above)
Wherein the acetylene compound represented by the formula is reacted with hypophosphorous acid. The method according to claim 3, wherein the reaction is performed in the presence of a metal complex catalyst. The method according to any one of claims 3 to 5, wherein the hypophosphorous acid is used as an aqueous solution.