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    • 21. 发明授权
    • Process for the preparation of 2-chloro-5-chloromethyl-1,3-thiazole
    • 制备2-氯-5-氯甲基-1,3-噻唑的方法
    • US06245927B1
    • 2001-06-12
    • US09547221
    • 2000-04-11
    • Hideki MatsudaGoro AsanumaManzo Shiono
    • Hideki MatsudaGoro AsanumaManzo Shiono
    • C07C33120
    • C07D277/32
    • According to the present invention, provided are (1) a process for the preparation of 2-chloro-5-chloromethyl-1,3-thiazole, by reacting 3- chloro-1-isothiocyanato-1-propene with a chlorinating agent, (2) a process for the preparation of 3-chloro-1-isocyanato-1-propene, by rearranging 3-chloro-1-thiocyanato-2-propene in the presence of a salt of one or more than one metal selected from the group consisting of metals belonging to Group 2A, Group 7A, Group 8 and Group 1B of the long-form periodic table, and (3) a process for the preparation of 3-chloro-1-thiocyanato-2-propene, by reacting 1,3-dichloropropene and a thiocyanate salt (a) in the presence of water, (b) in the presence of an organic solvent which is water-soluble and has a boiling point of 150° C. or lower, or (c) in an organic solvent in the presence of a phase transfer catalyst.
    • 根据本发明,提供了(1)通过使3-氯-1-异硫氰酸酯-1-丙烯与氯化剂反应制备2-氯-5-氯甲基-1,3-噻唑的方法( 2)制备3-氯-1-异氰酸基-1-丙烯的方法,通过在一种或多于一种选自下组的金属的存在下重排3-氯-1-氰硫基-2-丙烯: 由属于2A型,7A类,8类和1B类长金属元素周期表的金属组成,和(3)通过使1,1-二氯苯甲酸反应制备3-氯-1-氰硫基-2-丙烯的方法, (a)在水存在下,(b)在水溶性且沸点为150℃或更低的有机溶剂存在下,或(c)在 有机溶剂在相转移催化剂存在下进行。
    • 22. 发明授权
    • Process for the preparation of cyclopropylacetylene derivatives
    • 环丙基乙炔衍生物的制备方法
    • US06180835B2
    • 2001-01-30
    • US09245305
    • 1999-02-05
    • Goro AsanumaKazuya TakakiShigeo OhzonoManzo Shiono
    • Goro AsanumaKazuya TakakiShigeo OhzonoManzo Shiono
    • C07C2710
    • C07D307/20C07C1/20C07C33/05C07C2601/02Y02P20/55C07C13/04
    • A cyclopropylacetylene derivative of the formula (V): is prepared by reacting a propynol derivative of the formula (I): with a propane derivative of the formula (VI): in the presence of a base in an amount of 2 or more equivalents relative to the propynol derivative to give a cyclopropane derivative of the formula (III): deprotecting the protecting group for the hydroxyl group of the cyclopropane derivative to give a cyclopropylpropynol derivative of the formula (IV): and subjecting the cyclopropylpropynol derivative to retro-ethynylation. In the above formulas R1, R2, R3, R4 and R5 represent hydrogen; or an alkyl, alkenyl, aryl or aralkyl group, each of which may have a substituent, R6 and R7 is hydrogen; or an alkyl, alkenyl, aryl or aralkyl group, each of which may have a substituent, or R6 and R7 taken together form a ring, R8 is a protecting group for the hydroxyl group and X and Y are each a leaving group.
    • 式(Ⅴ)的环丙基乙炔衍生物通过使式(I)的丙炔醇衍生物与式(Ⅵ)的丙烷衍生物在碱的存在下反应制备:碱的量为2或更多当量相对 与丙炔衍生物反应,得到式(III)的环丙烷衍生物:使环丙烷衍生物的羟基的保护基脱保护,得到式(IV)的环丙基丙炔醇衍生物:使环丙基丙炔衍生物进行逆乙炔化反应。 在上式中,R 1,R 2,R 3,R 4和R 5表示氢; 或者可以具有取代基的烷基,烯基,芳基或芳烷基,R6和R7是氢; 或烷基,链烯基,芳基或芳烷基,其各自可以具有取代基,或者R6和R7一起形成环,R8是羟基的保护基,X和Y各自是离去基团。
    • 24. 发明授权
    • Process for the preparation of 2-chloro-5-chloromethyl-1,3-thiazole
    • 制备2-氯-5-氯甲基-1,3-噻唑的方法
    • US6103921A
    • 2000-08-15
    • US225292
    • 1999-01-05
    • Hideki MatsudaGoro AsanumaManzo Shiono
    • Hideki MatsudaGoro AsanumaManzo Shiono
    • C07C331/04C07C331/20C07D277/32
    • C07D277/32
    • According to the present invention, provided are(1) a process for the preparation of 2-chloro-5-chloromethyl-1,3-thiazole, by reacting 3-chloro-1-isothiocyanato-1-propene with a chlorinating agent,(2) a process for the preparation of 3-chloro-1-isocyanato-1-propene, by rearranging 3-chloro-1-thiocyanato-2-propene in the presence of a salt of one or more than one metal selected from the group consisting of metals belonging to Group 2A, Group 7A, Group 8 and Group 1B of the long-form periodic table, and(3) a process for the preparation of 3-chloro-1-thiocyanato-2-propene, by reacting 1,3-dichloropropene and a thiocyanate salt(a) in the presence of water,(b) in the presence of an organic solvent which is water-soluble and has a boiling point of 150.degree. C. or lower, or(c) in an organic solvent in the presence of a phase transfer catalyst.
    • 根据本发明,提供了(1)通过使3-氯-1-异硫氰酸酯-1-丙烯与氯化剂反应制备2-氯-5-氯甲基-1,3-噻唑的方法( 2)制备3-氯-1-异氰酸基-1-丙烯的方法,通过在一种或多于一种选自下组的金属的存在下重排3-氯-1-氰硫基-2-丙烯: 由属于2A型,7A类,8类和1B类长金属元素周期表的金属组成,和(3)通过使1,1-二氯苯甲酸反应制备3-氯-1-氰硫基-2-丙烯的方法, (a)在水存在下,(b)在水溶性且沸点为150℃或更低的有机溶剂存在下,或(c)在 有机溶剂在相转移催化剂存在下进行。