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    • 1. 发明公开
    • Process for producing phosphite
    • VERFAHREN ZUR HERSTELLUNG VON PHOSPHITEN
    • EP1484334A2
    • 2004-12-08
    • EP04252646.7
    • 2004-05-06
    • Sumitomo Chemical Company, Limited
    • Inoue, KikumitsuNishii, ShinjiKikuchi, Taketoshi
    • C07F9/6574
    • C07F9/65744
    • There is provided a process for producing a phosphite of the formula (I):
      wherein R 1 , R 2 , R 4 and R 5 each independently represent
         a hydrogen atom, a C1-8 alkyl group, a C5-8 cycloalkyl group,
         a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or
         a phenyl group or a phenyl group substituted with an alkyl or an alkoxy group;
         R 3 represents a hydrogen atom or a C1-8 alkyl group;
         A represents a C2-8 alkylene group or a *-C(=O)- or *-C(=O)-R 7 - group in which R 7 represents a C1-8 alkylene group, and the bond marked with * is the bond connected with the oxygen atom; and
         one of Y and Z represents a hydroxyl group, a C1-8 alkoxy group or a C7-12 aralkyloxy group and the other one represents a hydrogen atom or a C1-8 alkyl group,
      which process comprises the steps of

      (a) coupling a phenol compound of formula (II):
      wherein R 1 to R 3 are as defined above, in the presence of an inert solvent under oxidative conditions to produce a reaction mixture comprising a biphenol of formula (III):
      wherein R 1 to R 3 are as defined above,
      (b) extracting the biphenol compound of formula (III) from the reaction mixture with a hydrophobic organic solvent, and
      (c) reacting the biphenol compound of formula (III) in the solution of the hydrophobic organic solvent, with phosphorous trihalide, and
         a hydroxyl compound of formula (IV):

         wherein R 4 , R 5 , Y, Z and A are as defined above, in the presence of a dehydrohalogenating agent.
    • 提供了制备式(I)的亚磷酸酯的方法:其中R 1,R 2,R 4和R 5各自独立地表示氢原子,C 1-8烷基,C 5-8环烷基,C 6 -12烷基环烷基,C7-12芳烷基或苯基或被烷基或烷氧基取代的苯基; R3表示氢原子或C1-8烷基; A表示C 8-8亚烷基或* -C(= O) - 或* -C(= O)-R 7 - 基,其中R 7表示C 1-8亚烷基,并且用*表示的键是键 与氧原子连接; Y和Z中的一个表示羟基,C 1-8烷氧基或C 7-12芳烷氧基,另一个表示氢原子或C 1-8烷基,该方法包括以下步骤:(a) 式(II)的酚化合物:其中R 1至R 3如上定义,在惰性溶剂存在下,在氧化条件下制备包含式(III)的双酚的反应混合物:其中R1 对于R3如上所定义,(b)用疏水性有机溶剂从反应混合物中萃取式(III)的联苯酚化合物,和(c)使式(III)的联苯酚化合物在疏水性有机溶剂 ,和三卤代磷酸盐,和式(IV)的羟基化合物:其中R 4,R 5,Y,Z和A如上定义,在脱卤化氢剂的存在下。
    • 2. 发明公开
    • Process for producing optically active amines
    • 维尔法赫恩·赫斯特伦
    • EP0485069A1
    • 1992-05-13
    • EP91309150.0
    • 1991-10-07
    • SUMITOMO CHEMICAL COMPANY, LIMITED
    • Konya, NaotoYoneyoshi, YukioSakito, YojiNishii, ShinjiSuzukamo, GohfuSakane, Hiroko
    • C07C209/40
    • C07C209/40
    • Disclosed is a process for producing an optically active amine represented by the formula (IV)

      wherein R₇ and R₈ each independently denote an alkyl group, aryl group or aralkyl group which said alkyl, aryl or aralky group is optionally substitued, providing that they do not denote the same specific group at the same time, and * indicates an asymmetric carbon atom, which comprises reacting an asymmetric reducing agent obtained from (1) an optically active amine derivative represented by the formula (I)

      wherein R₁ denotes an alkyl group, aryl group, or aralkyl group; R₂ denotes a hydrogen atom, alkyl group or aralkyl group; R₃ denotes an alkyl group, an aryl group which said alkyl or aryl group is optionally substituted, or a substituent represented by the formula (II)

      wherein R₄ and R₅ each independently denote a hydrogen atom, alkyl group, aryl group or aralkyl group which said alkyl, aryl or aralkyl group is optionally substituted and * is a defined above, (2) a metal borohydride and (3) sulfuric acid,
      with either the syn-isomer or the anti-isomer of an oxime derivative represented by the formula (III) or with a mixture rich in either one of the two isomers

      wherein R₆ denotes an alkyl group, aralkyl group or alkyl-substituted silyl group, and R₇ and R₈ are as defined above.
      The optically active amine obtained can be used as a resolving agent for preparing medicinal agents, agricultural chemicals, or intermediates thereof.
    • 公开了由式(IV)表示的光学活性胺的方法,其中R 7和R 8各自独立地表示烷基,芳基或芳烷基,所述烷基,芳基或芳烷基任选被取代,条件是 它们不同时表示相同的特定基团,*表示不对称碳原子,其包括使由(1)由式(I)表示的光学活性胺衍生物获得的不对称还原剂与式 表示烷基,芳基或芳烷基; R2表示氢原子,烷基或芳烷基; R3表示烷基,所述烷基或芳基任选被取代的芳基或由式(II)表示的取代基其中R4和R5各自独立地表示氢原子,烷基,芳基或芳烷基 所述烷基,芳基或芳烷基任选被取代的基团,和*如上所定义,(2)金属硼氢化物和(3)硫酸,其中肟衍生物的顺式异构体或反式异构体由 式(III)或富含两种异构体之一的混合物,其中R6表示烷基,芳烷基或烷基取代的甲硅烷基,R7和R8如上所定义。 获得的光学活性胺可以用作制备药剂,农药或其中间体的拆分剂。
    • 5. 发明公开
    • Process for producing 1-substituted tetrahydroquinazolines
    • Verfahren zur Herstellung von 1-substitutionierten Tetrahydrochinazolinen
    • EP0878468A1
    • 1998-11-18
    • EP98303721.9
    • 1998-05-12
    • Sumitomo Chemical Company, Limited
    • Asada, SachikoKomatsu, MasashiNishii, Shinji
    • C07D239/96
    • C07D239/96
    • A process for producing a 1-substituted tetrahydroquinazoline represented by the formula (III):
      wherein Z represents a methylene group which is optionally substituted by an alkyl group; R 6 represents an alkyl group or an aralkyl group; R 1 and R 2 independently represent a hydrogen atom, a halogen atom, a nitro group, an azido group, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy groupm, an alkoxycarbonyl group, an acyloxy group, or an amino group represented by -XNR 4 R 5 in which X represents a direct bond, an alkylene group or a carbonyl group, and N, R 4 and R 5 may form together a five- or six-membered heterocyclic ring or R 4 and R 5 independently represent an alkyl group or an acyloxy alkyl group; and R 3 represents a hydrogen atom, a halogen atom, a nitro group, an azido group, an alkyl group, an alkenyl group, an aralkyl group,an alkoxy group, or an alkoxycarbonyl group which comprises reacting a tetrahydroquinazoline represented by the formula (I):
      wherein R 1 , R 2 and R 3 are as defined above with hexamethyldisilazane; and reacting the resultant product hexamethyldisilazane; and reacting the resultant product with a chloroalkanoate represented by the formula (II):

              Cl-Z-CO-O-R 6      (II)

      wherein Z and R 6 are as defined above in the presence of an iodide of an alkaline metal, followed by desilylation.
    • 一种由式(III)表示的1-取代的四氢喹唑啉的制备方法:其中Z表示任选被烷基取代的亚甲基; R6表示烷基或芳烷基; R1和R2独立地表示氢原子,卤素原子,硝基,叠氮基,烷基,烯基,芳烷基,烷氧基,烷氧基羰基,酰氧基或氨基 其中X表示直接键,亚烷基或羰基,N,R 4和R 5可以一起形成五元或六元杂环,或者R 4和R 5独立地表示烷基或酰氧基烷基 组; R 3表示氢原子,卤素原子,硝基,叠氮基,烷基,烯基,芳烷基,烷氧基或烷氧基羰基,其包括使由式(I)表示的四氢喹唑啉 ):其中R1,R2和R3如上定义与六甲基二硅氮烷; 并使所得产物六甲基二硅氮烷反应; 并使所得产物与由式(II)表示的氯代烷酸酯反应:其中Z和R 6如上所定义,在碱金属的碘化物的存在下进行脱甲硅烷基化。
    • 6. 发明公开
    • Process for producing phosphite
    • 用于生产磷酸盐
    • EP1484334A3
    • 2005-04-06
    • EP04252646.7
    • 2004-05-06
    • Sumitomo Chemical Company, Limited
    • Inoue, KikumitsuNishii, ShinjiKikuchi, Taketoshi
    • C07F9/6574
    • C07F9/65744
    • There is provided a process for producing a phosphite of the formula (I): wherein R 1 , R 2 , R 4 and R 5 each independently represent    a hydrogen atom, a C1-8 alkyl group, a C5-8 cycloalkyl group,    a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or    a phenyl group or a phenyl group substituted with an alkyl or an alkoxy group;    R 3 represents a hydrogen atom or a C1-8 alkyl group;    A represents a C2-8 alkylene group or a *-C(=O)- or *-C(=O)-R 7 - group in which R 7 represents a C1-8 alkylene group, and the bond marked with * is the bond connected with the oxygen atom; and    one of Y and Z represents a hydroxyl group, a C1-8 alkoxy group or a C7-12 aralkyloxy group and the other one represents a hydrogen atom or a C1-8 alkyl group, which process comprises the steps of (a) coupling a phenol compound of formula (II): wherein R1 to R3 are as defined above, in the presence of an inert solvent under oxidative conditions to produce a reaction mixture comprising a biphenol of formula (III): wherein R1 to R3 are as defined above, (b) extracting the biphenol compound of formula (III) from the reaction mixture with a hydrophobic organic solvent, and (c) reacting the biphenol compound of formula (III) in the solution of the hydrophobic organic solvent, with phosphorous trihalide, and    a hydroxyl compound of formula (IV):    wherein R 4 , R 5 , Y, Z and A are as defined above, in the presence of a dehydrohalogenating agent.
    • 9. 发明公开
    • Process for producing 1,4-dicyano-2-butene
    • Verfahren zur Herstellung von 1,4-Dicyano-2-buten。
    • EP0612720A1
    • 1994-08-31
    • EP94102587.6
    • 1994-02-21
    • SUMITOMO CHEMICAL COMPANY, LIMITED
    • Nishii, ShinjiWake, ShigeoOgawa, Takeshi
    • C07C253/16C07C255/09
    • C07C253/16Y02P20/582C07C255/09
    • The object of the present invention is to provide a process for producing 1,4-dicyano-2-butene in a high yield and in an industrially advantageous way.
      The present invention relates to a process for producing 1,4-dicyano-2-butene which comprises reacting a butene derivative represented by the formula [1]

              R₁-CH₂-CH=CH-CH₂-R₂   [1]


      or the formula [2]

              R₃-CH₂-CHR₄-CH=CH₂   [2]


      wherein each of R₁ and R₃ represents a hydroxy group, lower acyloxy group, lower alkoxy group or cyano group; and each of R₂ and R₄ represents a hydroxy group, lower acyloxy group or lower alkoxy group, with hydrogen cyanide in the presence of a catalyst comprising a product prepared from a cuprous halide, a non-aromatic amine hydrohalide and at least one member selected from the group consisting of Lewis acids and basic compounds.
    • 本发明的目的是提供以高产率和工业上有利的方式生产1,4-二氰基-2-丁烯的方法。 本发明涉及1,4-二氰基-2-丁烯的制备方法,该方法包括使由式[1] R1-CH2-CH = CH-CH2-R2 [1]表示的丁烯衍生物或式[2 ] R 3 -CH 2 -CHR 4 -CH = CH 2 [2]其中R 1和R 3各自表示羟基,低级酰氧基,低级烷氧基或氰基; R 2和R 4各自表示羟基,低级酰氧基或低级烷氧基,在含有由卤化亚铜,非芳族胺氢卤化物和至少一种选自 该组由路易斯酸和碱性化合物组成。