WO2013191227A1 - Procédé de fabrication d'estéramide d'acide phosphorique - Google Patents

Procédé de fabrication d'estéramide d'acide phosphorique Download PDF

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WO2013191227A1
WO2013191227A1 PCT/JP2013/066897 JP2013066897W WO2013191227A1 WO 2013191227 A1 WO2013191227 A1 WO 2013191227A1 JP 2013066897 W JP2013066897 W JP 2013066897W WO 2013191227 A1 WO2013191227 A1 WO 2013191227A1
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represented
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reaction
amine compound
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義一 青原
田中　良典
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Daikyo Chemical Co Ltd
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Daikyo Chemical Co Ltd
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Priority to CN201380032297.3A priority Critical patent/CN104395329B/zh
Priority to JP2014521498A priority patent/JP6154811B2/ja
Priority to KR1020147036268A priority patent/KR101970382B1/ko
Publication of WO2013191227A1 publication Critical patent/WO2013191227A1/fr
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    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2462—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of unsaturated acyclic amines
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2475—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aralkylamines
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring

Definitions

  • the present invention relates to a novel method for producing phosphoric ester amides.
  • Phosphoric ester amides are used as flame retardants in, for example, synthetic resin molded products and textile products (see, for example, Patent Document 1), and several methods for producing the same are conventionally known.
  • anilinodiphenyl phosphate which is one representative example of phosphoric ester amides
  • anilinodiphenyl phosphate 2 equivalents of aniline are used per 1 equivalent of diphenyl phosphorochloridate, and when 1 equivalent of aniline is used as a hydrogen chloride scavenger, anilinodiphenyl phosphate is used.
  • the yield of aniline does not exceed 50%.
  • the step of recovering aniline by neutralizing and purifying aniline hydrochloride after the completion of the reaction is complicated, and thus the above-described method can be obtained from aniline. It is economically disadvantageous.
  • a hydrogen chloride scavenger for example, a heterocyclic aromatic amine compound such as pyridine or an aliphatic tertiary amine such as triethylamine is used instead of aniline (for example, Patent Document 3). reference).
  • these amines may not function as effectively as hydrogen chloride scavengers as much as aromatic amines, and it is similarly complicated to recover and reuse amines from their hydrochlorides after completion of the reaction. Requires a process.
  • an odor due to the amine used in the obtained anilinodiphenyl phosphate may remain.
  • the present invention has been made in order to solve the above-mentioned problems in the production of conventional phosphoric ester amides, and is intended to achieve the target phosphorus without using an amine compound excessively with respect to phosphorochloridates. It is an object of the present invention to provide a novel method for producing phosphoric ester amides which can obtain acid ester amides in a high yield with respect to the amine compound.
  • the present invention uses an amine compound in the range of 0.5 equivalents or more and less than 2.0, preferably 0.8 to 1.2 equivalents per 1 equivalent of phosphorochloridates, It is an object of the present invention to provide a novel method for producing a phosphoric ester amide capable of obtaining a target phosphoric ester amide in a high yield with respect to the amine compound.
  • an aromatic monoamine compound or an aliphatic monoamine compound is used when the phosphoromonohalidate represented by the general formula (Ia) is subjected to a dehydrohalogenation reaction with a monoamine compound.
  • an aromatic diamine compound or an aliphatic diamine compound is used when the phosphorodihalidate represented by the general formula (Ib) is subjected to a dehydrohalogenation reaction with a monoamine compound.
  • the phosphoromonohalidates represented by the general formula (Ia) and the amine compound as the general formula (IIa) (In the formula, 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 arylalkyl group, and when Y 1 is an aryl group, Y 1 represents Ar
  • the aromatic monoamine compound represented by general formula (VIa) may be reacted with an aromatic monoamine compound represented by general formula (VIa):
  • the phosphoromonohalidates represented by the general formula (Ia) and the amine compound as the general formula (IIb) (In the formula, Ar 2 represents a divalent group containing an aromatic ring bonded to each of two nitrogen atoms in the molecule, and Y
  • a group, an aryl group or an arylalkyl group, and Y 2 and Y 3 may be the same or different.
  • Ay 2 and Y 5 may jointly form a 5- to 7-membered ring, or Ay 2 and Y 6 jointly form a 5- to 7-membered ring.
  • the reaction solvent is not necessarily used, but it is preferable to use the reaction solvent in order to make the reaction proceed smoothly.
  • the boiling point is 130 ° C. or higher.
  • These reaction solvents are used.
  • a reaction solvent having a boiling point of 130 ° C. or higher at least one selected from aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons and aromatic ethers having a boiling point of 130 ° C. or higher is preferably used.
  • the above-described amine compound is not used excessively with respect to the phosphorohalidates, that is, 0.5 equivalents or more and less than 2 equivalents, preferably 0.8 to 1.2.
  • the target phosphoric ester amides can be obtained in a high yield with respect to the amine compound.
  • the method for producing phosphoric ester amides according to the present invention comprises: (A) General formula (Ia) And phosphoromonohalidates represented by Formula (Ib) Phosphorodihalidates represented by At least one phosphorohalidate selected from: wherein R is 1 , R 2 And R 3 Each independently represents an alkyl group, cycloalkyl group, aryl group or arylalkyl group which may have a substituent which is inactive in the reaction, and X represents a halogen atom. ) At least one selected from a monoamine compound having one primary amino group and / or secondary amino group in the molecule and a diamine compound having two primary amino groups and / or two secondary amino groups in the molecule.
  • R 1 , R 2 And R 3 Each independently represents an alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group which may have a substituent inert to the reaction, and X represents a halogen atom.
  • the substituent inert to the reaction means a substituent that does not participate in the reaction between the phosphorohalidates according to the present invention and an amine compound, such as an alkoxy group such as a methoxy group, a nitro group,
  • an alkoxy group such as a methoxy group, a nitro group
  • a nitrile group and a halogen atom such as a chlorine atom
  • a heterocyclic group that does not participate in the reaction between the phosphorohalidates according to the present invention and an amine compound can be exemplified. The same applies hereinafter.
  • the alkyl group is preferably an alkyl group having 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 6 carbon atoms, and the alkyl group having 3 or more carbon atoms is linear. However, it may be branched, and examples of such an alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, dodecyl and the like.
  • the cycloalkyl group is a cycloalkyl group having a total number of carbon atoms of 5 to 20, preferably 5 to 12, which may have an alkyl group as a substituent on the carbon atoms forming the ring, Examples include cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl and the like.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and an alkyl group as a substituent on the aromatic ring, preferably an alkyl group having 1 to 6 carbon atoms, and / or One or a plurality of substituents inert to the reaction as described above may be included. Accordingly, examples of such aryl groups include phenyl, tolyl, xylenyl, trimethylphenyl, methoxyphenyl, naphthyl, methylnaphthyl, biphenylyl, and methylbiphenylyl groups. Examples of the arylalkyl group include a benzyl group and a phenylethyl group.
  • the arylalkyl group may also have an alkyl group having 1 to 6 carbon atoms on the aromatic ring or a substituent inert to the reaction as described above.
  • 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 phosphorohalidates are preferably phosphorochloridates.
  • R 1 , R 2 And R 3 are each independently an alkyl group having 1 to 6 carbon atoms on the aromatic ring or an aryl group optionally having a substituent inert to the reaction as described above, and particularly preferably a phenyl group, tolyl Group or a xylenyl group, and X is a chlorine atom.
  • phosphoromonohalidates represented by the general formula (Ia) include, for example, diphenyl phosphorochloridate, di (m-tolyl) phosphorochloridate, di (p Dixyles such as -tolyl) phosphorochloridate, di (2,6-xylenyl) phosphorochloridate, di (3,5-xylenyl) phosphorochloridate, di (2,5-xylenyl) phosphorochloridate Nyl phosphorochloridate, bis (isopropylphenyl) phosphorochloridate, bis (isobutylphenyl) phosphorochloridate, bis (t-butylphenyl) phosphorochloridate, di-1-naphthyl phosphorochloridate, di- 2-naphthyl phosphorochloridate, di-2-biphenylyl phosphorochloridate, di-3
  • phosphorodihalidates represented by the general formula (Ib) include, for example, phenyl phosphorodichloridate, m-tolyl phosphorodichloridate, p-tolyl phosphorodichloridate, 2, 6 -Xylenyl phosphorodichloridate such as xylenyl phosphorodichloridate, 3,5-xylenyl phosphorodichloridate, 2,5-xylenyl phosphorodichloridate, isopropylphenyl phosphorodichloridate, isobutyl Phenyl phosphorodichloridate, t-butylphenyl phosphorodichloridate, 1-naphthyl phosphorodichloridate, 2-naphthyl phosphorodichloridate, 2-biphenylyl phosphorod
  • such a phosphoromonohalidate is a monoamine compound having one primary amino group and / or one secondary amino group in the molecule, and a primary amino group and / or in the molecule.
  • the amine compound to be used by dehydrohalogenation reaction that is, condensation reaction, with at least one amine compound selected from diamine compounds having two secondary amino groups
  • the desired phosphoric ester amides can be obtained.
  • the phosphorodihalidates as described above are used as phosphorohalidates, they have one primary amino group and / or secondary amino group in the molecule.
  • the desired phosphoric ester amides can be obtained corresponding to the phosphorodihalidates used and the monoamine compound used.
  • the monoamine compound used in the present invention the monoamine compound having one primary amino group and / or secondary amino group in the molecule may be either an aromatic monoamine compound or an aliphatic monoamine compound.
  • the diamine compound having two primary amino groups and / or secondary amino groups in the molecule may be either an aromatic diamine compound or an aliphatic diamine compound.
  • the aromatic monoamine compound is preferably represented by the general 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 arylalkyl group; 1 Y is an aryl group, Y 1 Is Ar 1 May be the same or different. ).
  • the aryl group Ar 1 And Y 1 Are aryl groups, their aryl groups Ar 1 And Y 1 Is preferably an aryl group having 6 to 12 carbon atoms, and these aryl groups are alkyl groups on the aromatic ring as a substituent, preferably an alkyl group having 1 to 6 carbon atoms, One or a plurality of substituents inert to the reaction may be included. Accordingly, examples of such aryl groups include phenyl, tolyl, xylenyl, trimethylphenyl, methoxyphenyl, naphthyl, methylnaphthyl, biphenylyl, and methylbiphenylyl groups.
  • alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6 carbon atoms.
  • the three or more alkyl groups may be linear or branched, and examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, dodecyl and the like.
  • the alkyl group may have a heterocyclic group inert to the reaction as described above as a substituent.
  • Y above 1 When is an alkenyl group, such an alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and examples thereof include an allyl group and an isopropenyl group.
  • the alkenyl group may have a heterocyclic group inert to the reaction as described above as a substituent.
  • Y above 1 When is a cycloalkyl group, such a cycloalkyl group has an alkyl group having 1 to 6 carbon atoms on the number of carbon atoms forming the ring or a substituent inert to the reaction as described above. May be a cycloalkyl group having a total of 5 to 20 carbon atoms, preferably 5 to 12 carbon atoms.
  • cycloalkyl groups include, for example, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, Examples thereof include dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl and the like.
  • Y above 1 When is an arylalkyl group, examples of such an arylalkyl group include a benzyl group and phenylethyl.
  • the arylalkyl group may also have an alkyl group having 1 to 6 carbon atoms on the aromatic ring or a substituent inert to the reaction as described above.
  • preferable aromatic monoamine compounds include, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6 -Xylidines such as xylidine, nitroanilines, 1-naphthylamine, 2-naphthylamine, 2-biphenylylamine, 3-biphenylylamine, 4-biphenylylamine, N-methylaniline, N-ethylaniline, aminopyridines Etc.
  • the aromatic diamine compound preferably has the general formula (IIb) (Wherein Ar 2 Represents a divalent group containing an aromatic ring bonded to two nitrogen atoms in the molecule, Y 2 And Y 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an arylalkyl group; 2 And Y 3 May be the same or different. ). As described above, in the present invention, the divalent group Ar having the aromatic ring.
  • a divalent group Ar having such an aromatic ring 2 Is preferably an arylene group, and preferred examples thereof include an alkyl group having 1 to 6 carbon atoms and o-phenylene which may have a substituent inert to the reaction as described above, m -Phenylene, p-phenylene, naphthylene, biphenylylene group and the like can be mentioned.
  • a divalent group Ar having a preferred aromatic ring 2 As another one of the general formula (III) (Wherein the divalent group Z represents a divalent group selected from an alkylene group, a cycloalkylene group, an oxygen atom, a sulfur atom, a disulfide group, a sulfoxide group, a sulfonyl group and a carbonyl group). Can be mentioned.
  • such a divalent group Ar 2 Among these arylene groups, those in which the divalent group Z is, for example, an alkylene group or an oxygen atom are preferably used.
  • the alkylene group may have an aryl group such as a phenyl group as a substituent.
  • such alkylene group preferably has 1 to 6 carbon atoms, such as methylene, ethylene, ethylidene, dimethylmethylidene, methylethylmethylidene group Etc.
  • Examples of the alkylene group having a phenyl group as a substituent include phenylmethylidene and diphenylmethylidene.
  • the cyclohexylene group may have an alkyl group having 1 to 6 carbon atoms or a substituent inert to the reaction as described above on the carbon atoms forming the ring.
  • Y above 2 And Y 3 Are each independently Y 1 And each of the aryl groups Ar independently 1 May be the same. Therefore, the above Y 2 And Y 3 May be the same as or different from each other.
  • preferred aromatic diamine compounds include, for example, diaminotoluenes such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, and 2,6-diaminotoluene, , 8-diaminonaphthalene and the like, diaminobiphenyls such as 4,4′-diaminobiphenyl, bis (4-aminophenyl) methane, 1,1-bis (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'-diaminodiphenyl sulfone,
  • the aliphatic monoamine compound is preferably represented by the general formula (IVa) (Where Ay 1 Represents an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, Y 4 Represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, or Ay 1 And Y 4 May form a 5- to 7-membered ring, and in this case, the ring may contain an oxygen atom and / or a nitrogen atom as an atom forming the ring.
  • the alkyl group is preferably an alkyl group having 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 6 carbon atoms, and having 3 or more carbon atoms.
  • These alkyl groups may be linear or branched, and examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, dodecyl and the like.
  • the alkyl group may have a heterocyclic group inert to the reaction as described above as a substituent.
  • Ay above 1 When is an alkenyl group, such an 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 inert to the reaction as described above as a substituent.
  • Ay above 1 When is a cycloalkyl group such a cycloalkyl group has an alkyl group having 1 to 6 carbon atoms or a substituent inert to the reaction as described above on the carbon atoms forming the ring.
  • a cycloalkyl group having 5 to 20 carbon atoms, preferably 5 to 12 carbon atoms and specific examples of such cycloalkyl groups include, for example, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethyl Examples thereof include cyclohexyl, trimethylcyclohexyl, ethylcyclohexyl and the like.
  • Ay above 1 When is an arylalkyl group, examples of such an arylalkyl group include a benzyl group and a phenylethyl group.
  • aliphatic monoamine compound for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, hexylamine, heptylamine, 2-ethylhexylamine, Cyclohexylamine, piperidine, benzylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, di (2-ethylhexyl) Pipecolines such as amine, dicyclohexylamine, dibenzylamine, allylamine, morpholine, diallylamine, 1-aminoethyl-2-methylimidazole, 2-pipecoline, It may include any mixture of
  • the aliphatic diamine compound is preferably represented by the general formula (IVb) (Where Ay 2 Represents an alkylene group or a cycloalkylene group which may have an aromatic group on or between carbon atoms, and Y 5 And Y 6 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, or Ay 2 And Y 5 May jointly form a 5- to 7-membered ring, or Ay 2 And Y 6 May jointly form a 5- to 7-membered ring, or Ay 2 And Y 5 And Y 6 May jointly form a 5- to 7-membered ring. ).
  • the alkylene group may have an aryl group such as a phenyl group as a substituent.
  • the alkylene group preferably has 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylidene group, a dimethylmethylidene group, and a methylethylmethylidene group.
  • Examples of the alkylene group having a phenyl group as a substituent include phenylmethylidene, diphenylmethylidene, 1-phenylethylene, and 1,2-diphenylethylene group.
  • the above group Ay 2 Is a cycloalkylene group
  • the cycloalkylene group has an alkyl group having 1 to 6 carbon atoms or a substituent inert to the reaction as described above on the carbon atom forming the ring. Examples thereof include a cyclohexylene group and a cyclohexylidene group.
  • the above group Ay 2 When is an arylalkyl group, examples of such an arylalkyl group include a benzyl group and a phenylethyl group.
  • the alkylene group which may have an aromatic group between the carbon atoms is preferably represented by the general formula (V).
  • Y represents an arylene group which may have a substituent inert to the reaction as described above on the aromatic ring; 1 And A 2 Each independently represents an alkylene group having 1 to 6 carbon atoms.
  • the arylene group is, for example, a phenylene group, a naphthylene group, a biphenylene group, or the like, preferably a phenylene group, and the alkylene group is preferably It has 1 to 4 carbon atoms, and specific examples include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group and the like.
  • divalent group represented by the general formula (V) include the following. Therefore, in the present invention, as the aliphatic diamine compound, for example, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) Cyclohexane, 1,3-bis (2,2′-aminoethyl) benzene, 1,4-bis (2,2′-aminoethyl) benzene, piperazine, 4-aminopiperidine, 1,3-bis (aminomethyl) Examples include benzene and 2-methyl-4-imidazoline.
  • the aliphatic diamine compound for example, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexan
  • the phosphoromonohalidates are subjected to dehydrohalogenation reaction, that is, condensation reaction, with at least one amine compound selected from monoamine compounds and diamine compounds.
  • the target phosphoric ester amides can be obtained corresponding to the amine compounds used with the monohalidates.
  • phosphorodihalidates are used as phosphorohalidates, and the phosphorodihalides used by dehydrohalogenation reaction, that is, condensation reaction, with a monoamine compound.
  • the desired phosphoric ester amides can be obtained.
  • one equivalent of the phosphorohalidates is a value obtained by dividing one molar amount of the phosphorohalidates by the number of halogen atoms of the phosphorohalidates,
  • One equivalent refers to a value obtained by dividing one mole of the amine compound by the number of primary and secondary amino groups that the amine compound has.
  • 1 equivalent of diphenyl phosphorochloridate is its 1 molar amount and 1 equivalent of phenyl phosphorodichloridate is its 0.5 molar amount.
  • aniline has one primary amino group and piperidine has one secondary amino group, one equivalent thereof is a molar amount thereof. Since each of phenylenediamine and piperazine has two primary amino groups and secondary amino groups in the molecule, one equivalent thereof is the 0.5 molar amount thereof.
  • a reaction solvent is not necessarily used, but the reaction proceeds smoothly and the post-treatment after the reaction is easy.
  • a reaction solvent having a boiling point of 130 ° C.
  • the lower limit is not particularly limited, but usually 0.5 parts by weight or more, preferably 1 part by weight with respect to 1 part by weight of the phosphorohalidates used. It is more than part by weight.
  • the upper limit of the reaction solvent to be used is usually 5 parts by weight or less, preferably 2 parts by weight or less with respect to 1 part by weight of the phosphorohalidates used from the viewpoint of volume efficiency.
  • the phosphorohalidates and amine compounds in the proportions described above are usually at ambient temperature or, if necessary, at a somewhat heated temperature up to about 50 ° C., preferably with the reaction solvent.
  • the reaction vessel is charged to start the reaction, and then reacted at a temperature of 130 ° C. or higher, preferably at the reflux temperature of the reaction solvent used.
  • the present invention is characterized in that, when the phosphorohalidates in the above-mentioned proportion are reacted with an amine compound, the reaction is performed at a temperature of 130 ° C. or higher, that is, a reaction is performed at a temperature of 130 ° C. or higher. .
  • the reaction vessel may be heated at room temperature or, if necessary, at a somewhat heated temperature up to about 50 ° C.
  • the reaction mixture usually has a temperature of about 100 to 120, depending on the type of amine compound and phosphorohalidates used. From around the temperature, phosphoric ester amides are dissolved in the reaction solvent to form a dispersion in which only the hydrohalide salt of the amine compound is precipitated. Thereafter, when the reaction mixture is continuously heated to the initial reaction temperature, that is, a temperature of 130 ° C. or higher, preferably to the reflux temperature of the reaction solvent used, the amine compound that was not dissolved in the reaction solvent at the beginning of the reaction.
  • the solid of the hydrohalide salt gradually decreases with the progress of the reaction from the time when the temperature of the reaction mixture reaches about 130 ° C., and at the end of the reaction at the desired reaction temperature, the amine All of the compound's hydrohalide disappears and the reaction mixture becomes a homogeneous, clear solution. Thus, the reaction is terminated when the reaction mixture becomes a homogeneous and transparent solution. Therefore, in the present invention, as described above, the phosphoric ester amides are dissolved in the reaction solvent, and after obtaining a dispersion in which only the hydrohalide salt of the amine compound is precipitated, the desired reaction is performed. At the temperature, i.e.
  • the aspect in which the amine compound and phosphorohalidate are reacted is not limited to the above examples.
  • the amine compound is dissolved in a reaction solvent, and the temperature is about 100 to 130 ° C.
  • the phosphorohalidates may be similarly dissolved in the reaction solvent and heated to about 100 to 130 ° C., and the phosphorohalidates solution may be added to the amine compound solution to cause the reaction. Good.
  • the upper limit of the reaction temperature is usually 250 ° C. or less, preferably 240 ° C. or less, although it depends on the reaction solvent.
  • the reaction temperature is preferably in the range of 140 to 220 ° C., although it depends on the reaction solvent.
  • the reaction solvent having a boiling point of 130 ° C. or higher include aromatic hydrocarbon solvents such as xylene, mesitylene, cumene, pseudocumene, solvent naphtha, so-called naphtha solvents, aliphatic hydrocarbon solvents such as isoparaffin solvents, and monochlorobenzene.
  • Halogenated aromatic hydrocarbon solvents such as dichlorobenzene and trichlorobenzene, aromatic ether solvents such as diphenyl ether, and mixtures thereof are preferably used.
  • aromatic hydrocarbon solvents such as dichlorobenzene and trichlorobenzene
  • aromatic ether solvents such as diphenyl ether
  • mixtures thereof are preferably used.
  • an organic solvent having a boiling point of 130 ° C. or higher which is mainly composed of various aromatic hydrocarbons and is called a solvent naphtha or a naphtha solvent, is included in the above aromatic hydrocarbon solvent.
  • An organic solvent having a main hydrocarbon and a boiling point of 130 ° C. or higher is included in the aliphatic hydrocarbon solvent.
  • an excess of an amine compound is used with respect to 1 equivalent of phosphorohalidates, and 0.8 to 1.2 equivalents, more preferably Can obtain the target phosphoric ester amide in a high yield with respect to the amine compound by using about 1 equivalent.
  • the reason seems to be as follows. That is, first, when 1 equivalent of an amine compound and 1 equivalent of a phosphorohalidate are used, the amine compound acts as a hydrogen halide scavenger at the same time as the reactant, so that the reaction is accelerated.
  • 0.5 equivalents of amine compound and 0.5 equivalents of phosphorohalidate react at relatively low temperatures to produce the corresponding phosphate ester amides.
  • the remaining 0.5 equivalent of the amine compound captures the hydrogen halide generated by the above reaction to form a hydrohalide salt.
  • the remaining phosphorohalidates cannot react with 0.5 equivalents. Therefore, by further increasing the reaction temperature, the hydrogen halide gas is desorbed from the above-mentioned amine compound hydrohalide and leaves the reaction system, and the amine compound returns to the free amine compound again. Reacts with lohalidates.
  • the hydrogen halide generated at this time is not trapped by the amine compound under the high temperature reaction conditions, but leaves the reaction system, or even when trapped by the amine compound, the halogenation is similarly performed under the high temperature reaction conditions. It appears that hydrogen halide gas is desorbed from the hydrate and leaves the reaction system. Therefore, in the production of the phosphoric ester amides according to the present invention, the reaction system is external to the reaction system so that the hydrogen halide gas generated by the condensation reaction of the phosphorohalidates and the amine compound is removed from the reaction system. In particular, according to the present invention, the hydrogen halide gas desorbed from the hydrohalide salt of the amine compound is forcibly removed out of the reaction system, thereby It is desirable to promote smooth progress.
  • an inert gas such as nitrogen, helium, argon, carbon dioxide gas or air is blown into the reaction vessel, and such an inert gas is injected. It is preferable to carry out the reaction under an air stream or an air stream, or to carry out the reaction under reduced pressure by suction.
  • the obtained reaction mixture is cooled.
  • the reaction product is precipitated and collected by filtration, and then washed with an aqueous acid solution such as hydrochloric acid, an aqueous base solution such as sodium carbonate, and then with warm water to remove unreacted substances and dry.
  • an aqueous acid solution such as hydrochloric acid
  • an aqueous base solution such as sodium carbonate
  • warm water to remove unreacted substances and dry.
  • the desired phosphoric ester amides can be obtained. Thereafter, if necessary, it may be washed with a lower alcohol such as methanol or ethanol or acetone, or may be recrystallized from hot alcohol.
  • target phosphoric ester amides can thus be obtained corresponding to the phosphorohalidates and amine compounds.
  • phosphoric acid represented by the general formula (VIa) is obtained by reacting the phosphoromonohalidates represented by the general formula (Ia) with the aromatic monoamine compound represented by the general formula (IIa). Esteramides can be obtained, and the phosphoromonohalidates represented by the general formula (Ia) can be reacted with the aromatic diamine compound represented by the general formula (IIb). Phosphoric ester amides represented by (VIb) can be obtained.
  • examples of the phosphoric ester amides represented by the general formula (VIa) include the following.
  • examples of the phosphoric ester amides represented by the general formula (VIb) include the following.
  • Examples of the phosphoric ester amides represented by the general formula (VIIa) include the following.
  • Examples of the phosphoric ester amides represented by the general formula (VIIb) include the following.
  • Examples of the phosphoric ester amides represented by the general formula (VIIIa) include the following.
  • Examples of the phosphoric ester amides represented by the general formula (VIIIb) include the following.
  • fusing point is the value calculated
  • Example 1 At room temperature, 9.8 g (0.105 mol) of aniline and 35 mL of mesitylene were charged in a round bottom flask, and aniline was dissolved in mesitylene. While stirring the resulting solution, this solution was kept at 40 ° C. or lower, and 26.9 g (0.100 mol) of diphenyl phosphorochloridate was gradually added dropwise to this solution over 10 minutes.
  • anilinodiphenyl phosphate and aniline hydrochloride were precipitated from the solution, and the reaction mixture became a dispersion containing the precipitate.
  • the reaction mixture was gradually heated to 170 to 180 ° C. over 30 minutes, and reacted for 1 hour at the same temperature as above while refluxing mesitylene. From the time when the temperature of the reaction mixture exceeded 100 ° C., the anilinodiphenyl phosphate was dissolved in mesitylene and became a dispersion in which only aniline hydrochloride was precipitated.
  • Example 2 30.5 g of anilinodiphenyl phosphate was obtained in the same manner as in Example 1, except that 11.2 g (0.120 mol) of aniline was used. The yield based on aniline was 78.2%. Melting point 132.0 ° C.
  • Example 3 In Example 1, 29.5 g of anilinodiphenyl phosphate was obtained in the same manner except that 9.30 g (0.100 mol) of aniline and 33.6 g (0.125 mol) of diphenyl phosphorochloridate were used. . The yield based on diphenyl phosphorochloridate was 72.6%. Melting point 131.2 ° C.
  • Example 4 In Example 1, except that 11.3 g (0.122 mol) of aniline, 23.7 g (0.088 mol) of diphenyl phosphorochloridate and 2.9 g (0.014 mol) of phenyl phosphorodichloridate were used.
  • Example 5 In Example 1, anilinodi (2,6) was similarly used except that 32.5 g (0.100 mol) of di (2,6-xylenyl) phosphorochloridate was used instead of diphenylphosphorochloridate. -Xylenyl) phosphate 32.4 g was obtained.
  • Example 6 In Example 1, anilinodiphenyl was used in the same manner except that an isoparaffinic solvent (Isopar L manufactured by ExxonMobil Chemical) was used as a solvent instead of mesitylene and the temperature of the reaction mixture was changed to 190 to 200 ° C. 29.2 g of phosphate was obtained. The yield based on aniline was 85.6%. Melting point 133.2 [deg.] C.
  • an isoparaffinic solvent Isopar L manufactured by ExxonMobil Chemical
  • Example 7 In Example 1, 26.4 g of anilinodiphenyl phosphate was obtained in the same manner except that diphenyl ether was used as a solvent instead of mesitylene and the temperature of the reaction mixture was changed to 200 to 220 ° C. during the reaction. The yield based on aniline was 77.4%. Melting point 130.8 ° C.
  • Example 8 In the same manner as in Example 1, except that xylene was used as a solvent instead of mesitylene, the temperature of the reaction mixture at the time of reaction was 140 to 145 ° C., and the reaction time was 2 hours, anilinodiphenyl phosphate 25. 7 g was obtained. The yield based on aniline was 75.3%. Melting point 130.9 ° C.
  • Example 9 In Example 1, 23.9 g of morpholinodiphenyl phosphate was obtained in the same manner except that 9.1 g (0.105 mol) of morpholine was used instead of aniline. The yield based on morpholine was 71.4%. Melting point 76.1 ° C. (melting point 71 ° C. described in JP-A No. 2000-154277).
  • Example 10 In Example 1, 4.5 g (0.052 mol) of piperazine was used instead of aniline, the same isoparaffin as described above was used as a solvent instead of mesitylene, and the temperature of the reaction mixture during the reaction was 190 to 200 ° C.
  • Example 11 In Example 1, 21.6 g of 1,3-bis (diphenylphosphoroamino) benzene was obtained in the same manner except that 5.7 g (0.053 mol) of m-phenylenediamine was used instead of aniline. It was. The yield based on m-phenylenediamine was 71.5%. Melting point: 182.3 ° C. (melting point: 183 to 184 ° C.
  • Example 12 In Example 1, 5.7 g (0.053 mol) of p-phenylenediamine was used instead of aniline, and a naphtha solvent (Ipsol 150 manufactured by Idemitsu Kosan Co., Ltd.) was used instead of mesitylene. Except that the temperature of the reaction mixture was 200 ° C. and the reaction time was 4 hours, 22.9 g of 1,4-bis (diphenylphosphoroamino) benzene was obtained in the same manner. The yield based on p-phenylenediamine was 75.9%. Melting point 210.3 ° C. (melting point 210 to 211 ° C. described in J. Chem. Soc.
  • Example 13 In Example 12, 4,4′-diaminodiphenylmethane (10.4 g, 0.053 mol) was used in place of p-phenylenediamine, and the reaction time was changed to 5 hours. 30.8 g of bis (diphenylphosphorylamidophenyl) methane was obtained. The yield based on 4,4′-diaminodiphenylmethane was 88.6%. Melting point: 186.5 ° C. (melting point: 194 ° C. described in JP-A No. 2003-238580).
  • Comparative Example 1 A round bottom flask was charged with 30.0 g (0.323 mol) of aniline and 45 mL of toluene, and 40.8 g (0.152 mol) of diphenyl phosphorochloridate was gradually added dropwise to the above mixture while stirring at room temperature. After completion of the dropwise addition, the temperature of the reaction mixture was set at 80 ° C., and stirring was continued for 1 hour, followed by cooling to obtain a precipitate. The precipitate was collected by filtration, washed with water, and dried to obtain 45.1 g of anilinodiphenyl phosphate. The yield based on aniline was 43.0%. Melting point 131.6 ° C.
  • Example 2 Comparative Example 2 In Example 1, anilinodiphenyl phosphate 13 was similarly added except that diphenyl phosphorochloridate was added dropwise at room temperature, and after the completion, the reaction mixture was allowed to react at room temperature for 1 hour without heating. .4 g was obtained. The yield based on aniline was 39.3%. Melting point 131.1 ° C.

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Abstract

L'invention concerne un procédé destiné à fabriquer un estéramide d'acide phosphorique qui correspond à un phosphoromonohalidate, par réaction de déshydrohalogénation dudit phosphoromonohalidate, avec un composé amino possédant un ou deux groupes amino primaires et/ou goupes amino secondaires par molécule. Plus précisément, l'invention fournit un procédé incluant la réaction sous une température supérieure ou égale à 130°C dudit composé amino avec ledit phosphoromonohalidate, sans mise en œuvre excessive de composé amino par rapport à un phosphorohalidate.
PCT/JP2013/066897 2012-06-18 2013-06-12 Procédé de fabrication d'estéramide d'acide phosphorique Ceased WO2013191227A1 (fr)

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CN105732705A (zh) * 2016-01-27 2016-07-06 厦门大学 一种含磷氮阻燃单体及其制备方法
RU2858141C2 (ru) * 2023-10-23 2026-03-12 Публичное акционерное общество "СИБУР Холдинг" Фосфоразотсодержащий антипирен и его применение для полимерных материалов

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CN105753900A (zh) * 2016-03-22 2016-07-13 和夏化学(太仓)有限公司 一种芳香族磷酸酯酰胺化合物的合成方法及含该化合物的阻燃剂
CN107474309A (zh) * 2017-07-04 2017-12-15 长春工业大学 磷氮膨胀型阻燃剂及其制备方法和用途
JP7244085B2 (ja) * 2017-11-10 2023-03-22 大八化学工業株式会社 難燃剤組成物および該難燃剤組成物を含む難燃性熱可塑性樹脂組成物

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CN105732705A (zh) * 2016-01-27 2016-07-06 厦门大学 一种含磷氮阻燃单体及其制备方法
RU2858141C2 (ru) * 2023-10-23 2026-03-12 Публичное акционерное общество "СИБУР Холдинг" Фосфоразотсодержащий антипирен и его применение для полимерных материалов

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