TW201402590A - Method for producing phosphoric acid ester amides - Google Patents

Abstract

The present invention provides a method for producing a phosphoric acid ester amide corresponding to a phosphoromonohalidate, in which the phosphoromonohalidate and an amine compound having one or two primary amino groups and/or secondary amine groups in the molecule are brought into a dehydrohalogenation reaction, which includes: the phosphoromonohalidate and the amine compound are brought into reaction at 130 DEG C or more, without using an excess amount of the amine compound relative to the phosphoromonohalidate.

Description

Method for producing phosphate amides

The present invention is a novel process for the manufacture of phosphate amides.

The phosphate amide is used as a flame retardant (for example, Patent Document 1) in a molded article of a synthetic resin and a fiber product, and several methods have been known for the production method.

For example, anilino diphenyl phosphate, which is one of the representative examples of phosphate amides, can usually be subjected to condensation reaction with diphenyl phosphorochloridate and aniline, that is, dehydrochlorination reaction. And get it.

In this reaction, when 1 equivalent of each of diphenyl chlorophosphate and aniline is used, 0.5 equivalent of aniline will react with 0.5 equivalent of diphenyl chlorophosphate to form the desired diphenyl phenylphosphonate, but the remaining Since 0.5 equivalent of aniline acts as a hydrogen chloride scavenger to form a hydrochloride, 0.5 equivalent of diphenyl chlorophosphate is still unreacted.

Therefore, when diphenyl phenyl phosphate is produced by reacting diphenyl chlorophosphate with aniline, generally 2 equivalents of aniline are used relative to 1 equivalent of diphenyl chlorophosphate, wherein 1 equivalent of aniline is used. Diphenyl chlorophosphate 1 equivalent In the reaction, the aniline 1 equivalent is used as a hydrogen chloride scavenger, and the diphenyl chlorophosphate is effectively utilized in the reaction (see, for example, Patent Document 2).

However, in the production of diphenyl phenylphosphonate, when such an equivalent of 2 equivalents of aniline is used with respect to 1 equivalent of diphenyl chlorophosphate, and 1 equivalent of aniline is used as a hydrogen chloride scavenger, the anilinophenyl diphenyl phosphate The productivity is not more than 50% with respect to aniline. On the other hand, the step of neutralizing and purifying the aniline hydrochloride after the reaction is completed and recovering the aniline is also troublesome. Therefore, the above method is economically economical from the viewpoint of aniline. unfavorable.

Therefore, attempts have been made to use an aliphatic tertiary amine compound such as pyridine or an aliphatic tertiary amine such as triethylamine in place of aniline as a hydrogen chloride scavenger (see, for example, Patent Document 3). However, these amines have a function that they cannot effectively function as a hydrogen chloride scavenger like an aromatic amine. Further, after the reaction is completed, recovery of the amine from the hydrochloride and reuse of the same requires a complicated procedure. Further, when operating by such a method, there is a case where an odor remains due to the amine used in the obtained diphenyl phenylphosphonate.

[Previous Technical Literature] Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2003-193368

Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-154277

Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 10-175985

The present invention has been made in order to solve the above problems in the production of phosphate amides in the prior art, and an object thereof is to provide a novel method for producing phospholipid amides, which is relative to chlorophosphate (phosphorochloridate). In the case where an amine compound is used in an amount, the desired phosphate amide can be obtained with high productivity with respect to the above amine compound.

In particular, it is an object of the present invention to provide a novel method for producing a phosphate amide which is preferably used in an amount of 0.5 equivalent or more and less than 2.0 equivalents per equivalent of the chlorophosphate. In the state, 0.8 to 1.2 equivalents of an amine compound is used, whereby the desired phosphate amide can be obtained with high productivity with respect to the above amine compound.

The method provided by the present invention is a method for producing a phosphate amide of the following halogenated phosphates by the following (A) or (B): (A) from the following formula (Ia) At least one phosphorohalidate selected from the group consisting of phosphoromonohalidate and phosphorodihalidate represented by the formula (Ib)

(In the above formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent which is inactive in the reaction; X represents a halogen atom), and At least 1 selected from a monoamine compound having one primary amino group and/or a secondary amine group in the molecule and a diamine compound having two primary amine groups and/or a secondary amine group in the molecule The amine compound is subjected to a dehydrohalogenation reaction; or (B) the above-mentioned dihalogenated phosphate ester as a halogenated phosphate ester, and a monoamine compound having one first-order amine group and/or second-order amine group in the molecule, The dehydrohalogenation reaction is carried out; wherein the method comprises reacting the above halogenated phosphate with the above amine compound at a temperature of 130 ° C or higher.

In the present invention, when the monohalogenated phosphate ester represented by the above formula (Ia) is subjected to dehydrohalogenation reaction with a monoamine compound, an aromatic monoamine compound or an aliphatic monoamine compound is used.

In the present invention, when the monohalogenated phosphate ester represented by the above formula (Ia) and the diamine compound are subjected to dehydrohalogenation reaction, an aromatic diamine compound or an aliphatic diamine compound is used.

Further, in the present invention, when the dihalogenated phosphate represented by the above formula (Ib) is subjected to dehydrohalogenation reaction with a monoamine compound, an aromatic monoamine compound or an aliphatic monoamine compound is used.

That is, the present invention provides the following six methods as preferred embodiments.

(1) The monohalogenated phosphate represented by the above formula (Ia) is reacted with an aromatic monoamine compound represented by the formula (IIa) as an amine compound to produce a phosphoric acid represented by the formula (VIa) Method of ester amides: Wherein Ar ₁ represents an aryl group; Y ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group; when Y ₁ is an aryl group, Y ₁ and Ar ₁ may be the same, Can be different)

(2) The monohalogenated phosphate represented by the above formula (Ia) is reacted with an aromatic diamine compound represented by the formula (IIb) as an amine compound to produce a phosphoric acid represented by the formula (VIb) Method of ester amides: (wherein Ar ₂ represents a divalent group containing an aromatic ring bonded to two nitrogen atoms in the molecule; and Y ₂ and Y ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aromatic group; Or aralkyl group, and Y ₂ and Y ₃ may be the same or different)

(3) reacting a monohalogenated phosphate represented by the above formula (Ia) with an aliphatic monoamine compound represented by the formula (IVa) to produce a phosphate amide represented by the formula (VIIa) Method: (wherein Ay ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; Y ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; or Ay ₁ and Y ₄ may also be used. Forming a 5- to 7-membered ring together, in which case the ring may also contain an oxygen atom and/or a nitrogen atom as an atom forming a ring. However, when the atom forming the ring is a nitrogen atom, the nitrogen atom does not have a bond. Hydrogen atom on it)

(4) The monohalogenated phosphate represented by the above formula (Ia) is reacted with an aliphatic diamine compound represented by the formula (IVb) as an amine compound to produce a phosphoric acid represented by the formula (VIIb) Method of ester amides: (wherein, Ay ₂ represents an alkylene or a cycloalkylene which may have an aryl group on a carbon atom or between carbon atoms; and Y ₅ and Y ₆ each independently represent a hydrogen atom or an alkyl group; , alkenyl, cycloalkyl or aralkyl; or Ay ₂ and Y ₅ may together form a 5 to 7 membered ring, or Ay ₂ and Y ₆ may together form a 5 to 7 membered ring, or Ay ₂ And Y ₅ and Y ₆ can also form a 5 to 7 member ring)

(5) reacting the dihalogenated phosphate represented by the above formula (Ib) with an aromatic monoamine compound represented by the formula (IIa) as an amine compound to produce a phosphoric acid represented by the formula (VIIIa) Method of ester amides: Wherein Ar ₁ represents an aryl group; Y ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group; when Y ₁ is an aryl group, Y ₁ and Ar ₁ may be the same, Can be different)

(6) reacting the dihalogenated phosphate represented by the above formula (Ib) with an aliphatic monoamine compound represented by the formula (IVa) as an amine compound to produce a phosphoric acid represented by the formula (VIIIb) Method of ester amides: (wherein Ay ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; Y ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; or Ay ₁ and Y ₄ may also be used. Forming a 5- to 7-membered ring together, in which case the ring may also contain an oxygen atom and/or a nitrogen atom as an atom forming a ring. However, when the atom forming the ring is a nitrogen atom, the nitrogen atom does not have a bond. Hydrogen atom on it)

In the above method, in the above method, the amine compound is preferably reacted in an amount of 0.5 equivalent or more and less than 2 equivalents per 1 equivalent of the halogenated phosphate, and particularly preferably the amine compound is reacted at 0.8 to 1.2 equivalents.

Further, in the present invention, in the above method, the reaction solvent is not necessarily used, but in order to allow the reaction to proceed smoothly, it is preferred to use a reaction solvent. In this case, a reaction solvent having a boiling point of 130 ° C or higher can be used. The reaction solvent having a boiling point of 130 ° C or higher is preferably at least one selected from the group consisting of aromatic hydrocarbons having a boiling point of 130 ° C or higher, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, and aromatic ethers.

According to the method of the present invention, the amine compound is used in an excessive amount with respect to the halogenated phosphate, that is, 0.5 equivalent or more, less than 2 equivalents of the amine compound, more preferably 0.8 to 1.2 equivalents of the amine compound, that is, The desired phosphate amides can be obtained with high productivity with respect to the above amine compounds.

Embodiment of the invention

The method for producing a phosphate amide of the present invention is a method for producing a phosphate amide of the following halogenated phosphates by the following (A) or (B): (A) a general formula (A) At least one halogenated phosphate selected from the group consisting of monohalogenated phosphates represented by Ia) and dihalogenated phosphates represented by the formula (Ib) (In the above formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent which is inactive in the reaction; X represents a halogen atom), and a monoamine compound having one primary amino group and/or a secondary amine group in the molecule, and at least one amine compound selected from diamine compounds having two primary amine groups and/or secondary amine groups in the molecule Dehydrohalogenation reaction; or (B) dehalogenation of the above-mentioned dihalogenated phosphates as halogenated phosphates and monoamine compounds having one primary amine group and/or secondary amine group in the molecule A hydrogen reaction; wherein the method comprises reacting the above halogenated phosphate with the above amine compound at a temperature of 130 ° C or higher.

In the present invention, among the halogenated phosphates represented by the above formulas (Ia) and (Ib), R ₁ , R ₂ and R ₃ each independently represent an alkyl group which may have a substituent which is inactive in the reaction, A cycloalkyl, aryl or aralkyl group; X represents a halogen atom.

In the present invention, the above-mentioned substituent which is inactive in the reaction is intended The substituent which is not related to the reaction of the halogenated phosphates and the amine compound of the present invention may, for example, be a halogen atom such as an alkoxy group such as a methoxy group, a nitro group, a nitrile group or a chlorine atom, or a halogenated group of the present invention. A heterocyclic group or the like which is not related to the reaction of a phosphate or an amine compound. The same is true below.

The above alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms, wherein the number of carbon atoms is 3 or more. The alkyl group may be a straight chain or a branched chain, and examples of the alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group. Wait.

In the above cycloalkyl group, the carbon atom forming the ring may further contain an alkyl group as a substituent, and the total number of carbon atoms is preferably from 5 to 20, more preferably a cycloalkyl group having from 5 to 12 carbon atoms. Specific examples thereof include a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, an ethylcyclohexyl group, and the like.

Further, the above aryl group is preferably an aryl group having 6 to 12 carbon atoms, and the aromatic ring may further contain one or a plurality of substituents, and the substituent is an alkyl group (more preferably 1 to 6 carbon atoms). The alkyl group) and/or the aforementioned substituent which is inactive in the reaction. Therefore, examples of such an aryl group include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a methoxyphenyl group, a naphthyl group, a methylnaphthyl group, a biphenyl group, a methylbiphenyl group and the like.

Examples of the aralkyl group include a benzyl group and a phenylethyl group. The aralkyl group may also have an alkyl group having 1 to 6 carbon atoms or a substituent which is inactive in the reaction, in the aromatic ring.

Further, in the above halogenated phosphate, the halogen atom X is a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. That is, in the present invention, the above halogenated phosphates are preferably chlorophosphates.

In particular, in the present invention, among the halogenated phosphates represented by the above formulas (Ia) and (Ib), it is preferred that R ₁ , R ₂ and R ₃ each independently represent a carbon atom in the aromatic ring. The alkyl group of 1 to 6 or the above-mentioned aryl group which is an inactive substituent in the reaction is particularly preferably a phenyl group, a tolyl group or a xylyl group, and X is a chlorine atom.

Therefore, in the present invention, preferred examples of the monohalogenated phosphates represented by the above formula (Ia) include diphenyl phosphorochloridate, bis(m-tolyl) chlorophosphate, and Di(p-tolyl) chlorophosphate, bis(2,6-dimethylphenyl) chlorophosphate, bis(3,5-dimethylphenyl) chlorophosphate, bis(2,5-dimethylphenyl) chlorophosphate Ethyl dichlorophenyl chlorophosphate, di(isopropylphenyl) chlorophosphate, di(isobutylphenyl) chlorophosphate, di(tert-butylphenyl) chlorophosphate, chlorine Di(1-naphthyl) phosphate, di(2-naphthyl) chlorophosphate, bis(2-biphenyl) chlorophosphate, bis(3-biphenyl) chlorophosphate, bis(4) chloride a biphenyl ester or the like; and a mixture of any two or more of these.

Further, preferred examples of the dihalogenated chlorophosphates represented by the above formula (Ib) include phenyl phosphorodichloridate, m-tolyl dichlorophosphate, and dichlorophosphoric acid. Methylphenyl dichlorophosphate such as tolyl ester, 2,6-dimethylphenyl dichlorophosphate, 3,5-dimethylphenyl dichlorophosphate, 2,5-dimethylphenyl dichlorophosphate, dichloro Isopropylphenyl phosphate, isobutylphenyl dichlorophosphate, t-butylphenyl dichlorophosphate, (1-naphthyl) dichlorophosphate, (2-naphthyl) dichlorophosphate , (2-biphenyl) dichlorophosphate, (3-biphenyl) dichlorophosphate, (4-biphenyl) dichlorophosphate, and the like.

In the present invention, by having such monohalogenated phosphates, and having a monoamine compound having one primary amine group and/or a secondary amine group in the molecule, and having two primary amine groups in the molecule and/or At least one amine compound selected from the group 2 amine diamine compounds The dehydrohalogenation reaction, that is, the condensation reaction, can be carried out to obtain the desired phosphate amides in accordance with the monohalogenated phosphates and the amine compounds used.

Further, in the present invention, when the above-mentioned dihalogenated phosphates are used as the halogenated phosphates, they are separated from the monoamine compound having one primary amino group and/or secondary amine group in the molecule. The hydrogen halide reaction, that is, the condensation reaction, can be used to obtain the desired phosphate amides in accordance with the dihalogenated phosphates used and the monoamine compounds used.

In the monoamine compound used in the present invention, the monoamine compound having one primary amino group and/or secondary amino group in the above molecule may be any of an aromatic monoamine compound and an aliphatic monoamine compound. Similarly, the diamine compound having two primary amino groups and/or secondary amino groups in the above molecule may be either an aromatic diamine compound or an aliphatic diamine compound.

In the present invention, the aromatic monoamine compound is preferably those represented by the formula (IIa): Wherein Ar ₁ represents an aryl group; Y ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group; when Y ₁ is an aryl group, Y ₁ and Ar ₁ may be the same, Can be different).

When the above aryl groups Ar ₁ and Y ₁ are aryl groups, the aryl groups Ar ₁ and Y ₁ are preferably an aryl group having 6 to 12 carbon atoms, and the aryl groups may have 1 ring on the aromatic ring. Or a plurality of substituents, the substituent being an alkyl group (more preferably an alkyl group having 1 to 6 carbon atoms) and the aforementioned substituent which is inactive in the reaction. Therefore, examples of such an aryl group include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a methoxyphenyl group, a naphthyl group, a methylnaphthyl group, a biphenyl group, a methylbiphenyl group and the like.

When the above Y ₁ is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group having 3 or more carbon atoms may be linear or branched, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group. , 壬基, 12 base, etc. Further, the alkyl group may have a heterocyclic group which is inactive in the above reaction as a substituent.

When the above Y ₁ is an alkenyl group, the alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and examples thereof include an allyl group and an isopropenyl group. Further, the alkenyl group may have a heterocyclic group which is inactive in the above reaction as a substituent.

When the above Y ₁ is a cycloalkyl group, the cycloalkyl group may have an alkyl group having 1 to 6 carbon atoms or a substituent which is inactive in the reaction on the carbon atom forming the ring, and the total is The number of carbon atoms is preferably from 5 to 20, more preferably a cycloalkyl group having from 5 to 12 carbon atoms. Therefore, specific examples of the cycloalkyl group include, for example, a cyclopentyl group, a methylcyclopentyl group, and a cyclohexyl group. , methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl, and the like.

Further, when Y ₁ is an aralkyl group, examples of the aralkyl group include a benzyl group and a phenylethyl group. The aralkyl group may also have an alkyl group having 1 to 6 carbon atoms on the aromatic ring or a substituent which is inactive in the above reaction.

Therefore, in the present invention, preferred aromatic monoamine compounds are exemplified by aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 3,4. - Xylidines such as xylidine and 2,6-xylyleneamine, nitroanilines, 1-naphthylamine, 2-naphthylamine, 2-benzidine, 3-benzidine, 4-benzidine, N- Methylaniline, N-ethylaniline, aminopyridines, and the like.

In the present invention, the aromatic diamine compound is preferably one represented by the formula (IIb): (wherein Ar ₂ represents a divalent group containing an aromatic ring bonded to two nitrogen atoms in the molecule; and Y ₂ and Y ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aromatic group; Or an aralkyl group, and Y ₂ and Y ₃ may be the same or different).

As described above, in the present invention, the above-mentioned divalent group Ar ₂ having an aromatic ring is bonded to two nitrogen atoms in a molecule forming a diamine compound, and the aromatic ring may have a carbon atom thereon. An alkyl group of 1 to 6 or the aforementioned substituent which is inactive in the reaction.

Therefore, a preferred one of the divalent groups Ar ₂ having an aromatic ring is an exoaryl group, and preferred examples thereof include an alkyl group having 1 to 6 carbon atoms or the aforementioned inactive in the reaction. Substituents such as phenyl, m-phenyl, p-phenyl, naphthyl, and phenyl.

In the present invention, a preferred one of the divalent group Ar ₂ having an aromatic ring is exemplified by the formula (III): (wherein the divalent group Z represents a divalent group selected from an alkylene group, a cycloalkyl group, an oxygen atom, a sulfur atom, a disulfide group, a fluorenylene group, a sulfonyl group, and a carbonyl group).

In the present invention, among the above-mentioned aryl groups of the divalent group Ar ₂ , those in which the above-mentioned divalent group Z is an alkylene group or an oxygen atom are particularly suitable.

When the divalent group Z is an alkylene group, the alkylene group may have an aryl group such as a phenyl group as a substituent. When the divalent group Z is an alkylene group, the alkylene group is preferably in the range of 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylene group, and an ethylene group. Ethylidene), dimethyl methylidene, methyl ethyl methylidene. The alkylene group having a phenyl group as a substituent may, for example, be phenyl methylidene or diphenyl methylidene.

When the divalent group Z is a cycloalkyl group, for example, an alkyl group having 1 to 6 carbon atoms or a substituent which is inactive in the reaction may be present on the carbon atom forming the ring. Cyclohexylene and cyclohexylidene.

The above Y ₂ and Y ₃ may be independently the same as the above Y ₁ , or may be independently the same as the above-mentioned aryl group Ar ₁ . Therefore, the above Y ₂ and Y ₃ may be the same or different from each other.

Therefore, in the present invention, preferred aromatic diamine compounds may, for example, be o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene or 2,6-diaminotoluene. Diaminotoluenes, diaminonaphthalenes such as 1,8-diaminonaphthalene, diaminobiphenyls such as 4,4'-diaminobiphenyl, bis(4-aminophenyl)methane 1,1-di(4-aminophenyl)ethane, 1,2-bis(4-aminophenyl)ethane, 1,1-bis(4-aminophenyl)propane, 2, 2-bis(4-aminophenyl)propane, 1,1-bis(4-aminophenyl)butane, 4,4'-diaminodiphenyl ether, 4,4'-diamine Diphenyl hydrazine, diaminopyridine, and the like.

Further, in the present invention, the aliphatic monoamine compound is preferably one represented by the formula (IVa): (wherein Ay ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; Y ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; or Ay ₁ and Y ₄ may also be used. Forming a 5- to 7-membered ring together, in which case the ring may also contain an oxygen atom and/or a nitrogen atom as an atom forming a ring. However, when the atom forming the ring is a nitrogen atom, the nitrogen atom does not have a bond. The hydrogen atom on it).

When the above-mentioned group Ay ₁ is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms. a group wherein the alkyl group having 3 or more carbon atoms may be a straight chain or a branched chain, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group.壬 base, twelve base, etc. Further, the above alkyl group may have a heterocyclic group which is inactive in the above reaction as a substituent.

When the above Ay ₁ is an alkenyl group, the alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and examples thereof include an allyl group and an isopropenyl group. Further, the above alkenyl group may have a heterocyclic group which is inactive in the above reaction as a substituent.

When the above Ay ₁ is a cycloalkyl group, the cycloalkyl group may have an alkyl group having 1 to 6 carbon atoms or a substituent which is inactive in the reaction at the carbon atom forming the ring, and The number of carbon atoms is preferably from 5 to 20, more preferably a cycloalkyl group having from 5 to 12 carbon atoms. Therefore, specific examples of the cycloalkyl group include, for example, a cyclopentyl group, a methylcyclopentyl group, and a cyclohexyl group. , methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl, and the like.

When the above Ay ₁ is an aralkyl group, the aralkyl group may, for example, be a benzyl group or a phenylethyl group.

Therefore, in the present invention, examples of the aliphatic monoamine compound include, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and tert-butylamine. , hexylamine, heptylamine, 2-ethylhexylamine, cyclohexylamine, piperididine, benzylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropyl Amine, di-n-butylamine, diisobutylamine, di-tert-butylamine, dipentylamine, dihexylamine, di(2-ethylhexyl)amine, dicyclohexylamine, bis(benzyl) Amino, allylamine, morpholine, bis(allyl)amine, 1-aminoethyl-2-methylimidazole, 2-methylpiperidine, 2-pipecoline, etc. A pyridine, and a mixture of any two or more of these.

Further, in the present invention, the aliphatic diamine compound is preferably one represented by the formula (IVb): (wherein Ay ₂ represents an alkyl group or a cycloalkyl group which may have an aryl group at a carbon atom or between carbon atoms; and Y ₅ and Y ₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or a cycloalkane. Or a arylalkyl group; or Ay ₂ and Y ₅ may together form a 5 to 7 membered ring, or Ay ₂ and Y ₆ may together form a 5 to 7 membered ring, or Ay ₂ and Y ₅ and Y ₆ Can also form a 5 to 7 member ring).

When the above-mentioned group Ay ₂ is an alkylene group, the alkylene group may have an aryl group such as a phenyl group as a substituent. When the group Ay ₂ is an alkylene group, the alkylene group is preferably in the range of 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylene group, a dimethylmethylene group, and a methyl group. Ethyl methylene and the like. Examples of the alkylene group which may have a phenyl group as a substituent include a phenylmethylene group, a diphenylmethylene group, a 1-phenylethylidene group, a 1,2-diphenylethylidene group and the like.

When the above-mentioned group Ay ₂ is a cycloalkyl group, the cycloalkyl group may, for example, be an alkyl group having 1 to 6 carbon atoms in the ring-forming carbon atom or the aforementioned inactive in the reaction. The substituents are extended to cyclohexyl and cyclohexylene.

When the above-mentioned group Ay ₂ is an aralkyl group, the aralkyl group may, for example, be a benzyl group or a phenylethyl group.

Further, the above may also be an alkyl group having an aryl group between carbon atoms, preferably a divalent group -A ₁ -YA ₂ -(V) represented by the formula (V) (wherein Y represents An extended aryl group having the above-mentioned substituent which is inactive in the reaction on the aromatic ring; and A ₁ and A ₂ each independently represent an alkylene group having 1 to 6 carbon atoms).

In the divalent group represented by the above formula (V), the above-mentioned extended aryl group may, for example, be a phenylene group, an anthranyl group, a phenylene group or the like, preferably a phenyl group, and the above alkyl group is preferred. Specific examples of the carbon number of 1 to 4 include a methylene group, an ethyl group, a propyl group, a trimethylene group, and a tetramethylene group.

Therefore, preferred specific examples of the divalent group represented by the above formula (V) are as shown below.

Therefore, in the present invention, the aliphatic diamine compound may, for example, be ethylenediamine, propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(amino group A). Cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(2,2'-aminoethyl)benzene, 1,4-bis(2,2'- Aminoethyl)benzene, piperazine (piperazine), 4-aminopiperidine, 1,3-bis(aminomethyl)benzene, 2-methyl-4-imidazoline, and the like.

According to the present invention, as described above, the dehalogenation reaction, that is, the condensation reaction, can be carried out by subjecting the monohalogenated phosphates to at least one amine compound selected from the monoamine compound and the diamine compound. The monohalogenated phosphates and the amine compounds used are used to obtain the desired phosphate amides.

Further, according to the present invention, as described above, by using a dihalogenated phosphate as a halogenated phosphate and subjecting it to a dehydrohalogenation reaction with a monoamine compound, that is, a condensation reaction, it can be used correspondingly. The dihalogenated phosphates and the monoamine compounds used give the desired phosphate amides.

In the reaction of such a halogenated phosphate ester with an amine compound, according to the present invention, the amine compound is reacted at a temperature of 130 ° C or higher with respect to 1 equivalent of the halogenated phosphate ester, preferably 0.5 equivalent or more, more preferably 0.8 to 1.2 equivalent. Thereby, the corresponding phosphate amides can be obtained with high productivity with respect to the amine compound.

In the present invention, the equivalent amount of the halogenated phosphate is a value obtained by dividing the amount of one mole of the halogenated phosphate by the number of halogen atoms of the halogenated phosphate; The equivalent of 1 is the value obtained by dividing the amount of 1 mole of the amine compound by the number of amines of the first and second grades of the amine compound.

Therefore, 1 equivalent of diphenyl chlorophosphate is 1 mole of it, and 1 equivalent of phenyl dichlorophosphate is 0.5 mole of it. Further, aniline has one primary amine group, and piperidine has one secondary amine group, and therefore, one equivalent thereof is 1 mole per mole. Phenylenediamine and piperazine There are two primary amine groups and two amine groups in the molecule, respectively, so that one equivalent is 0.5 moles.

In the method of the present invention, when the halogenated phosphate is reacted with the amine compound, the reaction solvent is not necessarily used, but in order to facilitate the reaction and to facilitate the post-reaction treatment, it is preferred to use a boiling point of 130 ° C or higher. Reaction solvent. When the reaction solvent is used, the amount of the lower limit is not particularly limited, but is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, per part by weight of the halogenated phosphate to be used. On the other hand, the upper limit of the reaction solvent to be used is preferably 5 parts by weight or less, more preferably 2 parts by weight, based on 1 part by weight of the halogenated phosphate to be used. the following.

In the present invention, the halogenated phosphates and the amine compound in the above ratio are generally added to the reaction vessel at a temperature of normal temperature or, if necessary, slightly heated to about 50 ° C, and the reaction is started. The reaction is then carried out at a temperature above 130 ° C, more preferably at the reflux temperature of the reaction solvent used.

The present invention is characterized in that, when the halogenated phosphate ester of the above ratio is reacted with an amine compound, it is reacted at a temperature of 130 ° C or higher, that is, a step of reacting at a temperature of 130 ° C or higher.

Although it is not intended to limit the method of the present invention, in order to list one of the preferred aspects of the method of the present invention, an amine compound is added to the reaction vessel at a temperature of room temperature or, if necessary, slightly heated to about 50 ° C. Further, the reaction solvent dissolves the amine compound in the reaction solvent, and secondly, the halogenated phosphate ester is gradually added to the amine compound solution while stirring the obtained amine compound. Thus, during the period in which the halogenated phosphate ester is gradually added to the amine compound solution, it is precipitated from the amine compound solution. The desired phosphoric acid ester amides and amine compounds are hydrohalide salts, and the reaction mixture forms a dispersion of a hydrogen halide salt containing a phosphate amide and an amine compound.

Next, after the halogenated phosphate ester is added, the reaction mixture is gradually heated to a desired reaction temperature, that is, a temperature of 130 ° C or higher, more preferably until the temperature of the reaction solvent used is maintained, while maintaining At this temperature, the reaction is continued for 30 minutes to several hours. In this way, during the heating of the reaction mixture to the desired reaction temperature, depending on the type of amine compound and halogenated phosphate used, the temperature of the reaction mixture generally exceeds about 100 from the reaction mixture. When it is about 120 ° C, the phosphate amide is dissolved in the reaction solvent to form a dispersion of the hydrogen halide which precipitates only the amine compound.

Thereafter, the reaction mixture is continuously heated to a desired reaction temperature, that is, to a temperature of 130 ° C or higher, more preferably to the reflux temperature of the reaction solvent used, and is not dissolved in the reaction solvent at the initial stage of the reaction. The solid matter of the hydrogen halide of the amine compound also gradually decreases as the reaction progresses from the temperature of the reaction mixture to about 130 ° C, and the amine is at the final stage of the reaction at the desired reaction temperature. The hydrogen halide salt of the compound disappears completely and the reaction mixture becomes a homogeneous and transparent solution. Thus, when the reaction mixture becomes a homogeneous and transparent solution, the reaction is terminated.

Therefore, in the present invention, as described above, after the phosphate amide is dissolved in the reaction solvent to precipitate only the dispersion of the amine compound, until the desired reaction temperature, that is, More preferably, at a temperature above 130 ° C, the hydrogen halide of the amine compound disappears at the reflux temperature of the reaction solvent used, and the reaction mixture becomes a homogeneous and transparent solution, that is, until the reaction is completed, it must be continued. reaction. So until the temperature is above 130 ° C More preferably, the hydrogenation acid salt of the amine compound disappears at the reflux temperature of the reaction solvent used, and the time until the reaction mixture becomes a uniform and transparent solution, that is, the time until the end of the reaction, although The type of the amine compound and the halogenated phosphate to be used is generally in the range of from 30 minutes to several hours.

In the present invention, the aspect in which the amine compound and the halogenated phosphate are reacted is not limited to the above-listed ones. For example, the amine compound may be dissolved in the reaction solvent and heated to about 100 to 130 ° C, if necessary. The halogenated phosphate is also dissolved in the reaction solvent and heated to about 100 to 130 ° C, and a solution of the halogenated phosphate is added to the solution of the above amine compound to cause a reaction.

As described later, in the present invention, it is preferred to pass an inert gas or air in the reaction vessel during the above reaction, and the generated hydrogen halide gas is removed to the outside of the reaction system.

In the present invention, the upper limit of the reaction temperature is also determined depending on the reaction solvent when the reaction solvent is used, but is usually 250 ° C or lower, more preferably 240 ° C or lower. Particularly in the present invention, the reaction temperature is also determined depending on the reaction solvent when the reaction solvent is used, but the range of 140 to 220 ° C is preferred in practical use.

The above reaction solvent having a boiling point of 130 ° C or higher can be applied, for example, to xylene, mesitylene, cumene, 1,2,4-trimethylbenzene (pseudocumene), solvent naphtha (solvent naphtha). An aromatic hydrocarbon solvent such as a petroleum brain solvent; an aliphatic hydrocarbon solvent such as an isoparaffin solvent; a halogenated aromatic hydrocarbon solvent such as monochlorobenzene, dichlorobenzene or trichlorobenzene; An aromatic ether solvent such as an ether; or a mixture thereof.

In the present invention, an organic solvent having a boiling point of 130 ° C or higher, which is a solvent petroleum naphtha or a petroleum brain solvent, which is a main component of various aromatic hydrocarbons, is contained in the above aromatic hydrocarbon solvent, and further, an isoalkane. An organic solvent having a boiling point of 130 ° C or more as a main component of the hydrocarbon is contained in the above aliphatic hydrocarbon solvent.

According to the method for producing a phosphate amide of the present invention, in the case where an amine compound is used in an excessive amount with respect to 1 equivalent of the halogenated phosphate, in a preferred embodiment, an amine compound is used in an amount of 0.8 to 1.2 equivalents, more preferably. With about 1 equivalent, the desired phosphate guanamine can be obtained with high productivity relative to the amine compound. The reason is considered as follows.

That is, first, when 1 equivalent of the amine compound and 1 equivalent of the halogenated phosphate are used, the above amine compound acts as a hydrogen halide trapping agent to promote the reaction while acting as a reaction material, and therefore, the amine compound is equivalent to 1 equivalent. Among the equivalents of the halogenated phosphates, 0.5 equivalents of the amine compound and 0.5 equivalent of the halogenated phosphate can be reacted even at a relatively low temperature to form the corresponding phosphate amide. However, in this case, 0.5 equivalent of the remaining amine compound captures the hydrogen halide formed by the above reaction to form a hydrogen halide, and therefore, in the state of the hydrogen halide, it cannot be combined with the remaining halogenated phosphate. 0.5 equivalent reaction. Here, by further increasing the reaction temperature, the hydrogen halide gas is detached from the hydrogen halide of the above amine compound, and is removed to the reaction system, and the amine compound is again returned to the free amine compound and the halogenated phosphoric acid. Ester reaction. The hydrogen halide formed therein is presumed to be directly removed from the reaction system without being captured by the amine compound under high temperature reaction conditions, or hydrogen halide gas under high temperature reaction conditions even if captured by the amine compound. Similarly, it will be detached from the hydrogen halide and removed to the outside of the reaction system.

Therefore, when the phosphate amide is produced by the present invention, it is necessary to The reaction system is connected to the outside of the reaction system, so that the hydrogen halide gas formed by the condensation reaction of the halogenated phosphate and the amine compound can be removed to the outside of the reaction system, especially in the present invention, preferably by using an amine. The hydrogen halide gas desorbed from the hydrogen halide of the compound is forcibly removed to the outside of the reaction system, and the reaction proceeds smoothly.

Therefore, according to the present invention, when the halogenated phosphate is reacted with the amine compound, it is preferred to blow an inert gas such as nitrogen, helium, argon or carbon dioxide into the reaction vessel and under the flow of the inert gas or The reaction is carried out under a stream of air or under a reduced pressure of suction.

Under such an operation, if the desired phosphate amide is separated from the obtained reaction mixture after reacting the halogenated phosphate with the amine compound, for example, the obtained reaction mixture can be cooled, and the precipitation reaction can be carried out. The material is filtered and taken out, and then, an aqueous acid solution such as hydrochloric acid or an aqueous alkali solution such as sodium carbonate is used, and then washed with warm water to remove unreacted materials, followed by drying to obtain the desired phosphate amide. Thereafter, it may be washed with a lower alcohol such as methanol or ethanol or acetone, or may be recrystallized from a hot alcohol.

According to the present invention, in response to the above-mentioned halogenated phosphates and amine compounds, the desired phosphate amides can be obtained.

That is, the monohalogenated phosphate represented by the above formula (Ia) is reacted with the aromatic monoamine compound represented by the above formula (IIa) to obtain a phosphate amide represented by the formula (VIa). Further, by reacting the monohalogenated phosphate represented by the above formula (Ia) with the aromatic diamine compound represented by the above formula (IIb), the phosphoric acid represented by the formula (VIb) can be obtained. Ester amides.

Similarly, by reacting the monohalogenated phosphate represented by the above formula (Ia) with the aliphatic monoamine compound represented by the above formula (IVa), a phosphate decylamine represented by the formula (VIIa) can be obtained. Further, by reacting the monohalogenated phosphate represented by the above formula (Ia) with the aliphatic diamine compound represented by the above formula (IVb), a phosphate ester represented by the formula (VIIb) can be obtained. Amines.

Further, by reacting the dihalogenated phosphate represented by the above formula (Ib) with the aromatic monoamine compound represented by the above formula (IIa), a phosphate decylamine represented by the formula (VIIIa) can be obtained. Similarly, by reacting the dihalogenated phosphate represented by the above formula (Ib) with the aliphatic monoamine compound represented by the above formula (IVa), a phosphate represented by the formula (VIIIb) can be obtained. Amidoxis.

Therefore, in the present invention, the phosphate amides represented by the formula (VIa) can be exemplified below.

Examples of the phosphate amides represented by the formula (VIb) include the following By.

Examples of the phosphate amides represented by the formula (VIIa) include the following.

Examples of the phosphate amides represented by the formula (VIIb) include the following.

Examples of the phosphate amides represented by the formula (VIIIa) include the following.

Examples of the phosphate amides represented by the formula (VIIIb) include the following.

Example

The invention is illustrated by the following examples, but the invention is not limited by the examples. In the following, the melting point refers to a value obtained by peaks which first appear when the temperature is raised at 20 ° C /min in the differential thermogravimetric measurement.

Example 1

At room temperature, 9.8 g (0.105 mol) of aniline and 35 mL of 1,3,5-trimethylbenzene were placed in a round bottom flask to dissolve the aniline in 1,3,5-trimethylbenzene. While stirring the obtained solution, the solution was kept at 40 ° C or lower, and 26.9 g (0.100 mol) of diphenyl chlorophosphate was gradually dropped into the solution over 10 minutes. At this time, anilinophenyl diphenyl phosphate and aniline hydrochloride were precipitated from the solution, and the reaction mixture became a dispersion containing the above precipitate.

After the completion of the dropwise addition, the reaction mixture was gradually heated to 170 to 180 ° C over 30 minutes, and while reacting 1,3,5-trimethylbenzene, the mixture was reacted at the same temperature as above for 1 hour. When the temperature of the reaction mixture exceeds about 100 ° C, the diphenyl phenylphosphonate is dissolved in 1,3,5-trimethylbenzene to form a dispersion in which aniline hydrochloride is separately precipitated. When the temperature of the reaction mixture becomes 130 ° C or higher, the solid content of the aniline hydrochloride which is not dissolved in the 1,3,5-trimethylbenzene at the initial stage of the reaction gradually decreases as the reaction progresses. At the end of the reaction, the solids of the aniline hydrochloride disappeared and the reaction mixture became a homogeneous and clear solution.

During the above reaction, nitrogen gas was introduced into the round bottom flask, and 3.0 g of the produced hydrogen chloride gas was recovered. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a precipitate.

The precipitate was suction filtered, washed with a dilute aqueous hydrochloric acid solution, a saturated aqueous sodium carbonate solution and warm water, and then dried to obtain 27.8 g of phenylaminodiphenyl phosphate. Its productivity relative to aniline was 81.5%. The melting point is 131.5 ° C (the melting point described in JP-A-49-72346 is 130 ° C).

Example 2

Except that 11.2 g (0.120 mol) of aniline was used in Example 1, the same procedure was carried out to obtain 30.5 g of diphenylphenylphosphonate. It is relative to aniline The yield was 78.2%. The melting point is 132.0 ° C.

Example 3

Except that 9.30 g (0.100 mol) of aniline and 33.6 g (0.125 mol) of diphenyl chlorophosphate were used in Example 1, the same procedure was carried out to obtain 29.5 g of diphenylphenylphosphonate. Its productivity relative to diphenyl chlorophosphate was 72.6%. The melting point is 131.2 ° C.

Example 4

The same procedure was followed except that aniline 11.3 g (0.122 mol), diphenyl chlorophosphate 23.7 g (0.088 mol) and phenyl dichlorophosphate 2.9 g (0.014 mol) were used in Example 1. A mixture of diphenyl phosphate and phenyl diphenylamino phosphate was 30.1 g. Among them, the content of the monoanilide in the above mixture was 86.6% by weight as a result of liquid chromatography analysis. The productivity of the above mixture relative to aniline was 75.9%. The melting point is 130.8 ° C.

Example 5

Except that in Example 1, 32.5 g (0.100 mol) of bis(2,6-dimethylphenyl) chlorophosphate was used instead of diphenyl chlorophosphate, the same procedure was carried out to obtain aniline phosphate di(2,6- Xylyl) ester 32.4 g. Its productivity relative to aniline was 81.0%. The melting point is 127.2 ° C.

Example 6

Except that in Example 1, an isoparaffin-based solvent (ISOPAR L manufactured by Exxon Mobil Chemical Co., Ltd.) was used instead of 1,3,5-trimethylbenzene as a solvent, and the temperature of the reaction mixture at the time of the reaction was changed to 190 to 200 ° C. The same operation was carried out to obtain 29.2 g of anilinophenyl diphenyl phosphate. Its productivity relative to aniline was 85.6%. The melting point is 133.2 ° C.

Example 7

Except that in Example 1, diphenyl ether was used instead of 1,3,5-trimethylbenzene as a solvent, and the temperature of the reaction mixture at the time of the reaction was changed to 200 to 220 ° C, and the same operation was carried out to obtain anilinophosphoric acid. Diphenyl ester 26.4 g. Its productivity relative to aniline was 77.4%. The melting point is 130.8 ° C.

Example 8

Except that in Example 1, xylene was used instead of 1,3,5-trimethylbenzene as a solvent, and the temperature of the reaction mixture at the time of the reaction was changed to 140 to 145 ° C, and the reaction time was changed to 2 hours, similarly This was carried out to obtain 25.7 g of anilinophenyl diphenyl phosphate. Its productivity relative to aniline was 75.3%. The melting point is 130.9 ° C.

Example 9

Except that morpholine 9.1 g (0.105 mol) was used instead of aniline in Example 1, the same procedure was carried out to obtain 23.9 g of morpholinyl diphenyl phosphate. Its productivity relative to morpholine was 71.4%. The melting point is 76.1 ° C (the melting point described in JP-A-2000-154277 is 71 ° C).

Example 10

In addition to using piperazine in Example 1. 4.5 g (0.052 mol) instead of aniline, and using isoalkane instead of 1,3,5-trimethylbenzene as a solvent, and changing the temperature of the reaction mixture at the time of reaction to 190 to 200 ° C, similarly Operation, and 1,4-piper Base II (diphenyl phosphate) 18.5 g. Relative to piperazine The productivity is 64.3%. The melting point is 184 ° C (the melting point described in JP-A-2000-327834 is 184 ° C).

Example 11

In addition to the use of m-phenylenediamine 5.7 g (0.053 mol) in Example 1. The same procedure as in the case of aniline gave 21.6 g of 1,3-bis(diphenylphosphonium)benzene. Its productivity relative to m-phenylenediamine was 71.5%. The melting point is 182.3 ° C (J. Chem. Soc. (C), the melting point described in 1971 is 183 to 184 ° C).

Example 12

In addition to the use of p-phenylenediamine 5.7 g (0.053 mol) in place of aniline in Example 1, and the use of petroleum brain solvent (Ipsol 150 manufactured by Idemitsu Kosan Co., Ltd.) in place of 1,3,5-trimethylbenzene, and The temperature of the reaction mixture at the time of the reaction was changed to 200 ° C, and the reaction time was changed to 4 hours, and the same procedure was carried out to obtain 22.9 g of 1,4-bis(diphenylphosphonium)benzene. Its productivity relative to p-phenylenediamine was 75.9%. The melting point is 210.3 ° C (J. Chem. Soc. (C), the melting point described in 1971 is 210 to 211 ° C).

Example 13

Except that in Example 12, 4,4'-diaminodiphenylmethane 10.4 g (0.053 mol) was used instead of p-phenylenediamine, and the reaction time was changed to 5 hours, and the same operation was carried out to obtain 4, 4'-bis(diphenylphosphoniumnonylaminophenyl)methane 30.8 g. Its productivity relative to 4,4'-diaminodiphenylmethane was 88.6%. The melting point is 186.5 ° C (the melting point described in JP-A-2003-238580 is 194 ° C).

Comparative example 1

To the round bottom flask, 30.0 g (0.323 mol) of aniline and 45 mL of toluene were added, and 40.8 g (0.152 mol) of diphenyl chlorophosphate was gradually added dropwise to the mixture while stirring at room temperature. After the completion of the dropwise addition, the temperature of the reaction mixture was changed to 80 ° C, and the mixture was continuously stirred for 1 hour, and then cooled to obtain a precipitate. The precipitate was collected by filtration, washed with water and then dried to give 45.1 g of diphenyl phenylamine. Its productivity relative to aniline was 43.0%. The melting point is 131.6 ° C.

Comparative example 2

In the same manner as in the first embodiment, the diphenyl chlorophosphate was added dropwise at room temperature, and after the completion of the dropwise addition, the reaction mixture was not heated, but the reaction was directly carried out at room temperature for 1 hour, and the same operation was carried out. Aniline diphenyl phosphate 13.4 g. Its productivity relative to aniline was 39.3%. The melting point is 131.1 ° C.

Claims (14)

A method for producing a phosphate amide, which is a method for producing a phosphoric acid amide of the following phosphorohalidate by the following (A) or (B): (A) a general formula At least one halogenated phosphate selected from the group consisting of phosphoromonohalidate (1a) and phosphorodihalidate represented by the formula (Ib) (In the above formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent which is inactive in the reaction; X represents a halogen atom), And at least one amine selected from the group consisting of a monoamine compound having one primary amino group and/or a secondary amine group in the molecule and a diamine compound having two primary amine groups and/or a secondary amine group in the molecule The compound is subjected to a dehydrohalogenation reaction; or (B) the above-mentioned dihalogenated phosphate ester as a halogenated phosphate ester is removed from a monoamine compound having one primary amino group and/or a secondary amine group in the molecule. Hydrogen halide reaction; wherein the method comprises reacting the above halogenated phosphate with the above amine compound at a temperature of 130 ° C or higher. The method for producing a phosphate amide according to the first aspect of the invention, wherein the monohalogenated phosphate represented by the above formula (Ia) and the aromatic compound represented by the formula (IIa) as an amine compound are used. The monoamine compound is reacted to produce the phosphate amide of the formula (VIa): Wherein Ar ₁ represents an aryl group; Y ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group; when Y ₁ is an aryl group, Y ₁ and Ar ₁ may be the same, Can be different) The method for producing a phosphate amide according to the first aspect of the invention, wherein the monohalogenated phosphate represented by the above formula (Ia) and the aromatic compound represented by the formula (IIb) as an amine compound are used. The group diamine compound is reacted to produce the phosphate amide of the formula (VIb): (wherein Ar ₂ represents a divalent group containing an aromatic ring bonded to two nitrogen atoms in the molecule; and Y ₂ and Y ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aromatic group; Or aralkyl group, and Y ₂ and Y ₃ may be the same or different) The method for producing a phosphate amide according to the first aspect of the invention, wherein the monohalogenated phosphate represented by the above formula (Ia) is reacted with an aliphatic monoamine compound represented by the formula (IVa) And the production of the phosphate amides of the formula (VIIa): (wherein Ay ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; Y ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; or Ay ₁ and Y ₄ may also be used. Forming a 5- to 7-membered ring together, in which case the ring may also contain an oxygen atom and/or a nitrogen atom as an atom forming a ring; however, when the atom forming the ring is a nitrogen atom, the nitrogen atom does not have a bond Hydrogen atom on it) The method for producing a phosphate amide according to the first aspect of the invention, wherein the monohalogenated phosphate represented by the above formula (Ia) and the lipid represented by the formula (IVb) as an amine compound are used. The group diamine compound is reacted to produce the phosphate amide of the formula (VIIb): (wherein Ay ₂ represents an alkylene group or a cycloalkyl group which may also have an aryl group on a carbon atom or between carbon atoms; and Y ₅ and Y ₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or a cycloalkane. Or a arylalkyl group; or Ay ₂ and Y ₅ may together form a 5 to 7 membered ring, or Ay ₂ and Y ₆ may together form a 5 to 7 membered ring, or Ay ₂ and Y ₅ and Y ₆ Can also form a 5 to 7 member ring together) The method for producing a phosphate amide according to the first aspect of the invention, wherein the dihalogenated phosphate represented by the above formula (Ib) and the aromatic compound represented by the formula (IIa) as an amine compound are used. The monoamine compound is reacted to produce the phosphate amide of the formula (VIIIa): Wherein Ar ₁ represents an aryl group; Y ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group; when Y ₁ is an aryl group, Y ₁ and Ar ₁ may be the same, Can be different) The method for producing a phosphate amide according to the first aspect of the invention, wherein the dihalogenated phosphate represented by the above formula (Ib) and the lipid represented by the formula (IVa) as an amine compound are used. The monoamine compound is reacted to produce the phosphate amide of the formula (VIIIb): (wherein Ay ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; Y ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aralkyl group; or Ay ₁ and Y ₄ may also be used. Forming a 5- to 7-membered ring together, in which case the ring may also contain an oxygen atom and/or a nitrogen atom as an atom forming a ring; however, when the atom forming the ring is a nitrogen atom, the nitrogen atom does not have a bond Hydrogen atom on it) The method for producing a phosphate amide according to any one of the first to seventh aspects of the invention, wherein the amine compound is reacted in an amount of 0.5 equivalent or more and less than 2 equivalents per equivalent of the halogenated phosphate. The preparation of the phosphate amides according to any one of claims 1 to 7 In the method, the amine compound is reacted in an amount of from 0.8 to 1.2 equivalents based on 1 equivalent of the halogenated phosphate. The method for producing a phosphate amide according to any one of claims 1 to 9, wherein the halogenated phosphate is reacted with an amine compound in the presence of a reaction solvent. The method for producing a phosphate amide according to claim 10, wherein the reaction solvent is selected from the group consisting of aromatic hydrocarbons having a boiling point of 130 ° C or more, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, and aromatic ethers. At least one. The method for producing a phosphate amide according to claim 10, wherein the reaction solvent is xylene, mesitylene, monochlorobenzene, dichlorobenzene, At least one selected from the group consisting of benzene trichloride and diphenyl ether. The method for producing a phosphate amide according to any one of claims 1 to 12, wherein the halogenated phosphate and the amine compound are reacted under a stream of air or an inert gas. The method for producing a phosphate amide according to any one of claims 1 to 12, wherein the halogenated phosphate and the amine compound are reacted under suction and reduced pressure.