Classifications

• • 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
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
  • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
  • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
• • 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
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
  • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
  • C07F9/65719—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative
• • 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
  • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
  • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
  • C07F9/4841—Aromatic acids or derivatives (P-C aromatic linkage)

Definitions

• the present invention provides a compound represented by the general formula (2):
• R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may be the same or different.
• a bifunnel-based phosphorus compound represented by the general formula:
• the present invention relates to a method for producing an organic cyclic phosphorus compound represented by the formula:
• the compound represented by the general formula (3) itself is used as a stabilizer and a flame retardant for organic low-molecular and high-molecular compounds, and as an auxiliary agent for improving the quality and yield in the production thereof. Have been. Also from this It is also an important compound as a raw material for the production of many stabilizers, flame retardants and flame-retardant polymer compounds.
• the compound represented by the general formula (2) is important as a raw material for producing the compound represented by the general formula (3), and further as a stabilizer for low-molecular and high-molecular compounds and a raw material for producing a flame retardant. . Both compounds are expected to further expand their applications in the future.
• the compound is decomposed and precipitated by cooling, or poured into an aqueous alkali metal hydroxide solution, heated, hydrolyzed, cooled, and acidified to produce a compound represented by the general formula (2).
• the compound represented by the general formula (3) is manufactured by thermal dehydration cyclization (for example, JP-B-49-43597, JP-B-50-17979).
• a method for producing a compound represented by the general formula (3) by subjecting a compound represented by the general formula (1) to a hydrolysis reaction with water in an amount equivalent to that of the compound in the presence of an organic solvent see, Japanese Patent Application Laid-Open No. 7-145185).
• the compound represented by the general formula (1) may be purified by distillation under reduced pressure before hydrolysis, may be purified by recrystallization with an organic inert solvent, or the compound represented by the general formula (3) may be alkali metal hydroxide. Purification methods such as dissolving in an aqueous solution and treating with activated charcoal followed by acid precipitation and purification, or recrystallization with a mixture of alcohol and water, were attempted. Or, the removal of inorganic and / or organic impurities is insufficient, and the objective has not been achieved.
• the present invention provides a method capable of producing an object having a high degree of purity and quality without using alkalis or special chemicals, and without requiring complicated operations such as vacuum distillation or equipment of special materials. It is intended to be. Disclosure of the invention
• the present invention provides a compound represented by the general formula (1):
• R 1, R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may be the same or different, and X represents a chlorine atom or a bromine atom. Represents ]
• the organic cyclic phosphorus compound represented by is hydrolyzed at normal pressure or under pressure in the presence of an organic solvent insoluble in water and inert to the reaction system and excess water, and then the organic solvent layer is washed with water.
• O-phenylphenol (hereinafter abbreviated as “0 P PJ”) and a structural formula (5A)
• the organic cyclic phosphorus compound shown below (hereinafter abbreviated as “CC”) is produced.
• the molar ratio of 0 P P to phosphorus trichloride is about 1: 1-2, usually about 1: 1.1-1.5.
• the amount of the catalyst used is about 0.05 to 3 parts, usually about 0.1 to 1 part, per 100 parts by weight of PP (hereinafter simply referred to as "parts").
• the reaction temperature is about 30 to 25 CTC, usually about 50 to 230 ° C.
• Hydrogen chloride gas is generated as the condensation reaction proceeds, and finally rises to around 21 O'C.
• the reaction time depends on other reaction conditions such as the reaction temperature and the amount of catalyst used, but is usually 3 to 35 hours, usually 5 to 15 hours. However, if the reaction is performed too rapidly, a large amount of hydrogen chloride gas will be generated, resulting in loss of entrainment of phosphorus trichloride and unfavorable safe operation.
• the reaction mixture is cooled and cooled to 80 to 90 ° C, preferably an organic solvent insoluble in water and inert to the reaction system (hereinafter simply referred to as “solvent”). ) And dissolve.
• solvent an organic solvent insoluble in water and inert to the reaction system (hereinafter simply referred to as “solvent”). ) And dissolve.
• the solvent used here is about 30 to 100 parts, usually about 40 to 70 parts, per 100 parts of PP.
• This mixed solution is cooled to about 35 or less, and gradually added to a mixed solution of water and a solvent while stirring.
• the temperature of the mixed solution increases at 15 to 30.
• the amount of water used is equivalent to or more than equimolar to 0 PP, usually equivalent to 5 to 20 mol
• the amount of solvent is about 50 to 100 parts per 100 parts of 0 PP. It is always about 100 to 500 parts.
• the temperature is raised with stirring and the hydrolysis reaction is carried out at the reflux temperature.
• the hydrolysis reaction time is about 1 to 10 hours, usually about 2 to 5 hours.
• the hydrolysis reaction temperature can be increased under pressure to increase the hydrolysis rate or prevent precipitation of hydrolysis products.
• the reaction mixture was cooled to 60 to 9 CTC and allowed to stand, the aqueous layer was separated, water at 60 to 80 ° C was added to the oil layer, and the mixture was stirred, allowed to stand, and separated. You.
• This washing operation is usually repeated three times.
• the amount of warm water used is 0.2 to 1 times the volume of the reaction mixture, usually about 0.3 to 0.6 times.
• a hydrolysis product may precipitate depending on the solvent and / or amount used. In such a case, it is preferable to carry out the reaction under pressure.
• the degree of pressurization depends on the solvent used and the amount or amount used, but is usually about 1 to 10 m water column.
• the dehydration cyclization reaction is performed at 10 to 160 ° C.
• the dehydration cyclization reaction is about 1 to 10 hours at 120 to 160 ° C / 100 mm OgHg, and usually about 1 to 3 hours.
• HCA organic cyclic phosphorus compound
• an inert organic solvent which azeotropes with ordinary water, in particular, an organic solvent described below and a biphenyl compound represented by the general formula (2) are heated and azeotropically dehydrated.
• an organic solvent described below and a biphenyl compound represented by the general formula (2) are heated and azeotropically dehydrated.
• the azeotropic dehydration temperature in this case is about 100 to 130 ° C.
• the azeotropic point can be adjusted by increasing or decreasing the pressure as necessary depending on the type of the solvent.
• the HBP and HCA obtained in this way can be of extremely high purity and quality based on the melting point, melting color, liquid chromatographic analysis and the results of microanalysis of chlorine and zinc contained therein. It is confirmed.
• Examples of the phosphorus trihalide represented by the general formula (5) include phosphorus trichloride and phosphorus tribromide.
• organic solvent which is insoluble in water and inert to the reaction system examples include toluene, o-, m-, p-xylene, chlorobenzene, o-dichlorobenzene, dichloroethane and the like, and a mixed solvent thereof.
• the condensation reaction product was cooled to about 100 ° C, 120 gr of chlorobenzene was added, and further cooled to about 30 ° C.
• the reaction mixture was gradually poured under stirring into a reactor equipped with a reflux condenser equipped with 240 gr of water and 600 gr of chlorobenzene.
• the temperature of the contents increased from about 20 ° C to about 65 ° C.
• the mixture was further heated to carry out a hydrolysis reaction at a reflux temperature for about 3 hours.
• reaction mixture was kept at 70-80 ° C and allowed to stand.
• the aqueous layer was separated (reaction separated aqueous layer), and 120 gr of warm water at 50-60 ° C was added to the oil layer and stirred for about 1 hour. Then, the mixture was allowed to stand still at the same temperature, and the aqueous layer was separated (washing aqueous layer). This operation was repeated three times. After that, free water in the oil layer was azeotropically dehydrated, 2.6 gr of activated clay was added at 70 to 80 ° C, and the mixture was decolorized and filtered.After that, 60 gr of water was added and the mixture was cooled to 25 ° C or less, and the precipitate was removed.
• reaction separation aqueous layer and the washing water ⁇ are cooled to 20 ° C or less, and the precipitate is collected by filtration, and circulated to 8.4 gr of HBP (7.8 gr in terms of 14.8, 3% yield to OPP). Received. HCA total yield 97%.
• the condensation reaction product mixture obtained in the same manner as in Example 1 was cooled to about 100 ° C, 120 gr of toluene was added, and further cooled to about 30 ° C.
• the reaction mixture was gradually poured into a reactor equipped with a reflux condenser equipped with 240 gr of water and 600 gr of toluene under stirring, and then heated to carry out a hydrolysis reaction at a reflux temperature for about 3 hours. Was performed. Thereafter, the reaction mixture was washed under pressure (4 m water column) at 80 to 90 ° C three times with 150 ml of acidic hydrochloric acid 3 times, and twice with 1 O of water 15 Om, and then cooled under reflux.
• the vessel was switched to an outflow cooler, heated under normal pressure and subjected to azeotropic dehydration to carry out a closing reaction.
• HBP was converted to HC A, and the temperature of the content mixture reached about 115 ° C. By the way, there was no longer any azeotropic outflow of water.
• the content mixture was decolorized and filtered with 2.6 g of activated clay, cooled to about 5 ° C., and the precipitate was separated by filtration, washed with toluene, and dried to obtain 251.1 gr of a white powder. Melting point 118 ° C. Elemental analysis and infrared spectrum analysis confirmed that this was HCA. purity 99.9%. OPP, Zn, C1 and Na contents were all less than 1 ppm.
• the condensation reaction mixture obtained in the same manner as in Example 1 was cooled to about 100 ° C. and poured into 1,700 g of an 8.5% aqueous sodium hydroxide solution with stirring. During this time, the injection mixture rose from 25 ° C to 70 ° C. After stirring for about 1 hour, the pH was adjusted to 4.5 with dilute sulfuric acid, 15 g of activated carbon was added, and the mixture was stirred at 50 to 60 for 0.5 hour, and then filtered. The filtrate was acidified to pH 1.5 with dilute sulfuric acid at 25 ° C or lower, and the precipitate was filtered and washed with water to obtain white crystalline granular HBP.
• the condensation reaction mixture obtained in the same manner as in Example 1 was further kept under a reduced pressure of about 1 mmHg at about 210 ° C. under stirring to remove hydrogen chloride gas and phosphorus trichloride. After cooling to about 100 ° C, 220 gr of chlorobenzene was added and kept at about 70 ° C. To this, water (21.6 gr, 1.2 mol) was added in about 6 hours, and then the temperature was gradually raised and reacted at the reflux temperature for 9 to 10 hours. After the generation of hydrogen chloride gas stopped, the reaction mixture was reduced to about 100 after the reaction was completed.
• the compound represented by the general formula (3) itself is used as a stabilizer and a flame retardant for organic low-molecular and high-molecular compounds, and also as an auxiliary agent for improving the quality and yield in the production thereof. Have been. It is also an important compound as a raw material for the production of many more stabilizers, flame retardants and flame-retardant polymer compounds.
• the compound represented by the general formula (2) is important as a raw material for producing the compound represented by the general formula (3), and further as a raw material for producing a stabilizer and a flame retardant for organic low-molecular and high-molecular compounds. . Both compounds are expected to further expand their applications in the future.
• ADVANTAGE OF THE INVENTION According to the present invention, it is easy to operate without requiring special chemicals and equipment of high quality, high purity, high quality, and especially the content of raw materials and by-product organic compounds and inorganic compounds is extremely small. Can be produced in high yield.

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• 1996
  • 1996-08-19 JP JP21719496A patent/JP3938413B2/ja not_active Expired - Lifetime
  • 1996-10-25 EP EP96935440A patent/EP0906916B1/en not_active Expired - Lifetime
  • 1996-10-25 KR KR1019980702544A patent/KR100280908B1/ko not_active Expired - Fee Related
  • 1996-10-25 WO PCT/JP1996/003114 patent/WO1997015580A1/ja not_active Ceased
  • 1996-10-25 DE DE69626693T patent/DE69626693T2/de not_active Expired - Lifetime
  • 1996-11-05 TW TW085113477A patent/TW375616B/zh not_active IP Right Cessation
• 1998
  • 1998-04-23 US US09/065,126 patent/US6107506A/en not_active Expired - Lifetime
• 2000
  • 2000-07-26 KR KR20007008131A patent/KR100297624B1/ko not_active Expired - Fee Related

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