• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Tertiary phosphine oxides are reduced to the corresponding phosphines by halosilanes in the presence of a stoichiometric amount of a primary or secondary amine. The reduction in yield expected using a primary or secondary amine in place of the prior art tertiary amine is not observed.
    公开号:SU710518A3
    申请号:SU782631648
    申请日:1978-07-04
    公开日:1980-01-15
    发明作者:Роберт Дэвис Вильям；Дэвид Гордон Майкл
    申请人:М Энд Т Кемикалз Инк (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of chemistry of organophosphorus compounds with a C — P bond, and in particular, to an improved method for producing tertiary phosphines, which are important intermediates of organophosphorus synthesis.
    A known method of producing tertiary phosphines by reduction of tertiary phosphine oxides with various reducing agents, for example lithium aluminum hydride [1].
    The closest to the invention in technical essence and the achieved result is a method for producing tertiary phosphines by reduction of tertiary phosphine oxides with halogenosilanes in the presence of tertiary amines with a molar ratio of reactants 1: 0.5-2: 0.8-1.7, respectively, in an organic solvent with 50-250 ° C, followed by treatment of the resulting reaction mass with aqueous alkali. The yield of products reaches 80% [2].
    The disadvantages of this method include a relatively low yield of target products.
    The aim of the invention is to increase the yield of target products.
    The goal is achieved by the described method for producing tertiary phosphines, which consists in the fact that tertiary phosphine oxides are reduced with halogen silanes in the presence of a primary or secondary amine at a stoichiometric ratio of the reactants in an inert organic solvent under heating, preferably by boiling the resulting reaction mass, followed by its treatment with water alkali.
    The distinctive features of the method include the use of an amine as a primary or secondary amine. The use of a primary or secondary amine makes it possible to increase the yield of tertiary phosphines to 90–96%, which was unexpected since it was previously believed that primary or secondary amines, reacting with halo silanes, form aminosilanes that are unable to reduce tertiary phosphine oxides. ·
    The desired products are isolated by known techniques, for example, distillation or crystallization.
    Example. Into a reaction vessel equipped with a stirrer, loading funnel, refrigerator, heating
    cushion and s (0.75 mol)
    146.4 g (0.79 mol) of nitrogen, 208.7 g of nylphosphine oxide, di-n-hexylamine and 680 g of toluene are loaded with a trifol and gas.
    Under stirring, 107.0 g (0.79 mol) of silane are added to the reaction mixture over 30 minutes; the temperature of the mixture is from sodium to 45 ° C. Then the mixture is boiled to boiling point v and kept for 2.5. The reaction mixture is cooled and rolled by gradual transfer to a flask with a capacity of 0.5 containing a mixture obtained using sodium hydroxide 425 g of water. The resulting mixture was stirred for 30 minutes, during which time an aqueous silicate layer was isolated. The solid material remaining at the bottom of the organic phase is removed by washing with a solution containing 50 g of sodium hydroxide and 150 g of water. The organic layer is dried by azeotropic distillation and then filtered. Toluene is removed by distillation at atmospheric pressure, the pressure being further reduced to 100 mmHg. Following the release of low boiling fractions, 109.61 g of di-n-hexylamine are distilled off at 109-111 ° C. The residue in the reaction vessel consists of crude triphenylphosphine; its yield is 185.5 g (94.3% of theoretically possible).
    drops of trichloro-t κόμη agre (105 + 3 ° С) h. White and gide l, peisi
    Analysis using two independent methods (gas chromatography and potentiometric titration) showed that the residue was 95.7% triphenylphosphine. The remaining 4.3% is amine and unreacted triphenylphosphine oxide.
    The yield of pure triphenylphosphine is 90.2% based on triphenylphosphine oxide.
    The previous procedure is repeated using n-butylamine instead of di-n-hexylamine. The yield and purity of the final product are 96.4 and 95.8%, respectively.
    权利要求:
    Claims (2)
    [1]
    (54) METHOD FOR OBTAINING TERTIARY PHOSPHINS with a nitrogen gas bed and loading 208.7 g (0.75 mol) of trifine phosphine oxide, 146.4 g (0.79 mol of di-n-hexylamine and 680 g of toluene) are charged For 30 minutes while stirring, 107.0 g (0.79 mol) of trichlorol silane is added dropwise, the temperature of the mixture is from room temperature to 45 ° C. Then the mixture is heated to the boiling point (105 + 3 ° and kept for 2 , 5 h. Bela reaction mixture is cooled and hydrolyzed by its gradual transfer into a flask with a capacity of 0.5 l, containing the mixture obtained using hydroca sodium silicate and 425 g of water. The resulting mixture is stirred for 30 minutes, and during this period the aqueous silicate layer is released. The solid material, remaining at the bottom of the organic phase, is removed by washing with a solution containing 50 g of sodium hydroxide and 150 g of water. The organic layer was dried by azeotropic distillation and then subjected to filtration. The toluene was removed by distillation at atmospheric pressure, with the pressure further decreasing to 100 mm Hg. Following the yield of low-boiling fractions at 109-111 ° C, 125.6 g (83% of the amount injected) of di-n-hexylamine is distilled off. The residue in the reaction vessel consists of crude triphenylphosphine, its yield is 185.5 g (94.3% of the theoretically possible). Analysis using two independent methods (gas chromatography and potentiometric titration) showed that the residue consists of 95.7% triphenylphosphine. The remaining 4.3% is amine and unreacted triphenylphosphine oxide. The yield of pure triphenylphosphine is 90.2% based on triphenylphosphine oxide. The previous procedure is repeated using n-butylamine instead of di-n-hexylamine. The yield and purity of the final product are 96.4 and 95.8%, respectively. Claims 1 amine use primary or secondary amine. 2. Method POP.1, about aphids and y with and the fact that the process is carried out at the boiling of the reaction mass. Sources of information taken into account when examining 1.Purdela D. Vishchanu R. Chemistry of organic phosphorus compounds. Chemistry, M., 1972, p.83.
    [2]
    2. Patent CttlA No. 3261871, cl. 260606, 5, published. 1966 (prototype,
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    同族专利:
    公开号 | 公开日
    JPS5414947A|1979-02-03|
    BE868462A|1978-10-16|
    GB2000780A|1979-01-17|
    IL54925A|1982-01-31|
    ATA473678A|1979-09-15|
    NO782285L|1979-01-08|
    DE2828604A1|1979-01-25|
    FR2396763A1|1979-02-02|
    PL208160A1|1979-07-02|
    US4131624A|1978-12-26|
    GB2000780B|1982-01-27|
    AU3764278A|1980-01-03|
    YU154778A|1983-01-21|
    ES471408A1|1979-01-16|
    ZA783535B|1979-06-27|
    SE7807482L|1979-01-06|
    IT1161399B|1987-03-18|
    IT7809520D0|1978-07-04|
    NZ187700A|1980-05-27|
    IL54925D0|1978-08-31|
    AT356139B|1980-04-10|
    BR7804225A|1979-03-13|
    DE2828604C2|1982-12-30|
    DK302578A|1979-01-06|
    AU515469B2|1981-04-02|
    DK145379B|1982-11-08|
    DK145379C|1983-04-11|
    NL7807243A|1979-01-09|
    CA1088573A|1980-10-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL295914A|1962-07-31|
    DE1203773B|1964-05-16|1965-10-28|Shell Int Research|Process for the production of tertiary phosphines|
    US4008282A|1973-12-14|1977-02-15|Hoffmann-La Roche Inc.|Preparation of triaryl phosphines|US4507501A|1983-10-26|1985-03-26|Ethyl Corporation|Process for preparing tertiary phosphines|
    US4507502A|1983-10-26|1985-03-26|Ethyl Corporation|Process for preparing tertiary phosphines|
    US4514575A|1983-11-25|1985-04-30|Ethyl Corporation|Process for preparing tertiary phosphines|
    US4507504A|1983-11-25|1985-03-26|Ethyl Corporation|Process for preparing tertiary phosphines|
    US4507503A|1983-11-25|1985-03-26|Ethyl Corporation|Process for preparing tertiary phosphines|
    DE4142679A1|1991-12-23|1993-07-01|Basf Ag|METHOD FOR PRODUCING TERTIAL PHOSPHINES|
    CN101270132B|2007-11-08|2010-11-03|陈国君|Method for preparing triphenylphosphine with diphenylbenzene phosphine oxide|
    EP2417082B1|2009-04-06|2016-03-16|The Board Of Regents, The University Of Texas System|Catalytic wittig and mitsunobu reactions|
    CN106674278A|2016-12-16|2017-05-17|浙江先锋科技股份有限公司|Triphenylphosphine recovery process in triphenylphosphine oxide waste slag|
    WO2020077582A1|2018-10-18|2020-04-23|Rhodia Operations|A process for preparing tertiary phosphines|
    CN110343133A|2019-07-03|2019-10-18|闫福全|A kind of method of reduction method production triphenylphosphine|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/812,761|US4131624A|1977-07-05|1977-07-05|Reduction of phosphine oxides|
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