WO2012039473A1 - Organic phosphorus compound and method for producing same - Google Patents

Abstract

The present invention provides: an organic phosphorus compound which is represented by general formula (A) and has good heat resistance and hydrolysis resistance (moisture resistance and water absorption resistance); and a method for producing the organic phosphorus compound. The organic phosphorus compound can be used as a monomer for flame retardants or flame-retardant resins, a starting material intermediate for other organic materials or pharmaceutical and agrochemical products, an additive for industrial processing agents or the like, an additive for fertilizers, and the like. (In the formula, R¹, R², R⁴ and R⁷ each independently represents a specific substituent; p and q each independently represents a number of 0-5; r and s each independently represents a number of 0-4; R³ represents a hydrogen atom or a specific substituent; R⁵ represents a hydrogen atom or a specific substituent; and R⁶ represents a hydrogen atom or a specific substituent.)

Description

Organophosphorus compound and method for producing the same

The present invention relates to an organic phosphorus compound having an oxyphenyl group such as a hydroxyphenyl group or an alkoxyphenyl group, and a method for producing the same.

Organophosphorus compounds are chemical substances that are widely used in various products such as flame retardants, plasticizers, insecticides, medicines and agricultural chemicals, and ligands of complex catalysts.
In recent years, organic phosphorus compounds have attracted particular attention industrially as constituent materials such as flame retardants and flame retardant resins as functional materials.
So far, as a method for producing a flame retardant resin, for example, a method of mixing a low molecular compound such as a phosphorus compound with an existing resin has been reported. However, in the case of the method of mixing this low molecular weight compound into the resin, the low molecular weight compound precipitates on the resin surface or aggregates in the resin due to a phenomenon called bleed out. It is known that the physical properties of the resin may be reduced.

Therefore, in recent years, for the purpose of improving the balance between flame retardancy and other physical properties, for example, development of a flame retardant resin incorporating a phosphorus atom in a monomer skeleton, and 9,10-dihydro-9-oxa A curing agent for an epoxy resin using a compound in which a tri (hydroxyphenyl) methyl group is bonded to a phosphorus atom of -10-phosphaphenanthrene-10-oxide has been reported (for example, see Patent Documents 1 and 2). .

JP-A-5-39345 JP 2009-263363 A

However, since the compounds described in Patent Documents 1 and 2 are insufficient in heat resistance and hydrolysis resistance (moisture resistance and water absorption resistance), it is difficult to say that they are industrially suitable compounds.

The subject of the present invention is, for example, a flame retardant or flame retardant resin monomer having good heat resistance and hydrolysis resistance (moisture resistance, water absorption resistance), or other raw materials intermediates for organic materials and medical and agrochemical products, An object of the present invention is to provide an organic phosphorus compound useful as an additive for industrial processing agents, an additive for fertilizers, and the like, and a method for producing the same.

That is, this invention provides the organophosphorus compound shown by the following <1> and <2>, and its manufacturing method.
<1> An organophosphorus compound represented by the following general formula (A).

[In General Formula (A), R ¹ , R ² , R ⁴ and R ⁷ may each independently have a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or a substituent. An alkyl group, an alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group, p and q are each independently an integer of 0 to 5, and r and s are each independently 0 to 4 Is an integer. When p, q, r, and s are 2 or more, the plurality of R ¹ , R ² , R ^4, and R ⁷ may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
R ³ represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have, or a group represented by — (CH ₂ ) _n —Q ¹ is shown. Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown.
R ⁶ represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have, or a group represented by — (CH ₂ ) _m —Q ² . Here, Q ² is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^b ), An alkoxy group (—OR ^b ) or an optionally substituted phenyl group; R ^b represents an optionally substituted alkyl group; and m is an integer of 1 to 6. .
The organic phosphorus compound represented by the general formula (A) has 25 to 100 carbon atoms. ]

<2> A diarylphosphine oxide compound represented by the following general formula (1), an arylcarbonyl compound represented by the following general formula (2), and an aryl compound represented by the following general formula (3) are reacted in the presence of an acid catalyst. The manufacturing method of the organophosphorus compound shown by the following general formula (A) including the process to make.

In General Formula (1) ~ (3), R 7 R ^{1 to,} p, q, r and s are from R ¹ in the general formula ^{(A) R 7, p,} q, at r and s synonymous is there.
The diarylphosphine oxide compound represented by the general formula (1) has 12 to 46 carbon atoms, the arylcarbonyl compound represented by the general formula (2) has 7 to 32 carbon atoms, and the general formula (3) The aryl compound having an oxyl group represented by the above has 6 to 32 carbon atoms. ]

The organophosphorus compound represented by the general formula (A) of the present invention has a heat resistance characteristic of an arylphosphine oxide compound and a hydrolysis resistance (moisture resistance, resistance to resistance) derived from a molecular structure having no phosphate ester bond. It is a compound having water absorption). Therefore, the organophosphorus compound represented by the general formula (A) of the present invention is a flame retardant or flame retardant resin monomer containing the organophosphorus compound, or a raw material intermediate for various organic materials and medical and agrochemical products, industrial It is useful as an additive such as a treatment agent, and as an additive for fertilizer.
Moreover, according to the method of this invention, the organophosphorus compound shown by the said general formula (A) can be manufactured more efficiently.

4 is a thermogravimetric analysis (TG-DTA) chart of the cured phosphorus-containing resin obtained in Reference Example 1. FIG. 6 is a thermogravimetric analysis (TG-DTA) chart of the cured epoxy resin obtained in Reference Example 2. FIG.

[Organic phosphorus compound represented by formula (A)]
The organic phosphorus compound represented by the following general formula (A) of the present invention is a phosphorus-containing compound having an oxylphenyl group. The “oxylphenyl group” in the present invention is, for example, substituted with a group (oxyl group) bonded through an oxygen atom such as —OR ³ group and —OR ⁶ group in the following general formula (A). Represents a phenyl group.

(Substituents represented by R ¹ , R ² , R ⁴ and R ⁷ )
In general formula (A), R ¹ , R ² , R ⁴ and R ⁷ each represent a substituent, each independently having a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or a substituent. An alkyl group, an alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group may be used. In addition, the substituted position with respect to the benzene ring of these substituents is not specifically limited.

The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom.

The alkyl group preferably represents a linear or branched or cyclic aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and includes positional isomers. . Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, n-hexyl group, Examples thereof include a cyclohexyl group, an n-heptyl group, and an n-octyl group. Furthermore, one or more hydrogen atoms of the aliphatic hydrocarbon group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms. Specific examples of the substituted alkyl group include methoxyethyl group, methoxypropyl group, methoxybutyl group, 2-ethoxyethyl group, 2-ethoxypropyl group, 3-ethoxypropyl group, 2-ethoxybutyl group, 3-ethoxy. Butyl group, 4-ethoxybutyl group, 2-propoxyethyl group, 2-propoxypropyl group, 3-propoxypropyl group, 2-propoxybutyl group, 3-propoxybutyl group, 4-propoxybutyl group, 2-butoxyethyl group 2-butoxypropyl group, 3-butoxypropyl group, 2-butoxybutyl group, 3-butoxybutyl group, or 4-butoxybutyl group.

The alkenyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms in a straight chain, 3 to 6 carbon atoms in a branched chain, or a cyclic unsaturated aliphatic carbon having a carbon-carbon double bond. Indicates a hydrogen group and includes positional isomers. Specific examples of the alkenyl group include a vinyl group, isopropenyl group, allyl group, methallyl group, 2-butenyl group, 3-butenyl group, 2-cyclopropenyl group, 2-cyclobutynyl group, 2-cyclopentynyl group, Examples include 3-cyclopentynyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group and the like. Furthermore, one or more hydrogen atoms of the unsaturated aliphatic hydrocarbon group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms. Specific examples of the substituted alkenyl group include 4-methoxy-1-butenyl group, 4-ethoxy-1-butenyl group, 4-methoxy-2-butenyl group, 4-ethoxy-2-butenyl group, and 2-methyl. Examples include a 3-methoxy-1-propenyl group, a 2-methyl-3-ethoxy-1-propenyl group, a 4-methoxy-1-cyclohexenyl group, and a 4-ethoxy-1-cyclohexenyl group.

The alkynyl group is preferably an unsaturated aliphatic hydrocarbon group having a carbon-carbon triple bond having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Furthermore, one or more hydrogen atoms of the hydrocarbon group in the carbon-carbon triple bond may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms. Specific examples of the alkynyl group include ethynyl group and 1-propynyl group.

The alkyloxy group is preferably a group in which a linear or branched or cyclic aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms is bonded to an oxygen atom. And includes alkyl positional isomers. Specific examples of the alkyloxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropyloxy group, n-butoxy group, isobutyloxy group, cyclobutyloxy group, n-pentyloxy group and cyclopentyl. Examples thereof include an oxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, and an n-octyloxy group. Furthermore, one or more hydrogen atoms of the aliphatic hydrocarbon group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms. Specific examples of the substituted alkyloxy group include 2-methoxyethoxy group, 2-methoxypropoxy group, 3-methoxypropoxy group, 2-methoxybutoxy group, 3-methoxybutoxy group, 4-methoxybutoxy group, 2-methoxybutoxy group, Ethoxyethoxy group, 2-ethoxypropoxy group, 3-ethoxypropoxy group, 2-ethoxybutoxy group, 3-ethoxybutoxy group, 4-ethoxybutoxy group, 2-propoxyethoxy group, 2-propoxypropoxy group, 3-propoxypropoxy group Group, 2-propoxybutoxy group, 3-propoxybutoxy group, 4-propoxybutoxy group, 2-butoxyethoxy group, 2-butoxypropoxy group, 3-butoxypropoxy group, 2-butoxybutoxy group, 3-butoxybutoxy group, Or a 4-butoxybutoxy group is mentioned.

The aryl group is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. Further, one or more hydrogen atoms of the aromatic hydrocarbon group are, for example, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a halogen atom (fluorine atom, chlorine atom, bromine atom or It may be substituted with an iodine atom). The “alkyl group” and “alkyloxy group” have the same meanings as the alkyl group and alkyloxy group. Specific examples of the substituted aryl group include toluyl group, dimethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, cyclopropylphenyl group, n-butylphenyl group, t-butylphenyl group, methoxy Examples thereof include a phenyl group, an ethoxyphenyl group, an n-propoxyphenyl group, an isopropoxyphenyl group, a cyclopropoxyphenyl group, an n-butoxyphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodophenyl group. In addition, the substituted position with respect to the phenyl group of these substituents is not specifically limited. As specific examples of the substituted aryl group, a phenyl group or a naphthyl group which may have a substituent, preferably an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, more preferably carbon A phenyl group which may have a substituent with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, particularly preferably an unsubstituted phenyl group.

The aryloxy group represents a group in which the aryl group is bonded to an oxygen atom, and includes positional isomers. Specific examples of the aryloxy group include a phenyloxy group, a naphthyloxy group, and an anthranyloxy group. Furthermore, one or more hydrogen atoms of the aryl group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). In addition, the substituted position with respect to the aryloxy group of these substituents is not specifically limited.
Specific examples of the substituted aryloxy group include a toluoyloxy group, a dimethylphenyloxy group, an ethylphenyloxy group, an n-propylphenyloxy group, an isopropylphenyloxy group, a cyclopropylphenyloxy group, and an n-butylphenyloxy group. T-butylphenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, n-propoxyphenyloxy group, isopropoxyphenyloxy group, cyclopropoxyphenyloxy group, n-butoxyphenyloxy group, fluorophenyloxy group, chlorophenyl Examples thereof include an oxy group, a bromophenyloxy group, and an iodophenyloxy group.

Furthermore, in R ¹ , R ² , R ⁴ and R ⁷ of the present invention, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an alkyloxy group which may have a substituent, an allyl group which may have a substituent, an aryl group which may have a substituent, and a substituent A good aryloxy group may have one or more hydrogen atoms substituted with, for example, a halogen atom, a nitro group, a cyano group, an amino group, or a dimethylamino group.

From the above, the substituents R ¹ , R ² , R ⁴ and R ⁷ have a fluorine atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkyloxy group which may be substituted, an aryl group which may have a substituent, and an aryloxy group which may have a substituent are preferred.

p and q are each independently an integer of 0 to 5, preferably 0 or 1, more preferably 0. r and s are each independently an integer of 0 to 4, preferably 0 or 1, more preferably 0. When p, q, r, and s represent 0, it means unsubstituted. When p, q, r, and s represent an integer of 2 or more, the plurality of substituents R ¹ , R ² , R ⁴ , and R ⁷ may be the same as or different from each other. In addition, when a plurality of substituents R ¹ and R ² are each substituted by adjacent carbon atoms on the benzene ring, they are bonded to each other to form, for example, a cyclic structure such as a tetrahydroxynaphthalene ring or an alkylenedioxybenzene ring May be formed. The substituents R ¹ and R ² are preferably the same substituents.

(Substituent represented by R ³ )
In general formula (A), R ³ may have a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a group represented by — (CH ₂ ) _n —Q ¹ ; Here, Q ¹ is vinyl group, propenyl group, ethynyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group (oxiranyl group or oxetanyl group), carboxylic acid group (—COOH), carboxylic acid ester A group (—COOR ^a ), an alkoxy group (—OR ^a ), or an optionally substituted phenyl group, and R ^a represents an optionally substituted alkyl group; n represents the number of methylene groups (—CH ₂ —), and is an integer of 1 to 6, preferably 1 to 4, more preferably 1 or 2. The OR ³ group in the above general formula indicates that it is substituted with any carbon atom on the benzene ring.

The alkali metal atom is a metal atom of Group 1 of the periodic table of the elements, preferably lithium, sodium, potassium, cesium, more preferably sodium, potassium.

In R ³ , an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl which may have a substituent The group has the same meaning as that of the substituents R ¹ , R ² , R ⁴ and R ⁷ .

Examples of the phenyl group which may have a substituent include an unsubstituted phenyl group, or one or more hydrogen atoms of the phenyl group, for example, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms. A phenyl group substituted with an oxy group, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom) or the like is shown. In addition, the substituted position with respect to the phenyl group of these substituents is not specifically limited.

As the group represented by — (CH ₂ ) _n —Q ¹ in R ³ , —CH ₂ —Q ¹ , —C ₂ H ₄ —Q ¹ , —C ₃ H ₆ —Q ¹ , —C ₄ H ₈ -Q ¹ , -C ₅ H ₁₀ -Q ¹ , -C ₆ H ₁₂ -Q ¹ may be mentioned.

Q ¹ is a vinyl group, propenyl group, ethynyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group (oxiranyl group or oxetanyl group), carboxylic acid group (—COOH), carboxylic acid ester as described above. A group (—COOR ^a ), an alkoxy group (—OR ^a ), or an optionally substituted phenyl group, and R ^a represents an optionally substituted alkyl group; The alkyl group which may have a substituent in R ^a is as defined for the substituents R ¹ , R ² , R ⁴ and R ⁷ .

From Q ¹ above, specific examples of the group represented by — (CH ₂ ) _n —Q ¹ include

<When Q ¹ is a vinyl group or a propenyl group>
Allyl group, 2-propenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 2-methyl-2-propenyl group (methallyl group), 3- An alkenyl group such as a methyl-3-butenyl group, 4-methyl-4-pentenyl group, 5-methyl-5-hexenyl group, 6-methyl-6-heptenyl group, 7-methyl-7-octenyl group;

<When Q ¹ is an ethynyl group>
Alkynyl groups such as propargyl group, 3-butyne group, 4-pentyne group, 5-hexynyl group, 6-heptynyl group, 7-octynyl group;

<When Q ¹ is a hydroxyl group (—OH)>
Hydroxyalkyl groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group;

<When Q ¹ is a nitro group>
Nitroalkyl groups such as nitromethyl group, 2-nitroethyl group, 3-nitropropyl group, 4-nitrobutyl group, 5-nitropentyl group, 6-nitrohexyl group;

<When Q ¹ is a cyano group>
Cyanoalkyl groups such as cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, 5-cyanopentyl group, 6-cyanohexyl group;

<When Q ¹ is a cyclic ether group>
Oxiranyl alkyl groups such as glycidyl group, 2-oxiranylethyl group, 3-oxiranylpropyl group, 4-oxiranylbutyl group, 5-oxiranylpentyl group, 6-oxiranylhexyl group, ( 2-oxetanyl) methyl group, (3-oxetanyl) methyl group, (3-methyloxetan-3-yl) methyl group, (3-ethyloxetan-3-yl) methyl group, 2- (2-oxetanyl) ethyl group 2- (3-oxetanyl) ethyl group, 2- (3-methyloxetan-3-yl) ethyl group, 2- (3-ethyloxetan-3-yl) ethyl group, 3- (2-oxetanyl) propyl group , 3- (3-oxetanyl) propyl group, 3- (3-methyloxetanyl) propyl group, 3- (3-ethyloxetanyl) propyl group, 4- (2-oxetanyl) Butyl group, 4- (3-oxetanyl) butyl group, 4- (3-methyloxetanyl) butyl group, 4- (3-ethyloxetanyl) butyl group, 5- (2-oxetanyl) pentyl group, 5- (3- Oxetanyl) pentyl group, 5- (3-methyloxetanyl) pentyl group, 5- (3-ethyloxetanyl) pentyl group, 6- (2-oxetanyl) hexyl group, 6- (3-oxetanyl) hexyl group, 6- ( 3-methyl-oxetanyl) hexyl group, 6- (3-ethyloxetanyl) oxetanylmethyl alkyl groups such as hexyl group;

<When Q ¹ is a carboxylic acid group (—COOH)>
Hydroxycarbonylmethyl group, 2- (hydroxycarbonyl) ethyl group, 3- (hydroxycarbonyl) propyl group, 4- (hydroxycarbonyl) butyl group, 5- (hydroxycarbonyl) pentyl group, 6- (hydroxycarbonyl) hexyl group, etc. A (hydroxycarbonyl) alkyl group of

<When Q ¹ is a carboxylate group (—COOR ^a )>
Methoxycarbonylmethyl group, 2- (methoxycarbonyl) ethyl group, 3- (methoxycarbonyl) propyl group, 4- (methoxycarbonyl) butyl group, 5- (methoxycarbonyl) pentyl group, 6- (methoxycarbonyl) hexyl group, Ethoxycarbonylmethyl group, 2- (ethoxycarbonyl) ethyl group, 3- (ethoxycarbonyl) propyl group, 4- (ethoxycarbonyl) butyl group, 5- (ethoxycarbonyl) pentyl group, 6- (ethoxycarbonyl) hexyl group, Propyloxycarbonylmethyl group, 2- (propyloxycarbonyl) ethyl group, 3- (propyloxycarbonyl) propyl group, 4- (propyloxycarbonyl) butyl group, 5- (propyloxycarbonyl) pentyl group, 6- (propyl Oxycarbonyl) Xyl group, isopropyloxycarbonylmethyl group, 3- (isopropyloxycarbonyl) propyl group, 4- (isopropyloxycarbonyl) butyl group, 5- (isopropyloxycarbonyl) pentyl group, 6- (isopropyloxycarbonyl) hexyl group, butoxy Carbonylmethyl group, 2- (butoxycarbonyl) ethyl group, 3- (butoxycarbonyl) propyl group, 4- (butoxycarbonyl) butyl group, 5- (butoxycarbonyl) pentyl group, 6- (butoxycarbonyl) hexyl group, tert -Butoxycarbonylmethyl group, 2- (tert-butoxycarbonyl) ethyl group, 3- (tert-butoxycarbonyl) propyl group, 4- (tert-butoxycarbonyl) butyl group, 5- (tert-butoxycarbonyl) Pentyl group, 6- (tert-butoxycarbonyl) hexyl group (alkoxycarbonyl) alkyl group;

<When Q ¹ is an alkoxy group>
Methoxymethyl group, ethoxymethyl group, propyloxymethyl group, isopropyloxymethyl group, cyclopropyloxymethyl group, butoxymethyl group, pentyloxymethyl group, cyclopentyloxymethyl group, hexyloxymethyl group, cyclohexyloxymethyl group, 2- Methoxyethyl group, 2-ethoxyethyl group, 2-propyloxyethyl group, 2-isopropyloxyethyl group, 2-cyclopropyloxyethyl group, 2-butoxyethyl group, 2-pentyloxyethyl group, 2-cyclopentyloxyethyl Group, 2-hexyloxyethyl group, 2-cyclohexyloxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-propyloxypropyl group, 3-isopropyloxypropyl group, 3-cyclopropyloxypropyl group Pyl group, 3-butoxypropyl group, 3-pentyloxypropyl group, 3-cyclopentyloxypropyl group, 3-hexyloxypropyl group, 3-cyclohexyloxypropyl group, 3-butoxypropyl group, 4-methoxybutyl group, 4 -Ethoxybutyl group, 4-propyloxybutyl group, 4-isopropyloxybutyl group, 4-cyclopropyloxybutyl group, 4-butoxybutyl group, 4-pentyloxybutyl group, 4-cyclopentyloxybutyl group, 4-hexyl Oxybutyl group, 4-cyclohexyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-propyloxypentyl group, 5-isopropyloxypentyl group, 5-cyclopropyloxypentyl group, 5-butoxypentyl group , 5-pentyloxype Til group, 5-cyclopentyloxypentyl group, 5-hexyloxypentyl group, 5-cyclohexyloxypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-propyloxyhexyl group, 6-isopropyloxyhexyl group, Alkoxyalkyl groups such as 6-cyclopropyloxyhexyl group, 6-butoxyhexyl group, 6-pentyloxyhexyl group, 6-cyclopentyloxyhexyl group, 6-hexyloxyhexyl group, 6-cyclohexyloxyhexyl group;

<When Q ¹ is an optionally substituted phenyl group>
Benzyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, 5-phenylpentyl group, 6-phenylhexyl group, methoxybenzyl group, dimethoxybenzyl group, nitrobenzyl group, dinitrobenzyl group, etc. Examples include arylalkyl groups such as aralkyl groups (substitution positions are not particularly limited).

(Substituent represented by R ⁶ )
In general formula (A), R ⁶ may be a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a group represented by — (CH ₂ ) _m —Q ² ; Here, Q ² is vinyl group, propenyl group, ethynyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group (oxiranyl group or oxetanyl group), carboxylic acid group (—COOH), carboxylic acid ester A group (—COOR ^b ), an alkoxy group (—OR ^b ), or a phenyl group which may have a substituent, and R ^b represents an alkyl group which may have a substituent; m represents the number of methylene groups (—CH ₂ —), and is an integer of 1 to 6, preferably 1 to 4, more preferably 1 or 2.

That, R ⁶ has the same meaning as the R ^3, therefore, Q ² also has the same meaning as Q ¹ in R ^3, further R ^b have the same meanings as R ^a. Specific examples of R ⁶ also have the same meaning as R ³ .
Among the substituents represented by R ³ and R ⁶ , hydrogen atom, glycidyl group, (3-oxetanyl) methyl group, (3-methyloxetan-3-yl) methyl group, allyl group, alkali metal atom, hydroxy group are preferable. Ethyl group, more preferably hydrogen atom, glycidyl group, (3-oxetanyl) methyl group, (3-methyloxetan-3-yl) methyl group, allyl group, hydroxyethyl group, particularly preferably hydrogen atom, glycidyl group, allyl group Group, a hydroxyethyl group. Further, the substituents R ⁶ and R ³ may be the same or different from each other.

(Substituent represented by R ⁵ )
In general formula (A), R ⁵ is a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyloxy group having 1 to 6 carbon atoms, which may have a substituent having 1 to 6 carbon atoms. An alkyl group, or a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may have a substituent which is an alkyloxy group having 1 to 6 carbon atoms is shown.
Here, the alkyl group having 1 to 6 carbon atoms which may have a substituent represents a linear or branched or cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a regioisomer. Including. Furthermore, one or more hydrogen atoms of the alkyl group having 1 to 6 carbon atoms may be substituted with a halogen atom, a nitro group, a cyano group, or an alkyloxy group having 1 to 6 carbon atoms. The aryl group having 6 to 12 carbon atoms which may have a substituent is an aromatic hydrocarbon group, and one or more hydrogen atoms of the aryl group having 6 to 12 carbon atoms may be substituted with a nitro group. , A cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkyloxy group having 1 to 6 carbon atoms.
As R ⁵ , specifically, “an alkyl group which may have a substituent” or “having a substituent” in R ¹ , R ² , R ⁴ and R ⁷ described above for the general formula (A). Are optionally synonymous with “aryl group”, preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group, more preferably a hydrogen atom. An atom or a methyl group.

(The number of carbon atoms of the organophosphorus compound represented by the general formula (A))
The organic phosphorus compound represented by the general formula (A) has 25 to 100 carbon atoms.
Regarding the organophosphorus compound represented by the general formula (A) of the present invention, compounds having various carbon numbers by using various combinations of substituents are used as components of the various flame retardants or flame retardant resins. However, according to the production method of the present invention described later, an organic phosphorus compound having 25 to 100 carbon atoms represented by the general formula (A) can be suitably obtained.

[Method for producing organophosphorus compound represented by formula (A)]
The organophosphorus compound represented by the general formula (A) of the present invention can be produced by the method represented by the reaction formula [I] including the following steps 1 and 2. Specifically, it can be produced by two methods: Method 1 in which the following Step 2 is performed after performing the following Step 1, and Method 2 in which the following Steps 1 and 2 are simultaneously performed. According to this method, the organophosphorus compound represented by the general formula (A) of the present invention can be obtained by an industrially suitable method with high yield and high purity. Here, in reaction formula ^{(I), R 1 ~ R 7, p} , q, r and s, R ¹ ~ R ^7, p in the general formula (A), q, have the same meanings as r and s, thus The preferred range is also the same.

≪Method 1≫
<Step 1>
In the step 1, the diarylphosphine oxide compound represented by the general formula (1) is reacted with the arylcarbonyl compound having an oxyl group represented by the general formula (2) to obtain the phosphorus represented by the general formula (B). It is a process for producing a containing aryl alcohol compound.

<Diarylphosphine oxide compound represented by general formula (1)>
In step 1, the diarylphosphine oxide compound represented by the general formula (1) is used as a raw material for synthesis. In the general formula (1), R ¹ , R ² , p and q are synonymous with R ¹ , R ² , p and q described above for the general formula (A), and the preferred ranges are also the same.

Specific examples of the diarylphosphine oxide compound represented by the general formula (1) include diphenylphosphine oxide, bis (4-fluorophenyl) phosphine oxide, bis (4-chlorophenyl) phosphine oxide, and bis (4-nitrophenyl) phosphine oxide. Bis (4-dimethylaminophenyl) phosphine oxide, bis (4-cyanophenyl) phosphine oxide, bis (toluyl) phosphine oxide, bis (4-allylphenyl) phosphine oxide, bis (4-methoxyphenyl) phosphine oxide, bis (4-biphenyl) phosphine oxide, bis (4-phenoxyphenyl) phosphine oxide and the like.

The diarylphosphine oxide compound represented by the general formula (1) has 12 to 46 carbon atoms.

<Arylcarbonyl compound having an oxyl group represented by the general formula (2)>
In step 1, an arylcarbonyl compound having an oxyl group represented by the general formula (2) together with the diarylphosphine oxide compound represented by the general formula (1) is used as a synthesis raw material. In the general formula (2), R ³ to R ⁵ and r have the same meanings as R ³ to R ⁵ and r described above for the general formula (A), and the preferred ranges are also the same.

Specific examples of the arylcarbonyl compound represented by the general formula (2) include 4-hydroxybenzaldehyde, 4-hydroxyphenyl methyl ketone, 4-hydroxyphenyl ethyl ketone, 4-hydroxyphenyl propyl ketone, 4-hydroxyphenyl isopropyl ketone, 4-hydroxyphenylcarbonyl compounds having 7 to 32 carbon atoms such as 4-hydroxyphenylbutylketone;

4-methoxybenzaldehyde, 4-methoxyphenyl methyl ketone, 4-methoxyphenyl ethyl ketone, 4-methoxyphenyl propyl ketone, 4-methoxyphenyl isopropyl ketone, 4-methoxyphenyl butyl ketone, etc. Alkoxyphenylcarbonyl compounds;

4- (2-hydroxyethoxy) benzaldehyde, 4- (2-hydroxyethoxy) phenyl methyl ketone, 4- (2-hydroxyethoxy) phenyl ethyl ketone, 4- (2-hydroxyethoxy) phenyl propyl ketone, 4- (2 A 4- (2-hydroxyalkoxy) phenylcarbonyl compound having 9 to 32 carbon atoms, such as -hydroxyethoxy) phenylisopropylketone and 4- (2-hydroxyethoxy) phenylbutylketone;

4-vinyloxybenzaldehyde, 4-vinyloxyphenyl methyl ketone, 4-vinyloxyphenyl ethyl ketone, 4-vinyloxyphenyl propyl ketone, 4-vinyloxyphenyl isopropyl ketone, 4-vinyloxyphenyl butyl ketone, 4-propenyloxy Carbon such as benzaldehyde, 4-propenyloxyphenyl methyl ketone, 4-propenyloxyphenyl ethyl ketone, 4-propenyloxyphenyl propyl ketone, 4-propenyloxyphenyl isopropyl ketone, 4-propenyloxyphenyl butyl ketone, 4-propenyloxybenzaldehyde A 4- (alkenyloxy) phenylcarbonyl compound having a number of 9 to 32;

Carbon numbers such as 4-allyloxybenzaldehyde, 4-allyloxyphenyl methyl ketone, 4-allyloxyphenyl ethyl ketone, 4-allyloxyphenyl propyl ketone, 4-allyloxyphenyl isopropyl ketone, 4-allyloxyphenyl butyl ketone, etc. 10-32 4- (allyloxy) phenylcarbonyl compounds;

4-ethynyloxybenzaldehyde, 4-ethynyloxyphenyl methyl ketone, 4-ethynyloxyphenyl ethyl ketone, 4-ethynyloxyphenyl propyl ketone, 4-ethynyloxyphenyl isopropyl ketone, 4-ethynyloxyphenyl butyl ketone, 4-ethynyloxy Benzaldehyde, 4-ethynyloxyphenyl methyl ketone, 4-ethynyloxyphenyl ethyl ketone, 4-ethynyloxyphenyl propyl ketone, 4-ethynyloxyphenyl isopropyl ketone, 4-ethynyloxyphenyl butyl ketone, etc. having 9 to 32 carbon atoms 4- (ethynyloxy) phenylcarbonyl compound;

3-hydroxybenzaldehyde, 3-hydroxyphenyl methyl ketone, 3-hydroxyphenyl ethyl ketone, 3-hydroxyphenyl propyl ketone, 3-hydroxyphenyl isopropyl ketone, 3-hydroxyphenyl butyl ketone, etc. Hydroxyphenylcarbonyl compounds;

3-methoxybenzaldehyde, 3-methoxyphenyl methyl ketone, 3-methoxyphenyl ethyl ketone, 3-methoxyphenyl propyl ketone, 3-methoxyphenyl isopropyl ketone, 3-methoxyphenyl butyl ketone, etc. Alkoxyphenylcarbonyl compounds;

3- (2-hydroxyethoxy) benzaldehyde, 3- (2-hydroxyethoxy) phenyl methyl ketone, 3- (2-hydroxyethoxy) phenyl ethyl ketone, 3- (2-hydroxyethoxy) phenyl propyl ketone, 3- (2 A 3- (2-hydroxyalkoxy) phenylcarbonyl compound having 9 to 32 carbon atoms, such as -hydroxyethoxy) phenylisopropylketone and 3- (2-hydroxyethoxy) phenylbutylketone;

3-vinyloxybenzaldehyde, 3-vinyloxyphenyl methyl ketone, 3-vinyloxyphenyl ethyl ketone, 3-vinyloxyphenyl propyl ketone, 3-vinyloxyphenyl isopropyl ketone, 3-vinyloxyphenyl butyl ketone, 3-allyloxy Benzaldehyde, 3-propenyloxybenzaldehyde, 3-propenyloxyphenyl methyl ketone, 3-propenyloxyphenyl ethyl ketone, 3-propenyloxyphenyl propyl ketone, 3-propenyloxyphenyl isopropyl ketone, 4-propenyloxyphenyl butyl ketone, 3- 3- (alkenyloxy) phenylcarbonyl compounds having 9 to 32 carbon atoms such as propenyloxybenzaldehyde;

3- (allyloxy) phenylcarbonyl compounds having 10 to 32 carbon atoms such as 3-allyloxybenzaldehyde, 3-allyloxyphenyl methyl ketone, 3-allyloxyphenyl ethyl ketone, 3-allyloxyphenyl propyl ketone;

3-ethynyloxybenzaldehyde, 3-ethynyloxyphenyl isopropyl ketone, 3-ethynyloxyphenyl butyl ketone, 3-ethynyloxybenzaldehyde, 3-ethynyloxyphenyl methyl ketone, 3-ethynyloxyphenyl ethyl ketone, 3-ethynyloxyphenylpropyl 3- (ethynyloxy) phenylcarbonyl compounds having 9 to 32 carbon atoms, such as ketone, 3-ethynyloxyphenyl isopropyl ketone, 3-ethynyloxyphenyl butyl ketone;

2-hydroxybenzaldehyde, 2-hydroxyphenylmethylketone, 2-hydroxyphenylethylketone, 2-hydroxyphenylpropylketone, 2-hydroxyphenylisopropylketone, 2-hydroxyphenylbutylketone, etc. Hydroxyphenylcarbonyl compounds;

2-methoxybenzaldehyde, 2-methoxyphenyl methyl ketone, 2-methoxyphenyl ethyl ketone, 2-methoxyphenyl propyl ketone, 2-methoxyphenyl isopropyl ketone, 2-methoxyphenyl butyl ketone, etc. Alkoxyphenylcarbonyl compounds;

2- (2-hydroxyethoxy) benzaldehyde, 2- (2-hydroxyethoxy) phenyl methyl ketone, 2- (2-hydroxyethoxy) phenyl ethyl ketone, 2- (2-hydroxyethoxy) phenyl propyl ketone, 2- (2 A 2- (2-hydroxyalkoxy) phenylcarbonyl compound having 9 to 32 carbon atoms, such as -hydroxyethoxy) phenylisopropylketone and 2- (2-hydroxyethoxy) phenylbutylketone;

2- (vinyloxy) benzaldehyde, 2- (vinyloxy) phenylmethylketone, 2- (vinyloxy) phenylethylketone, 2- (vinyloxy) phenylpropylketone, 2- (vinyloxy) phenylisopropylketone, 2- (vinyloxy) phenylbutyl Ketone, 2- (allyloxy) benzaldehyde, 2- (propenyloxy) benzaldehyde, 2- (propenyloxy) phenylmethylketone, 2- (propenyloxy) phenylethylketone, 2- (propenyloxy) phenylpropylketone, 2- ( 2- (alkenyloxy) phenyl having 9 to 32 carbon atoms, such as propenyloxy) phenyl isopropyl ketone, 2- (propenyloxy) phenyl butyl ketone, 2- (propenyloxy) benzaldehyde Carbonyl compounds;

2- (allyloxy) phenylcarbonyl compounds having 10 to 32 carbon atoms such as 2- (allyloxy) benzaldehyde, 2- (allyloxy) phenyl methyl ketone, 2- (allyloxy) phenyl ethyl ketone, 2-allyloxyphenyl propyl ketone;

2- (ethynyloxy) benzaldehyde, 2- (ethynyloxy) phenyl isopropyl ketone, 2- (ethynyloxy) phenyl butyl ketone, 2- (ethynyloxy) benzaldehyde, 2- (ethynyloxy) phenyl methyl ketone, 2- (ethynyl) 2- (ethynyloxy) having 9 to 32 carbon atoms such as oxy) phenyl ethyl ketone, 2- (ethynyloxy) phenyl propyl ketone, 2- (ethynyloxy) phenyl isopropyl ketone and 2- (ethynyloxy) phenyl butyl ketone A phenyl carbonyl compound is mentioned.

The arylcarbonyl compound represented by the general formula (2) has 7 to 32 carbon atoms.

The amount of the arylcarbonyl compound represented by the general formula (2) used in the step 1 is not particularly limited, but in consideration of the stirring property during the reaction, the efficiency of removal after the reaction, the production cost, etc., the general formula (1 ) Is preferably 0.8 to 10 mol, more preferably 1 to 5 mol, still more preferably 1 to 2.5 mol, and particularly preferably 1 to 1.25 mol, relative to 1 mol of the diarylphosphine oxide compound represented by It is.

<Organic solvent>
The reaction of step 1 may be performed under the conditions in the absence or presence of an organic solvent.

The organic solvent is not particularly limited as long as it does not inhibit the reaction. For example, diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,2-dimethoxyethane, etc. Ethers; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenation such as methylene chloride and 1,2-dichloroethane Aliphatic hydrocarbons; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N'-dimethylimidazolidinone; chlorobenzene, 1,2-dichlorobenzene, 1, 3-dichlorobenzene, 1,4-dichlorobenzene, etc. Genated aromatic hydrocarbons; Nitrated aromatic hydrocarbons such as nitrobenzene; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Nitriles such as acetonitrile, propionitrile, benzonitrile; Methyl acetate, Ethyl acetate And at least one solvent selected from the group consisting of aliphatic carboxylic acid esters such as butyl acetate and ethyl propionate.

The organic solvent that can be used in Step 1 is preferably at least one solvent selected from the group consisting of ethers, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, nitriles, or aliphatic carboxylic acid esters, and more preferably. At least one solvent selected from the group consisting of tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, toluene, dichloromethane, and 1,2-dichloroethane is used.

The amount of the organic solvent used is appropriately determined depending on the uniformity of the reaction solution, the stirring ability, etc., but is preferably 0.1 to 1000 mL, based on 1 g of the diarylphosphine oxide compound represented by the general formula (1). The amount is preferably 0.5 to 750 mL, more preferably 1 to 500 mL, and particularly preferably 1 to 100 mL.

<Reaction conditions; reaction temperature, reaction pressure, etc.>
The reaction of step 1 is performed by mixing the raw material compounds and stirring. The reaction temperature is not particularly limited, but is preferably 0 to 150 ° C, more preferably 10 to 130 ° C. The reaction pressure is not particularly limited, and the reaction environment may be an open system environment, or an inert gas atmosphere such as argon or nitrogen gas, or an air stream.

<Phosphorus-containing aryl alcohol compound represented by formula (B)>
By the step 1, the phosphorus-containing aryl alcohol compound represented by the general formula (B) can be produced. In the general formula ^{(B), R 1 ~ R} 5, p, q and r are the general formula (1) R ¹ in and ^{(2) ~ R 5, p} , it is synonymous with q and r.

After completion of the reaction in Step 1, the obtained reaction solution is subjected to neutralization, liquid separation, washing with water, etc., distillation, recrystallization, column chromatography, etc., and the phosphorus-containing aryl represented by the general formula (B). Although the alcohol compound can be isolated and purified, it may be used in Step 2 without performing these isolation and purification operations.

The phosphorus-containing aryl alcohol compound represented by the general formula (B) can be used not only as a raw material for producing the organic phosphorus compound having an oxyl group represented by the general formula (A), but also, for example, a flame retardant phenol resin Flame retardant epoxy resin, flame retardant polyester, flame retardant polyamide, flame retardant polyether, flame retardant polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, flame retardant poly At least one flame retardant resin selected from the group consisting of alkylene resins, preferably flame retardant phenol resin, flame retardant epoxy resin, flame retardant polyester, flame retardant polyamide, flame retardant polyether, flame retardant Less selected from the group consisting of polycarbonate, flame retardant polycarbonate diol and flame retardant polyurethane It is also useful as one flame retardant resin of raw material (monomer). Moreover, from the group which consists of a flame retardant which uses the organophosphorus compound which has an oxyl group shown by the said general formula (B) as a flame retardant component, or an electric insulation oil, a heat-medium oil, peeling oil, rubber processing oil, rock drill oil It can also be used as an additive for at least one selected industrial lubricating oil, an additive for fertilizer, and the like.

<Step 2>
In the step 2, the phosphorus-containing aryl alcohol compound represented by the general formula (B) is reacted with the aryl compound having an oxyl group represented by the general formula (3) in the presence of an acid catalyst, and the general formula ( This is a step for producing an organophosphorus compound having an oxyl group represented by A).

<Phosphorus-containing aryl alcohol compound represented by formula (B)>
In step 2, the phosphorus-containing aryl alcohol compound represented by the general formula (B) is used as a raw material. This compound can be obtained by the step 1 of the above reaction formula [I]. The reaction solution after completion of the step 1 can be used as it is, or it can be isolated and purified. Either one is acceptable.

<Aryl compound having an oxyl group represented by the general formula (3)>
In step 2, an aryl compound having an oxyl group represented by the general formula (3) is used together with the phosphorus-containing aryl alcohol compound represented by the general formula (B). In the general formula (3), R ^6, R ⁷ and s is the general formula (A) has the same meaning as R ^6, R ⁷ and s as described above for, the preferred range is also the same. However, R ⁷ is bonded only to the ortho (o-) or meta (m-) position with respect to the oxyl group (—OR ⁶ ).

Specific examples of the aryl compound represented by the general formula (3) include phenol, catechol, resorcinol, anisole, guaiacol, (o- or m-) cresol, (o- or m-) ethylphenol, (o- or m-) n-propylphenol, (o- or m-) isopropylphenol, (o- or m-) n-butylphenol, (o- or m-) dimethylphenol, (o- or m-) diethylphenol, ( o- or m-) bromophenol, (o- or m-) iodophenol, 2,3-dibromophenol, 2,5-dibromophenol, 3,5-dibromophenol, 2,3-diiodophenol, 2, 5-diiodophenol, 3,5-diiodophenol, 3-methoxycatechol, 4-methoxycatechol, 2- Toki Sile sol maytansinol, 4-methoxy resorcinol, (o-or m-) cyanophenol, (o-or m-) nitro phenol, (o-or m-) dimethyl aminophenol.

The aryl compound having an oxyl group represented by the general formula (3) has 6 to 32 carbon atoms.

The amount of the aryl compound represented by the general formula (3) used in the step 2 is not particularly limited. However, from the viewpoints of stirring property during the reaction, removal efficiency after the reaction, production cost, and the like, the general formula ( The amount of the phosphorus-containing aryl alcohol compound represented by B) is preferably 0.1 to 100 mol, more preferably 0.8 to 50 mol, still more preferably 1.0 to 10 mol, particularly preferably 1 to 1 mol. 5 moles are used.

In addition, when using the reaction liquid after completion | finish of the said process 1 for the process 2 as it is, the usage-amount of the aryl compound shown by the said General formula (3) is 1 mol of diaryl phosphine oxide compounds shown by the said General formula (1). Is preferably 0.1 to 100 mol, more preferably 0.8 to 50 mol, still more preferably 1.0 to 10 mol, and particularly preferably 1 to 5 mol.

<Acid catalyst>
Examples of the acid catalyst used in step 2 include organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid; organic carboxylic acids such as acetic acid and oxalic acid; trifluoroacetic acid, trichloro Carboxylic acid having alkyl group substituted with halogen atom such as acetic acid; Inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid; Boron trifluoride, boron trichloride, aluminum chloride, zinc chloride, zinc bromide, iron (III) chloride And Lewis acidic compounds such as iron (III) bromide, titanium tetrachloride, tin chloride, tin triflate, scandium triflate, copper triflate, samarium triflate, and bismuth triflate. In addition, these acid catalysts can be used individually or in mixture of 2 or more types.

As the acid catalyst, preferably, the above-mentioned inorganic acid, organic sulfonic acid, organic carboxylic acid, carboxylic acid having an alkyl group substituted with a halogen atom, Lewis acidic compound, more preferably hydrochloric acid, sulfuric acid, organic sulfonic acid, halogen Carboxylic acid having an alkyl group substituted with an atom, Lewis acidic compound, more preferably hydrochloric acid, sulfuric acid, organic sulfonic acid, carboxylic acid having an alkyl group substituted with a halogen atom, particularly preferably sulfuric acid, benzenesulfonic acid, p Toluene sulfonic acid, camphor sulfonic acid, methane sulfonic acid, trifluoroacetic acid, trichloroacetic acid are used. In addition, these acid catalysts can be used individually or in mixture of 2 or more types.

The amount of the acid catalyst used in step 2 is not particularly limited, but from the viewpoint of the stirring property during the reaction and the efficiency of the isolation / purification operation after the reaction, 1 mol of the phosphorus-containing aryl alcohol compound represented by the formula (B) The amount is preferably 0.001 to 0.98 mol, more preferably 0.003 to 0.50 mol, and still more preferably 0.005 to 0.25 mol.

<Organic solvent>
The reaction of step 2 can be carried out under the conditions in the absence or presence of an organic solvent. In addition, the kind and the usage-amount of the organic solvent which can be used at the process 2 are the same as the said process 1.

<Reaction conditions; reaction temperature, reaction pressure, etc.>
The reaction in step 2 is performed by mixing the raw material compounds and stirring. The reaction temperature is not particularly limited, but is preferably 0 to 200 ° C, more preferably 25 to 150 ° C, still more preferably 40 to 130 ° C, and particularly preferably 50 to 130 ° C. The reaction pressure is not particularly limited, and the reaction atmosphere (reaction environment) may be an open system, or may be an inert gas atmosphere such as argon or nitrogen gas, or an air stream.

<Acquisition method of organophosphorus compound having oxyl group represented by general formula (A)>
After completion of the reaction in Step 2, the resulting reaction solution contains an organophosphorus compound having an oxyl group represented by the general formula (A), which is the target product. The organic phosphorus compound represented by the general formula (A) is obtained from the obtained reaction solution by, for example, neutralization, separation, washing with water, etc., distillation, recrystallization, or column chromatography, etc. Can also be performed. In addition, since it may be acquired as a solid by adding a precipitation solvent separately to the obtained reaction liquid, it is useful as an industrial manufacturing method.

<Precipitating solvent>
The precipitation solvent to be used is not particularly limited as long as it does not react with the organophosphorus compound represented by the general formula (A), which is the target product. For example, n-pentane, n-hexane, n- Aliphatic hydrocarbons such as heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, propanol, isopropanol and butanol; diethyl ether, diisopropyl ether, t-butyl methyl ether, Ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,2-dimethoxyethane; halogenated aromatics such as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene Hydrocarbons; methylene chloride, 1,2-dic Halogenated aliphatic hydrocarbons such as Roetan; acetonitrile, propionitrile, nitriles such as benzonitrile; methyl acetate, ethyl acetate, butyl acetate, aliphatic carboxylic acid esters or water, such as ethyl propionate. In addition, these precipitation solvent can be used individually or in mixture of 2 or more types.

The precipitation solvent in Step 2 of the present invention is preferably the above-mentioned aliphatic hydrocarbons, aromatic hydrocarbons, ethers, nitriles, aliphatic carboxylic acid esters, water, more preferably n-pentane, One selected from the group consisting of n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, diethyl ether, diisopropyl ether, t-butyl methyl ether, acetonitrile, ethyl acetate, methanol, ethanol, propanol, isopropanol and water One or more solvents selected from the group consisting of the above solvents, particularly preferably n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, acetonitrile, ethyl acetate, methanol, ethanol and water are used.

The amount of the precipitation solvent used is appropriately determined depending on the uniformity of the reaction solution, the stirring ability, etc., but is preferably 0.1 to 500 mL, more preferably 1 g of the organophosphorus compound represented by the general formula (A). Is 0.5 to 300 mL, more preferably 1 to 150 mL, and particularly preferably 1 to 100 mL.

<< Method 2 >>
Method 2 is a method in which Steps 1 and 2 are simultaneously performed, that is, in the presence of an acid catalyst, the diarylphosphine oxide compound represented by the general formula (1) and the arylcarbonyl represented by the general formula (2). In this method, the compound and the aryl compound represented by the general formula (3) are reacted.

In Method 2, the type and amount of the diarylphosphine oxide compound represented by General Formula (1) and the arylcarbonyl compound represented by General Formula (2) used are the same as those described in Step 1 of Method 1. The same.

In Method 2, the type of the aryl compound represented by the general formula (3) used is the same as that described in Step 2 of Method 1.

Further, the amount of the aryl compound represented by the general formula (3) is not particularly limited, but for example, from the viewpoint of the stirring property during the reaction, the efficiency of removal after the reaction, the production cost, etc. The amount is preferably 0.1 to 100 mol, more preferably 0.8 to 50 mol, more preferably 1.0 to 10 mol, particularly preferably 1 to 1 mol with respect to 1 mol of the diarylphosphine oxide compound represented by (1). 5 moles are used. The aryl compound represented by the general formula (3) can be easily recovered after completion of the reaction of the present invention. Therefore, in the present invention, the aryl compound represented by the general formula (3) may be recovered and reused.

In Method 2, the type of acid catalyst used is the same as that described in Step 2 of Method 1 above.

The amount of the acid catalyst used is not particularly limited. For example, the diarylphosphine oxide compound 1 represented by the general formula (1) is used from the viewpoint of the stirring ability during the reaction and the efficiency of the isolation / purification operation after the reaction. The amount is preferably 0.001 to 0.98 mol, more preferably 0.003 to 0.50 mol, and still more preferably 0.005 to 0.25 mol, relative to mol.

In Method 2, the mixing order of the diarylphosphine oxide compound represented by the general formula (1), the arylcarbonyl compound represented by the general formula (2), the aryl compound represented by the general formula (3), and the acid catalyst is as follows. Although not particularly limited, an acid is added after adding the diarylphosphine oxide compound represented by the general formula (1), the arylcarbonyl compound represented by the general formula (2), and the aryl compound represented by the general formula (3). It is preferred to add a catalyst.

In Method 2, the reaction conditions and post-treatment operations after the completion of the reaction are the same as those described in Step 2 of Method 1.

(Use of organophosphorus compound represented by general formula (A))
The organophosphorus compound represented by the general formula (A) of the present invention is, for example, a flame retardant phenol resin, a flame retardant epoxy resin, a flame retardant polyester, a flame retardant polyamide, a flame retardant polyether, or a flame retardant. At least one flame retardant resin selected from the group consisting of polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, and flame retardant polyalkylene resin, preferably flame retardant phenolic resin, flame retardant At least one flame retardant resin selected from the group consisting of a flame retardant epoxy resin, a flame retardant polyester, a flame retardant polyamide, a flame retardant polyether, a flame retardant polycarbonate, a flame retardant polycarbonate diol, and a flame retardant polyurethane. It is useful as a production raw material (monomer).
Moreover, from the group which consists of a flame retardant which uses the organophosphorus compound which has an oxyl group shown by the said general formula (A) as a flame retardant component, or an electric insulation oil, a heat medium oil, peeling oil, rubber processing oil, and rock drill oil It can be used as an additive for at least one selected industrial lubricating oil, an additive for fertilizer, and the like.

(Organic phosphorus compound represented by formula (A-1))
Among the organophosphorus compounds represented by the general formula (A) of the present invention, representative and preferred compounds include those represented by the following general formula (A-1) wherein R ³ and R ⁶ are each a hydrogen atom. A phosphorus compound is mentioned. In the formula (A-1), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , p, q, r and s are R ¹ , R ² , R described above for the general formula (A). ⁴ , R ⁵ , R ⁷ , p, q, r and s are synonymous, and the preferred range is also the same. The diarylphosphine oxide compound represented by the general formula (A-1) has 25 to 100 carbon atoms.

By reacting the organophosphorus compound represented by the general formula (A-1) with a dicarboxylic acid (or ester thereof) compound or a carbonate compound, flame retardant polyester or flame retardant polycarbonate can be provided.

(Organic phosphorus compound represented by formula (AN))
In the general formula (A), R ³ and R ⁶ are a group represented by — (CH ₂ ) _n —Q ¹ and a group represented by — (CH ₂ ) _m —Q ² , respectively. The organic phosphorus compound represented by (A-N) is also useful in the same manner as the organophosphorus compound represented by the general formula (A-1). For example, a flame retardant polyester, a flame retardant polyamide, and a flame retardant polyether are used. Various flame retardant resin materials such as flame retardant polycarbonate and flame retardant polycarbonate diol can be provided.

In the general formula (AN), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , p, q, r and s are R ¹ , R ² , R ^{4 in the} general formula (A-1). , R ⁵ , R ⁷ , p, q, r and s, and the preferred range is also the same. N represents a compound number and is an integer of 2 or more.

The organophosphorus compound having an oxyl group represented by the general formula (AN) includes, for example, an organophosphorus compound represented by the general formula (A-1) and a general formula as represented by the following reaction formula [II]. The alkyl compound represented by (4) can be produced according to Williamson's ether synthesis method (see, for example, J. Org. Chem., 67 6283 (2003)).

In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , p, q, r and s are R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ described above for the general formula (A). , P, q, r and s, and the preferred range is also the same. Note that the organic phosphorus compound represented by the general formula (A-1) has 25 to 100 carbon atoms.

In the general formula (4), Q has the same meaning as Q ¹ or Q ^2, and is vinyl group, propenyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group, carboxylic acid group (—COOH). , A carboxylate group (—COOR ^c ), an alkoxy group (—OR ^c ), an ethynyl group, or a phenyl group which may have a substituent, and R ^c has the same meaning as R ^a or R ^b . An alkyl group which may have a substituent, and l is an integer of 1 to 6 as defined above for n or m.
X represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a benzenesulfonyloxy group, or a toluenesulfonyloxy group.

Accordingly, the organophosphorus compound represented by the general formula (A-1) can be converted into an oxyl group (-OR ³ and -OR in the general formula (A) by performing an addition reaction such as the reaction formula [II]. ⁶ ) New compounds having various substituents introduced therein can be produced.

Specific examples thereof include an organic phosphorus compound represented by the general formula (A-1) and, for example, allyl bromide, hydroxyethyl chloride, 1-bromo-2-nitroethane, 4-bromobutanenitrile, epichlorohydrin, It is represented by the following general formulas (AN1) to (AN7) in which R ³ and R ⁶ are substituted by reacting with 3-ethyl-3-chloromethyloxetane or methyl 3-bromopropionate. An organophosphorus compound having an oxyl group having a substituent introduced therein can be produced.
Here, in the general formulas (AN1) to (AN7), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , p, q, r, and s are R in the general formula (A). ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , p, q, r and s are synonymous, and the preferred range is also the same. Further, and R ^c in the general formula (A-N7), it is synonymous with R ^c in Q in the general formula (4).

If the compound obtained from the above is used as a monomer component, for example, a flame retardant epoxy resin, a flame retardant polyester, a flame retardant polycarbonate or a flame retardant polycarbonate diol can be provided.

Further, the organic phosphorus compounds represented by the following general formula (AM) in which R ³ and R ⁶ in the general formula (A) are each an alkali metal atom include, for example, flame retardant phenol resins, flame retardant epoxy Group consisting of resin, flame retardant polyester, flame retardant polyamide, flame retardant polyether, flame retardant polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, flame retardant polyalkylene resin A flame retardant used in at least one flame retardant resin selected from: a derusting detergent, a rust inhibitor, a surface treatment agent, a paint release agent, and a degreasing detergent; It can be used as a treatment additive, a fertilizer additive, and the like.
In the general formula (AM), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , p, q, r and s are R ¹ , R ² , R in the general formula (A). ⁴ , R ⁵ , R ⁷ , p, q, r and s are synonymous, and the preferred range is also the same. M in the general formula (AM) represents an alkali metal atom.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1
<Production of organophosphorus compound represented by general formula (B) (R ³ = H, R ⁵ = H; (diphenylphosphoryl) (4-hydroxyphenyl) methanol) (Step 1 of Method 1)>
Tetrahydrofuran 3mL was put into a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device and a stirring measure, and 0.50 g (2.5 mmol) of diphenylphosphine oxide was added and dissolved therein. Next, 0.30 g (2.5 mmol) of 4-hydroxybenzaldehyde was added thereto, and the mixture was stirred at 50 ° C. for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 5 mL of ethyl acetate was added to the resulting reaction solution, whereby a precipitate was formed. The produced precipitate was filtered off and further washed with 10 mL of ethyl acetate. The obtained precipitate was dried to obtain 0.68 g of (diphenylphosphoryl) (4-hydroxyphenyl) methanol (acquisition yield: 85.0%) as a white powder.

The analytical value of the obtained (diphenylphosphoryl) (4-hydroxyphenyl) methanol was as follows.

¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 5.47 (1H, t), 6.26 (1H, dd), 6.54-6.59 (2H, brs), 7.00-7.06 (2H, brs), 7.42-7.58 (6H, brs), 7.74-7.85 (4H, brs), 9.28 (1H, s)

Example 2
<Production of organophosphorus compound represented by general formula (A) (R ³ = R ⁶ = H, R ⁵ = H; bis (4-hydroxyphenyl) methyldiphenylphosphine oxide) (Step 2 of Method 1)>
0.65 g (0.0020 mol) of (diphenylphosphoryl) (4-hydroxyphenyl) methanol produced in Example 1 was added to a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device, and a stirring means. Next, 1.35 g (0.014 mol) of phenol and 0.02 g (0.0001 mol) of p-toluenesulfonic acid were added and mixed, and the mixture was stirred at 120 ° C. for 7 hours to be reacted. After completion of the reaction, 10 mL of ethanol was added to the obtained reaction solution, and when this was dropped into 20 mL of hot water, a precipitate was formed. The generated precipitate was filtered off and further washed with 20 mL of hot water. The obtained precipitate was dried to obtain 0.53 g of the desired product bis (4-hydroxyphenyl) methyldiphenylphosphine oxide as a white powder (acquisition yield: 66.3%).

The analytical values of the obtained bis (4-hydroxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 401 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 5.28 (1H, d), 6.53 (4H, d), 7.32-7.43 (10 H, brs), 7.75-7.82 (4H, brs), 9.16 (2H, s)
Melting point: 301 ° C

Example 3
<Production of organophosphorus compound represented by general formula (A) (R ³ = R ⁶ = H, R ⁵ = H; bis (4-hydroxyphenyl) methyldiphenylphosphine oxide) (Method 2)>
To a glass reaction vessel equipped with a thermometer, temperature control device, dropping device and stirring means, 75 mL of toluene and 10.1 g (0.05 mol) of diphenylphosphine oxide were added, and then 6.1 g of 4-hydroxybenzaldehyde was added thereto. (0.05 mol) and 5.17 g (0.055 mol) of phenol were sequentially added, and the mixture was stirred at 65 ° C. for 1 hour. Thereafter, 0.2 g (0.001 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 8 hours to carry out a reaction. After completion of the reaction, the resulting reaction suspension was cooled to room temperature, the precipitate was filtered off, and further washed with 30 mL of toluene. The obtained solid was suspended in 100 mL of acetonitrile, stirred at 80 ° C. for 1 hour, then cooled to room temperature, the precipitate was filtered off, and washed with cold acetonitrile. The obtained solid was dried to obtain 16.9 g of the target product, bis (4-hydroxyphenyl) methyldiphenylphosphine oxide, as a white powder (acquisition yield: 84.3%).

The analytical values of the obtained bis (4-hydroxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 401 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 5.28 (1H, d), 6.53 (4H, d), 7.32-7.43 (10 H, brs), 7.75-7.82 (4H, brs), 9.16 (2H, s)
Melting point: 301 ° C

Example 4
<Production of organophosphorus compound represented by general formula (A) (R ³ = R ⁶ = H, R ⁵ = H; ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide) (Method 2) )>
To a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dripping device, and a stirring measure, 2.02 g (0.01 mol) of diphenylphosphine oxide was added, and then 1.22 g of 2-hydroxybenzaldehyde (0. 01 mol) and 5.70 g (0.05 mol) of phenol were added in order, and the mixture was stirred at 65 ° C. for 1.5 hours. Next, 0.02 g (0.0001 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 3 hours to carry out a reaction. After completion of the reaction, when the obtained reaction solution was dropped into 20 mL of toluene, a precipitate was formed. The produced precipitate was filtered off and further washed with 20 mL of toluene. The obtained precipitate was dried to obtain 3.21 g of the desired product ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide as a white powder (acquisition yield: 80.3%) .

The analytical value of the obtained ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide was as follows.

MS spectrum [CI-MS]: 401 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 5.49 (1H, d), 6.52 (2H, d), 6.65-6.69 (2H, brs), 6.89-6.94 (2H, brs), 7.22-7.26 (2H, brs), 7.34-7.46 (6H, brs), 7.64-7.79 (4H, brs) ), 7.91-7.94 (1H, brs), 9.20 (1H, s), 9.77 (1H, s)

Example 5
<Production of organophosphorus compound represented by general formula (B) (R ³ = H, R ⁵ = CH ₃ ; 1- (diphenylphosphoryl) -1- (4-hydroxyphenyl) ethanol)>
Tetrahydrofuran 3mL was put into a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device and a stirring measure, and 2.02 g (0.010 mol) of diphenylphosphine oxide was added and dissolved therein. Next, 1.36 g (0.010 mol) of (4-hydroxyphenyl) methyl ketone was added thereto, and the mixture was stirred at 50 ° C. for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 5 mL of ethyl acetate was added to the resulting reaction solution, whereby a precipitate was formed. The produced precipitate was filtered off and further washed with 10 mL of ethyl acetate. The obtained precipitate was dried to obtain 1.28 g of 1- (diphenylphosphoryl) -1- (4-hydroxyphenyl) ethanol as an objective product as a white powder (acquisition yield: 37.9%).

The analytical value of the obtained 1- (diphenylphosphoryl) -1- (4-hydroxyphenyl) ethanol was as follows.

¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 1.59 (3H, d), 6.20 (1H, d), 6.56 (2H, d), 7.16- 7.22 (2H, brs), 7.30-7.61 (6H, brs), 7.66-7.74 (2H, brs), 8.01-8.09 (2H, brs), 9. 22 (1H, s)

Example 6
<Production of organophosphorus compound represented by general formula (A) (R ³ = R ⁶ = H, R ⁵ = CH ₃ ; (1,1-bis (4-hydroxyphenyl) ethyl) diphenylphosphine oxide) (Method 2) )>
To a glass reaction vessel equipped with a thermometer, temperature control device, dropping device and stirring means, 2.02 g (0.010 mol) of diphenylphosphine oxide was added, and then 1.36 g of (4-hydroxyphenyl) methylketone. (0.010 mol) and 4.70 g (0.05 mol) of phenol were sequentially added, and the mixture was stirred at 65 ° C. for 1.5 hours. Next, 0.04 g (0.0002 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 7 hours to carry out a reaction. After completion of the reaction, the obtained reaction solution was added dropwise to ethyl acetate with stirring to produce a precipitate. The produced precipitate was filtered off and further washed with 10 mL of ethyl acetate. The obtained precipitate was dried to obtain 0.66 g of the desired product (1,1-bis (4-hydroxyphenyl) ethyl) diphenylphosphine oxide as a white powder (acquisition yield: 15.9%).

The analytical value of the obtained (1,1-bis (4-hydroxyphenyl) ethyl) diphenylphosphine oxide was as follows.

MS spectrum [CI-MS]: 415 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 1.81 (3H, d), 6.60-6.68 (4H, brs), 7.11-7.16 (4H , Brs), 7.34-7.68 (10H, brs), 9.16 (2H, s)

Example 7
<Production of organophosphorus compound represented by formula (B) (R ³ = CH ₃ , R ⁵ = H; (diphenylphosphoryl) (4-methoxyphenyl) methanol) (Step 1 of Method 1)>
Tetrahydrofuran 3mL was put into a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device and a stirring measure, and 0.50 g (2.5 mmol) of diphenylphosphine oxide was added and dissolved therein. Next, 4-methoxybenzaldehyde (0.34 g, 2.5 mmol) was added thereto, and the mixture was stirred at 50 ° C. for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and 5 mL of ethyl acetate was added to the resulting reaction solution, resulting in the formation of a precipitate. The produced precipitate was filtered off and further washed with 10 mL of ethyl acetate. The obtained precipitate was dried to obtain 0.65 g of (diphenylphosphoryl) (4-methoxyphenyl) methanol as a white powder (acquisition yield: 77.7%).

The analytical value of the obtained (diphenylphosphoryl) (4-methoxyphenyl) methanol was as follows.

¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 3.68 (3H, s), 5.55 (1H, d), 6.36 (1H, brs), 6.76 ( 2H, d), 7.13-7.19 (2H, brs), 7.42-7.59 (6H, brs), 7.75-7.86 (4H, brs)

Example 8
<Production of organophosphorus compound represented by general formula (A) (R ³ = R ⁶ = CH ₃ , R ⁵ = H; bis (4-methoxyphenyl) methyldiphenylphosphine oxide) (Step 2 of Method 1)>
To a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device and a stirring measure, 0.60 g (0.0018 mol) of (diphenylphosphoryl) (4-methoxyphenyl) methanol produced in Example 7 was added, Next, 0.97 g (0.0090 mol) of anisole and 0.02 g (0.0001 mol) of p-toluenesulfonic acid were added and mixed, and the mixture was stirred and reacted at 120 ° C. for 7 hours. After completion of the reaction, 10 mL of cyclohexane was added to the resulting reaction solution, and a precipitate was formed. The produced precipitate was filtered off and further washed with 10 mL of cyclohexane. The obtained precipitate was dissolved in a mixed solvent of 4 g of ethyl acetate and 4 g of toluene. By silica gel column chromatography (developing solvent (Vol / Vol): ethyl acetate / toluene = 1/1), 0.48 g of bis (4-methoxyphenyl) methyldiphenylphosphine oxide as a target product was obtained as a white powder ( Acquisition yield: 63.2%).

The analytical values of the obtained bis (4-methoxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 429 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 3.62 (6H, s), 5.47 (1H, d), 6.70-6.76 (4H, brs), 7.34-7.52 (10H, brs), 7.78-7.87 (4H, brs)

Example 9
<Production of organophosphorus compound represented by general formula (A) (R ³ = R ⁶ = CH ₃ , R ⁵ = H; bis (4-methoxyphenyl) methyldiphenylphosphine oxide) (Method 2)>
To a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device, and a stirring measure, 1.01 g (0.005 mol) of diphenylphosphine oxide was added, and then 0.68 g (0. 005 mol) and 2.7 g (0.025 mol) of anisole were sequentially added, followed by stirring at 65 ° C. for 1.5 hours. Next, 0.04 g (0.0002 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 5 hours to carry out a reaction. After completion of the reaction, 10 mL of cyclohexane was added to the resulting reaction solution, and a precipitate was formed. The produced precipitate was filtered off and further washed with 10 mL of cyclohexane. The obtained precipitate was dissolved in a mixed solvent of 4 g of ethyl acetate and 4 g of toluene. By silica gel column chromatography (developing solvent (Vol / Vol): ethyl acetate / toluene = 1/1), the resulting precipitate was dried as a white powder, and the desired product bis (4-methoxyphenyl) was obtained as a white powder. ) 1.20 g of methyldiphenylphosphine oxide was obtained (acquisition yield: 56.1%).

The analytical values of the obtained bis (4-methoxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 429 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 3.62 (6H, s), 5.47 (1H, d), 6.70-6.76 (4H, brs), 7.34-7.52 (10H, brs), 7.78-7.87 (4H, brs)

Example 10
<Production of organophosphorus compound represented by general formula (A-N5) (bis (4-glycidyloxyphenyl) methyldiphenylphosphine oxide)>
In a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device, and a stirring measure, 5.0 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide obtained in the same manner as in Example 2 or 3 (0 0.0125 mol) and 23.0 g (0.25 mol) of epichlorohydrin were added, and the mixture was heated to 105 ° C. and mixed. Subsequently, 3.1 g (0.0275 mol) of a 48% sodium hydroxide aqueous solution was slowly dropped into the mixture at the same temperature, and the mixture was further stirred for 2 hours after the completion of the dropwise addition. After completion of the reaction, the resulting mixture was cooled to room temperature, 50 g of dichloromethane and 50 g of water were added thereto, and the organic layer was separated. The obtained organic layer was further washed with 50 g of water, then dried over anhydrous sodium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 9.0 g of a concentrate. The obtained concentrate was recrystallized from 1-butanol to obtain 3.7 g of bis (4-glycidyloxyphenyl) methyldiphenylphosphine oxide as a target product as a white powder.

The analytical values of the obtained bis (4-glycidyloxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 513 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 2.62-2.64 (2H, brs), 2.77-2.80 (2H, brs), 3.21-3 .26 (2H, brs), 3.68-3.73 (2H, brs), 4.16-4.20 (2H, brs), 5.47 (1H, d), 6.75-6.78 (4H, brs), 7.34-7.50 (10H, brs), 7.78-7.85 (4H, brs)
Melting point: 192-195 ° C

Example 11
<Production of organophosphorus compound represented by general formula (A-N2) (bis (4- (2-hydroxyethoxy) phenyl) methyldiphenylphosphine oxide)>
Into a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device, and a stirring means, 1.0 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide obtained in the same manner as in Example 2 or 3 (0 .0025 mol) was dissolved in 10.0 g of dimethylformamide, 0.84 g (0.0061 mol) of potassium carbonate and 1.28 g (0.0102 mol) of 2-bromoethanol were sequentially added, and the temperature was raised to 80 ° C. The resulting mixture was stirred at 80 ° C. for 15 hours. After completion of the reaction, the mixture was cooled to room temperature, and 30 g of water was added thereto to precipitate a white solid. The obtained precipitate was filtered, washed with 30 g of water, and dissolved again in a mixed solvent of 2 g of ethyl acetate and 8 g of toluene. By silica gel column chromatography (developing solvent (Vol / Vol): ethyl acetate / toluene = 1/4), the desired product (bis (4- (2-hydroxyethoxy) phenyl) methyldiphenylphosphine oxide 0) was obtained as a white powder. Obtained .45 g (yield 36.9%).

The analytical values of the obtained (bis (4- (2-hydroxyethoxy) phenyl) methyldiphenylphosphine oxide) were as follows.

MS spectrum [CI-MS]: 489 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 3.59-3.66 (4H, brs), 3.82-3.87 (4H, t), 4.77 (2H , T), 5.45 (1H, d), 6.70-6.76 (4H, brs), 7.32-7.48 (10H, brs), 7.75-7.85 (4H, brs) )

Example 12
<Production of organophosphorus compound represented by general formula (A-N1) (bis (4-allyloxyphenyl) methyldiphenylphosphine oxide)>
Into a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device, and a stirring means, 1.0 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide obtained in the same manner as in Example 2 or 3 (0 .0025 mol) was dissolved in 10.0 g of dimethylformamide, 0.84 g (0.0061 mol) of potassium carbonate and 1.26 g (0.0104 mol) of allyl bromide were sequentially added, and the temperature was raised to 80 ° C. The resulting mixture was stirred at 80 ° C. for 15 hours. After completion of the reaction, the mixture was cooled to room temperature, and 30 g of water was added thereto to precipitate a white solid. The obtained precipitate was filtered, washed with 30 g of water, and dissolved again in a mixed solvent of 2 g of ethyl acetate and 8 g of toluene. By silica gel column chromatography (developing solvent (Vol / Vol): ethyl acetate / toluene = 1/4), 1.02 g of the desired product bis (4-allyloxyphenyl) methyldiphenylphosphine oxide as a white powder (yield) 85.0%) was obtained.

The analytical values of the obtained bis (4-allyloxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 481 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 4.43 (4H, d), 5.16-5.22 (2H, brs), 5.27-5.36 (2H , Brs), 5.45 (1H, d), 5.89-6.03 (2H, brs), 6.75 (4H, d), 7.34-7.51 (10H, brs), 7. 76-7.85 (4H, brs)

Example 13
<Organic phosphorus compound represented by general formula (A) (R ³ = R ⁶ = H, R ⁵ = H, R ⁷ = CH ₃ ; (4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyldiphenyl Production of phosphine oxide>
To a glass reaction vessel equipped with a thermometer, temperature control device, dropping device and stirring means, 75 mL of toluene and 10.1 g (0.05 mol) of diphenylphosphine oxide were added, and then 6.1 g of 4-hydroxybenzaldehyde was added thereto. (0.05 mol) and 5.95 g (0.055 mol) of cresol were sequentially added, and the mixture was stirred at 65 ° C. for 1 hour. Thereafter, 0.2 g (0.001 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 8 hours to carry out a reaction. After completion of the reaction, the resulting reaction suspension was cooled to room temperature, the precipitate was filtered off, and further washed with 30 mL of toluene. The obtained solid was suspended in 100 mL of acetonitrile and stirred at 80 ° C. for 1 hour, then cooled to 0 ° C., the precipitate was filtered off, and washed with cold acetonitrile. The obtained solid was dried to obtain 17.8 g of the desired product (4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyldiphenylphosphine oxide as a white powder (acquisition yield: 89.5). %).

The analytical values of the obtained (4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 415 [M + 1]
1H-NMR spectrum [300 MHz, d6-DMSO, δ (ppm)]: 1.96 (3H, d), 5.24 (1H, d), 6.51-6.54 (3H, brs), 7. 18-7.20 (2H, brs), 7.31-7.38 (8H, brs), 7.74-7.83 (4H, brs), 9.09 (2H, s)
Melting point: 252 ° C

Example 14
<Organic phosphorus compound represented by general formula (A) (R ³ = R ⁶ = H, R ⁵ = H, R ⁷ = OCH ₃ ; (4-hydroxyphenyl) (3-methoxy-4-hydroxyphenyl) methyldiphenyl Production of phosphine oxide>
To a glass reaction vessel equipped with a thermometer, temperature adjusting device, dropping device and stirring means, 15 mL of toluene and 2.02 g (0.01 mol) of diphenylphosphine oxide were added, and then 1.22 g of 4-hydroxybenzaldehyde was added thereto. (0.01 mol) and 1.37 g (0.011 mol) of guaiacol were sequentially added, and the mixture was stirred at 65 ° C. for 1 hour. Thereafter, 0.04 g (0.0002 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 7 hours to carry out a reaction. After completion of the reaction, the resulting reaction suspension was cooled to room temperature, and subjected to silica gel column chromatography (developing solvent: ethyl acetate) as a white powder as the desired product (4-hydroxyphenyl) (3-methoxy-4). -Hydroxyphenyl) methyldiphenylphosphine oxide 2.51 g was obtained (acquisition yield: 58.3%).

The analytical value of the obtained (4-hydroxyphenyl) (3-methoxy-4-hydroxyphenyl) methyldiphenylphosphine oxide was as follows.

MS spectrum [CI-MS]: 431 [M + 1]
1H-NMR spectrum [300 MHz, d6-DMSO, δ (ppm)]: 3.60 (3H, s), 5.30 (1H, d), 6.53-6.56 (3H, brs), 6. 92-6.96 (1H, brs), 7.08-7.10 (1H, brs), 7.34-7.40 (8H, brs), 7.76-7.84 (4H, brs), 8.73 (1H, s), 9.16 (1H, s)
Melting point: 231 ° C

Example 15
<Organic phosphorus compound represented by general formula (A) (R ⁵ = H, R ³ = R ⁶ = H, R ⁴ = R ⁷ = OCH ₃ ; bis (3-methoxy-4-hydroxyphenyl) methyldiphenylphosphine oxide Production>
To a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device, and a stirring measure, 15 mL of toluene and 2.02 g (0.01 mol) of diphenylphosphine oxide were added, and then 1.52 g (0. 01 mol) and 1.37 g (0.011 mol) of guaiacol were sequentially added, followed by stirring at 65 ° C. for 1 hour. Thereafter, 0.04 g (0.0002 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 8 hours to carry out a reaction. After completion of the reaction, the resulting reaction suspension was cooled to room temperature and purified by silica gel column chromatography (developing solvent: ethyl acetate) to give the desired product, bis (3-methoxy-4-hydroxyphenyl) methyl, as a yellow powder. 0.17 g of diphenylphosphine oxide was obtained (acquisition yield: 3.7%).

The analytical value of the obtained bis (3-methoxy-4-hydroxyphenyl) methyldiphenylphosphine oxide was as follows.

MS spectrum [CI-MS]: 461 [M + 1]
1H-NMR spectrum [300 MHz, d6-DMSO, δ (ppm)]: 3.60 (6H, s), 5.31 (1H, d), 6.53-6.58 (2H, brs), 6. 81 (2H, d), 7.35-7.42 (8H, brs), 7.77-7.86 (4H, brs), 8.14 (1H, s), 9.19 (1H, s)

Reference Example 1 (Phosphorus-containing epoxy resin cured product (5A-1a))
<Production of phosphorus-containing curable resin composition>
In a glass reaction vessel equipped with a thermometer, temperature control device, and stirring means, 0.2007 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide (formula (A-1a)) and phenol novolac resin (Maywa Kasei) HF-1M: Softening point 84 ° C., hydroxyl group equivalent 106 g / eq) 1.8052 g and 2-undecylimidazole 0.0172 g were added dimethylacetamide 1.9998 g to obtain a uniform solution at 100 ° C. To this solution, 2.1846 g of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate was added to obtain a phosphorus-containing curable resin composition as a uniform solution.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. When the obtained solid was analyzed, it was confirmed that dimethylacetamide was contained. Therefore, this solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide and to contain the target phosphorus-containing product. A cured resin (5A-1a) was obtained (the following reaction formula [5A-1a]).

About 10 mg of the obtained cured product was taken and accurately weighed, and thermogravimetric analysis (TGA) measurement was performed with TG / DTA320 (manufactured by Seiko Denshi Kogyo) (FIG. 1).

Reference example 2
To a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 1.0016 g of phenol novolac resin (HF-1M manufactured by Meiwa Kasei Co., Ltd., softening point 84 ° C., hydroxyl equivalent 106) and 2-undecylimidazole To a mixture of 0162 g, 1.0021 g of dimethylacetamide was added to obtain a uniform solution at room temperature. To this solution, 1.1809 g of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate was added to make a uniform solution, and this solution was filled in a circular container having a diameter of 4 cm, and then 160 to 170 in an oven. The cured product was obtained by heating at 0 ° C. for 5 hours (the following reaction formula [Ref. 2]).

About 10 mg of the obtained cured product was taken, accurately weighed, and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo) (FIG. 2).

From FIG. 2, in the cured product of Comparative Example 2 that does not contain bis (4-hydroxyphenyl) methyldiphenylphosphine oxide represented by the formula (A-1a), the residual weight ratio of carbide at 1000 ° C. is 4.2%. The cured phosphorus-containing resin of Reference Example 1 (FIG. 1, residual weight ratio 8.8%) containing bis (4-hydroxyphenyl) methyldiphenylphosphine oxide represented by the formula (A-1a) is better. It was found that the residual weight ratio after the heat resistance experiment was high, and it was difficult to burn even at high temperatures, that is, excellent in flame retardancy.

Since the organophosphorus compound represented by the general formula (A) of the present invention has a phosphorus atom incorporated in the monomer skeleton, the material using this has excellent flame retardancy and hydrolysis resistance. In particular, the organic phosphorus compound represented by the general formula (A) of the present invention includes, for example, a flame retardant phenol resin, a flame retardant epoxy resin, a flame retardant polyester, a flame retardant polyamide, a flame retardant polyether, Component of various flame retardant resins such as flame retardant polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, flame retardant polyalkylene resin (eg, polyethylene, polystyrene, etc.), or flame retardant It can be used as a flame retardant additive. Furthermore, the organophosphorus compound represented by the general formula (A) of the present invention is not limited to the use of the above-mentioned flame retardant material, but various organic materials and raw material intermediates for medical and agrochemical products, industrial treatments It is also useful as an additive such as a fertilizer and an additive for fertilizer.

Claims (18)

An organophosphorus compound represented by the following general formula (A).

[In General Formula (A), R ¹ , R ² , R ⁴ and R ⁷ may each independently have a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or a substituent. An alkyl group, an alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group, p and q are each independently an integer of 0 to 5, and r and s are each independently 0 to 4 Is an integer. When p, q, r, and s are 2 or more, the plurality of R ¹ , R ² , R ^4, and R ⁷ may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
R ³ represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have, or a group represented by — (CH ₂ ) _n —Q ¹ is shown. Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown.
R ⁶ represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have, or a group represented by — (CH ₂ ) _m —Q ² . Here, Q ² is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^b ), An alkoxy group (—OR ^b ) or an optionally substituted phenyl group; R ^b represents an optionally substituted alkyl group; and m is an integer of 1 to 6. .
The organic phosphorus compound represented by the general formula (A) has 25 to 100 carbon atoms. ] The organophosphorus compound according to claim 1, wherein R ³ and R ⁶ are both hydrogen atoms. The organophosphorus compound according to claim 1, wherein both R ³ and R ⁶ are glycidyl groups. The organophosphorus compound according to claim 1, wherein R ³ and R ⁶ are both alkali metal atoms. An organophosphorus compound represented by the following general formula (B).

[In General Formula (B), R ¹ , R ² and R ⁴ each independently represent a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an alkyl group which may have a substituent, An alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group, p and q are each independently an integer of 0 to 5, and r is an integer of 0 to 4. When p, q and r are 2 or more, the plurality of R ¹ , R ² and R ⁴ may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
R ³ represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have, or a group represented by — (CH ₂ ) _n —Q ¹ is shown. Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown. ] A flame retardant comprising the organophosphorus compound according to any one of claims 1 to 5. The organophosphorus compound according to any one of claims 1 to 5, which is a monomer for flame retardant resin. Flame retardant resin from flame retardant phenolic resin, flame retardant epoxy resin, flame retardant polyester, flame retardant polyamide, flame retardant polyether, flame retardant polycarbonate, flame retardant polycarbonate diol and flame retardant polyurethane The organophosphorus compound according to claim 7, which is any one selected. A flame retardant method using the organophosphorus compound according to any one of claims 1 to 5. A step of reacting a diarylphosphine oxide compound represented by the following general formula (1), an arylcarbonyl compound represented by the following general formula (2), and an aryl compound represented by the following general formula (3) in the presence of an acid catalyst. A method for producing an organophosphorus compound represented by the following general formula (A).

[In General Formula (1), R ¹ and R ² are each independently a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, An alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group is shown, and p and q are each independently an integer of 0 to 5. When p and q are 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
The diarylphosphine oxide compound represented by the general formula (1) has 12 to 46 carbon atoms. ]

[In General Formula (2), R ³ has a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkynyl group which may be substituted, an aryl group which may have a substituent, or a group represented by — (CH ₂ ) _n —Q ¹ ; Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁴ represents a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, alkynyl group, alkyloxy group, allyl group, aryl group or aryl group. Represents an oxy group, and r is an integer of 0-4. When r is 2 or more, the plurality of R ⁴ may be the same or different.
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown.
The arylcarbonyl compound represented by the general formula (2) has 7 to 32 carbon atoms. ]

[In General Formula (3), R ⁶ has a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkynyl group which may be substituted, an aryl group which may have a substituent, or a group represented by — (CH ₂ ) _m —Q ² ; Here, Q ² is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^b ), An alkoxy group (—OR ^b ) or an optionally substituted phenyl group; R ^b represents an optionally substituted alkyl group; and m is an integer of 1 to 6. .
R ⁷ represents a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, alkynyl group, alkyloxy group, allyl group, aryl group or aryl Represents an oxy group, and s is an integer of 0-4. When s is 2 or more, the plurality of R ⁷ may be the same as or different from each other. However, R ⁷ is bonded only to the o- or m-position with respect to the oxyl group (—OR ⁶ ).
The aryl compound having an oxyl group represented by the general formula (3) has 6 to 32 carbon atoms. ] Organophosphorus represented by the following general formula (A) comprising the step of reacting an organophosphorus compound represented by the following general formula (B) with an aryl compound represented by the following general formula (3) in the presence of an acid catalyst Compound production method.

[In General Formula (B), R ¹ , R ² and R ⁴ each independently represent a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an alkyl group which may have a substituent, An alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group, p and q are each independently an integer of 0 to 5, and r is an integer of 0 to 4. When p, q and r are 2 or more, the plurality of R ¹ , R ² and R ⁴ may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
R ³ represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have, or a group represented by — (CH ₂ ) _n —Q ¹ is shown. Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown. ]

[In General Formula (3), R ⁶ has a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkynyl group which may be substituted, an aryl group which may have a substituent, or a group represented by — (CH ₂ ) _m —Q ² ; Here, Q ² is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^b ), An alkoxy group (—OR ^b ) or an optionally substituted phenyl group; R ^b represents an optionally substituted alkyl group; and m is an integer of 1 to 6. .
R ⁷ represents a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, alkynyl group, alkyloxy group, allyl group, aryl group or aryl Represents an oxy group, and s is an integer of 0-4. When s is 2 or more, the plurality of R ⁷ may be the same as or different from each other. However, R ⁷ is bonded only to the o- or m-position with respect to the oxyl group (—OR ⁶ ).
The aryl compound having an oxyl group represented by the general formula (3) has 6 to 32 carbon atoms. ]

[In the general formula ^{(A), R 1 ~ R} 7, p, q, r and s is the general formula (B) and R ¹ ~ R ⁷ in (3), p, q, synonymous with r and s . ] The method for producing an organophosphorus compound according to claim 10 or 11, wherein the acid catalyst is at least one selected from the group consisting of sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid and methanesulfonic acid. The amount of the acid catalyst used is 0.001 to 0.98 mol with respect to 1 mol of the diarylphosphine oxide compound represented by the general formula (1) or the organophosphorus compound represented by the general formula (B). The method for producing an organophosphorus compound according to any one of claims 10 to 12. The step of isolating the organophosphorus compound represented by the general formula (A) includes, as a precipitation solvent, n-pentane, n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, diethyl ether, diisopropyl ether, The method for producing an organophosphorus compound according to any one of claims 10 to 13, which is carried out using at least one solvent selected from the group consisting of t-butyl methyl ether, acetonitrile, ethyl acetate and water. The method for producing an organophosphorus compound according to claim 14, wherein the amount of the precipitation solvent used is 0.5 to 500 mL with respect to 1 g of the organophosphorus compound represented by the general formula (A). An organophosphorus compound represented by the general formula (B) is produced by reacting a diarylphosphine oxide compound represented by the following general formula (1) with an arylcarbonyl compound represented by the following general formula (2). The method for producing an organophosphorus compound according to claim 11.

[In General Formula (1), R ¹ and R ² are each independently a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, An alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group is shown, and p and q are each independently an integer of 0 to 5. When p and q are 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
The diarylphosphine oxide compound represented by the general formula (1) has 12 to 46 carbon atoms. ]

[In General Formula (2), R ³ has a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkynyl group which may be substituted, an aryl group which may have a substituent, or a group represented by — (CH ₂ ) _n —Q ¹ ; Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁴ represents a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, alkynyl group, alkyloxy group, allyl group, aryl group or aryl group. Represents an oxy group, and r is an integer of 0-4. When r is 2 or more, the plurality of R ⁴ may be the same or different.
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown.
The arylcarbonyl compound represented by the general formula (2) has 7 to 32 carbon atoms. ] An organophosphorus compound represented by the following general formula (AN), comprising a step of reacting an organophosphorus compound represented by the following general formula (A-1) with an alkyl compound represented by the following general formula (4): Production method.

[In general formula (A-1), R ¹ , R ² , R ⁴ and R ⁷ each independently have a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or a substituent. Represents an alkyl group, an alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group, p and q are each independently an integer of 0 to 5, and r and s are each independently 0 It is an integer of ~ 4. When p, q, r, and s are 2 or more, each of the plurality of R ¹ , R ² , R ^4, and R ⁷ may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown. ]

[In general formula (4), Q represents a hydrogen atom, a vinyl group, a propenyl group, an allyl group, a methallyl group, an ethynyl group, an optionally substituted phenyl group, a hydroxyl group (—OH), a nitro group, A cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^c ), or an alkoxy group (—OR ^c ), and R ^c is an alkyl which may have a substituent. Represents a group, and l is an integer of 1 to 6. X represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a benzenesulfonyloxy group, or a toluenesulfonyloxy group. ]

[In the general formula (AN), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , p, q, r and s are R ¹ , R ² , R ^{4 in the} general formula (A-1). , R ⁵ , R ⁷ , p, q, r and s. ] The organophosphorus compound represented by the general formula (B), which is produced by reacting the diarylphosphine oxide compound represented by the following general formula (1) and the arylcarbonyl compound represented by the following general formula (2). Manufacturing method.

[In General Formula (1), R ¹ and R ² are each independently a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, An alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group is shown, and p and q are each independently an integer of 0 to 5. When p and q are 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
The diarylphosphine oxide compound represented by the general formula (1) has 12 to 46 carbon atoms. ]

[In General Formula (2), R ³ has a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkynyl group which may be substituted, an aryl group which may have a substituent, or a group represented by — (CH ₂ ) _n —Q ¹ ; Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁴ represents a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an optionally substituted alkyl group, alkenyl group, alkynyl group, alkyloxy group, allyl group, aryl group or aryl group. Represents an oxy group, and r is an integer of 0-4. When r is 2 or more, the plurality of R ⁴ may be the same or different.
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown.
The arylcarbonyl compound represented by the general formula (2) has 7 to 32 carbon atoms. ]

[In General Formula (B), R ¹ , R ² and R ⁴ each independently represent a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or an alkyl group which may have a substituent, An alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group, p and q are each independently an integer of 0 to 5, and r is an integer of 0 to 4. When p, q and r are 2 or more, the plurality of R ¹ , R ² and R ⁴ may be the same as or different from each other. Further, a plurality of substituents R ¹ and R ² are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
R ³ represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent. An aryl group which may have, or a group represented by — (CH ₂ ) _n —Q ¹ is shown. Here, Q ¹ is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR ^a ), An alkoxy group (—OR ^a ) or an optionally substituted phenyl group, R ^a represents an optionally substituted alkyl group, and n is an integer of 1 to 6 .
R ⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown. ]

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