JP2003252882A - Organophosphorus compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organophosphorus compound useful as a flame retardant, plasticizer or stabilizer, and a method for producing the same. <P>SOLUTION: This organophosphorus compound expressed by formula (1) is prepared by performing the reaction of a 5-membered alcohol expressed by formula (2) with a phosphorus-containing compound expressed by formula (3) [wherein, Ar<SP>1</SP>, Ar<SP>2</SP>are the same or different and are each an aryl which may have a substitutent; X is a halogen atom, hydroxyl or an alkoxy; R<SP>1</SP>is an alkyl, an alkenyl, hydroxyl or an alkoxy and adjacent R's may bond each other to form a ring; (m) is 1-5 integer; (n) is 0-4 integer; and (m+n) is ≤5]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organophosphorus compound useful as a flame retardant, a plasticizer, a stabilizer and the like and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in order to impart flame retardancy and stability,
Additives such as flame retardants and stabilizers are added to organic polymer compounds. Examples of such additives include inorganic compounds, phosphorus-containing compounds (aromatic phosphate esters, phosphorus-containing aliphatic condensation compounds, etc.), halogen-containing compounds (organic halogen compounds, halogen-containing organic phosphorus compounds, etc.), and the like. Among these additives, halogen-containing compounds, particularly halogen-containing organic phosphorus compounds, exhibit excellent flame retardancy. Representative examples of the halogen-containing compound include tetrabromodiphenyl ether, tetrabromobisphenol A, tri (dichloropropyl) phosphate, tri (dibromopropyl) phosphate and the like.

However, the halogen-containing compound thermally decomposes in the resin molding process to generate hydrogen halide, which not only corrodes the mold and deteriorates the resin, but also deteriorates the working environment. In addition, poisonous gas (hydrogen halide, etc.) generated by combustion adversely affects the human body and environment.

On the other hand, among the halogen-free additives, inorganic compounds such as metal hydroxides (magnesium hydroxide, aluminum hydroxide, etc.) and metal oxides (antimony oxide, alumina, etc.) have a low flame retardant effect. To obtain the desired flame retardancy, it is necessary to add a large amount of inorganic compound. Therefore, there is a possibility that the original characteristics of the resin may be lost.

Aromatic phosphates such as triphenyl phosphate (hereinafter sometimes referred to as TPP) and tricresyl phosphate are used as an additive which does not contain halogen and imparts relatively high flame retardancy. ing. In particular, TPP is widely used because it shows excellent flame retardancy, but it is highly volatile and volatilizes during the molding process of the resin composition, contaminating the mold and causing a poor appearance on the surface of the molded product. There is.

Examples of low-volatile organic phosphorus compounds include, for example, Japanese Examined Patent Publication No. 51-19858 and Japanese Examined Patent Publication No. 2-18.
Japanese Patent Laid-Open No. 336 and Japanese Patent Application Laid-Open No. 5-1079 describe low-volatile condensed organophosphorus compounds for increasing the flame retardancy of various resins (polyester resin, polyamide resin, polycarbonate resin, etc.). Although these condensed phosphoric acid esters have higher heat resistance than TPP, it is difficult to impart high flame retardancy.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an organophosphorus compound which has excellent heat resistance and is useful as a flame retardant, a plasticizer, a stabilizer and the like, and a method for producing the same.

Another object of the present invention is to provide a non-halogenated organic phosphorus compound which has low volatility and can impart high flame retardancy to a resin, and a method for producing the same.

Still another object of the present invention is to provide a method for producing a highly pure organophosphorus compound capable of imparting high flame retardancy to a resin simply and in high yield.

[0010]

Means for Solving the Problems As a result of earnest studies to achieve the above-mentioned object, the present inventors have found that when a five-membered cyclic alcohol (diol or the like) is reacted with a phosphoric acid ester reactant, heat resistance is improved. The inventors have found that a highly pure organophosphorus compound, which is highly useful as a flame retardant, a plasticizer, a stabilizer, etc., can be easily obtained in a high yield, and completed the present invention.

That is, the organic phosphorus compound of the present invention is represented by the following formula (1).

[0012]

[Chemical 5]

(In the formula, Ar ¹ and Ar ² are the same or different and each represents an aryl group which may have a substituent;
¹ represents an alkyl group, an alkenyl group, a hydroxyl group or an alkoxy group, and adjacent R ^1's may combine with each other to form a ring. m represents an integer of 1 to 5, n is 0
Indicates an integer of 4 and m + n ≦ 5. ) Formula (1)
In the compound represented by, when adjacent R ¹ 's are bonded to each other to form a benzene ring, the aryl groups represented by Ar ¹ and Ar ² usually have a substituent.

In the above formula (1), Ar¹And Ar
²Are the same or different and may have a substituent.
Reel groups (eg, unsubstituted C_6-10An aryl group, or
Halogen atom, C_1-8Alkyl group, hydroxyl group and
C_1-8At least one selected from the group consisting of alkoxy groups
Also has one substituent C_6-10Even an aryl group)
Well, R¹Is an alkyl group (C_1-8Alkyl group), alk
Nyl group (C_1-8Alkenyl group), hydroxyl group or
Lucoxy group (C_1-8Alkoxy group). m
Is usually an integer of 1 to 3. Such a compound
For example, 1,2-bis (di-C_6-10Aryl phospho
Roxy) cyclopentane, 1,3-bis (diC _6-10Ants
Examples include phosphoryloxy) cyclopentane.

In the method of the present invention, a five-membered ring alcohol represented by the following formula (2) is reacted with a phosphorus-containing compound represented by the following formula (3), and represented by the following formula (1). An organophosphorus compound is produced.

[0016]

[Chemical 6]

(In the formula, R ¹ represents an alkyl group, an alkenyl group, a hydroxyl group or an alkoxy group, and adjacent R ^1's may combine with each other to form a ring.
5 represents an integer of 5, n represents an integer of 0 to 4, and m + n ≦ 5
Is. Ar ¹ and Ar ² are the same or different and each represents an aryl group which may have a substituent, and X represents a halogen atom, a hydroxyl group or an alkoxy group. )

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (1), R¹Table
Examples of the alkyl group include methyl group, ethyl group
Group, propyl group, isopropyl group, butyl group, isobutyl
Group, t-butyl group, t-pentyl group, isooctyl group
Group, C such as 2-ethylhexyl group_1-8Alkyl group, etc.
Can be illustrated. Preferred alkyl groups are methyl and ethyl.
C, such as a vinyl group, an isopropyl group, and a t-butyl group._1-6Al
Kill group, especially C such as methyl group_1-4It is an alkyl group.
Examples of the alkenyl group include vinyl group and 1-propene group.
Nyl group, 2-propenyl group, isopropenyl group, butenyl
C, such as ruthel group and pentenyl group _2-8Examples include alkenyl groups
I can show you. Preferred alkenyl groups are vinyl group and 1-propyl group.
Lopenyl group, 2-propenyl group, isopropenyl group,
C such as tonyl group_2-4It is an alkenyl group.

Examples of the alkoxy group include C such as methoxy group, ethoxy group, propoxy group, isopropoxy group, isobutoxy group, t-butoxy group, t-pentyloxy group, isooctyloxy group and 2-ethylhexyloxy group. _{A 1-8} alkoxy group etc. can be illustrated. Preferred alkoxy groups are C _1-4 alkoxy groups such as methoxy group, ethoxy group, isopropoxy group and t-butoxy group.

When the cyclopentane ring has a plurality of substituents R ¹ adjacent to each other, the adjacent R ¹ and R ¹ may combine with each other to form a ring. Examples of such a ring include a cycloalkane ring [for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring,
Cyclononane ring, monocyclic hydrocarbon ring such as cyclooctane ring, polycyclic hydrocarbon ring such as norbornane ring, etc., especially C _3-8 cycloalkane ring], cycloalkene ring [eg cyclopentene ring, cyclohexene ring, benzene Examples thereof include monocyclic unsaturated hydrocarbon rings such as rings, polycyclic unsaturated hydrocarbon rings such as norbornene rings, etc., and particularly C _3-8 cycloalkene rings].

Preferred R ¹ is a hydroxyl group, a C _1-4 alkyl group or a C _1-4 alkenyl group, and adjacent R ¹ and R ¹ are bonded to each other to form a C _5-6 cycloalkane ring or C _{5-. 6}
A cycloalkene ring may be formed.

Examples of the aryl group represented by Ar ¹ and Ar ² include C _6-10 aryl groups such as phenyl group and naphthyl group. As the substituent of Ar ¹ and Ar ² , a halogen atom (fluorine, chlorine, bromine or iodine atom), an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group) Group, t-pentyl group, isooctyl group, 2-ethylhexyl group, etc., C _1-8 alkyl group, preferably C _1-6 alkyl group, especially C _1-4 alkyl group such as methyl group), hydroxyl group, alkoxy group (For example, C such as methoxy group, ethoxy group, propoxy group, isopropoxy group, isobutoxy group, t-butoxy group, t-pentyloxy group, isooctyloxy group, 2-ethylhexyloxy group, etc.
_1-8 alkoxy group, preferably C _1-4 alkoxy group such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group), carboxyl group, cyano group, nitro group,
An amino group etc. can be illustrated. These substituents may be substituted alone or in combination of two or more. Preferred substituents are halogen atoms (for example, chlorine atom and bromine atom), C _1-4 alkyl group, hydroxyl group, C _1-4 alkoxy group.

The number of substituents for the aryl group represented by Ar ¹ and Ar ² is not particularly limited and may be an unsubstituted aryl group (unsubstituted C _6-10 aryl group), for example, 1 or Plural (for example, 2 to 5, preferably 2 to 3)
It may be a substituted aryl group having a degree of substitution.
Examples of the substituted aryl group include, for example, a substituted phenyl group [o-, m-, p-tolyl group, 2,3-, 2,4
-, 2,6-xylyl group, 2,4,6-trimethylphenyl group, 2,3,4,5,6-pentamethylphenyl group and other methyl-substituted phenyl groups, etc.], corresponding to these substituted phenyl groups C _2-4 alkyl-substituted phenyl group, hydroxyphenyl group, and halogen-substituted phenyl can be mentioned.

In the above formula (1), m represents an integer of 1 to 5, usually 1 to 3, particularly 2 or 3. Further, n represents an integer of 0 to 4, and m + n ≦ 5 (preferably m + n = 1 to 4, more preferably 2 to 4).

In the above formula (1), adjacent R ¹ are rings (non-aromatic ring such as non-aromatic hydrocarbon ring, hetero ring,
Aromatic rings such as benzene ring and heterocycle) may not be formed, or they may be bonded to each other to form a ring. When the ring forms a benzene ring, the aryl group represented by Ar ¹ and Ar ² usually has a substituent. Examples of the aryl group having such a substituent include the substituted aryl groups exemplified above, particularly a methyl-substituted phenyl group [the above-mentioned tolyl group, xylyl group, etc.].

The preferred organic phosphorus compound is represented by the above formula (1)
In, the following combination can be used.

R ¹ : C _1-2 alkyl group Ar ¹ and Ar ² : a phenyl group which may have a halogen atom, a C _1-2 alkyl group, a hydroxyl group or a C _1-2 alkoxy group (particularly a methyl-substituted group). Phenyl group or hydroxyphenyl group) m: 2 or 3 n: 1 or 0.

A typical compound represented by the formula (1) is a compound in which n = 0 and Ar ¹ and Ar ² are optionally substituted C _6-10 aryl groups, for example, , 1,
2-bis (diphenylphosphoroxy) cyclopentane,
1,2-bis (ditolylphosphoroxy) cyclopentane, 1,2-bis (dixylylphosphoroxy) cyclopentane, 1,2-bis (dicresylphosphoroxy) cyclopentane, and other 1,2-bis (di) C _6-10 arylphosphoroxy) cyclopentanes; 1,3-bis (diphenylphosphoroxy) cyclopentane, 1,3-bis (ditoluylphosphoroxy) cyclopentane, 1,3-bis (dixylylphosphoroxy) Cyclopentane, 1,3-
1,3-bis (diC _6-10 arylphosphoroxy) cyclopentanes such as bis (dicresylphosphoroxy) cyclopentane; adjacent R ¹ and R ¹ bond to each other to form a benzene ring, and Ar C in which ¹ and Ar ² have a substituent
Compounds having _6-10 aryl groups, for example, 1,2-bis (ditoluylphosphoroxy) indane, 1,2-bis (dixylylphosphoroxy) indane, 1,2-bis (dicresylphosphoroxy) indane, etc. 1,2-bis (diC _6-10 arylphosphoroxy) indanes;
3-bis (ditoluylphosphoroxy) indane, 1,3
-Bis (dixylylphosphoroxy) indane, 1,3-
1,3 such as bis (dicresyl phosphoroxy) indane
-Bis ( _diC6-10 arylphosphoroxy) indanes and the like.

Of these organophosphorus compounds, 1,2-
Bis (di-C _6-10 aryl phosphorodithioates carboxymethyl) cyclopentane compounds (in particular, 1,2-bis (diphenyl phosphorodithioate carboxymethyl) cyclopentane, etc.), 1,3-bis (di-C _6-10 aryl phosphorodithioates carboxymethyl) cyclopentane compound (In particular, 1,3-bis (diphenylphosphoroxy) cyclopentane and the like) are preferable. In these compounds, the benzene ring as Ar ¹ and Ar ² has one or more substituents (eg, halogen atom, C _1-2 alkyl group, hydroxyl group or C _1-2
It may have an alkoxy group).

[Production Method] The organic phosphorus compound (1) of the present invention is obtained by reacting a five-membered ring alcohol represented by the following formula (2) with a phosphorus-containing compound represented by the following formula (3). Can be prepared by According to this method, the organophosphorus compound represented by the above formula (1) can be easily obtained with a high yield. In particular, a high-purity organophosphorus compound can be obtained.

[0031]

[Chemical 7]

(In the formula, X represents a halogen atom, a hydroxyl group or an alkoxy group, and Ar ¹ , Ar ² , R ¹ , m and n are the same as above.) In this method, the compound (1) exemplified above is used. In addition, compounds in which R ¹ adjacent to each other in the formula (2) are bonded to each other to form a benzene ring and Ar ¹ and Ar ² are unsubstituted aryl groups, for example, 1,2-bis (diphenylphosphoroxy) ) 1,2-bis (diC _6-10 arylphosphoroxy) indanes such as indane; 1,3-bis (diC) such as 1,3-bis (diphenylphosphoroxy) indane
_6-10 arylphosphoroxy) indanes and the like can be efficiently obtained.

The halogen atom represented by X includes, for example,
It contains a fluorine, chlorine, bromine or iodine atom. Preferred halogen atoms are chlorine or bromine atoms. Examples of the alkoxy group represented by X include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an isobutoxy group, a t-butoxy group, a t-pentyloxy group, an isooctyloxy group and a 2-ethylhexyloxy group. C
_{A 1-8} alkoxy group etc. can be illustrated. In the 5-membered ring alcohol, preferred X is a halogen atom (especially chlorine atom), a hydroxyl group, a C _1-4 alkoxy group (especially a methoxy group or an ethoxy group).

Examples of the five-membered ring alcohol represented by the formula (2) include cyclopentanemonools (alkyl-substituted cyclopentanemonool such as cyclopentanemonool, methylcyclopentanemonool and dimethylcyclopentanemonool, dichloro). Halogen-substituted cyclopentanemonool such as cyclopentanemonool),
Cyclopentanediols (cyclopentanediol,
Alkyl-substituted cyclopentanediol such as methylcyclopentanediol, halogen-substituted cyclopentanediol such as dichlorocyclopentanediol), cyclopentanetriols (alkyl-substituted cyclopentanetriol such as cyclopentanetriol and methylcyclopentanetriol, chlorocyclopentane) Halogen-substituted cyclopentanetriol such as triol), cyclopentanetetraols (alkyl-substituted cyclopentanetetraol such as cyclopentanetetraol and methylcyclopentanetetraol, halogen-substituted cyclopentanetetraol such as chlorocyclopentanetetraol) ) Etc. can be illustrated.

Preferred five-membered ring alcohols include cyclopentane monools, cyclopentane diols and cyclopentane triols. Representative compounds of the cyclopentane diols, for example, cyclopentane diol [cyclopentane-1,2-diol, cyclopentane-1,3-diol], C _1-4
Alkyl-substituted cyclopentanediols [3-methyl-
Cyclopentane-1,2-diol, 4-methyl-cyclopentane-1,2-diol, 3,4-dimethyl-cyclopentane-1,2-diol, etc.], C _2-4 alkenyl-substituted cyclopentanediols [ 3-vinyl-cyclopentane-1,2-diol, 4-vinyl-cyclopentane-1,2-diol, 3,4-divinyl-cyclopentane-1,2-diol, etc.] and adjacent R ¹ 's are bonded to each other. To form a cycloalkane ring (preferably a C _3-8 cycloalkane ring) [hexahydroindane-1,2-diol, hexahydroindane-1,3-diol, bicyclo [3.
3.0] Octane-2,3-diol, bicyclo [3.
3.0] Octane-2,4-diol, decahydroazulene-1,2-diol, decahydroazulene-1,3
-Diol, tricyclo [5.2.1.0 ^2,6 ] decane-3,4-diol, tricyclo [5.2.1.
0 ^2,6 ] decane-3,5-diol, etc.], adjacent R ¹
Are bonded to each other to form a cycloalkene ring (preferably C _3-8
Cyclopentanediols forming a (cycloalkene ring) [3a, 4,7,7a-tetrahydroindane-
1,2-diol, 3a, 4,7,7a-tetrahydroindane-1,3-diol, 1,2,3,3a, 4
6a-hexahydro-1,2-pentalenediol,
1,2,3,3a, 4,6a-hexahydro-1,3-
Pentalenediol, 2,3,3a, 4,7,7a-hexahydro-4,7-methanoindene-1,2-diol, 2,3,3a, 4,7,7a-hexahydro-4,
7-methanoindene-1,3-diol, etc.] and the like. The cyclopentane monools and cyclopentane triols include compounds corresponding to the cyclopentane diols.

These compounds may also be compounds derived from the corresponding epoxides. Further, these compounds may be a simple substance or a mixture of various isomers (positional and / or stereoisomers). Preferred five-membered ring alcohols are cyclopentane-1,2-
Examples thereof include diol and cyclopentane-1,3-diol.

Examples of the phosphorus-containing compound represented by the formula (3) include diarylphosphoric acid halides [diphenylphosphoric acid chloride, ditoluylphosphoric acid chloride, dixylylphosphoric acid chloride, dicresylphosphoric acid chloride, etc.], diarylphosphoric acid [diphenylphosphoric acid. Acid, ditoluyl phosphoric acid, dixylyl phosphoric acid, dicresyl phosphoric acid, etc.], triaryl phosphates [triphenyl phosphate (TPP), tricresyl phosphate, etc.]
And so on. Preferred phosphorus-containing compound, di-C _6-10 aryl phosphate chlorides such as diphenyl phosphate chloride, di C _6-10 aryl phosphates such as diphenyl phosphate, tri C _6-10 aryl phosphates such as TPP.

The amount of the phosphorus-containing compound (3) used can be selected from the range of about 0.1 to 50 mol, preferably about 0.2 to 30 mol, relative to 1 mol of the five-membered ring alcohol (2). For example, in the reaction between diphenylphosphoric acid chloride and a five-membered ring diol, the amount of diphenylphosphoric acid chloride used is 0.1 to 5 per 1 mol of the five-membered ring diol.
It is about 0 mol, preferably about 0.2 to 30 mol.
The amount of the phosphorus-containing compound (3) used is usually 1 mol of the hydroxyl group of the five-membered ring alcohol (2),
0.5-5 mol, preferably 0.8-3 mol, especially 1-
It may be about 2 mol.

The reaction may be carried out in the absence of a solvent, but it is usually carried out in the presence of a solvent. As a solvent,
There is no particular limitation as long as it does not inhibit the reaction, and examples thereof include non-basic nitrogen-containing compounds (for example, nitrile solvents such as acetonitrile and benzonitrile), aliphatic hydrocarbons (hexane, cyclohexane, heptane, octane, etc.) ), Aromatic hydrocarbons (benzene, toluene,
Xylene, ethylbenzene, etc.), oxygen-containing hydrocarbons (ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, esters such as ethyl acetate), halogenated hydrocarbons (Carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, dichlorobenzene, etc.), sulfoxides (dimethyl sulfoxide, etc.) and the like can be mentioned. These solvents may be used alone or as a mixed solvent.

Preferred solvents include nitriles such as acetonitrile; C _6-8 aliphatic hydrocarbons such as hexane and heptane; C _6-12 aromatic hydrocarbons such as toluene and xylene; diethyl ether, tetrahydrofuran, 1,
Examples thereof include ethers such as 4-dioxane, halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane. More preferably, acetonitrile, tetrahydrofuran, 1,2-dichloroethane, dichloromethane, chloroform and the like are used.

The amount of the solvent used is not particularly limited as long as it does not impair the reaction, and is, for example, 0.1 to 500 mol, preferably 1 mol based on 1 mol of the five-membered ring alcohol represented by the formula (2). ˜100 mol, more preferably about 1 to 50 mol.

In the formula (2), the reaction proceeds by a dehydrohalogenation reaction when a compound in which X is a halogen atom is used, and by a dehydration reaction when a compound in which X is a hydroxyl group is used, When a compound in which is an alkoxy group is used, the target compound (1) can be obtained by the transesterification reaction. These reactions may be carried out in the presence or absence of a conventional catalyst (eg esterification catalyst).

The dehydrohalogenation reaction may be carried out in the presence or absence of a dehydrohalogenating agent. Examples of the dehydrohalogenating agent include bases (amines, heterocyclic bases (aromatic or non-aromatic bases), organic bases such as amides, inorganic bases such as alkali metal or alkaline earth metal compounds, and the like. ) Is mentioned. These dehydrohalogenating agents may be used alone or in combination of two or more kinds. Further, the dehydrohalogenating agent may be used as a reaction solvent.

Examples of amines include C _1-8 alkylamines such as primary amines [t-butylamine, t-pentylamine, t-hexylamine, t-octylamine and alkanolamines (fats). Group primary amines), C such as cyclohexylamine
_3-8 cycloalkylamine (alicyclic primary amine), C _6-10 arylamine such as aniline (aromatic primary amine)], secondary amine [di-t-butylamine, di-t
-Pentylamine, di-t-hexylamine, di-t-
Di-C _1-8 alkylamines such as octylamine and dialkanolamines (aliphatic secondary amines) such as diethanolamine, di-C _3-8 cycloalkylamines (alicyclic secondary amines) such as dicyclohexylamine, N -C _1-4 alkylaniline (aromatic secondary amine) such as methylaniline], tertiary amine [tri C _1-8 alkylamine such as trimethylamine and triethylamine, alkanolamine such as triethanolamine and dimethylaminoethanol] (Aliphatic tertiary amine), tri-C _3-8 cycloalkylamine (tricyclic cyclohexylamine) (alicyclic tertiary amine), N, N-diC _1-4 alkyl such as N, N-diethylaniline Aniline (aromatic tertiary amine)] and the like.

Among the heterocyclic bases, aromatic bases include, for example, five-membered ring compounds (pyrrole, 3-pyrroline,
Pyrazole, 2-pyrazoline, imidazole, 1,2,
Heterocyclic compounds having 1 to 3 nitrogen atoms such as 3-triazole and 1,2,4-triazole), 6-membered ring compounds (pyridine, 4- (dimethylamino) pyridine, 2-piperidinopyridine, 3- N-substituted pyridines such as piperidinopyridine, 4-piperidinopyridine, 2-pyrrolidinopyridine, 3-pyrrolidinopyridine and 4-pyrrolidinopyridine, N-such as pyridazine, pyrimidine, pyrazine and 2-methylpyrazine Heterocyclic compounds having 1 to 3 nitrogen atoms such as substituted pyrazine, s-triazine and picoline), polycyclic heterocyclic compounds (indole, quinoline,
Fused heterocyclic compounds of aromatic hydrocarbon rings and heterocycles such as isoquinoline, cinnoline, quinoxaline, quinazoline, phthalazine, and 1,10-phenanthroline, 2,2
-Ring assembly heterocyclic compounds such as bipyridyl) and the like.

Non-aromatic bases among the heterocyclic bases include, for example, five-membered ring compounds (pyrrolidine, N-methylpyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 2-aminopyrrolidine, 3-amino). N-substituted pyrrolidines such as pyrrolidine, pyrazolidine and the like, six-membered ring compounds (piperidine, N-methylpiperidine, o-aminopiperidine, m-aminopiperidine, p-aminopiperidine and other N-substituted piperidines, piperylhydrazine, morpholine , Piperazine, N-methylpiperazine,
N-substituted piperazines such as 2-methylpiperazine and N, N-dimethylpiperazine), polycyclic heterocyclic compounds (quinacridine, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [3. 2.1] octane, 1,5-diazabicyclo [3.3.0] octane,
1,4-diazabicyclo [4.2.0] octane, 1,
5-diazabicyclo [3.3.1] nonane, 1,5-diazabicyclo [5.3.0] decane, 1,5-diazacyclo [3.3.0.0 ^2,6 ] octane, 1,8-diazabicyclo [5.4.0] Undec-7-ene, 1,5-
Diazabicyclo [4.3.0] nonane-5-ene, hexamethylenetetramine, and other crosslinked cyclic compounds).

Examples of the amides include N, N-diC _1-4 alkyl-substituted amides such as N, N-dimethylformamide and N, N-dimethylacetamide.

As the inorganic base, a hydroxide of an alkali metal or an alkaline earth metal (for example, sodium hydroxide,
Examples thereof include potassium hydroxide, calcium hydroxide, magnesium hydroxide), carbonates (sodium carbonate, calcium carbonate, etc.) and hydrogen carbonates (sodium hydrogen carbonate, calcium hydrogen carbonate, etc.).

Preferred dehydrohalogenating agents include, for example, tertiary amines (tri-C such as triethylamine).
_1-4 alkylamines), heterocyclic tertiary amines (heterocyclic compounds such as pyridine), alicyclic bases (6-membered heterocyclic compounds such as piperazine and N-methylpiperazine, quinacridine, 1,4- Examples thereof include crosslinked cyclic compounds such as diazabicyclo [2.2.2] octane and hexamethylenetetramine), amides (N, N-dimethylformamide and the like), and metal hydroxides (sodium hydroxide and the like). In particular, heterocyclic tertiary amines such as pyridine are often used as dehydrohalogenating agents.

The amount of the dehydrohalogenating agent (such as pyridine) used is 0.5 to 100 mol, preferably 0.7 to 50 mol, based on 1 mol of the acid halide represented by the formula (3). It is preferably about 1 to 25 mol.

The dehydration reaction and / or transesterification reaction is
It may be carried out in the presence or absence of a conventional catalyst (acid catalyst, base catalyst). Examples of the acid catalyst include Lewis acids (aluminum chloride, magnesium chloride, titanium tetrachloride, antimony pentachloride, zinc chloride, tin chloride, etc.), protic acids (inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, p-toluene sulfone). Acid, organic acids such as benzenesulfonic acid) and the like. Examples of the base catalyst include Cs such as amines (t-butylamine, t-pentylamine, t-hexylamine, t-octylamine).
_1-8 alkylamine, di-t-butylamine, di-t-
Di-t-hexylamine, di-t-octylamine and other diC _1-8 alkylamines, trimethylamine, triethylamine, tributylamine and other tri-C _1-8 alkylamines, heterocyclic amines, etc.) Organic bases, alkali metal or alkaline earth metal hydroxides (sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.), carbonates (sodium carbonate, potassium carbonate, calcium carbonate, etc.), hydrogen carbonates (sodium hydrogen carbonate) Etc.) and the like.

In the reaction, the order of addition of each component is not particularly limited. For example, in the dehydrohalogenation reaction,
First, the compound (2) may be dissolved in the solvent exemplified above, and the compound (3) may be added to the reaction system for reaction. Further, the dehydrohalogenating agent may be dissolved in a solvent together with the compound (2), and may be added by dropping or the like together with or after the addition of the compound (3).

The reaction temperature is in a wide range, for example, -80 to
Can be selected from the range of about 300 ℃, -50 ~ 250 ℃,
Preferably -30 to 200 ° C, more preferably 0 to 1
It is about 20 ° C.

Organophosphorus compound (1) produced by the reaction
Can be easily separated and purified by a conventional method, for example, a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or a combination of these separation means.

The organophosphorus compound (1) of the present invention can be used as a flame retardant, a plasticizer, a stabilizer and the like for various compounds and compositions. Examples thereof include hot-melt adhesives, heat-sensitive adhesives and delayed. Tack adhesive, thermal transfer image receiving material,
It is useful as an additive for color photographic sensitizers, melt-type inkjet inks, vibration absorbing materials, pencil leads, compositions such as vinyl chloride resins, organic compounds (particularly organic polymer compounds), lubricating oils, heat media and the like.

[0056]

INDUSTRIAL APPLICABILITY According to the present invention, an organophosphorus compound useful as a flame retardant, a plasticizer, a stabilizer and the like can be easily obtained in high yield and high purity. Since the organophosphorus compound of the present invention has excellent heat resistance and can impart high flame retardancy, when used in combination with various materials (particularly molding resins),
Material properties (stability, etc.) can be greatly improved.

[0057]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 Preparation of cyclopentane-1,2-bis (diphenyl phosphate) (a) Preparation of cyclopentane-1,2-diol In a 50 ml two-necked flask, 12 g (143 mmol) of cyclopentene oxide and 30 ml of water were added. Was stirred, 15 μl of concentrated sulfuric acid was added to the reaction system, and the mixture was stirred for 1 hour. After the reaction solution was neutralized with a 5% aqueous sodium hydroxide solution, water was distilled off to quantitatively obtain cyclopentane-1,2-diol.

(B) Preparation of cyclopentane-1,2-bis (diphenyl phosphate) In a 300 ml three-necked flask equipped with a dropping funnel and a calcium chloride tube, the cyclopentane-1, prepared above was prepared.
2-diol 18.3g (179mmol) and pyridine 175.1g (2.21mol) were added, and it stirred at room temperature. Diphenylphosphoric chloride 12 was added to this reaction system.
0 g (448 mmol) was added dropwise over 1 hour, and then 5
Reaction was carried out at 0 ° C. for 6 hours to complete the reaction.

The reaction solution was poured into 1300 g of ice water to precipitate the desired product, which was collected by filtration. Then, the target product was washed in 200 ml of cold methanol and collected by filtration. The target product (cyclopentane-1,2-bis (diphenyl phosphate)) was recrystallized from 200 ml of acetone for purification.

Yield: 94.3 g (Yield: 93%, Purity:
95% (HPLC area ratio)) Melting point: 96 ° C. (pyrolysis temperature: 262 ° C.) IR spectrum (cm ⁻¹ ): 1590, 1489, 12
93, 1190, 1161, 1067, 1048, 10
25, 963, 938, 776, 689, 527, 51
^{9 1 H NMR (400MHz, CDCl} 3, ppm):
7.33-7.14 (m, 20H), 5.07 (s (b
r), 2H), 2.11 to 1.69 (m, 6H) (HPLC analysis conditions) Column: YMC J'sphere ODS-M8
0 JM08S04-2546WT, 250 mm x 4.
6 mm Eluent: acetonitrile / water = 60 / 40-80 / 20
(Volume ratio) Outflow rate: 0.8 ml / min Measurement wavelength: 254 nm Column tank temperature: 40 ° C. Example 2 Production of trans-1,2-bis (diphenylphosphoroxy) indane 500 ml equipped with a dropping funnel and a calcium chloride tube
Indane-1,2-diol 10.
1 g (67.5 mmol), acetonitrile 100 m
1, 132 ml (168 mol) of pyridine were added, and the mixture was stirred at room temperature. Diphenyl phosphate chloride 3 in the mixture
7.7 g (140 mmol) was added dropwise over 1 hour and reacted at room temperature for 5 hours.

300 ml of ethyl acetate was added to the reaction mixture, the target compound was extracted, and then purified by column chromatography using a mixed solvent of hexane / ethyl acetate (2: 1 by volume) as an elution solvent.

Yield of colorless liquid 19.4 g (yield 47%, purity 98% (HPLC area ratio)) Thermal decomposition temperature: 217 ° C. IR spectrum (cm ⁻¹ ): 3056, 1592, 14
89, 1291, 1266, 1217, ll90, ll
63, 1073, 1024, 1011, 961 ¹ HNMR (400 MHz, CDCl ₃ , ppm): 7.
42-7.12 (m, 24H), 6.12-6.09
(Q, 1H), 5.42-5.40 (m, 1H), 3.
54-3.48 (q, 1H), 3.11-3.06
(Q, 1H)

Claims (5)

[Claims] 1. The following formula (1): (In the formula, Ar ¹ and Ar ² are the same or different and each represents an aryl group which may have a substituent, R ¹ represents an alkyl group, an alkenyl group, a hydroxyl group or an alkoxy group, and they are adjacent to each other. R ¹ may combine with each other to form a ring, m represents an integer of 1 to 5, n represents an integer of 0 to 4, and m + n ≦ 5). . 2. Ar ¹ and Ar ² are the same or different,
It is an aryl group which may have a substituent, and R ¹ is
The organophosphorus compound according to claim 1, which is an alkyl group, an alkenyl group, a hydroxyl group or an alkoxy group, and m is an integer of 1 to 3. 3. Ar ¹ and Ar ² are the same or different,
Unsubstituted C _6-10 aryl group, halogen atom, C
A C _6-10 aryl group having at least one substituent selected from the group consisting of a _1-8 alkyl group, a hydroxyl group and a C _1-8 alkoxy group, wherein R ¹ is a C _1-8 alkyl group, C _The organophosphorus compound according to claim 1, which is a _1-8 alkenyl group, a hydroxyl group or a C _1-8 alkoxy group. 4. The organophosphorus compound according to claim 1, which is 1,2-bis (diC _6-10 arylphosphoroxy) cyclopentane or 1,3-bis (diC _6-10 arylphosphoroxy) cyclopentane. . 5. The following formula (2): (In the formula, R ¹ represents an alkyl group, an alkenyl group, a hydroxyl group or an alkoxy group, and adjacent R ¹ may be bonded to each other to form a ring. M represents an integer of 1 to 5, n represents an integer of 0 to 4 and m + n ≦ 5), and a five-membered ring alcohol represented by the following formula (3): (In the formula, Ar ¹ and Ar ² are the same or different and each represents an aryl group which may have a substituent, and X represents a halogen atom, a hydroxyl group or an alkoxy group.) A compound represented by the following formula (1): (In the formula, R ¹ , Ar ¹ , Ar ² , m and n are the same as above)
A method for producing an organophosphorus compound represented by: