JP4863258B2 - Phosphorus compound and method for producing the same - Google Patents

Description

  The present invention is industrially useful, having a reactive carbon-carbon double bond, and providing a flame retardant polymer material by copolymerization with a flame retardant or other olefins or by homopolymerization of itself. The present invention relates to a novel phosphorus compound.

Conventionally, it is known that an adduct in which a carboxy group is bonded to a carbon-carbon double bond is obtained by nucleophilic addition of a pentacoordinated cyclic phosphorus hydrogen compound to an electron-deficient 2-butyric acid or ester ( Non-patent document 1).
However, this method is not general and does not apply to addition to ordinary acetylene. Moreover, what was obtained here belongs to unsaturated carboxylic acid and its derivative (s), and is not the alkenyl pentacoordinate cyclic phosphorus compound made into the object of this invention.

Phosphorus Sulfur, 1980 pages 285-292; 1982 pages 85-96

  The present invention is industrially useful, having a reactive carbon-carbon double bond, and providing a flame retardant polymer material by copolymerization with a flame retardant or other olefins or by homopolymerization of itself. It is an object to provide a novel phosphorus compound.

  In order to avoid the above-mentioned problems, the present invention has been conducted as a result of intensive studies on the reaction between a readily available pentacoordinated cyclic phosphorus hydrogen compound and an acetylene compound. The present inventors have found that a novel alkenyl pentacoordinate cyclic phosphorus compound corresponding in terms of rate and selectivity is obtained, and based on these facts, the present invention has been completed.

（R^１〜R^２は前記と同じ。）
一般式（５） HP[OC(R^３R^４)C(R^５R^６)O)][OC(R^７R^８)C(R^９R^１０)O)]で表される五配位環状リン化合物を反応させることを特徴とする、一般式（１） R^１CH＝CR^２｛P[OC(R^３R^４)C(R^５R^６)O)][OC(R^７R^８)C(R^９R^１０)O)]｝で表されるリン化合物の製造方法。
（R^１〜R^１０は、前記と同じ）
（５）パラジウム触媒の存在下、一般式（６）で表されるジアセチレン化合物に、

（R^１１〜R^１３は、前記と同じ）
一般式（５） HP[OC(R^３R^４)C(R^５R^６)O)][OC(R^７R^８)C(R^９R^１０)O)]で表される五配位環状リン化合物を反応させることを特徴とする、一般式（２） R^１１C｛P[OC(R^３R^４)C(R^５R^６)O)][OC(R^７R^８)C(R^９R^１０)O)]｝＝CH−R^１２−CH=CR^１３｛P[OC(R^３R^４)C(R^５R^６)O)][OC(R^７R^８)C(R^９R^１０)O)]｝または、一般式（３） R^１１CH=C｛P[OC(R^３R^４)C(R^５R^６)O)][OC(R^７R^８)C(R^９R^１０)O)]｝−R^１２−C｛P[OC(R^３R^４)C(R^５R^６)O)][OC(R^７R^８)C(R^９R^１０)O)]｝=CHR^１３で表されるリン化合物の製造方法。
(式中、R^３〜R^１３は、前記と同じ)
（６）酸を存在させることを特徴とする上記（４）又は（５）に記載のリン化合物の製造方法。 That is, according to this application, the following invention is provided.
(1) In formula ^{(1) R 1 CH = CR} 2 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O )]}.
(R ^{1 to} R ² are hydrogen, alkyl group, cycloalkyl group, aryl group or aralkyl group, heteroaryl group, alkenyl group, alkoxy group, aryloxy group or silyl group, and R ^{3 to} R ¹⁰ are hydrogen atoms. Represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.)
(2) General formula ^{(2) R 11 C {P} [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} in ^{= CH-R 12 -CH = CR} 13 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} Phosphorus compounds shown.
(In the formula, R ^{3 to} R ¹⁰ are the same as above. R ¹¹ and R ¹³ are hydrogen, alkyl group, cycloalkyl group, aryl group or aralkyl group, heteroaryl group, alkenyl group, alkoxy group, aryloxy group. And R ¹² represents a divalent group selected from an alkylene group, a cycloalkylylene group, and an arylene group.
(3) In formula ^{(3) R 11 CH = C} {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O) ]} − R ¹² −C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} = CHR ¹³ Phosphorus compounds shown.
(Wherein R ^{3 to} R ¹³ are the same as described above.)
(4) In the presence of a palladium catalyst, an acetylene compound represented by the following general formula (4):

(R ^{1 to} R ² are the same as above.)
Formula (5) HP [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)] pentacoordinated annular represented by General formula (1) R ¹ CH═CR ² {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ), characterized by reacting a phosphorus compound C (R ⁹ R ¹⁰ ) O)]}.
(R ^{1 to} R ¹⁰ are the same as above)
(5) In the presence of a palladium catalyst, the diacetylene compound represented by the general formula (6)

(R ^{11 to} R ¹³ are the same as above)
Formula (5) HP [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)] pentacoordinated annular represented by R ¹¹ C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R, characterized by reacting a phosphorus compound ^{9 R 10) O)]}} = CH-R 12 -CH = CR 13 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R ¹⁰ ) O)]} or general formula (3) R ¹¹ CH═C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ^{9 R 10) O)]}} - R 12 -C {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O) ]} = a manufacturing method of a phosphorus compound represented by CHR ^13.
(Wherein R ^{3 to} R ¹³ are the same as above)
(6) The method for producing a phosphorus compound as described in (4) or (5) above, wherein an acid is present.

  The phosphorus compound obtained by the present invention has a reactive carbon-carbon double bond and gives a flame retardant polymer material by copolymerization with a flame retardant or other olefins or by homopolymerization of itself. It is extremely useful industrially.

One of the phosphorus compounds according to the present invention is represented by the general formula (1) R ¹ CH═CR ² {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]}.
(Wherein R ^{1 to} R ² are hydrogen, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a silyl group, and R ^{3 to} R ¹⁰ are And represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.)

Other phosphorus compounds according to the present invention are represented by the general formula (2) R ¹¹ C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ^{9 R 10) O)]} =} CH-R 12 -CH = CR 13 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R ¹⁰ ) O)]}.

Furthermore, other phosphorus compounds according to the present invention are represented by the general formula (3) R ¹¹ CH═C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) ^{C (R 9 R 10) O} )]} - R 12 -C {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10 ) O)]} = CHR ¹³ is a phosphorus compound.
(In the formula, R ^{3 to} R ¹⁰ are the same as above. R ¹¹ and R ¹³ are hydrogen, alkyl group, cycloalkyl group, aryl group or aralkyl group, heteroaryl group, alkenyl group, alkoxy group, aryloxy group. And R ¹² represents a divalent group selected from an alkylene group, a cycloalkylylene group, and an arylene group.

General formula (1) according to the present invention R ¹ CH═CR ² {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} is a phosphorus compound (R ^{1 to} R ¹⁰ are the same as described above), for example, in the presence of a palladium catalyst, the acetylene compound represented by the general formula (4) is converted to the general formula (5). It is obtained by reacting a pentacoordinate cyclic phosphorus compound represented by

The acetylene compound used as a raw material in the present invention is represented by the general formula (4), in which R ^{1 to} R ² are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a heteroaryl group. , A monovalent group selected from an alkenyl group, an alkoxy group, an aryloxy group, and a silyl group.

The alkyl group has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, hexyl, decyl and the like.
The cycloalkyl group has 5 to 18 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples thereof include cyclohexyl, cyclooctyl, cyclododecyl and the like.

  The aryl group has 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include phenyl, naphthyl, and their substitution (tolyl, naphthyl, benzylphenyl, etc.).

  The heteroaryl group is derived from various cyclic compounds containing heteroatoms (oxygen, nitrogen, sulfur, etc.), and the number of atoms contained therein is 4 to 12, preferably 4 to 8. Specific examples thereof include thienyl group, furyl group, pyridyl group, pyrrolyl group and the like.

The aralkyl group has 7 to 13 carbon atoms, preferably 7 to 9 carbon atoms. Specific examples thereof include benzyl, phenethyl, phenylbenzyl, naphthylmethyl and the like.
The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms. Specific examples thereof include vinyl and 3-butenyl.
The alkoxy group has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples thereof include methoxy, ethoxy, butoxy and the like.
The aryloxy group has 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include phenoxy and naphthyloxy.
Examples of the silyl group include those substituted with an alkyl group, an aryl group, an aralkyl group, or an alkoxy group. Specific examples thereof include trimethylsilyl, triethylsilyl, triphenylsilyl, phenyldimethylsilyl, trimethoxysilyl and the like.

R ^{1 to} R ² may be further substituted with a functional group inert to the reaction, for example, methoxy, cyano, dimethylamino, fluoro, chloro, hydroxy and the like.

  Examples of the acetylene compound preferably used in the present invention include, but are not limited to, unsubstituted acetylene, butyne, octyne, phenylacetylene, trimethylsilylacetylene, ethynylthiophene, hexinonitrile, cyclohexenylacetylene, and the like.

The pentacoordinate cyclic phosphorus hydrogen compound used as a reaction raw material in the present invention is represented by the general formula (5), wherein R ^{3 to} R ¹⁰ are a hydrogen atom, an alkyl group, a cycloalkyl group, An aralkyl group or an aryl group;
The alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, hexyl and the like.
The cycloalkyl group has 3 to 12 carbon atoms, preferably 5 to 6 carbon atoms. Specific examples thereof include cyclohexyl, cyclooctyl, cyclododecyl and the like.
The aryl group has 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms. Specific examples thereof include phenyl, naphthyl, and their substitution (tolyl, naphthyl, benzylphenyl, etc.).

Formula according to the present invention ^{(2) R 11 C {P} [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)] ^{} = CH-R 12 -CH =} CR 13 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} Or
Formula ^{(3) R 11 CH = C} {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} - R ¹² −C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} = CHR ¹³ The phosphorus compound (R ^{3 to} R ¹³ are the same as described above) is a pentacoordinate cyclic phosphorus compound represented by the general formula (5) in the general formula (6) diacetylene compound in the presence of a palladium catalyst. It is obtained by reacting.

The diacetylene compound used as the reaction raw material is represented by the general formula (6), in which R ¹¹ and R ¹³ are hydrogen, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, A monovalent group selected from a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, and a silyl group, and R ¹² represents a divalent group selected from among an alkylene group, a cyclohexylene group, and an arylene group. .

The alkyl group has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, hexyl, decyl and the like.
The cycloalkyl group has 5 to 18 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples thereof include cyclohexyl, cyclooctyl, cyclododecyl and the like.
The aryl group has 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include phenyl, naphthyl, and substituted products thereof (tolyl, benzylphenyl, etc.).
The heteroaryl group is derived from various cyclic compounds containing heteroatoms (oxygen, nitrogen, sulfur, etc.), and the number of atoms contained therein is 4 to 12, preferably 4 to 8. Specific examples thereof include thienyl group, furyl group, pyridyl group, pyrrolyl group and the like.

The aralkyl group has 7 to 13 carbon atoms, preferably 7 to 9 carbon atoms. Specific examples thereof include benzyl, phenethyl, phenylbenzyl, naphthylmethyl and the like.
The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms. Specific examples thereof include vinyl and 3-butenyl.
The alkoxy group has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples thereof include methoxy, ethoxy, butoxy and the like.
The aryloxy group has 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include phenoxy and naphthyloxy.
Examples of the silyl group include those substituted with an alkyl group, an aryl group, an aralkyl group, or an alkoxy group. Specific examples thereof include trimethylsilyl, triethylsilyl, triphenylsilyl, phenyldimethylsilyl, trimethoxysilyl and the like.

The alkylene group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include a methylene group and a tetramethylene group.
The cycloalkylene group has 5 to 18 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples thereof include a cyclopentylene group and a cyclohexylene group.
The arylene group has 6 to 30 carbon atoms, preferably 6 to 14 carbon atoms. Specific examples thereof include a phenylene group and a naphthylene group.
Examples of the diacetylene compound preferably used in the present invention include 1,4-pentadiyne, 1,8-nonadiyne, and diethynylbenzene, but are not limited thereto.

  Further, as the pentacoordinate cyclic phosphorus hydrogen compound used as the reaction raw material, those represented by the general formula (5) can be used as they are.

In any of the above reactions, the use of a palladium catalyst is indispensable for efficiently generating the target product. As the catalyst, those having various structures can be used. For example, metallic palladium black powder, supported palladium such as silica, alumina, activated carbon, and various organic and inorganic palladium-containing compounds. Specific examples of the palladium-containing inorganic compound include palladium oxide, palladium acetate, palladium trifluoroacetate, palladium sulfate, palladium nitrate, palladium hydroxide and the like.
Moreover, although a ligand is not necessarily required, a palladium complex coordinated and stabilized by tertiary phosphine or tertiary phosphite may be used. Further, a complex not containing tertiary phosphine or tertiary phosphite as a ligand is mixed with tertiary phosphine or phosphite in the reaction system, and tertiary phosphine or phosphite is used as the ligand in the reaction system. A method of generating a complex is also a preferred embodiment.

  Examples of ligands that can be suitably used include triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,4-bis (diphenylphosphino) butane, 1,4-bis (diphenylphosphino) propane, 1 , 4-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triphenyl phosphite and the like.

  Examples of the phosphine or phosphite complex include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, dimethylbis (dimethylphenylphosphine) palladium, dimethylbis (triethylphosphine) palladium, (ethylene) bis ( Triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium and the like.

Palladium catalysts that do not contain tertiary phosphine or tertiary phosphite as a coordination, which are used in combination, include bis (dibenzylideneacetone) palladium (Pd ₂ (dba) ₃ ), bis (acetylacetone) palladium (Pd ( acac) ₂ ), palladium acetate and the like, but are not limited thereto.

  The amount of these catalysts used may be a so-called catalytic amount, and generally 20 mol% or less is sufficient with respect to the acetylene compound. The use ratio of the acetylene compound and the pentacoordinated cyclic phosphorus hydrogen compound is generally preferably 1: 1 by molar ratio, but it does not inhibit the occurrence of the reaction, even if it is larger or smaller than this. The reaction is not particularly required to use a solvent, but can be carried out in a solvent if necessary. As the solvent, a hydrocarbon-based or ether-based solvent is generally used. The reaction temperature is selected from the range of 20 ° C. to 300 ° C., preferably from room temperature 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. Implemented in a range.

  This reaction proceeds in air or in an inert gas atmosphere such as nitrogen, argon, or methane. Separation of the product from the reaction mixture is readily accomplished by chromatography, distillation or recrystallization.

  The reaction proceeds without the addition of acid, but proceeds more quickly by the presence of a catalytic amount of acid.

    The acid that can be used for this purpose can be either an organic acid or an inorganic acid. Specific examples include, but are not limited to, acetic acid, trifluoroacetic acid, diphenylphosphinic acid, phosphoric acid, sulfuric acid, and the like.

The phosphorus compounds represented by the general formulas (1) to (3) according to the present invention have a reactive carbon-carbon double bond, and are copolymerized with flame retardants and other olefins, for example. A flame retardant polymer material is obtained by homopolymerization of the polymer.
Moreover, when these phosphorus compounds are heated or hydrolyzed, the corresponding phosphorus compounds are obtained by the following hydrolysis reaction.

[1] General formula ^{(1) R 1 CH = CR} 2 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O )]} → R ¹ CH = CR ² {P (O) (OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)]}
[2] General formula (1) R ¹ CH═CR ² {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O )]} → R ¹ CH = CR ² [P (O) (OH) ₂ ]
[3] General formula ^{(2) R 11 C {P} [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} ^{= CH-R 12 -CH = CR} 13 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} → ^{R 11 C {P (O)} [OC (R 3 R 4) C (R 5 R 6) O)]} = CH-R 12 -CH = CR 13 {P (O) [OC (R 3 R 4) C (R ⁵ R ⁶ ) O)]}
[4] General formula (2) R ¹¹ C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} ^{= CH-R 12 -CH = CR} 13 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} → ^{R 11 C [P (O)} (OH) 2] = CH-R 12 -CH = CR 13 [P (O) (OH) 2]
[5] General formula ^{(3) R 11 CH = C} {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O) ]} − R ¹² −C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} = CHR ¹³ → R ¹¹ CH = C {P (O) [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)]} − R ¹² −C {P (O) [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)]} = CHR ¹³
[6] the general formula ^{(3) R 11 CH = C} {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O) ]} − R ¹² −C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} = CHR ¹³ → R ¹¹ CH = C [P (O) (OH) ₂ ] −R ¹² −C [P (O) (OH) ₂ ] = CHR ¹³
(Each symbol in the formula is the same as above)

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

Example 1
To 1 ml of toluene, 1 mmol of HP (OCMe ₂ -Me ₂ CO) _2, 1 mmol of 1-octyne and Pd (OAc) ₂ (3 mol%) as a catalyst were added and reacted at 80 ° C. for 2 hours in a nitrogen atmosphere. It was. The reaction solution was concentrated and isolated and purified by liquid chromatography to obtain 2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxa-5- (2-hexenyl) -5-phosphaspiro [4.5] nonane was obtained in 88% yield.
This compound is a novel substance not yet described in the literature, and its spectrum data is as follows.
¹ H NMR (500 MHz, CDCl ₃ ) δ0.88 (3H, t, J = 6.9 Hz), 1.14 (12H, s), 1.26 (12H, s), 1.24- 1.39 (6H, m), 1.52 (2H , quint, J = 7.5 Hz), 2.38 (2H, dd, J _HP = 10.2 Hz, J _HH = 6.7 Hz), 5.38 (1H, dd, J _HP = 55.3 Hz, J _HH = 1.5 Hz), 5.76 (1H , dd, J _HP = 25.0 Hz, J _HH = 0.9 Hz).
¹³ C NMR (125.4 MHz, CDCl ₃ ) δ 14.04, 22.60, 23.70 (4C, d, J _CP = 7.1 Hz), 24.44 (4C, d, J _CP = 5.1 Hz), 28.11 (d, J _CP = 8.3 Hz ), 29.10, 31.77, 32.77 (d, J _CP = 11.4 Hz), 78.22, 120.51 (d, J _CP = 8.3 Hz), 150.25 (d, J _CP = 204.7 Hz).
³¹ P NMR (201.9 MHz, CDCl ₃ ) δ-31.59.
Elemental analysis: calculated C, 64.14; H, 10.50. Found: C, 63.95; H, 10.49.

Examples 2-14
The results of using various acetylene compounds in the same manner as in Example 1 are summarized in Table 1. However, in the table [P] represents a _{-P (OCMe 2 -Me 2 CO)} 2.

Examples 16-24
Table 2 summarizes the results of using other Pd catalysts in place of Pd (OAc) _{2 in} the same manner as in Example 1.

Example 25
2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxa-5- (2-hexenyl) -5-phosphaspiro [4.5] nonane 1 mmol in 4 ml dioxane After dissolution, 0.3 ml of 2M hydrochloric acid was added and stirred at room temperature for 10 minutes. The reaction solution was concentrated and isolated and purified by liquid chromatography to obtain 4,4,5,5-tetramethyl-2- (2-hexenyl) -1,3-dioxa-2-phosphorane 2-oxide in a yield of 77. Obtained in%.

Example 26
2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxa-5- (2-hexenyl) -5-phosphaspiro [4.5] nonane 1 mmol in 4 ml dioxane After dissolution, 0.3 ml of 2M hydrochloric acid was added and heated at 100 ° C. for 5 hours. The solvent and volatile compound were distilled off under reduced pressure to obtain 2-methyleneoctylphosphonic acid in a yield of 95%.

Example 27
2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxa-5- (2-hexenyl) -5-phosphaspiro [4.5] nonane 1 mmol of toluene in 4 ml Dissolved and heated at 100 degrees for 3 days. The reaction solution was concentrated and isolated and purified by liquid chromatography to obtain 4,4,5,5-tetramethyl-2- (2-hexenyl) -1,3-dioxa-2-phosphorane 2-oxide in a yield of 75. Obtained in%.

Claims (6)

Formula ^{(1) R 1 CH = CR} 2 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} A phosphorus compound represented by
(R ¹ and R ² are hydrogen, alkyl group, cycloalkyl group, cyclohexenyl group, ferrocene group, aryl group or aralkyl group, heteroaryl group, alkenyl group, alkoxy group, aryloxy group, silyl group, or dimethyl phosphonate. 1 represents a monovalent group selected from an ester group, and a group other than hydrogen may be substituted with an alkoxy group, a cyano group, a dialkylamino group, a halogen atom, or a hydroxy group, R ^{3 to} R ¹⁰ And represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.) Formula ^{(2) R 11 C {P} [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} = CH- R ¹² —CH═CR ¹³ {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} Compound.
(Wherein R ^{3 to} R ¹⁰ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. R ¹¹ and R ¹³ represent hydrogen, an alkyl group, a cycloalkyl group, a cyclohexenyl group, ferrocene, Represents a monovalent group selected from a group, an aryl group or an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, a silyl group or a phosphonic acid dimethyl ester group. A group, a cyano group, a dialkylamino group, a halogen atom, or a hydroxy group, R ¹² represents a divalent group selected from an alkylene group, a cycloalkylene group, and an arylene group. Formula ^{(3) R 11 CH = C} {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)]} - R ¹² −C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ⁹ R ¹⁰ ) O)]} = phosphorus represented by CHR ¹³ Compound.
(Wherein R ^{3 to} R ¹⁰ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. R ¹¹ and R ¹³ represent hydrogen, an alkyl group, a cycloalkyl group, a cyclohexenyl group, ferrocene, Represents a monovalent group selected from a group, an aryl group or an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group, a silyl group or a phosphonic acid dimethyl ester group. A group, a cyano group, a dialkylamino group, a halogen atom, or a hydroxy group, R ¹² represents a divalent group selected from an alkylene group, a cycloalkylene group, and an arylene group. In the presence of a palladium catalyst, an acetylene compound represented by the following general formula (4):

(R ¹ and R ² are hydrogen, alkyl group, cycloalkyl group, cyclohexenyl group, ferrocene group, aryl group or aralkyl group, heteroaryl group, alkenyl group, alkoxy group, aryloxy group, silyl group, or dimethyl phosphonate. A monovalent group selected from ester groups is shown, and groups other than hydrogen may be substituted with a substituent inert to the reaction.
Formula (5) HP [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)] pentacoordinated annular represented by General formula (1) R ¹ CH═CR ² {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ), characterized by reacting a phosphorus compound C (R ⁹ R ¹⁰ ) O)]}.
(R ¹ and R ² are the same as described above. R ^{3 to} R ¹⁰ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.) The presence of a palladium catalyst, a diacetylene compound represented by the following general formula (6),

(R ¹¹ and R ¹³ are hydrogen, alkyl group, cycloalkyl group, cyclohexenyl group, ferrocene group, aryl group or aralkyl group, heteroaryl group, alkenyl group, alkoxy group, aryloxy group, silyl group, or dimethyl phosphonate. 1 represents a monovalent group selected from ester groups , among which a group other than hydrogen may be substituted with a substituent inert to the reaction, and R ¹² represents an alkylene group, a cycloalkylene group, or an arylene group. A divalent group selected from among them is shown.)
Formula (5) HP [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O)] pentacoordinated annular represented by R ¹¹ C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R, characterized by reacting a phosphorus compound ^{9 R 10) O)]}} = CH-R 12 -CH = CR 13 {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R ¹⁰ ) O)]} or general formula (3) R ¹¹ CH═C {P [OC (R ³ R ⁴ ) C (R ⁵ R ⁶ ) O)] [OC (R ⁷ R ⁸ ) C (R ^{9 R 10) O)]}} - R 12 -C {P [OC (R 3 R 4) C (R 5 R 6) O)] [OC (R 7 R 8) C (R 9 R 10) O) ]} = a manufacturing method of a phosphorus compound represented by CHR ^13.
(Wherein R ^{3 to} R ¹⁰ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. R ^{11 to} R ¹³ are the same as described above.)   6. The method for producing a phosphorus compound according to claim 4, wherein an acid is present.