公开(公告)号：US20100256418A1

公开(公告)日：2010-10-07

申请号：US12726196

申请日：2010-03-17

申请人： Sebastian Peer SMIDT ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

发明人： Sebastian Peer SMIDT ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

IPC分类号： C07C205/04

CPC分类号： C07C201/12 ,  C07C209/68 ,  C07C211/52 ,  C07C205/12

摘要： A process for preparing substituted biphenyls of the formula I in which the substituents are defined as follows: X is fluorine or chlorine; R1 is nitro, amino or NHR3; R2 is cyano, nitro, halogen, C1-C6-alkyl, C1-C-6-alkenyl, C1-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkyl, C1-C6-alkylcarbonyl or phenyl; R3 is C1-C4-alkyl, C1-C4-alkenyl or C1-C4-alkynyl; n is 1, 2 or 3, where in case that n is 2 or 3, the R.sup.2 radicals may also be different, which comprises reacting the compound of the formula II in which Hal is halogen and X and R1 are as defined above, in the presence of a base and of a palladium catalyst selected from the group of:3 a) palladium-triarylphosphine or -trialkylphosphine complex with palladium in the zero oxidation state, b) salt of palladium in the presence of triarylphospine or trialkylphosphine as a complex ligand or c) metallic palladium, optionally applied to support, in the presence of triarylphosphine or trialkylphosphine, in a solvent, with a diphenylborinic acid (III) in which R2 and n are as defined above, where the triarylphosphines or trialkylphosphines used may be substituted.

摘要翻译： 制备式I取代的联苯的方法，其中取代基定义如下：X是氟或氯; R1是硝基，氨基或NHR3; R2是氰基，硝基，卤素，C1-C6-烷基，C1-C6-6烯基，C1-C6-炔基，C1-C6-烷氧基，C1-C6-卤代烷基，C1-C6烷基羰基或苯基; R3是C1-C4-烷基，C1-C4-烯基或C1-C4-炔基; n为1,2或3，其中在n为2或3的情况下，R 2基团也可以不同，其包括使其中Hal为卤素且X和R 1的式II化合物与 在碱存在下和选自以下组中的钯催化剂存在下：a）钯 - 三芳基膦或三烷基膦配合物与钯在零氧化状态，b）钯在三芳基膦或三烷基膦存在下的盐 作为络合配体或c）金属钯，任选地在三芳基膦或三烷基膦存在下，在溶剂中与二苯基硼酸（III）反应，其中R 2和n如上所定义，其中使用三芳基膦或三烷基膦 可以被替代。

公开(公告)号：US08115012B2

公开(公告)日：2012-02-14

申请号：US12513003

申请日：2007-11-02

申请人： Martin Sukopp ,  Michael Rack ,  Sebastian Peer Smidt ,  Sandra Löhr ,  Michael Keil ,  Jochen Dietz ,  Joachim Rheinheimer ,  Thomas Grote ,  Thomas Zierke ,  Jan Klaas Lohmann

发明人： Martin Sukopp ,  Michael Rack ,  Sebastian Peer Smidt ,  Sandra Löhr ,  Michael Keil ,  Jochen Dietz ,  Joachim Rheinheimer ,  Thomas Grote ,  Thomas Zierke ,  Jan Klaas Lohmann

IPC分类号： C07D231/10 ,  C07F7/08

CPC分类号： C07D231/14

摘要： The present invention relates to a process for preparing difluoromethyl-substituted pyrazol-4-ylcarboxylates of the formula I in which R1 is C1-C8-alkyl, C3-C8-cycloalkyl, C1-C4-alkoxy-C1-C4-alkyl, etc.; and R2 is hydrogen, C1-C4-alkyl, benzyl or phenyl, wherein a) a compound of the general formula II in which X is fluorine, chlorine or bromine, R1 has one of the meanings given above and R4 is C1-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, benzyl or phenyl, is reacted with a silane compound of the general formula R3nSiCl(4-n) in which n is 1, 2 or 3 and the substituents R3 are independently of one another selected from the group consisting of C1-C8-alkyl and phenyl and with a metal selected from the metals of groups 1, 2, 3, 4 and 12 of the Periodic Table of the Elements having a redox potential of less than −0.7 V, based on a normal hydrogen electrode (at 25° C. and 101.325 kPa); and b) the reaction mixture from step a) is reacted with a compound of the general formula III R2HN—NH2  (III) in which R2 has one of the meanings given above.

摘要翻译： 本发明涉及制备式Ⅰ的二氟甲基取代的吡唑-4-基羧酸酯的方法，其中R 1是C 1 -C 8烷基，C 3 -C 8环烷基，C 1 -C 4烷氧基-C 1 -C 4烷基等 。 R 2是氢，C 1 -C 4 - 烷基，苄基或苯基，其中a）通式II的化合物，其中X是氟，氯或溴，R 1具有上面给出的含义之一，R 4是C 1 -C 8 - 烷基，C 3 -C 8 - 环烷基，C 2 -C 8 - 烯基，苄基或苯基与通式R 3 n SiCl（4-n）的硅烷化合物反应，其中n为1,2或3，取代基R 3独立地为 选自由C 1 -C 8 - 烷基和苯基组成的组中的一种，以及选自元素周期表第1,2,3,4和12族金属的金属，其氧化还原电位小于-0.7 V，基于正常的氢电极（在25℃和101.325kPa）; 和b）将来自步骤a）的反应混合物与通式III的化合物R2HN-NH2（III）反应，其中R2具有上述含义之一。

公开(公告)号：US20100069646A1

公开(公告)日：2010-03-18

申请号：US12513003

申请日：2007-11-02

申请人： Martin Sukopp ,  Michael Rack ,  Sebastian Peer Smidt ,  Sandra Löhr ,  Michael Keil ,  Jochen Dietz ,  Joachim Rheinheimer ,  Thomas Grote ,  Thomas Zierke ,  Jan Klaas Lohmann

发明人： Martin Sukopp ,  Michael Rack ,  Sebastian Peer Smidt ,  Sandra Löhr ,  Michael Keil ,  Jochen Dietz ,  Joachim Rheinheimer ,  Thomas Grote ,  Thomas Zierke ,  Jan Klaas Lohmann

IPC分类号： C07D231/10 ,  C07F7/08

CPC分类号： C07D231/14

摘要： The present invention relates to a process for preparing difluoromethyl-substituted pyrazol-4-ylcarboxylates of the formula I in which R1 is C1-C8-alkyl, C3-C8-cycloalkyl, C1-C4-alkoxy-C1-C4-alkyl, etc.; and R2 is hydrogen, C1-C4-alkyl, benzyl or phenyl, wherein a) a compound of the general formula II in which X is fluorine, chlorine or bromine, R1 has one of the meanings given above and R4 is C1-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, benzyl or phenyl, is reacted with a silane compound of the general formula R3nSiCl(4-n) in which n is 1, 2 or 3 and the substituents R3 are independently of one another selected from the group consisting of C1-C8-alkyl and phenyl and with a metal selected from the metals of groups 1, 2, 3, 4 and 12 of the Periodic Table of the Elements having a redox potential of less than −0.7 V, based on a normal hydrogen electrode (at 25° C. and 101.325 kPa); and b) the reaction mixture from step a) is reacted with a compound of the general formula III R2HN—NH2   (III) in which R2 has one of the meanings given above.

摘要翻译： 本发明涉及制备式Ⅰ的二氟甲基取代的吡唑-4-基羧酸酯的方法，其中R 1是C 1 -C 8烷基，C 3 -C 8环烷基，C 1 -C 4烷氧基-C 1 -C 4烷基等 。 并且R 2是氢，C 1 -C 4 - 烷基，苄基或苯基，其中a）通式II的化合物，其中X是氟，氯或溴，R 1具有上面给出的含义之一，R 4是C 1 -C 8 - 烷基，C 3 -C 8 - 环烷基，C 2 -C 8 - 烯基，苄基或苯基与通式R 3 n SiCl（4-n）的硅烷化合物反应，其中n为1,2或3，取代基R 3独立地为 选自由C 1 -C 8 - 烷基和苯基组成的组中的一种，以及选自元素周期表第1,2,3,4和12族金属的金属，其氧化还原电位小于-0.7 V，基于正常的氢电极（在25℃和101.325kPa）; 和b）将来自步骤a）的反应混合物与通式III的化合物R2HN-NH2（III）反应，其中R2具有上述含义之一。

公开(公告)号：US20090005597A1

公开(公告)日：2009-01-01

申请号：US12087345

申请日：2007-05-31

申请人： Sebastian Peer Smidt ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

发明人： Sebastian Peer Smidt ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

IPC分类号： C07C201/12 ,  C07C209/68

CPC分类号： C07C201/12 ,  C07C209/68 ,  C07C211/52 ,  C07C205/12

摘要： A process for preparing substituted biphenyls of the formula I in which the substituents are defined as follows: X is fluorine or chlorine; R1 is nitro, amino or NHR3; R2 is cyano, nitro, halogen, C1-C6-alkyl, C1-C6-alkenyl, C1-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkyl, C1-C6-alkylcarbonyl or phenyl; R3 is C1-C4-alkyl, C1-C4-alkenyl or C1-C4-alkynyl; n is 1, 2 or 3, where in case that n is 2 or 3, the R2 radicals may also be different, which comprises reacting the compound of the formula II in which Hal is halogen and X and R1 are as defined above, in the presence of a base and of a palladium catalyst selected from the group of: a) palladium-triarylphosphine or -trialkylphosphine complex with palladium in the zero oxidation state, b) salt of palladium in the presence of triarylphospine or trialkylphosphine as a complex ligand or c) metallic palladium, optionally applied to support, in the presence of triarylphosphine or trialkylphosphine, in a solvent, with a diphenylborinic acid (III) in which R2 and n are as defined above, where the triarylphosphines or trialkylphosphines used may be substituted.

摘要翻译： 制备式I取代的联苯的方法，其中取代基定义如下：X是氟或氯; R1是硝基，氨基或NHR3; R2是氰基，硝基，卤素，C1-C6-烷基，C1-C6-烯基，C1-C6-炔基，C1-C6-烷氧基，C1-C6-卤代烷基，C1-C6-烷基羰基或苯基; R3是C1-C4-烷基，C1-C4-烯基或C1-C4-炔基; n为1,2或3，其中在n为2或3的情况下，R2基团也可以不同，其包括使Hal为卤素的化合物与X和R 1如上所定义的化合物反应在 存在碱和钯催化剂，其选自：a）钯 - 三芳基膦或三烷基膦配合物与钯在零氧化状态，b）钯在三芳基膦或三烷基膦作为络合配体的存在下的盐，或 c）金属钯，任选地在三芳基膦或三烷基膦存在下，在溶剂中与其中R 2和n如上定义的二苯基硼酸（III）反应，其中所用的三芳基膦或三烷基膦可以被取代。

公开(公告)号：US08030527B2

公开(公告)日：2011-10-04

申请号：US12726196

申请日：2010-03-17

申请人： Sebastian Peer Smidt ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

发明人： Sebastian Peer Smidt ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

IPC分类号： C07C205/06

CPC分类号： C07C201/12 ,  C07C209/68 ,  C07C211/52 ,  C07C205/12

摘要： A process for preparing substituted biphenyls of the formula I in which the substituents are defined as follows: X is fluorine or chlorine; R1 is nitro, amino or NHR3; R2 is cyano, nitro, halogen, C1-C6-alkyl, C1-C-6-alkenyl, C1-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkyl, C1-C6-alkylcarbonyl or phenyl; R3 is C1-C4-alkyl, C1-C4-alkenyl or C1-C4-alkynyl; n is 1, 2 or 3, where in case that n is 2 or 3, the R.sup.2 radicals may also be different, which comprises reacting the compound of the formula II in which Hal is halogen and X and R1 are as defined above, in the presence of a base and of a palladium catalyst selected from the group of:3 a) palladium-triarylphosphine or -trialkylphosphine complex with palladium in the zero oxidation state, b) salt of palladium in the presence of triarylphospine or trialkylphosphine as a complex ligand or c) metallic palladium, optionally applied to support, in the presence of triarylphosphine or trialkylphosphine, in a solvent, with a diphenylborinic acid (III) in which R2 and n are as defined above, where the triarylphosphines or trialkylphosphines used may be substituted.

摘要翻译： 制备式I取代的联苯的方法，其中取代基定义如下：X是氟或氯; R1是硝基，氨基或NHR3; R2是氰基，硝基，卤素，C1-C6-烷基，C1-C6-6烯基，C1-C6-炔基，C1-C6-烷氧基，C1-C6-卤代烷基，C1-C6-烷基羰基或苯基; R3是C1-C4-烷基，C1-C4-烯基或C1-C4-炔基; n为1,2或3，其中在n为2或3的情况下，R 2基团也可以不同，其包括使其中Hal为卤素且X和R 1的式II化合物与 在碱存在下和选自以下组中的钯催化剂存在下：a）钯 - 三芳基膦或三烷基膦配合物与钯在零氧化状态，b）钯在三芳基膦或三烷基膦存在下的盐 作为络合配体或c）金属钯，任选地在三芳基膦或三烷基膦存在下，在溶剂中与二苯基硼酸（III）反应，其中R 2和n如上所定义，其中使用三芳基膦或三烷基膦 可以被替代。

公开(公告)号：US07709684B2

公开(公告)日：2010-05-04

申请号：US12087345

申请日：2007-05-31

申请人： Sebastian Peer Smidt ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

发明人： Sebastian Peer Smidt ,  Jochen Dietz ,  Michael Keil ,  Thomas Grote

IPC分类号： C07C211/45 ,  C07C211/48 ,  C07C205/06

CPC分类号： C07C201/12 ,  C07C209/68 ,  C07C211/52 ,  C07C205/12

摘要： A process for preparing substituted biphenyls of the formula I in which the substituents are defined as follows: X is fluorine or chlorine; R1 is nitro, amino or NHR3; R2 is cyano, nitro, halogen, C1-C6-alkyl, C1-C6-alkenyl, C1-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkyl, C1-C6-alkylcarbonyl or phenyl; R3 is C1-C4-alkyl, C1-C4-alkenyl or C1-C4-alkynyl; n is 1, 2 or 3, where in case that n is 2 or 3, the R2 radicals may also be different, which comprises reacting the compound of the formula II in which Hal is halogen and X and R1 are as defined above, in the presence of a base and of a palladium catalyst selected from the group of: a) palladium-triarylphosphine or -trialkylphosphine complex with palladium in the zero oxidation state, b) salt of palladium in the presence of triarylphospine or trialkylphosphine as a complex ligand or c) metallic palladium, optionally applied to support, in the presence of triarylphosphine or trialkylphosphine, in a solvent, with a diphenylborinic acid (III) in which R2 and n are as defined above, where the triarylphosphines or trialkylphosphines used may be substituted.

摘要翻译： 制备式I取代的联苯的方法，其中取代基定义如下：X是氟或氯; R1是硝基，氨基或NHR3; R2是氰基，硝基，卤素，C1-C6-烷基，C1-C6-烯基，C1-C6-炔基，C1-C6-烷氧基，C1-C6-卤代烷基，C1-C6-烷基羰基或苯基; R3是C1-C4-烷基，C1-C4-烯基或C1-C4-炔基; n为1,2或3，其中在n为2或3的情况下，R2基团也可以不同，其包括使Hal为卤素的化合物与X和R 1如上所定义的化合物反应在 存在碱和钯催化剂，其选自：a）钯 - 三芳基膦或三烷基膦配合物与钯在零氧化状态，b）钯在三芳基膦或三烷基膦作为络合配体存在下的盐，或 c）金属钯，任选地在三芳基膦或三烷基膦存在下，在溶剂中与其中R 2和n如上定义的二苯基硼酸（III）反应，其中所用的三芳基膦或三烷基膦可以被取代。

公开(公告)号：US20120289706A1

公开(公告)日：2012-11-15

申请号：US13515064

申请日：2010-12-13

申请人： Jens Renner ,  Jochen Dietz ,  Thomas Grote ,  Joachim Gebhardt ,  Markus Nett ,  Michael Keil

发明人： Jens Renner ,  Jochen Dietz ,  Thomas Grote ,  Joachim Gebhardt ,  Markus Nett ,  Michael Keil

IPC分类号： C07D405/06 ,  C07D303/36

CPC分类号： C07D249/12

摘要： The present invention relates to a new process for the preparation of substituted thiotriazolo groups of the general formula (I) wherein the variables have the meanings as given in the claims and the description.

摘要翻译： 本发明涉及制备通式（I）的取代的三优唑基的新方法，其中变量具有权利要求书和说明书中给出的含义。

公开(公告)号：US20110004002A1

公开(公告)日：2011-01-06

申请号：US12919842

申请日：2009-02-27

申请人： Volker Maywald ,  Sebastian Peer Smidt ,  Bernd Wolf ,  Christopher Koradin ,  Thomas Zierke ,  Michael Rack ,  Michael Keil

发明人： Volker Maywald ,  Sebastian Peer Smidt ,  Bernd Wolf ,  Christopher Koradin ,  Thomas Zierke ,  Michael Rack ,  Michael Keil

IPC分类号： C07D231/14 ,  C07C69/66

CPC分类号： C07D231/14 ,  C07C67/343 ,  C07C69/72

摘要： A process for preparing alkyl 2-alkoxymethylene-4,4-difluoro-3-oxobutyrates (VI) where R is methyl or ethyl, from crude reaction mixtures of alkyl 4,4-difluoroacetoacetates (I) by a) reacting where M is a sodium or potassium ion, and without additional solvent to form an enolate (V) b) releasing the corresponding alkyl 4,4-difluoroacetoacetate (I) from the enolate (V) by means of acid, c) removing the salt formed from cation M and acid anion as a solid and d) converting (I), without isolation from the crude reaction mixture, to the alkyl 2-alkoxymethylene-4,4-difluoro-3-oxobutyrate (VI), and the use of (VI) for preparing 1-methyl-3-difluoromethyl-pyrazol-3-ylcarboxyates VII

摘要翻译： 由烷基4,4-二氟乙酰乙酸酯（I）的粗反应混合物制备R为甲基或乙基的2-烷氧基亚甲基-4,4-二氟-3-氧代丁酸烷基酯（VI）的方法，通过a）使M 钠离子或钾离子，无另外的溶剂以形成烯醇化物（Ⅴ）b）通过酸从烯醇化物（Ⅴ）中释出相应的4,4-二氟乙酰乙酸烷基酯（Ⅰ），c）除去由阳离子M形成的盐 和酸阴离子作为固体，以及d）将（I）从粗反应混合物中分离出来，转化为2-烷氧基亚甲基-4,4-二氟-3-氧代丁酸烷基酯（VI），以及（VI）用于 制备1-甲基-3-二氟甲基 - 吡唑-3-基羧酸酯VII

公开(公告)号：US08586750B2

公开(公告)日：2013-11-19

申请号：US12990364

申请日：2009-04-30

申请人： Thomas Zierke ,  Volker Maywald ,  Michael Rack ,  Sebastian Peer Smidt ,  Michael Keil ,  Bernd Wolf ,  Christopher Koradin

发明人： Thomas Zierke ,  Volker Maywald ,  Michael Rack ,  Sebastian Peer Smidt ,  Michael Keil ,  Bernd Wolf ,  Christopher Koradin

IPC分类号： C07D295/145 ,  C07D211/34 ,  C07D265/30

CPC分类号： C07D295/145 ,  C07D231/14

摘要： The present invention relates to a process for preparing 2-(aminomethylidene)-4,4-dihalo-3-oxobutyric esters of the formula (I), wherein R1, R2, R3 are C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C3-C10-cycloalkyl or benzyl, and/or R2 together with R3 and the nitrogen atom to which the two radicals are attached are a heterocyclic radical, in which a corresponding 3-aminoacrylic ester is reacted with a halogen-substituted acetyl fluoride in the presence of at least one alkali or alkaline earth metal fluoride; and the further conversion of halogen-substituted 2-(aminomethylidene)-3-oxobutyric esters of the formula (I) to halomethyl-substituted pyrazol-4-ylcarboxylic acids and their esters.

摘要翻译： 本发明涉及制备式（I）的2-（氨基亚甲基）-4,4-二卤代-3-氧代丁酸酯的方法，其中R1，R2，R3是C1-C6-烷基，C1-C6-卤代烷基 ，C 2 -C 6 - 烯基，C 3 -C 10 - 环烷基或苄基，和/或R 2与R 3和两个基团所连接的氮原子是杂环基团，其中相应的3-氨基丙烯酸酯与 卤素取代的乙酰氟在至少一种碱金属或碱土金属氟化物的存在下; 以及将式（I）的卤素取代的2-（氨基亚甲基）-3-氧代丁酸酯进一步转化为卤代甲基取代的吡唑-4-基羧酸及其酯。

公开(公告)号：US08461390B2

公开(公告)日：2013-06-11

申请号：US13001070

申请日：2009-06-22

申请人： Sebastian Peer Smidt ,  Volker Maywald ,  Kathrin Wissel-Stoll ,  Joachim Schmidt-Leithoff ,  Ansgar Gereon Altenhoff ,  Michael Keil

发明人： Sebastian Peer Smidt ,  Volker Maywald ,  Kathrin Wissel-Stoll ,  Joachim Schmidt-Leithoff ,  Ansgar Gereon Altenhoff ,  Michael Keil

IPC分类号： C07C205/06

CPC分类号： C07C205/11 ,  C07C201/12

摘要： A process for preparing substituted biphenyls of the formula I where R1=nitro or amino, R2=cyano, halogen, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-haloalkylthio, n=from 0 to 3, and R3=hydrogen, cyano or halogen, which comprises reacting a halobenzene of the formula II in which Hal is chlorine or bromine, in the presence of a base and of a palladium catalyst which consists of palladium and a bidentate phosphorus ligand of the formula III where Ar is phenyl which is substituted if desired and R4 and R5 are each C1-C8-alkyl or C3-C6-cycloalkyl or together form a 2- to 7-membered bridge which may, if desired, bear a C1-C6-alkyl substituent, in a solvent or diluent, with a phenylboronic acid IVa a diphenylborinic acid IVb or a mixture of IVa and IVb.

摘要翻译： 制备式I的取代的联苯的方法，其中R 1 =硝基或氨基，R 2 =氰基，卤素，C 1 -C 4卤代烷基，C 1 -C 4卤代烷氧基或C 1 -C 4卤代烷硫基，n = 0至3， =氢，氰基或卤素，其包括在碱的存在下使Hal为氯或溴的式II的卤代苯与由式III的二齿磷配体组成的钯催化剂反应，其中Ar 是如果需要被取代的苯基，并且R 4和R 5各自是C 1 -C 8 - 烷基或C 3 -C 6 - 环烷基或一起形成2-7元桥，如果需要，其可以具有C 1 -C 6烷基取代基， 在溶剂或稀释剂中与苯基硼酸IVa为二苯基硼酸IVb或IVa和IVb的混合物。