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WO2012039473A1 - Composé phosphoré organique et sa méthode de production - Google Patents

Composé phosphoré organique et sa méthode de production Download PDF

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Publication number
WO2012039473A1
WO2012039473A1 PCT/JP2011/071682 JP2011071682W WO2012039473A1 WO 2012039473 A1 WO2012039473 A1 WO 2012039473A1 JP 2011071682 W JP2011071682 W JP 2011071682W WO 2012039473 A1 WO2012039473 A1 WO 2012039473A1
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group
general formula
carbon atoms
substituent
aryl
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Japanese (ja)
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泰 中本
弘津　健二
修二 山田
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Ube Corp
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Ube Industries Ltd
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Priority to JP2012535080A priority Critical patent/JP5892067B2/ja
Priority to CN2011800454225A priority patent/CN103119049A/zh
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5333—Arylalkane phosphine oxides or thioxides

Definitions

  • the present invention relates to an organic phosphorus compound having an oxyphenyl group such as a hydroxyphenyl group or an alkoxyphenyl group, and a method for producing the same.
  • Organophosphorus compounds are chemical substances that are widely used in various products such as flame retardants, plasticizers, insecticides, medicines and agricultural chemicals, and ligands of complex catalysts.
  • organic phosphorus compounds have attracted particular attention industrially as constituent materials such as flame retardants and flame retardant resins as functional materials.
  • a method for producing a flame retardant resin for example, a method of mixing a low molecular compound such as a phosphorus compound with an existing resin has been reported.
  • the low molecular weight compound precipitates on the resin surface or aggregates in the resin due to a phenomenon called bleed out. It is known that the physical properties of the resin may be reduced.
  • Patent Documents 1 and 2 are insufficient in heat resistance and hydrolysis resistance (moisture resistance and water absorption resistance), it is difficult to say that they are industrially suitable compounds.
  • the subject of the present invention is, for example, a flame retardant or flame retardant resin monomer having good heat resistance and hydrolysis resistance (moisture resistance, water absorption resistance), or other raw materials intermediates for organic materials and medical and agrochemical products
  • An object of the present invention is to provide an organic phosphorus compound useful as an additive for industrial processing agents, an additive for fertilizers, and the like, and a method for producing the same.
  • this invention provides the organophosphorus compound shown by the following ⁇ 1> and ⁇ 2>, and its manufacturing method.
  • ⁇ 1> An organophosphorus compound represented by the following general formula (A).
  • R 1 , R 2 , R 4 and R 7 may each independently have a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or a substituent.
  • An alkyl group, an alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group, p and q are each independently an integer of 0 to 5, and r and s are each independently 0 to 4 Is an integer.
  • the plurality of R 1 , R 2 , R 4, and R 7 may be the same as or different from each other.
  • R 1 and R 2 are each, when substituted on adjacent carbon atoms in the benzene ring, it may form a ring structure by bonding with each other.
  • R 3 represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent.
  • An aryl group which may have, or a group represented by — (CH 2 ) n —Q 1 is shown.
  • Q 1 is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR a ),
  • R 5 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, or a nitro group, a cyano group, carbon
  • An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms are shown.
  • R 6 represents a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent.
  • An aryl group which may have, or a group represented by — (CH 2 ) m —Q 2 .
  • Q 2 is a vinyl group, a propenyl group, an ethynyl group, a hydroxyl group (—OH), a nitro group, a cyano group, a cyclic ether group, a carboxylic acid group (—COOH), a carboxylic acid ester group (—COOR b ), An alkoxy group (—OR b ) or an optionally substituted phenyl group; R b represents an optionally substituted alkyl group; and m is an integer of 1 to 6. .
  • the organic phosphorus compound represented by the general formula (A) has 25 to 100 carbon atoms. ]
  • a diarylphosphine oxide compound represented by the following general formula (1), an arylcarbonyl compound represented by the following general formula (2), and an aryl compound represented by the following general formula (3) are reacted in the presence of an acid catalyst.
  • the manufacturing method of the organophosphorus compound shown by the following general formula (A) including the process to make.
  • R 7 R 1 to, p, q, r and s are from R 1 in the general formula (A) R 7, p, q, at r and s synonymous is there.
  • the diarylphosphine oxide compound represented by the general formula (1) has 12 to 46 carbon atoms
  • the arylcarbonyl compound represented by the general formula (2) has 7 to 32 carbon atoms
  • the general formula (3) The aryl compound having an oxyl group represented by the above has 6 to 32 carbon atoms.
  • the organophosphorus compound represented by the general formula (A) of the present invention has a heat resistance characteristic of an arylphosphine oxide compound and a hydrolysis resistance (moisture resistance, resistance to resistance) derived from a molecular structure having no phosphate ester bond. It is a compound having water absorption). Therefore, the organophosphorus compound represented by the general formula (A) of the present invention is a flame retardant or flame retardant resin monomer containing the organophosphorus compound, or a raw material intermediate for various organic materials and medical and agrochemical products, industrial It is useful as an additive such as a treatment agent, and as an additive for fertilizer. Moreover, according to the method of this invention, the organophosphorus compound shown by the said general formula (A) can be manufactured more efficiently.
  • thermogravimetric analysis (TG-DTA) chart of the cured phosphorus-containing resin obtained in Reference Example 1.
  • FIG. 6 is a thermogravimetric analysis (TG-DTA) chart of the cured epoxy resin obtained in Reference Example 2.
  • TG-DTA thermogravimetric analysis
  • Organic phosphorus compound represented by formula (A) is a phosphorus-containing compound having an oxylphenyl group.
  • the “oxylphenyl group” in the present invention is, for example, substituted with a group (oxyl group) bonded through an oxygen atom such as —OR 3 group and —OR 6 group in the following general formula (A). Represents a phenyl group.
  • R 1 , R 2 , R 4 and R 7 each represent a substituent, each independently having a halogen atom, a nitro group, a cyano group, an amino group, a dimethylamino group, or a substituent.
  • An alkyl group, an alkenyl group, an alkynyl group, an alkyloxy group, an allyl group, an aryl group or an aryloxy group may be used.
  • the substituted position with respect to the benzene ring of these substituents is not specifically limited.
  • the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom.
  • the alkyl group preferably represents a linear or branched or cyclic aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and includes positional isomers. .
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, n-hexyl group, Examples thereof include a cyclohexyl group, an n-heptyl group, and an n-octyl group.
  • one or more hydrogen atoms of the aliphatic hydrocarbon group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms.
  • the substituted alkyl group include methoxyethyl group, methoxypropyl group, methoxybutyl group, 2-ethoxyethyl group, 2-ethoxypropyl group, 3-ethoxypropyl group, 2-ethoxybutyl group, 3-ethoxy.
  • the alkenyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms in a straight chain, 3 to 6 carbon atoms in a branched chain, or a cyclic unsaturated aliphatic carbon having a carbon-carbon double bond. Indicates a hydrogen group and includes positional isomers.
  • alkenyl group examples include a vinyl group, isopropenyl group, allyl group, methallyl group, 2-butenyl group, 3-butenyl group, 2-cyclopropenyl group, 2-cyclobutynyl group, 2-cyclopentynyl group, Examples include 3-cyclopentynyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group and the like.
  • one or more hydrogen atoms of the unsaturated aliphatic hydrocarbon group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms.
  • substituted alkenyl group examples include 4-methoxy-1-butenyl group, 4-ethoxy-1-butenyl group, 4-methoxy-2-butenyl group, 4-ethoxy-2-butenyl group, and 2-methyl.
  • substituted alkenyl group examples include 4-methoxy-1-butenyl group, 4-ethoxy-1-butenyl group, 4-methoxy-2-butenyl group, 4-ethoxy-2-butenyl group, and 2-methyl.
  • Examples include a 3-methoxy-1-propenyl group, a 2-methyl-3-ethoxy-1-propenyl group, a 4-methoxy-1-cyclohexenyl group, and a 4-ethoxy-1-cyclohexenyl group.
  • the alkynyl group is preferably an unsaturated aliphatic hydrocarbon group having a carbon-carbon triple bond having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Furthermore, one or more hydrogen atoms of the hydrocarbon group in the carbon-carbon triple bond may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms. Specific examples of the alkynyl group include ethynyl group and 1-propynyl group.
  • the alkyloxy group is preferably a group in which a linear or branched or cyclic aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms is bonded to an oxygen atom. And includes alkyl positional isomers. Specific examples of the alkyloxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropyloxy group, n-butoxy group, isobutyloxy group, cyclobutyloxy group, n-pentyloxy group and cyclopentyl.
  • Examples thereof include an oxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, and an n-octyloxy group.
  • one or more hydrogen atoms of the aliphatic hydrocarbon group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms.
  • substituted alkyloxy group examples include 2-methoxyethoxy group, 2-methoxypropoxy group, 3-methoxypropoxy group, 2-methoxybutoxy group, 3-methoxybutoxy group, 4-methoxybutoxy group, 2-methoxybutoxy group, Ethoxyethoxy group, 2-ethoxypropoxy group, 3-ethoxypropoxy group, 2-ethoxybutoxy group, 3-ethoxybutoxy group, 4-ethoxybutoxy group, 2-propoxyethoxy group, 2-propoxypropoxy group, 3-propoxypropoxy group Group, 2-propoxybutoxy group, 3-propoxybutoxy group, 4-propoxybutoxy group, 2-butoxyethoxy group, 2-butoxypropoxy group, 3-butoxypropoxy group, 2-butoxybutoxy group, 3-butoxybutoxy group, Or a 4-butoxybutoxy group is mentioned.
  • the aryl group is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group.
  • one or more hydrogen atoms of the aromatic hydrocarbon group are, for example, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a halogen atom (fluorine atom, chlorine atom, bromine atom or It may be substituted with an iodine atom).
  • the “alkyl group” and “alkyloxy group” have the same meanings as the alkyl group and alkyloxy group.
  • substituted aryl group examples include toluyl group, dimethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, cyclopropylphenyl group, n-butylphenyl group, t-butylphenyl group, methoxy
  • examples thereof include a phenyl group, an ethoxyphenyl group, an n-propoxyphenyl group, an isopropoxyphenyl group, a cyclopropoxyphenyl group, an n-butoxyphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodophenyl group.
  • substituted position with respect to the phenyl group of these substituents is not specifically limited.
  • a phenyl group or a naphthyl group which may have a substituent, preferably an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, more preferably carbon
  • a phenyl group which may have a substituent with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, particularly preferably an unsubstituted phenyl group.
  • the aryloxy group represents a group in which the aryl group is bonded to an oxygen atom, and includes positional isomers.
  • Specific examples of the aryloxy group include a phenyloxy group, a naphthyloxy group, and an anthranyloxy group.
  • one or more hydrogen atoms of the aryl group may be substituted with, for example, an alkyloxy group having 1 to 4 carbon atoms or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).
  • the substituted position with respect to the aryloxy group of these substituents is not specifically limited.
  • substituted aryloxy group examples include a toluoyloxy group, a dimethylphenyloxy group, an ethylphenyloxy group, an n-propylphenyloxy group, an isopropylphenyloxy group, a cyclopropylphenyloxy group, and an n-butylphenyloxy group.
  • T-butylphenyloxy group methoxyphenyloxy group, ethoxyphenyloxy group, n-propoxyphenyloxy group, isopropoxyphenyloxy group, cyclopropoxyphenyloxy group, n-butoxyphenyloxy group, fluorophenyloxy group, chlorophenyl Examples thereof include an oxy group, a bromophenyloxy group, and an iodophenyloxy group.
  • an alkyl group which may have a substituent an alkenyl group which may have a substituent, or a substituent.
  • a good aryloxy group may have one or more hydrogen atoms substituted with, for example, a halogen atom, a nitro group, a cyano group, an amino group, or a dimethylamino group.
  • the substituents R 1 , R 2 , R 4 and R 7 have a fluorine atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent.
  • An alkyloxy group which may be substituted, an aryl group which may have a substituent, and an aryloxy group which may have a substituent are preferred.
  • p and q are each independently an integer of 0 to 5, preferably 0 or 1, more preferably 0.
  • r and s are each independently an integer of 0 to 4, preferably 0 or 1, more preferably 0.
  • p, q, r, and s represent 0, it means unsubstituted.
  • the plurality of substituents R 1 , R 2 , R 4 , and R 7 may be the same as or different from each other.
  • substituents R 1 and R 2 are each substituted by adjacent carbon atoms on the benzene ring, they are bonded to each other to form, for example, a cyclic structure such as a tetrahydroxynaphthalene ring or an alkylenedioxybenzene ring May be formed.
  • the substituents R 1 and R 2 are preferably the same substituents.
  • R 3 may have a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
  • a good alkynyl group an aryl group which may have a substituent, or a group represented by — (CH 2 ) n —Q 1 ;
  • Q 1 is vinyl group, propenyl group, ethynyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group (oxiranyl group or oxetanyl group), carboxylic acid group (—COOH), carboxylic acid ester A group (—COOR a ), an alkoxy group (—OR a ), or an optionally substituted phenyl group, and R a represents an optionally substituted alkyl group;
  • n represents the number of methylene groups (—CH 2 —), and is an integer of 1 to 6, preferably 1 to 4, more preferably 1 or 2.
  • the OR 3 group in the above general formula indicates that it is substituted with any carbon atom on the benzene ring.
  • the alkali metal atom is a metal atom of Group 1 of the periodic table of the elements, preferably lithium, sodium, potassium, cesium, more preferably sodium, potassium.
  • R 3 an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl which may have a substituent
  • the group has the same meaning as that of the substituents R 1 , R 2 , R 4 and R 7 .
  • phenyl group which may have a substituent examples include an unsubstituted phenyl group, or one or more hydrogen atoms of the phenyl group, for example, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms.
  • a phenyl group substituted with an oxy group, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom) or the like is shown.
  • the substituted position with respect to the phenyl group of these substituents is not specifically limited.
  • Q 1 is a vinyl group, propenyl group, ethynyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group (oxiranyl group or oxetanyl group), carboxylic acid group (—COOH), carboxylic acid ester as described above.
  • the alkyl group which may have a substituent in R a is as defined for the substituents R 1 , R 2 , R 4 and R 7 .
  • Q 1 is a vinyl group or a propenyl group> Allyl group, 2-propenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 2-methyl-2-propenyl group (methallyl group), 3- An alkenyl group such as a methyl-3-butenyl group, 4-methyl-4-pentenyl group, 5-methyl-5-hexenyl group, 6-methyl-6-heptenyl group, 7-methyl-7-octenyl group;
  • Q 1 is an ethynyl group> Alkynyl groups such as propargyl group, 3-butyne group, 4-pentyne group, 5-hexynyl group, 6-heptynyl group, 7-octynyl group;
  • Q 1 is a hydroxyl group (—OH)> Hydroxyalkyl groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group;
  • Nitroalkyl groups such as nitromethyl group, 2-nitroethyl group, 3-nitropropyl group, 4-nitrobutyl group, 5-nitropentyl group, 6-nitrohexyl group;
  • Cyanoalkyl groups such as cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, 5-cyanopentyl group, 6-cyanohexyl group;
  • Q 1 is a cyclic ether group>
  • Oxiranyl alkyl groups such as glycidyl group, 2-oxiranylethyl group, 3-oxiranylpropyl group, 4-oxiranylbutyl group, 5-oxiranylpentyl group, 6-oxiranylhexyl group, ( 2-oxetanyl) methyl group, (3-oxetanyl) methyl group, (3-methyloxetan-3-yl) methyl group, (3-ethyloxetan-3-yl) methyl group, 2- (2-oxetanyl) ethyl group 2- (3-oxetanyl) ethyl group, 2- (3-methyloxetan-3-yl) ethyl group, 2- (3-ethyloxetan-3-yl) ethyl group, 3- (2-oxetanyl) propyl group , 3- (3-oxetanyl) propyl group, 3-
  • Q 1 is a carboxylic acid group (—COOH)> Hydroxycarbonylmethyl group, 2- (hydroxycarbonyl) ethyl group, 3- (hydroxycarbonyl) propyl group, 4- (hydroxycarbonyl) butyl group, 5- (hydroxycarbonyl) pentyl group, 6- (hydroxycarbonyl) hexyl group, etc.
  • Q 1 is an alkoxy group> Methoxymethyl group, ethoxymethyl group, propyloxymethyl group, isopropyloxymethyl group, cyclopropyloxymethyl group, butoxymethyl group, pentyloxymethyl group, cyclopentyloxymethyl group, hexyloxymethyl group, cyclohexyloxymethyl group, 2- Methoxyethyl group, 2-ethoxyethyl group, 2-propyloxyethyl group, 2-isopropyloxyethyl group, 2-cyclopropyloxyethyl group, 2-butoxyethyl group, 2-pentyloxyethyl group, 2-cyclopentyloxyethyl Group, 2-hexyloxyethyl group, 2-cyclohexyloxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-propyloxypropyl group, 3-isopropyloxypropyl group, 3-cyclopropyl
  • Q 1 is an optionally substituted phenyl group> Benzyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, 5-phenylpentyl group, 6-phenylhexyl group, methoxybenzyl group, dimethoxybenzyl group, nitrobenzyl group, dinitrobenzyl group, etc.
  • Examples include arylalkyl groups such as aralkyl groups (substitution positions are not particularly limited).
  • R 6 may be a hydrogen atom, an alkali metal atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
  • Q 2 is vinyl group, propenyl group, ethynyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group (oxiranyl group or oxetanyl group), carboxylic acid group (—COOH), carboxylic acid ester A group (—COOR b ), an alkoxy group (—OR b ), or a phenyl group which may have a substituent, and R b represents an alkyl group which may have a substituent;
  • m represents the number of methylene groups (—CH 2 —), and is an integer of 1 to 6, preferably 1 to 4, more preferably 1 or 2.
  • R 6 has the same meaning as the R 3, therefore, Q 2 also has the same meaning as Q 1 in R 3, further R b have the same meanings as R a. Specific examples of R 6 also have the same meaning as R 3 .
  • substituents represented by R 3 and R 6 hydrogen atom, glycidyl group, (3-oxetanyl) methyl group, (3-methyloxetan-3-yl) methyl group, allyl group, alkali metal atom, hydroxy group are preferable.
  • Ethyl group more preferably hydrogen atom, glycidyl group, (3-oxetanyl) methyl group, (3-methyloxetan-3-yl) methyl group, allyl group, hydroxyethyl group, particularly preferably hydrogen atom, glycidyl group, allyl group Group, a hydroxyethyl group.
  • the substituents R 6 and R 3 may be the same or different from each other.
  • R 5 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyloxy group having 1 to 6 carbon atoms, which may have a substituent having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms which may have a substituent represents a linear or branched or cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a regioisomer. Including. Furthermore, one or more hydrogen atoms of the alkyl group having 1 to 6 carbon atoms may be substituted with a halogen atom, a nitro group, a cyano group, or an alkyloxy group having 1 to 6 carbon atoms.
  • the aryl group having 6 to 12 carbon atoms which may have a substituent is an aromatic hydrocarbon group, and one or more hydrogen atoms of the aryl group having 6 to 12 carbon atoms may be substituted with a nitro group.
  • R 5 specifically, “an alkyl group which may have a substituent” or “having a substituent” in R 1 , R 2 , R 4 and R 7 described above for the general formula (A).
  • aryl group preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group, more preferably a hydrogen atom.
  • the organic phosphorus compound represented by the general formula (A) has 25 to 100 carbon atoms.
  • the organophosphorus compound represented by the general formula (A) of the present invention compounds having various carbon numbers by using various combinations of substituents are used as components of the various flame retardants or flame retardant resins.
  • an organic phosphorus compound having 25 to 100 carbon atoms represented by the general formula (A) can be suitably obtained.
  • the organophosphorus compound represented by the general formula (A) of the present invention can be produced by the method represented by the reaction formula [I] including the following steps 1 and 2. Specifically, it can be produced by two methods: Method 1 in which the following Step 2 is performed after performing the following Step 1, and Method 2 in which the following Steps 1 and 2 are simultaneously performed. According to this method, the organophosphorus compound represented by the general formula (A) of the present invention can be obtained by an industrially suitable method with high yield and high purity.
  • R 1 ⁇ R 7, p , q, r and s R 1 ⁇ R 7, p in the general formula (A), q, have the same meanings as r and s, thus The preferred range is also the same.
  • Step 1 the diarylphosphine oxide compound represented by the general formula (1) is reacted with the arylcarbonyl compound having an oxyl group represented by the general formula (2) to obtain the phosphorus represented by the general formula (B). It is a process for producing a containing aryl alcohol compound.
  • step 1 the diarylphosphine oxide compound represented by the general formula (1) is used as a raw material for synthesis.
  • R 1 , R 2 , p and q are synonymous with R 1 , R 2 , p and q described above for the general formula (A), and the preferred ranges are also the same.
  • diarylphosphine oxide compound represented by the general formula (1) examples include diphenylphosphine oxide, bis (4-fluorophenyl) phosphine oxide, bis (4-chlorophenyl) phosphine oxide, and bis (4-nitrophenyl) phosphine oxide.
  • the diarylphosphine oxide compound represented by the general formula (1) has 12 to 46 carbon atoms.
  • step 1 an arylcarbonyl compound having an oxyl group represented by the general formula (2) together with the diarylphosphine oxide compound represented by the general formula (1) is used as a synthesis raw material.
  • R 3 to R 5 and r have the same meanings as R 3 to R 5 and r described above for the general formula (A), and the preferred ranges are also the same.
  • arylcarbonyl compound represented by the general formula (2) examples include 4-hydroxybenzaldehyde, 4-hydroxyphenyl methyl ketone, 4-hydroxyphenyl ethyl ketone, 4-hydroxyphenyl propyl ketone, 4-hydroxyphenyl isopropyl ketone, 4-hydroxyphenylcarbonyl compounds having 7 to 32 carbon atoms such as 4-hydroxyphenylbutylketone;
  • 3-vinyloxybenzaldehyde 3-vinyloxyphenyl methyl ketone, 3-vinyloxyphenyl ethyl ketone, 3-vinyloxyphenyl propyl ketone, 3-vinyloxyphenyl isopropyl ketone, 3-vinyloxyphenyl butyl ketone, 3-allyloxy Benzaldehyde, 3-propenyloxybenzaldehyde, 3-propenyloxyphenyl methyl ketone, 3-propenyloxyphenyl ethyl ketone, 3-propenyloxyphenyl propyl ketone, 3-propenyloxyphenyl isopropyl ketone, 4-propenyloxyphenyl butyl ketone, 3- 3- (alkenyloxy) phenylcarbonyl compounds having 9 to 32 carbon atoms such as propenyloxybenzaldehyde;
  • 3- (allyloxy) phenylcarbonyl compounds having 10 to 32 carbon atoms such as 3-allyloxybenzaldehyde, 3-allyloxyphenyl methyl ketone, 3-allyloxyphenyl ethyl ketone, 3-allyloxyphenyl propyl ketone;
  • 2- (allyloxy) phenylcarbonyl compounds having 10 to 32 carbon atoms such as 2- (allyloxy) benzaldehyde, 2- (allyloxy) phenyl methyl ketone, 2- (allyloxy) phenyl ethyl ketone, 2-allyloxyphenyl propyl ketone;
  • the arylcarbonyl compound represented by the general formula (2) has 7 to 32 carbon atoms.
  • the amount of the arylcarbonyl compound represented by the general formula (2) used in the step 1 is not particularly limited, but in consideration of the stirring property during the reaction, the efficiency of removal after the reaction, the production cost, etc., the general formula (1 ) Is preferably 0.8 to 10 mol, more preferably 1 to 5 mol, still more preferably 1 to 2.5 mol, and particularly preferably 1 to 1.25 mol, relative to 1 mol of the diarylphosphine oxide compound represented by It is.
  • step 1 may be performed under the conditions in the absence or presence of an organic solvent.
  • the organic solvent is not particularly limited as long as it does not inhibit the reaction.
  • diethyl ether diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,2-dimethoxyethane, etc.
  • Ethers aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenation such as methylene chloride and 1,2-dichloroethane Aliphatic hydrocarbons; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N'-dimethylimidazolidinone; chlorobenzene, 1,2-dichlorobenzene, 1, 3-dichlorobenzene, 1,4-dichlorobenzene, etc.
  • aromatic hydrocarbons such as nitrobenzene; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Nitriles such as acetonitrile, propionitrile, benzonitrile; Methyl acetate, Ethyl acetate And at least one solvent selected from the group consisting of aliphatic carboxylic acid esters such as butyl acetate and ethyl propionate.
  • the organic solvent that can be used in Step 1 is preferably at least one solvent selected from the group consisting of ethers, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, nitriles, or aliphatic carboxylic acid esters, and more preferably. At least one solvent selected from the group consisting of tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, toluene, dichloromethane, and 1,2-dichloroethane is used.
  • the amount of the organic solvent used is appropriately determined depending on the uniformity of the reaction solution, the stirring ability, etc., but is preferably 0.1 to 1000 mL, based on 1 g of the diarylphosphine oxide compound represented by the general formula (1).
  • the amount is preferably 0.5 to 750 mL, more preferably 1 to 500 mL, and particularly preferably 1 to 100 mL.
  • reaction temperature is not particularly limited, but is preferably 0 to 150 ° C, more preferably 10 to 130 ° C.
  • the reaction pressure is not particularly limited, and the reaction environment may be an open system environment, or an inert gas atmosphere such as argon or nitrogen gas, or an air stream.
  • R 1 ⁇ R 5, p, q and r are the general formula (1) R 1 in and (2) ⁇ R 5, p , it is synonymous with q and r.
  • the obtained reaction solution is subjected to neutralization, liquid separation, washing with water, etc., distillation, recrystallization, column chromatography, etc., and the phosphorus-containing aryl represented by the general formula (B).
  • the alcohol compound can be isolated and purified, it may be used in Step 2 without performing these isolation and purification operations.
  • the phosphorus-containing aryl alcohol compound represented by the general formula (B) can be used not only as a raw material for producing the organic phosphorus compound having an oxyl group represented by the general formula (A), but also, for example, a flame retardant phenol resin Flame retardant epoxy resin, flame retardant polyester, flame retardant polyamide, flame retardant polyether, flame retardant polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, flame retardant poly At least one flame retardant resin selected from the group consisting of alkylene resins, preferably flame retardant phenol resin, flame retardant epoxy resin, flame retardant polyester, flame retardant polyamide, flame retardant polyether, flame retardant Less selected from the group consisting of polycarbonate, flame retardant polycarbonate diol and flame retardant polyurethane It is also useful as one flame retardant resin of raw material (monomer).
  • a flame retardant which uses the organophosphorus compound which has an oxyl group shown by the said general formula (B) as a flame retardant component, or an electric insulation oil, a heat-medium oil, peeling oil, rubber processing oil, rock drill oil It can also be used as an additive for at least one selected industrial lubricating oil, an additive for fertilizer, and the like.
  • Step 2 the phosphorus-containing aryl alcohol compound represented by the general formula (B) is reacted with the aryl compound having an oxyl group represented by the general formula (3) in the presence of an acid catalyst, and the general formula ( This is a step for producing an organophosphorus compound having an oxyl group represented by A).
  • step 2 the phosphorus-containing aryl alcohol compound represented by the general formula (B) is used as a raw material.
  • This compound can be obtained by the step 1 of the above reaction formula [I].
  • the reaction solution after completion of the step 1 can be used as it is, or it can be isolated and purified. Either one is acceptable.
  • step 2 an aryl compound having an oxyl group represented by the general formula (3) is used together with the phosphorus-containing aryl alcohol compound represented by the general formula (B).
  • R 6, R 7 and s is the general formula (A) has the same meaning as R 6, R 7 and s as described above for, the preferred range is also the same. However, R 7 is bonded only to the ortho (o-) or meta (m-) position with respect to the oxyl group (—OR 6 ).
  • aryl compound represented by the general formula (3) examples include phenol, catechol, resorcinol, anisole, guaiacol, (o- or m-) cresol, (o- or m-) ethylphenol, (o- or m-) n-propylphenol, (o- or m-) isopropylphenol, (o- or m-) n-butylphenol, (o- or m-) dimethylphenol, (o- or m-) diethylphenol, ( o- or m-) bromophenol, (o- or m-) iodophenol, 2,3-dibromophenol, 2,5-dibromophenol, 3,5-dibromophenol, 2,3-diiodophenol, 2, 5-diiodophenol, 3,5-diiodophenol, 3-methoxycatechol, 4-methoxycatechol, 2- Toki Sile sol maytansinol, 4-methoxy
  • the aryl compound having an oxyl group represented by the general formula (3) has 6 to 32 carbon atoms.
  • the amount of the aryl compound represented by the general formula (3) used in the step 2 is not particularly limited. However, from the viewpoints of stirring property during the reaction, removal efficiency after the reaction, production cost, and the like, the general formula ( The amount of the phosphorus-containing aryl alcohol compound represented by B) is preferably 0.1 to 100 mol, more preferably 0.8 to 50 mol, still more preferably 1.0 to 10 mol, particularly preferably 1 to 1 mol. 5 moles are used.
  • the usage-amount of the aryl compound shown by the said General formula (3) is 1 mol of diaryl phosphine oxide compounds shown by the said General formula (1). Is preferably 0.1 to 100 mol, more preferably 0.8 to 50 mol, still more preferably 1.0 to 10 mol, and particularly preferably 1 to 5 mol.
  • the acid catalyst used in step 2 examples include organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, and methanesulfonic acid; organic carboxylic acids such as acetic acid and oxalic acid; trifluoroacetic acid, trichloro Carboxylic acid having alkyl group substituted with halogen atom such as acetic acid; Inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid; Boron trifluoride, boron trichloride, aluminum chloride, zinc chloride, zinc bromide, iron (III) chloride And Lewis acidic compounds such as iron (III) bromide, titanium tetrachloride, tin chloride, tin triflate, scandium triflate, copper triflate, samarium triflate, and bismuth triflate.
  • these acid catalysts can be organic sulfonic acids
  • the acid catalyst preferably, the above-mentioned inorganic acid, organic sulfonic acid, organic carboxylic acid, carboxylic acid having an alkyl group substituted with a halogen atom, Lewis acidic compound, more preferably hydrochloric acid, sulfuric acid, organic sulfonic acid, halogen Carboxylic acid having an alkyl group substituted with an atom, Lewis acidic compound, more preferably hydrochloric acid, sulfuric acid, organic sulfonic acid, carboxylic acid having an alkyl group substituted with a halogen atom, particularly preferably sulfuric acid, benzenesulfonic acid, p Toluene sulfonic acid, camphor sulfonic acid, methane sulfonic acid, trifluoroacetic acid, trichloroacetic acid are used.
  • these acid catalysts can be used individually or in mixture of 2 or more types.
  • the amount of the acid catalyst used in step 2 is not particularly limited, but from the viewpoint of the stirring property during the reaction and the efficiency of the isolation / purification operation after the reaction, 1 mol of the phosphorus-containing aryl alcohol compound represented by the formula (B)
  • the amount is preferably 0.001 to 0.98 mol, more preferably 0.003 to 0.50 mol, and still more preferably 0.005 to 0.25 mol.
  • step 2 can be carried out under the conditions in the absence or presence of an organic solvent.
  • the kind and the usage-amount of the organic solvent which can be used at the process 2 are the same as the said process 1.
  • reaction in step 2 is performed by mixing the raw material compounds and stirring.
  • the reaction temperature is not particularly limited, but is preferably 0 to 200 ° C, more preferably 25 to 150 ° C, still more preferably 40 to 130 ° C, and particularly preferably 50 to 130 ° C.
  • the reaction pressure is not particularly limited, and the reaction atmosphere (reaction environment) may be an open system, or may be an inert gas atmosphere such as argon or nitrogen gas, or an air stream.
  • the resulting reaction solution contains an organophosphorus compound having an oxyl group represented by the general formula (A), which is the target product.
  • the organic phosphorus compound represented by the general formula (A) is obtained from the obtained reaction solution by, for example, neutralization, separation, washing with water, etc., distillation, recrystallization, or column chromatography, etc. Can also be performed.
  • it since it may be acquired as a solid by adding a precipitation solvent separately to the obtained reaction liquid, it is useful as an industrial manufacturing method.
  • the precipitation solvent to be used is not particularly limited as long as it does not react with the organophosphorus compound represented by the general formula (A), which is the target product.
  • the precipitation solvent in Step 2 of the present invention is preferably the above-mentioned aliphatic hydrocarbons, aromatic hydrocarbons, ethers, nitriles, aliphatic carboxylic acid esters, water, more preferably n-pentane, One selected from the group consisting of n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, diethyl ether, diisopropyl ether, t-butyl methyl ether, acetonitrile, ethyl acetate, methanol, ethanol, propanol, isopropanol and water
  • One or more solvents selected from the group consisting of the above solvents, particularly preferably n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, acetonitrile, ethyl
  • the amount of the precipitation solvent used is appropriately determined depending on the uniformity of the reaction solution, the stirring ability, etc., but is preferably 0.1 to 500 mL, more preferably 1 g of the organophosphorus compound represented by the general formula (A). Is 0.5 to 300 mL, more preferably 1 to 150 mL, and particularly preferably 1 to 100 mL.
  • Method 2 is a method in which Steps 1 and 2 are simultaneously performed, that is, in the presence of an acid catalyst, the diarylphosphine oxide compound represented by the general formula (1) and the arylcarbonyl represented by the general formula (2). In this method, the compound and the aryl compound represented by the general formula (3) are reacted.
  • Method 2 the type of the aryl compound represented by the general formula (3) used is the same as that described in Step 2 of Method 1.
  • the amount of the aryl compound represented by the general formula (3) is not particularly limited, but for example, from the viewpoint of the stirring property during the reaction, the efficiency of removal after the reaction, the production cost, etc.
  • the amount is preferably 0.1 to 100 mol, more preferably 0.8 to 50 mol, more preferably 1.0 to 10 mol, particularly preferably 1 to 1 mol with respect to 1 mol of the diarylphosphine oxide compound represented by (1). 5 moles are used.
  • the aryl compound represented by the general formula (3) can be easily recovered after completion of the reaction of the present invention. Therefore, in the present invention, the aryl compound represented by the general formula (3) may be recovered and reused.
  • Method 2 the type of acid catalyst used is the same as that described in Step 2 of Method 1 above.
  • the amount of the acid catalyst used is not particularly limited.
  • the diarylphosphine oxide compound 1 represented by the general formula (1) is used from the viewpoint of the stirring ability during the reaction and the efficiency of the isolation / purification operation after the reaction.
  • the amount is preferably 0.001 to 0.98 mol, more preferably 0.003 to 0.50 mol, and still more preferably 0.005 to 0.25 mol, relative to mol.
  • the mixing order of the diarylphosphine oxide compound represented by the general formula (1), the arylcarbonyl compound represented by the general formula (2), the aryl compound represented by the general formula (3), and the acid catalyst is as follows.
  • an acid is added after adding the diarylphosphine oxide compound represented by the general formula (1), the arylcarbonyl compound represented by the general formula (2), and the aryl compound represented by the general formula (3). It is preferred to add a catalyst.
  • Method 2 the reaction conditions and post-treatment operations after the completion of the reaction are the same as those described in Step 2 of Method 1.
  • the organophosphorus compound represented by the general formula (A) of the present invention is, for example, a flame retardant phenol resin, a flame retardant epoxy resin, a flame retardant polyester, a flame retardant polyamide, a flame retardant polyether, or a flame retardant.
  • At least one flame retardant resin selected from the group consisting of polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, and flame retardant polyalkylene resin, preferably flame retardant phenolic resin, flame retardant At least one flame retardant resin selected from the group consisting of a flame retardant epoxy resin, a flame retardant polyester, a flame retardant polyamide, a flame retardant polyether, a flame retardant polycarbonate, a flame retardant polycarbonate diol, and a flame retardant polyurethane. It is useful as a production raw material (monomer).
  • a flame retardant which uses the organophosphorus compound which has an oxyl group shown by the said general formula (A) as a flame retardant component, or an electric insulation oil, a heat medium oil, peeling oil, rubber processing oil, and rock drill oil It can be used as an additive for at least one selected industrial lubricating oil, an additive for fertilizer, and the like.
  • Organophosphorus compound represented by formula (A-1) Among the organophosphorus compounds represented by the general formula (A) of the present invention, representative and preferred compounds include those represented by the following general formula (A-1) wherein R 3 and R 6 are each a hydrogen atom. A phosphorus compound is mentioned.
  • R 1 , R 2 , R 4 , R 5 , R 7 , p, q, r and s are R 1 , R 2 , R described above for the general formula (A). 4 , R 5 , R 7 , p, q, r and s are synonymous, and the preferred range is also the same.
  • the diarylphosphine oxide compound represented by the general formula (A-1) has 25 to 100 carbon atoms.
  • R 3 and R 6 are a group represented by — (CH 2 ) n —Q 1 and a group represented by — (CH 2 ) m —Q 2 , respectively.
  • the organic phosphorus compound represented by (A-N) is also useful in the same manner as the organophosphorus compound represented by the general formula (A-1).
  • a flame retardant polyester, a flame retardant polyamide, and a flame retardant polyether are used.
  • Various flame retardant resin materials such as flame retardant polycarbonate and flame retardant polycarbonate diol can be provided.
  • R 1 , R 2 , R 4 , R 5 , R 7 , p, q, r and s are R 1 , R 2 , R 4 in the general formula (A-1). , R 5 , R 7 , p, q, r and s, and the preferred range is also the same.
  • N represents a compound number and is an integer of 2 or more.
  • the organophosphorus compound having an oxyl group represented by the general formula (AN) includes, for example, an organophosphorus compound represented by the general formula (A-1) and a general formula as represented by the following reaction formula [II].
  • the alkyl compound represented by (4) can be produced according to Williamson's ether synthesis method (see, for example, J. Org. Chem., 67 6283 (2003)).
  • R 1 , R 2 , R 4 , R 5 , R 7 , p, q, r and s are R 1 , R 2 , R 4 , R 5 , R 7 described above for the general formula (A). , P, q, r and s, and the preferred range is also the same. Note that the organic phosphorus compound represented by the general formula (A-1) has 25 to 100 carbon atoms.
  • Q has the same meaning as Q 1 or Q 2, and is vinyl group, propenyl group, hydroxyl group (—OH), nitro group, cyano group, cyclic ether group, carboxylic acid group (—COOH).
  • An alkyl group which may have a substituent, and l is an integer of 1 to 6 as defined above for n or m.
  • X represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a benzenesulfonyloxy group, or a toluenesulfonyloxy group.
  • the organophosphorus compound represented by the general formula (A-1) can be converted into an oxyl group (-OR 3 and -OR in the general formula (A) by performing an addition reaction such as the reaction formula [II]. 6 ) New compounds having various substituents introduced therein can be produced.
  • an organic phosphorus compound represented by the general formula (A-1) and, for example, allyl bromide, hydroxyethyl chloride, 1-bromo-2-nitroethane, 4-bromobutanenitrile, epichlorohydrin, It is represented by the following general formulas (AN1) to (AN7) in which R 3 and R 6 are substituted by reacting with 3-ethyl-3-chloromethyloxetane or methyl 3-bromopropionate.
  • An organophosphorus compound having an oxyl group having a substituent introduced therein can be produced.
  • R 1 , R 2 , R 4 , R 5 , R 7 , p, q, r, and s are R in the general formula (A).
  • R 2 , R 4 , R 5 , R 7 , p, q, r and s are synonymous, and the preferred range is also the same.
  • R c in the general formula (A-N7) it is synonymous with R c in Q in the general formula (4).
  • a flame retardant epoxy resin for example, a flame retardant polyester, a flame retardant polycarbonate or a flame retardant polycarbonate diol can be provided.
  • organic phosphorus compounds represented by the following general formula (AM) in which R 3 and R 6 in the general formula (A) are each an alkali metal atom include, for example, flame retardant phenol resins, flame retardant epoxy Group consisting of resin, flame retardant polyester, flame retardant polyamide, flame retardant polyether, flame retardant polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, flame retardant polyalkylene resin
  • R 1 , R 2 , R 4 , R 5 , R 7 , p, q, r and s are R 1 , R 2 , R in the general formula (A). 4 , R 5 , R 7 , p, q, r and s are synonymous, and the preferred range is also the same.
  • M in the general formula (AM) represents an alkali metal atom.
  • To a glass reaction vessel equipped with a thermometer, temperature control device, dropping device and stirring means 75 mL of toluene and 10.1 g (0.05 mol) of diphenylphosphine oxide were added, and then 6.1 g of 4-hydroxybenzaldehyde was added thereto. (0.05 mol) and 5.17 g (0.055 mol) of phenol were sequentially added, and the mixture was stirred at 65 ° C. for 1 hour.
  • Tetrahydrofuran 3mL was put into a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping
  • the reaction solution was cooled to room temperature, and 5 mL of ethyl acetate was added to the resulting reaction solution, whereby a precipitate was formed.
  • the produced precipitate was filtered off and further washed with 10 mL of ethyl acetate.
  • the obtained precipitate was dried to obtain 1.28 g of 1- (diphenylphosphoryl) -1- (4-hydroxyphenyl) ethanol as an objective product as a white powder (acquisition yield: 37.9%).
  • a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device and a stirring measure 0.60 g (0.0018 mol) of (diphenylphosphoryl) (4-methoxyphenyl) methanol produced in Example 7 was added, Next, 0.97 g (0.0090 mol) of anisole and 0.02 g (0.0001 mol) of p-toluenesulfonic acid were added and mixed, and the mixture was stirred and reacted at 120 ° C.
  • Example 10 ⁇ Production of organophosphorus compound represented by general formula (A-N5) (bis (4-glycidyloxyphenyl) methyldiphenylphosphine oxide)>
  • A-N5 bis (4-glycidyloxyphenyl) methyldiphenylphosphine oxide
  • a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device, and a stirring measure 5.0 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide obtained in the same manner as in Example 2 or 3 (0 0.0125 mol) and 23.0 g (0.25 mol) of epichlorohydrin were added, and the mixture was heated to 105 ° C. and mixed.
  • Example 11 Provide of organophosphorus compound represented by general formula (A-N2) (bis (4- (2-hydroxyethoxy) phenyl) methyldiphenylphosphine oxide)>
  • A-N2 bis (4- (2-hydroxyethoxy) phenyl) methyldiphenylphosphine oxide
  • A-N2 bis (4- (2-hydroxyethoxy) phenyl) methyldiphenylphosphine oxide
  • Example 12 Provide of organophosphorus compound represented by general formula (A-N1) (bis (4-allyloxyphenyl) methyldiphenylphosphine oxide)>
  • A-N1 bis (4-allyloxyphenyl) methyldiphenylphosphine oxide
  • A-N1 bis (4-allyloxyphenyl) methyldiphenylphosphine oxide
  • To a glass reaction vessel equipped with a thermometer, temperature control device, dropping device and stirring means 75 mL of toluene and 10.1 g (0.05 mol) of diphenylphosphine oxide were added, and then 6.1 g of 4-hydroxybenzaldehyde was added thereto. (0.05 mol) and 5.95 g (0.055 mol) of cresol were sequentially added, and the mixture was stirred at 65 ° C. for 1 hour.
  • Reference Example 1 Phosphorus-containing epoxy resin cured product (5A-1a)) ⁇ Production of phosphorus-containing curable resin composition>
  • a glass reaction vessel equipped with a thermometer, temperature control device, and stirring means 0.2007 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide (formula (A-1a)) and phenol novolac resin (Maywa Kasei) HF-1M: Softening point 84 ° C., hydroxyl group equivalent 106 g / eq) 1.8052 g and 2-undecylimidazole 0.0172 g were added dimethylacetamide 1.9998 g to obtain a uniform solution at 100 ° C.
  • thermogravimetric analysis (TGA) measurement was performed with TG / DTA320 (manufactured by Seiko Denshi Kogyo) (FIG. 1).
  • the organophosphorus compound represented by the general formula (A) of the present invention has a phosphorus atom incorporated in the monomer skeleton, the material using this has excellent flame retardancy and hydrolysis resistance.
  • the organic phosphorus compound represented by the general formula (A) of the present invention includes, for example, a flame retardant phenol resin, a flame retardant epoxy resin, a flame retardant polyester, a flame retardant polyamide, a flame retardant polyether, Component of various flame retardant resins such as flame retardant polycarbonate, flame retardant polycarbonate diol, flame retardant polyurethane, flame retardant polybenzoxazine, flame retardant polyalkylene resin (eg, polyethylene, polystyrene, etc.), or flame retardant It can be used as a flame retardant additive.
  • organophosphorus compound represented by the general formula (A) of the present invention is not limited to the use of the above-mentioned flame retardant material, but various organic materials and raw material intermediates for medical and agrochemical products, industrial treatments It is also useful as an additive such as a fertilizer and an additive for fertilizer.

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Abstract

La présente invention concerne : un composé phosphoré organique de formule générale (A) qui présente une bonne résistance thermique et une bonne résistance à l'hydrolyse (résistance à l'humidité et résistance à l'absorption d'eau) ; et une méthode de production du composé phosphoré organique. Le composé phosphoré organique peut être utilisé comme monomère dans les ignifugeants ou les résines ignifugeantes, intermédiaire de produits de départ d'autres substances organiques ou produits pharmaceutiques et agrochimiques, adjuvant pour agents de transformation industriels, etc., adjuvant pour engrais, etc. (Dans la formule, chacun des radicaux R1, R2, R4 et R7 représente indépendamment un substituant spécifique ; chacun des nombres p et q est indépendamment égal à un nombre compris entre 0 et 5 inclus ; chacun des nombres r et s est indépendamment égal à un nombre compris entre 0 et 4 inclus ; R3 représente un atome d'hydrogène ou un substituant spécifique ; R5 représente un atome d'hydrogène ou un substituant spécifique ; et R6 représente un atome d'hydrogène ou un substituant spécifique.)
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