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    • 3. 发明授权
    • Intermediates for producing pyridine derivatives
    • 制备吡啶衍生物的中间体
    • US6111111A
    • 2000-08-29
    • US175958
    • 1998-10-21
    • Hideki MatsudaGoro AsanumaTakanobu ShinManzo ShionoShigeki Kikuyama
    • Hideki MatsudaGoro AsanumaTakanobu ShinManzo ShionoShigeki Kikuyama
    • C07D491/04C07D491/048C07D495/04
    • C07D491/04
    • A pyridine alcohol derivative represented by General Formula III ##STR1## (where A represents a divalent organic group which may contain one to three oxygen atoms, nitrogen atoms and/or sulfur atoms, wherein A may form a 5-, 6-, 7-, or 8-membered ring together with two bonded carbon atoms, where said ring may form a condensed ring with one or more additional rings; R.sup.5 represents a hydrogen atom, --CHR.sup.1 R.sup.2, or an alkenyl group, an aryl group or an aralkyl group which may be substituted; R.sup.1 and R.sup.2 each independently represent a hydrogen atom or a hydrocarbon group which may be substituted; and R.sup.6 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group which may be substituted), is produced by:reacting a pyridine ester derivative represented by General Formula I-1 ##STR2## (where Z.sup.1 represents --COX; X represents an alkoxyl group, an alkenyloxy group, an aryloxy group or an aralkyloxy group which may be substituted; and A is the same as above)with a reducing agent, an alkylating agent, an alkenylating agent, an arylating agent or an aralkylating agent to obtain a pyridine carbonyl derivative represented by General Formula II ##STR3## (where A and R.sup.5 are the same as above); and reacting the resulting pyridine carbonyl derivative with a reducing agent, an alkylating agent, an alkenylating agent, an arylating agent or an aralkylating agent to obtain the pyridine alcohol derivative of the General Formula III.
    • 由通式III表示的吡啶醇衍生物(其中A表示可含有1-3个氧原子的二价有机基团,氮原子和/或硫原子,其中A可以形成5-,6-,7-或8- 其中所述环可以与一个或多个另外的环形成稠环; R 5表示氢原子,-CHR 1 R 2或链烯基,芳基或可被取代的芳烷基 ; R 1和R 2各自独立地表示氢原子或可以被取代的烃基; R 6表示氢原子,烷基,链烯基,芳基或可被取代的芳烷基)由 :使由通式I-1表示的吡啶酯衍生物(其中Z1表示-COX; X表示烷氧基,烯氧基,芳氧基或可被取代的芳烷氧基),A与上述相同) 用还原剂, 烷基化剂,烯化剂,芳基化剂或芳烷基化剂,得到通式II所示的吡啶羰基衍生物(其中A和R5与上述相同); 并使所得到的吡啶羰基衍生物与还原剂,烷化剂,烯化剂,芳基化剂或芳烷基化剂反应,得到通式Ⅲ的吡啶醇衍生物。
    • 4. 发明授权
    • Method for producing pyridine derivatives
    • 制备吡啶衍生物的方法
    • US06342606B2
    • 2002-01-29
    • US09862615
    • 2001-05-23
    • Hideki MatsudaGoro AsanumaTakanobu ShinManzo ShionoShigeki Kikuyama
    • Hideki MatsudaGoro AsanumaTakanobu ShinManzo ShionoShigeki Kikuyama
    • C07D491048
    • C07D491/04
    • A pyridine alcohol derivative represented by General Formula III (where A represents a divalent organic group which may contain one to three oxygen atoms, nitrogen atoms and/or sulfur atoms, wherein A may form a 5-, 6-, 7-, or 8-membered ring together with two bonded carbon atoms, where said ring may form a condensed ring with one or more additional rings; R6 represents a hydrogen atom, —CHR1R2, or an alkenyl group, an aryl group or an aralkyl group which may be substituted; R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group which may be substituted; and R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group which may be substituted), is produced by: reacting a pyridine ester derivative represented by General Formula I-1
    • 由通式III表示的吡啶醇衍生物(其中A表示可含有1-3个氧原子的二价有机基团,氮原子和/或硫原子,其中A可以形成5-,6-,7-或8- 其中所述环可以与一个或多个另外的环形成稠环; R 6表示氢原子,-CHR 1 R 2或链烯基,芳基或可被取代的芳烷基 ; R 1和R 2各自独立地表示氢原子或可被取代的烃基; R表示氢原子,烷基,烯基,芳基或可被取代的芳烷基)由 :使由通式I-1表示的吡啶酯衍生物反应
    • 5. 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
    • US06222057B1
    • 2001-04-24
    • US09545349
    • 2000-04-07
    • Hideki MatsudaGoro AsanumaManzo Shiono
    • Hideki MatsudaGoro AsanumaManzo Shiono
    • C07C33104
    • 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。
    • 6. 发明授权
    • Method for producing pyridine derivatives
    • 制备吡啶衍生物的方法
    • US06265580B1
    • 2001-07-24
    • US09527916
    • 2000-03-17
    • Hideki MatsudaGoro AsanumaTakanobu ShinManzo ShionoShigeki Kikuyama
    • Hideki MatsudaGoro AsanumaTakanobu ShinManzo ShionoShigeki Kikuyama
    • C07D491048
    • C07D491/04
    • A pyridine alcohol derivative represented by General Formula III (where A represents a divalent organic group which may contain one to three oxygen atoms, nitrogen atoms and/or sulfur atoms, wherein A may form a 5-, 6-, 7-, or 8-membered ring together with two bonded carbon atoms, where said ring may form a condensed ring with one or more additional rings; R5 represents a hydrogen atom, —CHR1R2, or an alkenyl group, an aryl group or an aralkyl group which may be substituted; R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group which may be substituted; and R6 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group which may be substituted), is produced by: reacting a pyridine ester derivative represented by General Formula I-1  (where Z1 represents —COX; X represents an alkoxyl group, an alkenyloxy group, an aryloxy group or an aralkyloxy group which may be substituted; and A is the same as above) with a reducing agent, an alkylating agent, an alkenylating agent, an arylating agent or an aralkylating agent to obtain a pyridine carbonyl derivative represented by General Formula II  (where A and R5 are the same as above); and reacting the resulting pyridine carbonyl derivative with a reducing agent, an alkylating agent, an alkenylating agent, an arylating agent or an aralkylating agent to obtain the pyridine alcohol derivative of the General Formula III.
    • 由通式III表示的吡啶醇衍生物(其中A表示可含有1-3个氧原子的二价有机基团,氮原子和/或硫原子,其中A可以形成5-,6-,7-或8- 其中所述环可以与一个或多个另外的环形成稠环; R 5表示氢原子,-CHR 1 R 2或链烯基,芳基或可被取代的芳烷基 ; R 1和R 2各自独立地表示氢原子或可以被取代的烃基; R 6表示氢原子,烷基,链烯基,芳基或可被取代的芳烷基)由 :使由通式I-1表示的吡啶酯衍生物(其中Z1表示-COX; X表示烷氧基,烯氧基,芳氧基或可被取代的芳烷氧基),A与上述相同) 用还原剂,a 烷基化剂,烯化剂,芳基化剂或芳烷基化剂,得到通式II所示的吡啶羰基衍生物(其中A和R5与上述相同); 并用还原剂,烷化剂,烯化剂,芳基化剂或芳烷基化剂对所得吡啶羰基衍生物进行反应,得到通式III的吡啶醇衍生物。
    • 7. 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。
    • 8. 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。
    • 10. 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。