PROCESS FOR PREPARING SUBSTITUTED BIPHENYLS
    1.
    发明申请
    PROCESS FOR PREPARING SUBSTITUTED BIPHENYLS 有权
    制备替代BIPHENYLS的方法

    公开(公告)号:US20100256418A1

    公开(公告)日:2010-10-07

    申请号:US12726196

    申请日:2010-03-17

    IPC分类号: C07C205/04

    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。

    Process for preparing difluoromethylpyrazolyl carboxylates
    2.
    发明授权
    Process for preparing difluoromethylpyrazolyl carboxylates 失效
    制备二氟甲基吡唑羧酸酯的方法

    公开(公告)号:US08115012B2

    公开(公告)日:2012-02-14

    申请号:US12513003

    申请日:2007-11-02

    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。

    Process for preparing difluoromethylpyrazolyl carboxylates
    3.
    发明申请
    Process for preparing difluoromethylpyrazolyl carboxylates 失效
    制备二氟甲基吡唑羧酸酯的方法

    公开(公告)号:US20100069646A1

    公开(公告)日:2010-03-18

    申请号:US12513003

    申请日:2007-11-02

    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。

    Process for Preparing Substituted Biphenyls
    4.
    发明申请
    Process for Preparing Substituted Biphenyls 失效
    制备取代联苯的方法

    公开(公告)号:US20090005597A1

    公开(公告)日:2009-01-01

    申请号:US12087345

    申请日:2007-05-31

    IPC分类号: C07C201/12 C07C209/68

    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。

    Process for preparing substituted biphenyls
    5.
    发明授权
    Process for preparing substituted biphenyls 有权
    制备取代联苯的方法

    公开(公告)号:US08030527B2

    公开(公告)日:2011-10-04

    申请号:US12726196

    申请日:2010-03-17

    IPC分类号: C07C205/06

    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。

    Process for preparing substituted biphenyls
    6.
    发明授权
    Process for preparing substituted biphenyls 失效
    制备取代联苯的方法

    公开(公告)号:US07709684B2

    公开(公告)日:2010-05-04

    申请号:US12087345

    申请日:2007-05-31

    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。

    Method for Producing Difluoromethyl-Substituted Pyrazole Compounds
    7.
    发明申请
    Method for Producing Difluoromethyl-Substituted Pyrazole Compounds 有权
    二氟甲基取代吡唑化合物的制备方法

    公开(公告)号:US20100184994A1

    公开(公告)日:2010-07-22

    申请号:US12664448

    申请日:2008-06-13

    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。

    Method for producing difluoromethyl-substituted pyrazole compounds
    8.
    发明授权
    Method for producing difluoromethyl-substituted pyrazole compounds 有权
    二氟甲基取代的吡唑化合物的制备方法

    公开(公告)号:US08188295B2

    公开(公告)日:2012-05-29

    申请号:US12664448

    申请日:2008-06-13

    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: 本发明涉及一种制备式(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。