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。

公开(公告)号：US08344157B2

公开(公告)日：2013-01-01

申请号：US13054642

申请日：2009-07-10

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

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

IPC分类号： C07D231/10

CPC分类号： C07D233/90

摘要： A process for preparing 1,3-disubstituted pyrazolecarboxylic esters of the formula (I) where X, Y, Z=hydrogen or halogen and R1=C1-C6-alkyl, by metering an enol ether of the formula III where R2 is C1-C6-alkyl at from (−41) to (−80)° C. into an alkyl hydrazine of the formula II H2N—NH-lower alkyl   (II).

摘要翻译： 通过计量式III的烯醇醚制备其中X，Y，Z =氢或R 1 = C 1 -C 6烷基的式（I）的1,3-二取代吡唑羧酸酯的方法，其中R2是C1- （-41）至（-80）℃的C 6 - 烷基转化为式II的烷基肼H 2 NH-NH-低级烷基（II）。

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：US20100184994A1

公开(公告)日：2010-07-22

申请号：US12664448

申请日：2008-06-13

申请人： Markus Nett ,  Thomas Grote ,  Jan Klaas Lohmann ,  Jochen Dietz ,  Sebastian Peer Smidt ,  Michael Rack ,  Thomas Zierke

发明人： Markus Nett ,  Thomas Grote ,  Jan Klaas Lohmann ,  Jochen Dietz ,  Sebastian Peer Smidt ,  Michael Rack ,  Thomas Zierke

IPC分类号： C07D231/14 ,  C07C229/06

CPC分类号： C07D231/12 ,  C07D231/14

摘要： The present invention relates to a process for preparing 3-difluoromethyl-substituted pyrazole compounds of the formula (I) in which R1 is H, halogen, nitro, C1-C8-alkyl, C1-C8-haloalkyl, C3-C8-cycloalkyl, phenyl, naphthyl, hetaryl, cyano, —C(═O)—OR1a, —C(═O)—NR1bR1c, —C(═O)—SR1d or —C(═S)—SR1e; R2 is H, C1-C4-alkyl, benzyl or phenyl; R3 is H, halogen, C1-C8-alkoxy, C1-C8-haloalkoxy, C3-C8-cycloalkoxy, C2-C8-alkenyloxy, C1-C8-alkylthio, C1-C8-haloalkylthio, C3-C8-cyclo-alkylthio or C2-C8-alkenylthio; compounds of the formula (II.a) or (II.b), in which R1 and R3 each have one of the definitions given above; R4 is halogen, —OR4a, —SR4a, —O—SO2—R4a or an —NR4bR4c group; R5 and R6 are each C1-C8-alkyl, C1-C8-haloalkyl, C3-C8-cycloalkyl, benzyl or phenyl, or, together with the nitrogen atom to which they are bonded, are a 3- to 8-membered heterocycle; Lewis acid adducts of compounds of the formula (II.b); the use of compounds of the formula (II.a) or (II.b) and of the Lewis acid adducts for preparing compounds of the formula (I) or (VI); and to a process for converting such compounds to the corresponding 3-difluoro-pyrazol-4-ylcarboxylic acids.

摘要翻译： 本发明涉及制备式（I）的3-二氟甲基取代的吡唑化合物的方法，其中R 1是H，卤素，硝基，C 1 -C 8 - 烷基，C 1 -C 8 - 卤代烷基，C 3 -C 8 - 环烷基， 苯基，萘基，杂芳基，氰基，-C（= O）-OR1a，-C（= O）-NR1bR1c，-C（= O）-SR1d或-C（= S）-SR1e; R2是H，C1-C4-烷基，苄基或苯基; R 3是H，卤素，C 1 -C 8 - 烷氧基，C 1 -C 8 - 卤代烷氧基，C 3 -C 8 - 环烷氧基，C 2 -C 8 - 烯氧基，C 1 -C 8 - 烷硫基，C 1 -C 8 - 卤代烷硫基，C 3 -C 8环 - C 2 -C 8 - 烯硫基; 式（II.a）或（II.b）化合物，其中R 1和R 3各自具有上述定义之一; R4是卤素，-OR4a，-SR4a，-O-SO2-R4a或-NR4bR4c基团; R 5和R 6各自为C 1 -C 8 - 烷基，C 1 -C 8 - 卤代烷基，C 3 -C 8 - 环烷基，苄基或苯基，或与它们所键合的氮原子一起为3-至8-元杂环; 式（II.b）化合物的路易斯酸加合物; 使用式（II.a）或（II.b）化合物和路易斯酸加成物制备式（I）或（VI）化合物的方法; 以及将这些化合物转化为相应的3-二氟 - 吡唑-4-基羧酸的方法。

公开(公告)号：US20100056820A1

公开(公告)日：2010-03-04

申请号：US12522211

申请日：2008-01-21

申请人： Volker Maywald ,  Christian Ott ,  Bernd Wolf ,  Manfred Ehresmann ,  Michael Rack ,  Michael Keil ,  Sebastian Peer Smidt

发明人： Volker Maywald ,  Christian Ott ,  Bernd Wolf ,  Manfred Ehresmann ,  Michael Rack ,  Michael Keil ,  Sebastian Peer Smidt

IPC分类号： C07C69/34

CPC分类号： C07C17/12 ,  C07C67/343 ,  C07C25/13 ,  C07C69/65

摘要： The present invention relates to a process for preparing substituted 2-arylmalonic esters of the general formula I in which R is C1-C6-alkyl or C1-C4-alkoxy-C1-C4-alkyl; Ar is phenyl or a heteroaromatic 5- or 6-membered ring; where each carbon atom present in the radicals mentioned above optionally carries a substituent RA; RA is F, Cl, CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, etc., or two adjacent substituents RA together with the carbon atoms to which they are attached form a ring; and where a malonic ester is reacted with a base and an aryl bromide in the presence of a copper salt, which comprises employing from 0.1 to 0.65 molar equivalents of the base per molar equivalent of the malonic ester.

摘要翻译： 本发明涉及制备通式Ⅰ的取代的2-芳基丙二酸酯的方法，其中R是C 1 -C 6 - 烷基或C 1 -C 4 - 烷氧基-C 1 -C 4烷基; Ar是苯基或杂芳族5或6元环; 其中存在于上述基团中的每个碳原子任选地带有取代基RA; RA是F，Cl，CN，NO 2，C 1 -C 4 - 烷基，C 1 -C 4卤代烷基，C 1 -C 4 - 烷氧基，C 1 -C 4 - 卤代烷氧基等，或两个相邻的取代基RA与它们 连接形成环; 并且其中丙二酸酯在铜盐存在下与碱和芳基溴反应，其包括使用每摩尔当量丙二酸酯0.1至0.65摩尔当量的碱。

公开(公告)号：US07595426B2

公开(公告)日：2009-09-29

申请号：US11911971

申请日：2006-04-21

申请人： Michael Rack ,  Sebastian Peer Smidt ,  Manuel Budich ,  Volker Maywald ,  Michael Keil ,  Bernd Wolf

发明人： Michael Rack ,  Sebastian Peer Smidt ,  Manuel Budich ,  Volker Maywald ,  Michael Keil ,  Bernd Wolf

IPC分类号： C07C22/00 ,  C07C17/00

CPC分类号： C07C25/13 ,  C07C17/12 ,  C07C17/208 ,  C07C17/23

摘要： Method for the production of 1,3,5-trifluoro-2,4,6-trichlorobenzene from fluorobenzene comprising steps A) and B): A) chlorination of fluorobenzene derivatives of formula (II), in which X=fluorine of H, Z=nitro, bromo or chloro and n=0 or 1-4 and B) fluorination of the distillation residue and separation by distillation of the 1,3,5-trifluoro-2,4,6-trichlorobenzene thus produced.

摘要翻译： 由氟代苯制备1,3,5-三氟-2,4,6-三氯苯的方法，包括步骤A）和B）：A）氯化式（II）的氟代苯衍生物，其中X = H的氟， Z =硝基，溴或氯，n = 0或1-4，B）氟化蒸馏残余物并通过蒸馏分离由此制得的1,3,5-三氟-2,4,6-三氯苯。

公开(公告)号：US08350046B2

公开(公告)日：2013-01-08

申请号：US12990892

申请日：2009-05-06

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

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

IPC分类号： C07D213/82 ,  C07D231/14

CPC分类号： C07C231/02 ,  C07C2601/14 ,  C07D213/82 ,  C07D231/14 ,  C07D231/16 ,  C07C233/65 ,  C07C233/75

摘要： A process for preparing arylcarboxamides of the formula (I) where Ar=a mono- to trisubstituted phenyl, pyridyl or pyrazolyl ring, where the substituents are selected from halogen, C1-C4-alkyl and C1-C4-haloalkyl; M=thienyl or phenyl, which may bear a halogen substituent; Q=direct bond, cyclopropylene, fused bicyclo[2.2.1]heptane or bicyclo[2.2.1]heptene ring; R1=hydrogen, halogen, C1-C6-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, mono- to trisubstituted phenyl, where the substituents are selected from halogen and trifluoromethylthio, or cyclopropyl; by reacting an acid chloride of the formula (II) with an arylamine (III) in a suitable nonaqueous solvent, wherein, in the absence of an auxiliary base, a) the acid chloride (II) is initially charged, b) a pressure of from 0 to 700 mbar is established, c) the arylamine (III) is metered in an approximately stoichiometric amount and d) the product of value is isolated.

摘要翻译： 制备式（I）的芳基羧酰胺的方法，其中Ar =单 - 三取代的苯基，吡啶基或吡唑基环，其中取代基选自卤素，C 1 -C 4 - 烷基和C 1 -C 4卤代烷基; M =噻吩基或苯基，其可以带有卤素取代基; Q =直接键合，亚环丙基，稠合双环[2.2.1]庚烷或双环[2.2.1]庚烯环; R1 =氢，卤素，C1-C6-烷基，C1-C4-烷氧基，C1-C4-卤代烷氧基，一至三取代的苯基，其中取代基选自卤素和三氟甲硫基，或环丙基; 通过使式（II）的酰氯与芳基胺（III）在合适的非水溶剂中反应，其中在没有辅助碱的情况下，a）最初加入酰氯（II），b） 建立0至700毫巴，c）芳基胺（III）以约化学计量的量计量，并且d）分离产物的值。

公开(公告)号：US20080214878A1

公开(公告)日：2008-09-04

申请号：US11911971

申请日：2006-04-21

申请人： Michael Rack ,  Sebastian Peer Smidt ,  Manuel Budich ,  Volker Maywald ,  Michael Keil ,  Bernd Wolf

发明人： Michael Rack ,  Sebastian Peer Smidt ,  Manuel Budich ,  Volker Maywald ,  Michael Keil ,  Bernd Wolf

IPC分类号： C07C17/12

CPC分类号： C07C25/13 ,  C07C17/12 ,  C07C17/208 ,  C07C17/23

摘要： Method for the production of 1,3,5-trifluoro-2,4,6-trichlorobenzene from fluorobenzene comprising steps A) and B): A) chlorination of fluorobenzene derivatives of formula (II), in which X=fluorine of H, Z=nitro, bromo or chloro and n=0 or 1-4 and B) fluorination of the distillation residue and separation by distillation of the 1,3,5-trifluoro-2,4,6-trichlorobenzene thus produced.

摘要翻译： 由氟代苯制备1,3,5-三氟-2,4,6-三氯苯的方法，包括步骤A）和B）：A）氯化式（II）的氟代苯衍生物，其中X = H的氟， Z =硝基，溴或氯，n = 0或1-4，B）氟化蒸馏残余物并通过蒸馏分离由此制得的1,3,5-三氟-2,4,6-三氯苯。

公开(公告)号：US08101780B2

公开(公告)日：2012-01-24

申请号：US12668242

申请日：2008-07-07

申请人： Heidi Emilia Saxell ,  Jochen Dietz ,  Sebastian Peer Smidt ,  Cedric Dieleman

发明人： Heidi Emilia Saxell ,  Jochen Dietz ,  Sebastian Peer Smidt ,  Cedric Dieleman

IPC分类号： C07D231/10

CPC分类号： C07D231/14

摘要： The present invention relates to a new crystalline form of 3-(Difluormethyl)-1-methyl-N-(3′,4′,5′-trifluor[1,1′-biphenyl]-2-yl)-1H-pyrazol-4-carboxamide. The invention also relates to processes for the production of this crystalline form and formulations for plant protection which contain the crystalline form of 3-(Difluormethyl)-1-methyl-N-(3′,4′,5′-trifluor[1,1′-biphenyl]-2-yl)-1H-pyrazol-4-carboxamide.

摘要翻译： 本发明涉及3-（二甲基甲基）-1-甲基-N-（3'，4'，5'-三氟[1,1'-联苯] -2-基）-1H-吡唑的新结晶形式 -4-甲酰胺。 本发明还涉及生产该结晶形式的方法和用于植物保护的制剂，其含有3-（二甲基甲基）-1-甲基-N-（3'，4'，5'-三氟[ 联苯] -2-基）-1H-吡唑-4-甲酰胺。