公开(公告)号：US6111111A

公开(公告)日：2000-08-29

申请号：US175958

申请日：1998-10-21

申请人： Hideki Matsuda ,  Goro Asanuma ,  Takanobu Shin ,  Manzo Shiono ,  Shigeki Kikuyama

发明人： Hideki Matsuda ,  Goro Asanuma ,  Takanobu Shin ,  Manzo Shiono ,  Shigeki Kikuyama

IPC分类号： C07D491/04 ,  C07D491/048 ,  C07D495/04

CPC分类号： C07D491/04

摘要： 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.

摘要翻译： 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。

公开(公告)号：US06342606B2

公开(公告)日：2002-01-29

申请号：US09862615

申请日：2001-05-23

申请人： Hideki Matsuda ,  Goro Asanuma ,  Takanobu Shin ,  Manzo Shiono ,  Shigeki Kikuyama

发明人： Hideki Matsuda ,  Goro Asanuma ,  Takanobu Shin ,  Manzo Shiono ,  Shigeki Kikuyama

IPC分类号： C07D491048

CPC分类号： C07D491/04

摘要： 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

摘要翻译： 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

公开(公告)号：US06265580B1

公开(公告)日：2001-07-24

申请号：US09527916

申请日：2000-03-17

申请人： Hideki Matsuda ,  Goro Asanuma ,  Takanobu Shin ,  Manzo Shiono ,  Shigeki Kikuyama

发明人： Hideki Matsuda ,  Goro Asanuma ,  Takanobu Shin ,  Manzo Shiono ,  Shigeki Kikuyama

IPC分类号： C07D491048

CPC分类号： C07D491/04

摘要： 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.

摘要翻译： 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。

公开(公告)号：US06222057B1

公开(公告)日：2001-04-24

申请号：US09545349

申请日：2000-04-07

申请人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

发明人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

IPC分类号： C07C33104

CPC分类号： C07D277/32

摘要： 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.

摘要翻译： 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。

公开(公告)号：US5894073A

公开(公告)日：1999-04-13

申请号：US804401

申请日：1997-02-21

申请人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

发明人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

IPC分类号： C07C331/04 ,  C07C331/20 ,  C07D277/32

CPC分类号： C07D277/32

摘要： 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.

公开(公告)号：US06245927B1

公开(公告)日：2001-06-12

申请号：US09547221

申请日：2000-04-11

申请人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

发明人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

IPC分类号： C07C33120

CPC分类号： C07D277/32

摘要： 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.

摘要翻译： 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。

公开(公告)号：US6103921A

公开(公告)日：2000-08-15

申请号：US225292

申请日：1999-01-05

申请人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

发明人： Hideki Matsuda ,  Goro Asanuma ,  Manzo Shiono

IPC分类号： C07C331/04 ,  C07C331/20 ,  C07D277/32

CPC分类号： C07D277/32

摘要： 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.

摘要翻译： 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。

公开(公告)号：US5955627A

公开(公告)日：1999-09-21

申请号：US989412

申请日：1997-12-12

申请人： Makoto Nakazawa ,  Toshimichi Mitani ,  Yoichi Satake ,  Shigeo Oozono ,  Goro Asanuma ,  Manzo Shiono

发明人： Makoto Nakazawa ,  Toshimichi Mitani ,  Yoichi Satake ,  Shigeo Oozono ,  Goro Asanuma ,  Manzo Shiono

IPC分类号： C07C1/26 ,  C07C13/04 ,  C07C17/00 ,  C07C22/00 ,  C07C51/353 ,  C07C51/363 ,  C07C67/307 ,  C07C67/343 ,  C07C51/377 ,  C07C67/317

CPC分类号： C07C67/307 ,  C07C1/26 ,  C07C13/04 ,  C07C17/00 ,  C07C22/00 ,  C07C51/353 ,  C07C51/363 ,  C07C67/343 ,  C07C2101/02 ,  Y02P20/55

摘要： According to the present invention, a process for the preparation of a cyclopropylacetylene derivative represented by the following formula (III): ##STR1## is provided, which comprises reacting a cyclopropylacrylic acid derivative represented by the following formula (I): ##STR2## with a halogenating agent to obtain a halogenocyclopropylpropionic acid derivative represented by the following formula (II): ##STR3## and reacting the halogenocyclopropylpropionic acid derivative with a base.

摘要翻译： 根据本发明，提供了制备由下式（III）表示的环丙基乙炔衍生物的方法：包括使下式（I）表示的环丙基丙烯酸衍生物与卤化剂反应，得到 由下式（II）表示的卤代环丙基丙酸衍生物：使卤代环丙基丙酸衍生物与碱反应。

公开(公告)号：US06180835B2

公开(公告)日：2001-01-30

申请号：US09245305

申请日：1999-02-05

申请人： Goro Asanuma ,  Kazuya Takaki ,  Shigeo Ohzono ,  Manzo Shiono

发明人： Goro Asanuma ,  Kazuya Takaki ,  Shigeo Ohzono ,  Manzo Shiono

IPC分类号： C07C2710

CPC分类号： C07D307/20 ,  C07C1/20 ,  C07C33/05 ,  C07C2601/02 ,  Y02P20/55 ,  C07C13/04

摘要： 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.

摘要翻译： 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。

公开(公告)号：US06118005A

公开(公告)日：2000-09-12

申请号：US68115

申请日：1998-05-06

申请人： Tomoya Kuwayama ,  Shinichi Inoue ,  Goro Asanuma ,  Manzo Shiono

发明人： Tomoya Kuwayama ,  Shinichi Inoue ,  Goro Asanuma ,  Manzo Shiono

IPC分类号： C07D213/61 ,  C07D213/62 ,  C07D213/71

CPC分类号： C07D213/61 ,  C07D213/62 ,  C07D213/71

摘要： A process for preparing halogenopyridine derivatives represented by the general formula (II) ##STR1## wherein X and Y each independently represent a halogen atom, comprises reacting a halogeno-2-sulfonylpyridine derivative represented by the general formula (I) ##STR2## wherein X is as defined above and R.sup.1 represents an alkyl group etc., with a halogenating agent.The halogenopyridine derivatives can be produced with high purity and in a simple and easy and industrially advantageous manner.

摘要翻译： PCT No.PCT / JP97 / 03144 Sec。 371日期：1998年5月6日 102（e）日期1998年5月6日PCT提交1997年9月8日PCT公布。 公开号WO98 / 11071 日期：1998年3月19日制备由通式（II）表示的卤代吡啶衍生物的方法，其中X和Y各自独立地表示卤素原子，包括使通式（I）表示的卤代-2-磺酰基吡啶衍生物，其中X为 如上所定义，R 1表示烷基等，与卤化剂反应。 卤代吡啶衍生物可以以高纯度和简单且容易和工业上有利的方式制备。