CN100357273C - 取代的烟酸酯的制备方法 - Google Patents

取代的烟酸酯的制备方法 Download PDF

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CN100357273C
CN100357273C CNB2004800049084A CN200480004908A CN100357273C CN 100357273 C CN100357273 C CN 100357273C CN B2004800049084 A CNB2004800049084 A CN B2004800049084A CN 200480004908 A CN200480004908 A CN 200480004908A CN 100357273 C CN100357273 C CN 100357273C
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D·A·杰克逊
M·C·鲍丹
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Abstract

本发明涉及式I化合物的制备方法，其中所述取代基如权利要求1中所定义，该方法包括使式II化合物其中R3是C1-C8烷基或C3-C6环烷基和R4和R05如权利要求1中对式I所定义，与式III化合物，其中R，R1，R2和X1如权利要求1中对式I所定义，在质子源的存在下于惰性溶剂中反应。

Description

取代的烟酸酯的制备方法
本发明涉及一种新的制备6-卤代烷基-3-烟酸酯的方法以及还涉及用于该方法中的新颖的烯胺中间体。
6-卤代烷基-3-烟酸酯是用于制备除草剂，例如WO 01/94339中描述的那些除草剂的重要中间体。
由Heterocycles，Vol.48，No.4，1998，第779-785页，已知可根据以下流程通过脱氢和随后的式B化合物的氧化来制备对应于式A的在4-位被芳基取代的6-三氟-3-烟酸乙酯。
Figure C20048000490800041
由于该过程是多步骤的、不经济的，该方法并不是很适合大规模制备6-卤代烷基-3-烟酸乙酯。
根据Heterocycles，Vol.46，1997，第129-132页，在2-位被苯基或烷基取代的6-三氟-3-烟酸甲酯(对应于式C)可通过式E化合物与式D化合物在苯中和在三氟乙酸的存在下反应来制备。除了产率不能够令人满意之外，该方法还具有以下严重的缺点：对于大规模生产而言，在储存过程中由于聚合反应导致用作原料的烯胺(E)的质量不断下降，因此很难以保证产品质量的一致性。
Figure C20048000490800051
本发明的目的因此就是提供一种新颖的制备6-卤代烷基-3-烟酸酯的方法，所述方法使得可以高产率和良好的质量生产这些化合物。
本发明因此涉及式I化合物的制备方法：
Figure C20048000490800052
其中
R是C1-C6烷基；
R05是氢，C1-C3烷基，C1-C3卤代烷基或C1-C3烷基-C1-C3烷氧基；
R1是C1-C6亚烷基，C3-C6亚烯基或C3-C6亚炔基链，它们可以被卤素和/或R5取代一次或多次，所述链中的不饱和键不直接与取代基X1相连；
R4是C1-C4卤代烷基；
X1是氧，-O(CO)-，-(CO)O-，-O(CO)O-，-N(R6)-O-，-O-NR17-，硫，亚磺酰基，磺酰基，-SO2NR7-，-NR18SO2-，-N(SO2R18a)-，-N(R18b)C(O)-或-NR8-；
R18a是C1-C6烷基；
R2是氢或C1-C8烷基，或者是可以被取代基取代一次或多次的C1-C8烷基，C3-C6烯基或C3-C6炔基，所述取代基选自卤素，羟基，氨基，甲酰基，硝基，氰基，巯基，氨基甲酰基，C1-C6烷氧基，C1-C6烷氧基羰基，C2-C6烯基，C2-C6卤代烯基，C2-C6炔基，C2-C6卤代炔基，C3-C6环烷基，卤素取代的C3-C6环烷基，C3-C6烯氧基，C3-C6炔氧基，C1-C6卤代烷氧基，C3-C6卤代烯氧基，氰基-C1-C6烷氧基，C1-C6烷氧基-C1-C6烷氧基，C1-C6烷氧基-C1-C6烷氧基-C1-C6烷氧基，C1-C6烷硫基-C1-C6烷氧基，C1-C6烷基亚磺酰基-C1-C6烷氧基，C1-C6烷基磺酰基-C1-C6烷氧基，C1-C6烷氧基羰基-C1-C6烷氧基，C1-C6烷基羰基，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷硫基，C1-C6卤代烷基亚磺酰基，C1-C6卤代烷基磺酰基，环氧乙烷基(其又可以被C1-C6烷基取代)，(3-氧杂环丁烷基)氧基(其又可以被C1-C6烷基取代)，苄氧基，苄硫基，苄基亚磺酰基，苄基磺酰基，C1-C6烷基氨基，二(C1-C6烷基)氨基，R9S(O)2O-，R10N(R11)SO2-，硫氰基，苯基，苯氧基，苯硫基，苯基亚磺酰基和苯磺酰基；
含有苯基-或苄基-的基团本身可以被一个或多个C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，C1-C6卤代烷氧基，卤素，氰基，羟基或硝基取代，或者
R2是苯基，它可以被C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，C1-C6卤代烷氧基，卤素，氰基，羟基或硝基取代一次或多次；或者
R2是C3-C6环烷基，C1-C6烷氧基-或C1-C6烷基-取代的C3-C6环烷基，3-氧杂环丁烷基或C1-C6烷基-取代的3-氧杂环丁烷基；或者
R2是三至十元单环或稠合双环的环系统，所述环系统可以是芳香的、部分饱和的或完全饱和的，并且可以含有1至4个选自氮、氧、硫的杂原子，和/或可以含有基团-C(＝O)-，-C(＝S)-，-C(＝NR19)-，-(N＝O)-，-S(＝O)-或-SO2-，所述环系统直接连接于所述取代基X1或者通过C1-C4亚烷基，C2-C4亚烯基，C2-C4亚炔基，-N(R12)-C1-C4亚烷基，-O-C1-C4亚烷基，-S-C1-C4亚烷基，-SO-C1-C4亚烷基或-SO2-C1-C4亚烷基连接于所述取代基X1，并且每一个环系统含有不超过2个氧原子和不超过2个硫原子，和每一个环系统本身可以被以下基团取代一次或多次：C1-C6烷基，C1-C6卤代烷基，C2-C6烯基，C2-C6卤代烯基，C2-C6炔基，C2-C6卤代炔基，C1-C6烷氧基，C1-C6卤代烷氧基，C3-C6烯氧基，C3-C6炔氧基，巯基，氨基，羟基，C1-C6烷硫基，C1-C6卤代烷硫基，C3-C6烯硫基，C3-C6卤代烯硫基，C3-C6炔硫基，C1-C3烷氧基-C1-C3烷硫基，C1-C4烷基羰基-C1-C3烷硫基，C1-C4烷氧基羰基-C1-C3烷硫基，氰基-C1-C3烷硫基，C1-C6烷基亚磺酰基，C1-C6卤代烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基磺酰基，氨基磺酰基，C1-C2烷基氨基磺酰基，N，N-二(C1-C2烷基)氨基磺酰基，二(C1-C4烷基)氨基，卤素，氰基，硝基或苯基，苯基基团本身又可以被羟基，C1-C6烷硫基，C1-C6卤代烷硫基，C3-C6烯硫基，C3-C6卤代烯硫基，C3-C6炔硫基，C1-C3烷氧基-C1-C3烷硫基，C1-C4烷基羰基-C1-C3烷硫基，C1-C4烷氧基羰基-C1-C3烷硫基，氰基-C1-C3烷硫基，C1-C6烷基亚磺酰基，C1-C6卤代烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基磺酰基，氨基磺酰基，C1-C2烷基氨基磺酰基，N，N-二(C1-C2烷基)氨基磺酰基，二(C1-C4烷基)氨基，卤素，氰基或硝基取代，杂环中氮原子上的取代基不能是卤素；
R5是羟基，C1-C6烷氧基，C3-C6环烷氧基，C1-C6烷氧基-C1-C6烷氧基，C1-C6烷氧基-C1-C6烷氧基-C1-C6烷氧基或C1-C2烷基磺酰氧基；R6，R7，R8，R9，R10 R11，R12，R17，R18和R18b彼此独立地是氢，C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基羰基，C1-C6烷基羰基，C1-C6烷氧基-C1-C6烷基，被C1-C6烷氧基取代的C1-C6烷氧基-C1-C6烷基，苄基或苯基，苯基和苄基本身又可以被C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，C1-C6卤代烷氧基，卤素，氰基，羟基或硝基取代一次和多次；当R9是氢，C1-C6烷氧基羰基或C1-C6烷基羰基时，R6不为氢；
或者基团-R1-X1-R2一起是C1-C6烷基，C2-C6烯基，C2-C6卤代烯基，C2-C6炔基，C2-C6卤代炔基，C3-C6环烷基，C1-C6烷氧基，C1-C6卤代烷氧基，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基，C1-C6卤代烷硫基，C1-C6卤代烷基亚磺酰基，C1-C6卤代烷基磺酰基，C1-C6烷氧基羰基，C1-C6烷基羰基，C1-C6烷基氨基，二(C1-C6烷基)氨基，C1-C6烷基氨基磺酰基，二(C1-C6烷基)氨基磺酰基，-NH-S-R13，-N-(C1-C4烷硫基)-R13，-NH-SO-R14，-N-(C1-C4烷基磺酰基)-R14，-NH-SO2-R15，-N-(C1-C4烷基磺酰基)-R15，硝基，氰基，卤素，羟基，氨基，甲酰基，硫氰基-C1-C6烷基，氰基-C1-C6烷基，环氧乙烷基，C3-C6烯氧基，C3-C6炔氧基，C1-C6烷氧基-C1-C6烷氧基，氰基-C1-C6烯氧基，C1-C6烷氧基羰基氧基-C1-C6烷氧基，C3-C6炔氧基，氰基-C1-C6烷氧基，C1-C6烷氧基羰基-C1-C6烷氧基，C1-C6烷硫基-C1-C6烷氧基，C1-C6烷氧基羰基-C1-C6烷硫基，C1-C6烷氧基羰基-C1-C6烷基亚磺酰基，C1-C6烷氧基羰基-C1-C6烷基磺酰基，C1-C6烷基磺酰氧基，C1-C6卤代烷基磺酰氧基，苯基，苄基，苯氧基，苯硫基，苯基亚磺酰基，苯磺酰基，苄硫基，苄基亚磺酰基或苄基磺酰基，所述苯基基团可以被卤素，甲基，乙基，三氟甲基，甲氧基或硝基取代一次或多次；
或者所述基团-R1-X1-R2一起是三至十元单环或稠合双环的环系统，所述环系统可以是芳香的、部分饱和的或完全饱和的，并且可以含有1至4个选自氮、氧、硫的杂原子，和/或可以含有一个或两个选自-C(＝O)-，-C(＝S)-，-C(＝NR20)-，-(N＝O)-，-S(＝O)-和-SO2-的基团，所述环系统可以经由碳原子直接相连于所述吡啶环或者通过C1-C4亚烷基，C2-C4亚烯基或C2-C4亚炔基链经由碳原子或氮原子连接于所述吡啶环，并且每一个环系统可含有不超过2个的氧原子和不超过2个的硫原子，和每一个环系统本身可以被取代基取代一、二或三次，所述取代基选自C1-C6烷基，C1-C6卤代烷基，C3-C6烯基，C3-C6卤代烯基，C3-C6炔基，C3-C6卤代炔基，C3-C6环烷基，羟基，C1-C6烷氧基，C1-C6卤代烷氧基，C3-C6烯氧基，C3-C6炔氧基，巯基，C1-C6烷硫基，C1-C6卤代烷硫基，C3-C6烯硫基，C3-C6卤代烯硫基，C3-C6炔硫基，C1-C3烷氧基-C1-C3烷硫基，C1-C3烷基羰基-C1-C3烷硫基，C1-C4烷氧基羰基-C1-C3烷硫基，氰基-C1-C3烷硫基，C1-C6烷基亚磺酰基，C1-C6卤代烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基磺酰基，氨基磺酰基，C1-C2烷基氨基磺酰基，二(C1-C6烷基)氨基磺酰基，C1-C3亚烷基-R16，氨基，C1-C6烷基氨基，C1-C6烷氧基氨基，二(C1-C6烷基)氨基，(N-C1-C6烷基)-C1-C6烷氧基氨基，卤素，氰基，硝基，苯基，苄氧基和苄硫基，苯基，苄氧基和苄硫基本身在苯环上又可以被C1-C3烷基，C1-C3卤代烷基，C1-C3烷氧基，C1-C3卤代烷氧基，卤素，氰基或硝基取代，并且杂环中的氮原子上的取代基不为卤素；
R13是N(H)-C1-C6烷基，N(H)-C1-C6烷氧基，N-(C1-C6烷基)-C1-C6烷基，N-(C1-C6烷基)-C1-C6烷氧基，C1-C6烷氧基，C1-C6卤代烷氧基，C1-C6烷基，C1-C6卤代烷基，C3-C6烯基，C3-C6卤代烯基，C3-C6炔基，C3-C6卤代炔基，C3-C6环烷基或苯基，苯基本身又可以被C1-C3烷基，C1-C3卤代烷基，C1-C3烷氧基，C1-C3卤代烷氧基，卤素，氰基或硝基取代；
R14是N(H)-C1-C6烷基，N(H)-C1-C6烷氧基，N-(C1-C6烷基)-C1-C6烷基，N-(C1-C6烷基)-C1-C6烷氧基，C1-C6烷氧基，C1-C6卤代烷氧基，C1-C6烷基，C1-C6卤代烷基，C3-C6烯基，C3-C6卤代烯基，C3-C6炔基，C3-C6卤代炔基，C3-C6环烷基或苯基，苯基本身又可以被C1-C3烷基，C1-C3卤代烷基，C1-C3烷氧基，C1-C3卤代烷氧基，卤素，氰基或硝基取代；
R15是N(H)-C1-C6烷基，N(H)-C1-C6烷氧基，N-(C1-C6烷基)-C1-C6烷基，N-(C1-C6烷基)-C1-C6烷氧基，C1-C6烷氧基，C1-C6卤代烷氧基，C1-C6烷基，C1-C6卤代烷基，C3-C6烯基，C3-C6卤代烯基，C3-C6炔基，C3-C6卤代炔基，C3-C6环烷基或苯基，苯基本身又可以被C1-C3烷基，C1-C3卤代烷基，C1-C3烷氧基，C1-C3卤代烷氧基，卤素，氰基或硝基取代；
R16是C1-C3烷氧基，C2-C4烷氧基羰基，C1-C3烷硫基，C1-C3烷基亚磺酰基，C1-C3烷基磺酰基或苯基，苯基本身又可以被C1-C3烷基，C1-C3卤代烷基，C1-C3烷氧基，C1-C3卤代烷氧基，卤素，氰基或硝基取代；和
R19和R20彼此独立地是氢，羟基，C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，氰基，C1-C6烷基羰基，C1-C6烷氧基羰基或C1-C6烷基磺酰基；该方法包括使式II化合物
Figure C20048000490800091
其中R3是C1-C8烷基或C3-C6环烷基和R4和R05如式I中所定义，与式III化合物
Figure C20048000490800101
其中R，R1，R2和X1如式I中所定义，
在质子源的存在下于惰性溶剂中反应。
取代基中出现的所述可以是直链或支链的，例如，甲基，乙基，正丙基，异丙基，正丁基，仲丁基，异丁基，叔丁基，戊基，己基，庚基和辛基以及还有它们的支链异构体。烷氧基，烯基和炔基衍生自所述的烷基。所述烯基和炔基可以是单或多-不饱和的。
卤素通常是氟，氯，溴或碘，优选氟或氯。相应地，这同样也适合卤素与其它的定义相结合的情况，例如卤代烷基或卤代苯基。
卤代烷基优选具有1至6个碳原子的链长。卤代烷基是，例如，氟甲基，二氟甲基，三氟甲基，氯甲基，二氯甲基，三氯甲基，2，2，2-三氟乙基，2-氟乙基，2-氯乙基，五氟乙基，1，1-二氟-2，2，2-三氯乙基，2，2，3，3-四氟乙基或2，2，2-三氯乙基；  优选三氯甲基，二氟氯甲基，二氟甲基，三氟甲基或二氯氟甲基。
作为卤代烯基，这里应该考虑烯基被卤素取代一次或多次，卤素为氟，氯，溴或碘，尤其是氟或氯，例如2，2-二氟-1-甲基乙烯基，3-氟丙烯基，3-氯丙烯基，3-溴丙烯基，2，3，3-三氟丙烯基，2，3，3-三氯丙烯基和4，4，4-三氟-丁-2-烯-1-基。在被卤素取代一次、两次或三次的C3-C6烯基中，优选链长为3至5个碳原子的那些。
作为卤代炔基，这里应该考虑炔基被卤素取代一次或多次，卤素为溴，碘或，尤其是氟或氯，例如3-氟丙炔基，3-氯丙炔基，3-溴丙炔基，3，3，3-三氟丙炔基和4，4，4-三氟-丁-2-炔-1-基。在被卤素取代一次或多次的炔基中，优选链长为3至5个碳原子的那些。
烷氧基优选具有1至6个碳原子的链长。烷氧基是，例如甲氧基，乙氧基，丙氧基，异丙氧基，正丁氧基，异丁氧基，仲丁氧基或叔丁氧基或戊基氧基或己基氧基异构体；优选甲氧基或乙氧基。烷基羰基优选是乙酰基或丙酰基。烷氧基羰基是，例如甲氧基羰基，乙氧基羰基，丙氧基羰基，异丙氧基羰基，正丁氧基羰基，异丁氧基羰基，仲丁氧基羰基或叔丁氧基羰基；优选甲氧基羰基或乙氧基羰基。卤代烷氧基优选具有1至8个碳原子的链长。卤代烷氧基是，例如氟甲氧基，二氟甲氧基，三氟甲氧基，2，2，2-三氟乙氧基，1，1，2，2-四氟乙氧基，2-氟乙氧基，2-氯乙氧基，2，2-二氟乙氧基或2，2，2-三氯乙氧基；优选二氟甲氧基，2-氯乙氧基或三氟甲氧基。  烷硫基优选具有1至8个碳原子的链长。烷硫基是，例如甲硫基，乙硫基，丙硫基，异丙硫基，正丁硫基，异丁硫基，仲丁硫基或叔丁硫基，优选甲硫基或乙硫基。烷基亚磺酰基是，例如甲基亚磺酰基，乙基亚磺酰基，丙基亚磺酰基，异丙基亚磺酰基，正丁基亚磺酰基，异丁基亚磺酰基，仲丁基亚磺酰基或叔丁基亚磺酰基；优选甲基亚磺酰基或乙基亚磺酰基。
烷基磺酰基是，例如甲基磺酰基，乙基磺酰基，丙基磺酰基，异丙基磺酰基，正丁基磺酰基，异丁基磺酰基，仲丁基磺酰基或叔丁基磺酰基；优选甲基磺酰基或乙基磺酰基。烷氧基烷氧基优选具有1至8个碳原子的链长。烷氧基烷氧基的例子是：甲氧基甲氧基，甲氧基乙氧基，甲氧基丙氧基，乙氧基甲氧基，乙氧基乙氧基，丙氧基甲氧基和丁氧基丁氧基。烷基氨基是，例如甲基氨基，乙基氨基，正丙基氨基，异丙氨基或丁胺异构体。二烷基氨基是，例如二甲基氨基，甲基乙基氨基，二乙基氨基，正丙基甲基氨基，二丁基氨基或二异丙基氨基。优选具有1至4个碳原子的链长的烷基氨基。烷氧基烷基优选具有2至6个碳原子的链长。烷氧基烷基是，例如甲氧基甲基，甲氧基乙基，乙氧基甲基，乙氧基乙基，正丙氧基甲基，正丙氧基乙基，异丙氧基甲基或异丙氧基乙基。烷硫基烷基优选具有2至8个碳原子。烷硫基烷基是，例如甲硫基甲基，甲硫基乙基，乙硫基甲基，乙硫基乙基，正丙硫基甲基，正丙硫基乙基，异丙硫基甲基，异丙硫基乙基，丁硫基甲基，丁硫基乙基或丁硫基丁基。环烷基优选具有3至8个环碳原子，例如环丙基，环丁基，环戊基，环己基，环庚基和环辛基。苯基，包括作为取代基的一部分的苯基，例如苯氧基，苄基，苄氧基，苯甲酰基，苯硫基，苯基烷基和苯氧基烷基，可以为取代的形式，在这种情况下，取代基可以是位于邻-、间-和/或对-位。优选的取代基位置是所述环连接位置的邻位和对位。
根据本发明的方法，优选制备这些式I化合物，其中
R4是卤代甲基或卤代乙基；
R05是氢；
X1是氧，-O(CO)-，-(CO)O-，-O(CO)O-，-N(R6)-O-，-O-NR17-，硫，亚磺酰基，磺酰基，-SO2NR7-，-NR18SO2-或-NR8-；
R2是氢或C1-C8烷基，或被取代基取代一次或多次的C1-C8烷基，C3-C6烯基或C3-C6炔基，所述取代基为卤素，羟基，氨基，甲酰基，硝基，氰基，巯基，氨基甲酰基，C1-C6烷氧基，C1-C6烷氧基羰基，C2-C6烯基，C2-C6卤代烯基，C2-C6炔基，C2-C6卤代炔基，C3-C6环烷基，卤素取代的C3-C6环烷基，或C3-C6烯氧基，C3-C6炔氧基，C1-C6卤代烷氧基，C3-C6卤代烯氧基，氰基-C1-C6烷氧基，C1-C6烷氧基-C1-C6烷氧基，C1-C6烷氧基-C1-C6烷氧基-C1-C6烷氧基，C1-C6烷硫基-C1-C6烷氧基，C1-C6烷基亚磺酰基-C1-C6烷氧基，C1-C6烷基磺酰基-C1-C6烷氧基，C1-C6烷氧基羰基-C1-C6烷氧基，C1-C6烷氧基羰基，C1-C6烷基羰基，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷硫基，C1-C6卤代烷基亚磺酰基，C1-C6卤代烷基磺酰基，环氧乙烷基(其又可以被C1-C6烷基取代)，或被(3-氧杂环丁烷基)氧基(其又可以被C1-C6烷基取代)，或苄硫基，苄基亚磺酰基，苄基磺酰基，C1-C6烷基氨基，二(C1-C6烷基)氨基，R9S(O)2O-，R10N(R11)SO2-，硫氰基，苯基，苯氧基，苯硫基，苯基亚磺酰基或苯磺酰基；含有苯基-或苄基-的基团本身可以被一个或多个C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，C1-C6卤代烷氧基，卤素，氰基，羟基或硝基取代，或者
R2是苯基，它可以被C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，C1-C6卤代烷氧基，卤素，氰基，羟基或硝基取代一次或多次；或者
R2是C3-C6环烷基，C1-C6烷氧基-或C1-C6烷基-取代的C3-C6环烷基，3-氧杂环丁烷基或C1-C6烷基-取代的3-氧杂环丁烷基；
或者R2是五至十元单环或稠合双环的环系统，所述环系统可以是芳香的、部分饱和的或完全饱和的，并且可以含有1至4个选自氮、氧、硫的杂原子，和/或可以含有基团-C(＝O)-，-C(＝S)-，-C(＝NR19)-，-(N＝O)-，-S(＝O)-或-SO2-，所述环系统直接连接于所述取代基X1或者通过C1-C4亚烷基，C2-C4烯基-C1-C4亚烷基，C2-C4炔基-C1-C4亚烷基，-N(R12)-C1-C4亚烷基，-SO-C1-C4亚烷基或-SO2-C1-C4亚烷基连接于所述取代基X1，并且每一个环系统含有不超过2个的氧原子和不超过2个的硫原子，和每一个环系统本身可以被以下基团取代一次和多次：C1-C6烷基，C1-C6卤代烷基，C2-C6烯基，C2-C6卤代烯基，C2-C6炔基，C2-C6卤代炔基，C1-C6烷氧基，C1-C6卤代烷氧基，C3-C6烯氧基，C3-C6炔氧基，巯基，氨基，羟基，C1-C6烷硫基，C1-C6卤代烷硫基，C3-C6烯硫基，C3-C6卤代烯硫基，C3-C6炔硫基，C1-C3烷氧基-C1-C3烷硫基，C1-C4烷基羰基-C1-C3烷硫基，C1-C4烷氧基羰基-C1-C3烷硫基，氰基-C1-C3烷硫基，C1-C6烷基亚磺酰基，C1-C6卤代烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基磺酰基，氨基磺酰基，C1-C2烷基氨基磺酰基，N，N-二(C1-C2烷基)氨基磺酰基，二(C1-C4烷基)氨基，卤素，氰基，硝基或苯基，苯基基团本身可以被羟基，C1-C6烷硫基，C1-C6卤代烷硫基，C3-C6烯硫基，C3-C6卤代烯硫基，C3-C6炔硫基，C1-C3烷氧基-C1-C3烷硫基，C1-C4烷基羰基-C1-C3烷硫基，C1-C4烷氧基羰基-C1-C3烷硫基，氰基-C1-C3烷硫基，C1-C6烷基亚磺酰基，C1-C6卤代烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基磺酰基，氨基磺酰基，C1-C2烷基氨基磺酰基，N，N-二(C1-C2烷基)氨基磺酰基，二(C1-C4烷基)氨基，卤素，氰基或硝基取代，杂环中氮原子上的取代基不能是卤素；
R6，R7，R8，R9，R10 R11，R12，R17和R18彼此独立地是氢，C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基羰基，C1-C6烷基羰基，C1-C6烷氧基-C1-C6烷基，被C1-C6烷氧基取代的C1-C6烷氧基-C1-C6烷基，苄基，或苯基，苯基和苄基本身又可以被C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，C1-C6卤代烷氧基，卤素，氰基，羟基或硝基取代一次和多次；当R9是氢，C1-C6烷氧基羰基或C1-C6烷基羰基时，R6不为氢；
或者基团-R1-X1-R2一起是C1-C6烷基，C2-C6烯基，C2-C6卤代烯基，C2-C6炔基，C2-C6卤代炔基，C3-C6环烷基，C1-C6烷氧基，C1-C6卤代烷氧基，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基，C1-C6卤代烷硫基，C1-C6卤代烷基亚磺酰基，C1-C6卤代烷基磺酰基，C1-C6烷氧基羰基，C1-C6烷基羰基，C1-C6烷基氨基，二(C1-C6烷基)氨基，C1-C6烷基氨基磺酰基，二(C1-C6烷基)氨基磺酰基，-NH-S-R13，-N-(C1-C4烷硫基)-R13，-NH-SO-R14，-N-(C1-C4烷基磺酰基)-R14，-NH-SO2-R15，-N-(C1-C4烷基磺酰基)-R15，硝基，氰基，卤素，羟基，氨基，甲酰基，硫氰基-C1-C6烷基，氰基-C1-C6烷基，环氧乙烷基，C3-C6烯氧基，C3-C6炔氧基，C1-C6烷氧基-C1-C6烷氧基，氰基-C1-C6烯氧基，C1-C6烷氧基羰基氧基-C1-C6烷氧基，C3-C6炔氧基，氰基-C1-C6烷氧基，C1-C6烷氧基羰基-C1-C6烷氧基，C1-C6烷硫基-C1-C6烷氧基，烷氧基羰基-C1-C6烷硫基，烷氧基羰基-C1-C6烷基亚磺酰基，烷氧基羰基-C1-C6烷基磺酰基，C1-C6烷基磺酰氧基，C1-C6卤代烷基磺酰氧基，苯基，苄基，苯氧基，苯硫基，苯基亚磺酰基，苯磺酰基，苄硫基，苄基亚磺酰基或苄基磺酰基，所述苯基基团可以被卤素，甲基，乙基，三氟甲基，甲氧基或硝基取代一次或多次；
或者所述基团-R1-X1-R2一起是五至十元单环或稠合双环的环系统，所述环系统可以是芳香的或部分饱和的并且可以含有1至4个选自氮、氧、硫的杂原子，所述环系统直接相连于所述吡啶环或者通过C1-C4亚烷基连接于所述吡啶环，并且每一个环系统可含有不超过2个的氧原子和不超过2个的硫原子，和/或含有基团-C(＝O)-，-C(＝S)-，-C(＝NR20)-，-(N＝O)-，-S(＝O)-或-SO2-；
并且所述环系统本身可以被取代基取代一、二或三次，所述取代基为：C1-C6烷基，C1-C6卤代烷基，C3-C6烯基，C3-C6卤代烯基，C3-C6炔基，C3-C6卤代炔基，C1-C6烷氧基，C1-C6卤代烷氧基，C3-C6烯氧基，C3-C6炔氧基，巯基，C1-C6烷硫基，C1-C6卤代烷硫基，C3-C6烯硫基，C3-C6卤代烯硫基，C3-C6炔硫基，C2-C5烷氧基烷硫基，C3-C5乙酰基烷硫基，C3-C6烷氧基羰基烷硫基，C2-C4氰基烷硫基，C1-C6烷基亚磺酰基，C1-C6卤代烷基亚磺酰基，C1-C6烷基磺酰基，C1-C6卤代烷基磺酰基，氨基磺酰基，C1-C2烷基氨基磺酰基，C2-C4二烷基氨基磺酰基，C1-C3亚烷基-R16，N(H)-C1-C6烷基，N(H)-C1-C6烷氧基，N-(C1-C6烷基)-C1-C6烷基，N-(C1-C6烷基)-C1-C6烷氧基，卤素，氰基，硝基，苯基和苄硫基，苯基和苄硫基本身在苯环上又可以被C1-C3烷基，C1-C3卤代烷基，C1-C3烷氧基，C1-C3卤代烷氧基，卤素，氰基或硝基取代，并且杂环中的氮原子上的取代基不为卤素；和
R19和R20彼此独立地是氢，羟基，C1-C6烷基，C1-C6卤代烷基，C1-C6烷氧基，C1-C6烷基羰基，C1-C6烷氧基羰基或C1-C6烷基磺酰基。
根据本发明的方法尤其适合于制备这些式I化合物，其中R1是-CH2-，-CH2CH2-，-CH2CH2CH2-，-CF2-，-CH＝CHCH2-，-CH(CH3)-或-C≡CCH2-，但优选-CH2-，在每种情况下位于左边的自由价键与所述吡啶环相连接。进一步优选制备这些式I化合物，其中X1是氧，磺酰基或基团-NR18SO2-，尤其是氧。
根据本发明的方法，尤其优选的是制备这些式I化合物，其中R2是CH3，CH2CH3，CH2OCH3，CH2OCH2CH3，CH2CH2OCH3，CH2CH2OCH2CH3，CH2CF3，炔丙基，环丙基甲基，苄基，CH2CH2SO2CH3或CH2CH2OCH2CH2OCH3，但优选CH2CH2OCH3，特别优选其中X1是氧和R1是-CH2-的这些化合物。
根据本发明的方法，优选制备这些式I化合物，其中R05是氢，CH3，CH2Cl，CH2Br或CH2OCH3，但尤其是氢。
在该组中，尤其可以有利制备其中R是乙氧基或甲氧基这些化合物。
另外，根据本发明的方法，可以有利地制备这些式I化合物，其中R2是
或
Figure C20048000490800171
在R2的这些优选定义中没有自由价键的情况下，例如在
Figure C20048000490800172
的情况下，所述连接位置为标有″CH″的碳原子。
另外，还可以有利地制备这些化合物，其中基团-R1-X1-R2一起是四至十元单环或稠合双环的环系统，所述环系统可以是芳香的、部分饱和的或饱和的，并且可以含有1至4个选自氮、氧和硫的杂原子和/或可以含有一个或两个选自-C(＝O)-，-C(＝S)-，-C(＝NR20)-和-SO2-的基团，所述环系统可以通过C1-C4亚烷基链、尤其是亚甲基链经由碳原子或优选氮原子连接于所述吡啶环。在这些环系统中，尤其可以提到下述优选的四至七元环系统，其经由氮原子连接于所述亚甲基，连接位置在每种情况下左下边：
Figure C20048000490800173
Figure C20048000490800181
Figure C20048000490800182
和
Figure C20048000490800183
其中r是0，1或2；R51，R53，R56和R65彼此独立地是氢，卤素，C1-C6烷基，C1-C6卤代烷基，C3-C6环烷基，C3-C6烯基，C3-C6炔基，C1-C3烷氧基-C1-C3烷基，C1-C6烷氧基，C3-C6烯氧基，C3-C6炔氧基，C1-C6烷硫基，C1-C6烷基亚磺酰基，C1-C6烷基磺酰基，C3-C6烯硫基或C3-C6炔硫基；R52是氢，C1-C6烷基，C1-C6卤代烷基，C3-C6环烷基，C3-C6烯基，C3-C6炔基，C1-C6烷氧基，氨基，或苯基，其本身又可以被R70取代；R54，R55和R60彼此独立地是氢，C1-C6烷基，C1-C6卤代烷基，C3-C6烯基，C3-C6炔基或C3-C6环烷基；R57，R63，R66，R67，R68和R69彼此独立地是C1-C6烷基，或苯基其本身又可以被R70取代；R64是C1-C6烷基，C1-C6卤代烷基，C3-C6环烷基，C3-C6烯基，C3-C6炔基，或苯基其本身又可以被R70取代；R58和R61是氢，卤素，C1-C6烷基或C1-C6卤代烷基；R59是C1-C6烷基，C1-C6卤代烷基，C1-C3烷氧基-C1-C3烷基，C3-C6烯基或C3-C6炔基；R62是氢，C1-C6烷基，C1-C4烷氧基羰基或C1-C4烷硫羰基；或R51与R52一起，或R54与相邻基团R56一起，或R58与相邻基团R59一起，或R60与相邻基团R61一起，或者，当r是2时，两个相邻基团R56或两个相邻基团R61一起可以形成饱和或不饱和的C1-C5亚烷基或C3-C4亚烯基桥，所述的C1-C5亚烷基或C3-C4亚烯基桥本身又可以被基团R70取代或被氧、硫或氮间断；各个R70独立地是卤素，C1-C3烷基，C1-C3卤代烷基，羟基，C1-C3烷氧基，C1-C3卤代烷氧基，氰基或硝基；X是氧，硫或NR6；X3，X4和X5是氧或硫；X6和X7是氧，硫，S(O)或SO2；和X8是CH2，氧，硫，S(O)，SO2或NR71，其中R71是氢或C1-C6烷基。
在本发明中，优选R1-X1-R2一起是C1-C6烷基，C1-C6卤代烷基，C2-C6烯基，C2-C6卤代烯基，C2-C6炔基，C2-C6卤代炔基，C3-C6环烷基，C1-C6烷氧基或C1-C6烷硫基，例如甲基，乙基，正丙基，异丙基，环丙基，正丁基，氟甲基，2-氟乙基，二氟乙基，三氟乙基，乙烯基，1-丙烯基，甲氧基，乙氧基，甲硫基或乙硫基。
在本发明中，R优选为R为甲基，乙基，正丙基或异丙基，尤其是乙基。
R3优选是甲基或乙基，尤其是乙基。
R4优选是三氟甲基，二氟甲基，氯二氟甲基，五氟乙基，2，2，2-三氟乙基，尤其是三氟甲基，氯二氟甲基或二氟甲基。
作为本发明方法的惰性溶剂，适宜的有，例如芳族溶剂，如苯，氯苯，氟苯，二甲苯，甲苯，或醇，如甲醇或乙醇，以及还有乙酸乙酯，乙腈，二甲基亚砜，二甲基甲酰胺，二甲基乙酰胺，N-甲基-2-吡咯烷酮，丙酮，丁酮，卤代的溶剂，例如，二氯甲烷，三氯甲烷，二氯乙烯或三氯乙烷，醚，例如四氢呋喃，二乙基醚，1，2-二甲氧基乙烷，二氧杂环己烷或甲基叔丁基醚。  尤其优选乙醇和甲苯。
有机或无机酸适合作为所述的质子源。适宜的质子源的例子是HCl，HBr，H2SO4，羧酸，例如乙酸及其衍生物，例如三氟乙酸和三氯乙酸，磺酸，例如甲磺酸或对甲苯磺酸以及还有碳酸。作为用于本发明方法的质子源，尤其优选三氟乙酸。
所述反应可以在室温或者升高的温度下进行。通常，在室温至所述溶剂的沸点的温度，尤其是20至140℃，优选40至120℃的温度下加入反应物，然后加热所述的反应混合物，有利地加热至所述溶剂的沸点。
式II化合物是已知的或者可以通过已知方法获得。式II化合物的制备方法描述在，例如J.Org Chem.(1995)vol 95，3523，H.Amil，T.Kobayashi，H.Terasawa，K.Uneyama，Org.Lett.3(20)，3103-3105(2001)以及还有A.Colla，G.Clar，S.Krimmer，P.Fischer，M.A.P.Martins，Synthesis-Stuttgart(6)，483-486(1991)。
一些式III化合物是已知的。这些化合物的制备方法描述在H.G.O.Becker，J.Prak t.Chem.(1961)，Vol 12，294.，WO 00/24714以及还有D.H.Wu，W.Wang，J.Labelled Compd.Rad 39(2)，105-107(1997)。
其中-R1-X1-R2是-CH2-O-CH2-CH2-O-CH3的式III化合物，也就是说式IIIa化合物
Figure C20048000490800201
其中R是如式III中所定义，是全新的，并且是为制备式I化合物而专门开发的，本发明因此也涉及这些化合物。在优选的式IIIa中，R是甲基或乙基。
式III化合物可以采用本领域技术人员已知的方法制备，例如通过使相应的不饱和的酮与氨气如下文的制备实施例P1中所述制备。
在本发明方法的优选的实施方案中，式III的原料化合物由基于它们的3-氧代-羧酸酯通过引入氨气以及随后，无需进一步分离，直接与式II化合物反应来制备。对于大规模制备式I化合物而言，该方法尤其有利的。
式I化合物可以在反应混合物中直接用于进一步反应，或者也可以被分离。式I化合物的分离可以，例如通过萃取反应混合物和随后通过常规方法从含有产物的相中除去溶剂来进行。
下面的制备实施例进一步详细解释和说明本发明的方法：
实施例P1：3-氨基-4-甲氧基乙氧基-丁-2-烯酸乙基酯：
将1.37g(6mmol)3-氧代-4-甲氧基乙氧基-丁酸乙酯(1)于13ml乙醇中的混合物加入到反应容器中，用冰/水浴冷却至0℃。
在搅拌的条件下，通入氨气30分钟，并在0℃的温度下进一步搅拌所述反应化合物20分钟。撤掉冷却浴之后，让反应混合物升温至20℃，然后再通入氨气1小时。之后，搅拌该反应化合物20小时。
真空除去溶剂之后，得到1.3g(理论值的95％)3-氨基-4-甲氧基乙氧基-丁-2-烯酸乙酯(2)，为橙色油状物。
1H NMR(CDCl3)：1.30(t，3H，C H 3CH2O-)，3.40(s，3H，C H 3O-)，3.55(m，2H，OC H 2CH2O)，3.60(m，2H，OCH2C H 2O)，4.10(s，2H，C＝CC H 2O-)，4.15(q，2H，CH3C H 2O-)，4.50(s，1H，C H＝CNH2).
13C NMR(CDCl3)：14.7(CH3)，58.9(CH2)，59.2(CH3)，70.0(CH2)，71.0(CH2)，71.8(CH2)，81.9(CH)，159.7(C)，170.3(C).MS：203(M+)，158，157，144，129，114，100，98，83，71，59，45.
实施例P2：2-甲氧基乙氧基甲基-3-乙氧基羰基-6-三氟甲基吡啶(4) 的制备：
Figure C20048000490800221
将52.3g(0.24mol)3-氧代-4-甲氧基乙氧基-丁酸乙酯(1)于150ml甲苯中的混合物加入到装有分水器的反应容器中。
然后，在搅拌的条件下向反应混合物中通入氨气2小时。之后，回流30分钟，水收集在分水器中。将所述混合物冷却至20℃后，重复该过程。在搅拌的条件下，再次通入氨气1.5小时，之后回流该反应混合物以分离出水。
冷却所述反应混合物(含有3-氨基-4-甲氧基乙氧基-丁-2-烯酸乙基酯(2))，至20℃，加入48g(0.248mol)1-乙氧基-3-氧代-4-三氟丁烯(3)，并在20℃下搅拌18小时。然后加入1.5ml三氟乙酸，在20℃下搅拌2小时，进一步回流2小时。
然后，让反应混合物冷却至20℃，随后用100ml 1M NaHCO3洗涤。分出水相，然后用150ml甲苯萃取，之后用MgSO4干燥合并的有机相。
真空除去溶剂之后，得到65.4g(理论值的62％)2-甲氧基乙氧基甲基-3-乙氧基羰基-6-三氟甲基吡啶，为深棕色油状物。1H NMR(CDCl3)：1.40(t，3H，C H 3CH2O-)，3.35(s，3H，C H 3O-)，3.55(m，2H，OC H 2CH2O)，3.70(m，2H，OCH2C H 2O)，4.45(q，2H，CH3C H 2O-)，5.00(s，2H，ArC H 2O-)，7.70(s，1H，Ar H)，8.30(s，1H，Ar H).MS：307(M+)，262，248，233，204，202，161，128，109，59，45
表1所列举的其他化合物也可以该方式制备。
在下面的表中，位于基团R1左边的价键连接于所述的吡啶环。在取代基R2没有给出自由价键的情况下，例如在
Figure C20048000490800231
的情况下，所述连接位置为标有″CH″的碳原子。
表1：式Ia化合物
Figure C20048000490800241
其中R是甲基或乙基：
Figure C20048000490800242
Figure C20048000490800251
Figure C20048000490800261
Figure C20048000490800271
Figure C20048000490800281
Figure C20048000490800291
Figure C20048000490800301
Figure C20048000490800311
Figure C20048000490800321
Figure C20048000490800331
Figure C20048000490800341
Figure C20048000490800351
Figure C20048000490800361
Figure C20048000490800371
Figure C20048000490800381
Figure C20048000490800391
Figure C20048000490800401
Figure C20048000490800421
Figure C20048000490800431
Figure C20048000490800441
Figure C20048000490800451
Figure C20048000490800461
Figure C20048000490800471
Figure C20048000490800481
Figure C20048000490800491
Figure C20048000490800501
Figure C20048000490800511
Figure C20048000490800521
Figure C20048000490800531
Figure C20048000490800541
Figure C20048000490800551
Figure C20048000490800561
Figure C20048000490800571
Figure C20048000490800581
Figure C20048000490800591
Figure C20048000490800601
Figure C20048000490800611
Figure C20048000490800621
Figure C20048000490800631
Figure C20048000490800641
Figure C20048000490800651
Figure C20048000490800681
Figure C20048000490800691
根据本发明的方法尤其可以有利地用于制备下面的表2中的化合物：
在表2中，各个杂环基团R2结构与取代基R1-X1-，或与连接所述R2杂环和式I的母体结构的C1-C4亚烷基，C2-C4烯基-C1-C4亚烷基，C2-C4炔基-C1-C4亚烷基，-N(R12)-C1-C4亚烷基，-SO-C1-C4亚烷基或-SO2-C1-C4亚烷基的连接位置是位于与下面的例子中所示出的相同几何位置的氮原子。
例如，在化合物A1.001的情况下，基团
Figure C20048000490800701
的连接位置是箭头所指的位置：
Figure C20048000490800702
这些结构中自由价键代表末端CH3基团，就如同，例如在结构
Figure C20048000490800703
的情况下，其也可以如下表示：
Figure C20048000490800704
表2：式Ia化合物，其中R是甲基或乙基：
Figure C20048000490800711
Comp.     R4      -R1-    -X1-R2
no.
A1.001    CF2Cl   CH2
Figure C20048000490800712
A1.002    CF2H    CH2
Figure C20048000490800713
A1.003    CF3     CH2
Figure C20048000490800714
A1.004    CF3     CH2OCH2CH2
Figure C20048000490800715
A1.005    CF2Cl   CH2OCH2CH2
Figure C20048000490800716
A1.006    CHF2    CH2OCH2CH2
Figure C20048000490800717
A1.007    CF3     CH2
Figure C20048000490800718
A1.008    CF2Cl   CH2
Figure C20048000490800719
A1.009    CHF2    CH2
Comp.     R4      -R1-         -X1-R2
no.
A1.010    CF3     CH2OCH2CH2
Figure C20048000490800721
A1.011    CF2Cl   CH2OCH2CH2
Figure C20048000490800722
A1.012    CHF2    CH2OCH2CH2
Figure C20048000490800723
A1.013    CF3     CH2
Figure C20048000490800724
A1.014    CF2Cl   CH2
Figure C20048000490800725
A1.015    CHF2    CH2
A1.016    CF3     CH2OCH2CH2
Figure C20048000490800727
A1.017    CF2Cl   CH2OCH2CH2
Figure C20048000490800728
A1.018    CHF2    CH2OCH2CH2
Figure C20048000490800729
A1.019    CF3     CH2
Figure C200480004908007210
A1.020    CF2Cl   CH2
Figure C200480004908007211
A1.021    CHF2    CH2
Comp.     R4      -R1-         -X1-R2
no.
A1.022    CF3     CH2OCH2CH2
Figure C20048000490800731
A1.023    CF2Cl   CH2OCH2CH2
Figure C20048000490800732
A1.024    CHF2    CH2OCH2CH2
Figure C20048000490800733
A1.025    CF3     CH2
Figure C20048000490800734
A1.026    CF2Cl   CH2
Figure C20048000490800735
A1.027    CHF2    CH2
Figure C20048000490800736
A1.028    CF3     CH2OCH2CH2
Figure C20048000490800737
A1.029    CF2Cl   CH2OCH2CH2
Figure C20048000490800738
A1.030    CHF2    CH2OCH2CH2
Figure C20048000490800739
A1.031    CF3     CH2
Figure C200480004908007310
A1.032    CF2Cl   CH2
Figure C200480004908007311
A1.033    CHF2    CH2
Figure C200480004908007312
Comp.     R4      -R1-        -X1-R2
no.
A1.034    CF3     CH2OCH2CH2
Figure C20048000490800741
A1.035    CF2Cl   CH2OCH2CH2
Figure C20048000490800742
A1.036    CHF2    CH2OCH2CH2
A1.037    CF3     CH2
Figure C20048000490800744
A1.038    CF2Cl   CH2
Figure C20048000490800745
A1.039    CHF2    CH2
Figure C20048000490800746
A1.040    CF3     CH2OCH2CH2
A1.041    CF2Cl   CH2OCH2CH2
Figure C20048000490800748
A1.042    CHF2    CH2OCH2CH2
A1.043    CF3     CH2
Figure C200480004908007410
A1.044    CF2Cl   CH2
A1.045    CHF2    CH2
Figure C200480004908007412
Comp.     R4      -R1-       -X1-R2
no.
A1.046    CF3     CH2OCH2CH2
Figure C20048000490800751
A1.047    CF2Cl   CH2OCH2CH2
Figure C20048000490800752
A1.048    CHF2    CH2OCH2CH2
Figure C20048000490800753
A1.049    CF3     CH2
Figure C20048000490800754
A1.050    CF2Cl   CH2
Figure C20048000490800755
A1.051    CHF2    CH2
Figure C20048000490800756
A1.052    CF3     CH2OCH2CH2
Figure C20048000490800757
A1.053    CF2Cl   CH2OCH2CH2
Figure C20048000490800758
A1.054    CHF2    CH2OCH2CH2
Figure C20048000490800759
A1.055    CF3     CH2
Figure C200480004908007510
A1.056    CF2Cl   CH2
A1.057    CHF2    CH2
Figure C200480004908007512
Comp.     R4      -R1-         -X1-R2
no.
A1.058    CF3     CH2OCH2CH2
Figure C20048000490800761
A1.059    CF2Cl   CH2OCH2CH2
Figure C20048000490800762
A1.060    CHF2    CH2OCH2CH2
Figure C20048000490800763
A1.061    CF3     CH2
Figure C20048000490800764
A1.062    CF2Cl   CH2
Figure C20048000490800765
A1.063    CHF2    CH2
Figure C20048000490800766
A1.064    CF3     CH2OCH2CH2
Figure C20048000490800767
A1.065    CF2Cl   CH2OCH2CH2
Figure C20048000490800768
A1.066    CHF2    CH2OCH2CH2
Figure C20048000490800769
A1.067    CF3     CH2
Figure C200480004908007610
A1.068    CF2Cl   CH2
Figure C200480004908007611
Comp.     R4      -R1-        -X1-R2
no.
A1.069    CHF2    CH2
Figure C20048000490800771
A1.070    CF3     CH2OCH2CH2
Figure C20048000490800772
A1.071    CF2Cl   CH2OCH2CH2
Figure C20048000490800773
A1.072    CHF2    CH2OCH2CH2
A1.073    CF3     CH2
A1.074    CF2Cl   CH2
Figure C20048000490800776
A1.075    CHF2    CH2
Figure C20048000490800777
A1.076    CF3     CH2OCH2CH2
Figure C20048000490800778
A1.077    CF2Cl   CH2OCH2CH2
Figure C20048000490800779
A1.078    CHF2    CH2OCH2CH2
Figure C200480004908007710
A1.079    CF3     CH2
Figure C200480004908007711
A1.080    CF2Cl   CH2
A1.081    CHF2    CH2
Figure C200480004908007713
A1.082    CF3     CH2OCH2CH2
Figure C200480004908007714
Comp.     R4       -R1-         -X1-R2
no.
A1.083    CF2Cl    CH2OCH2CH2
Figure C20048000490800781
A1.084    CHF2     CH2OCH2CH2
Figure C20048000490800782
A1.085    CF3      CH2
A1.086    CF2Cl    CH2
Figure C20048000490800784
A1.087    CHF2     CH2
Figure C20048000490800785
A1.088    CF3      CH2OCH2CH2
Figure C20048000490800786
A1.089    CF2Cl    CH2OCH2CH2
Figure C20048000490800787
A1.090    CHF2     CH2OCH2CH2
Figure C20048000490800788
A1.091    CF3      CH2
Figure C20048000490800789
A1.092    CF2Cl    CH2
Figure C200480004908007810
A1.093    CHF2     CH2
Figure C200480004908007811
A1.094    CF3      CH2OCH2CH2
Figure C200480004908007812
A1.095    CF2Cl    CH2OCH2CH2
Figure C200480004908007813
A1.096    CHF2     CH2OCH2CH2
Figure C200480004908007814
A1.097    CF3      CH2
Figure C200480004908007815
A1.098    CF2Cl    CH2
Figure C200480004908007816
A1.099    CHF2     CH2
A1.100    CF3      CH2OCH2CH2
Figure C200480004908007818
Comp.     R4      -R1-        -X1-R2
no.
A1.101    CF2Cl   CH2OCH2CH2
A1.102    CHF2    CH2OCH2CH2
Figure C20048000490800792
A1.103    CF3     CH2
Figure C20048000490800793
A1.104    CF2Cl   CH2
Figure C20048000490800794
A1.105    CHF2    CH2
Figure C20048000490800795
A1.106    CF3     CH2OCH2CH2
Figure C20048000490800796
A1.107    CF2Cl   CH2OCH2CH2
Figure C20048000490800797
A1.108    CHF2    CH2OCH2CH2
Figure C20048000490800798
A1.109    CF3     CH2
Figure C20048000490800799
A1.110    CF2Cl   CH2
Figure C200480004908007910
A1.111    CHF2    CH2
A1.112    CF3     CH2OCH2CH2
Figure C200480004908007912
A1.113    CF2Cl   CH2OCH2CH2
Figure C200480004908007913
A1.114    CHF2    CH2OCH2CH2
Figure C200480004908007914
A1.115    CF3     CH2
Figure C200480004908007915
A1.116    CF2Cl   CH2
Figure C200480004908007916
A1.117    CHF2    CH2
Figure C200480004908007917
A1.118    CF3     CH2OCH2CH2
Figure C200480004908007918
Comp.     R4       -R1-        -X1-R2
no.
A1.119    CF2Cl   CH2OCH2CH2
Figure C20048000490800801
A1.120    CHF2    CH2OCH2CH2
Figure C20048000490800802
A1.121    CF3     CH2
Figure C20048000490800803
A1.122    CF2Cl   CH2
Figure C20048000490800804
A1.123    CHF2    CH2
Figure C20048000490800805
A1.124    CF3     CH2OCH2CH2
Figure C20048000490800806
A1.125    CF2Cl   CH2OCH2CH2
Figure C20048000490800807
A1.126    CHF2    CH2OCH2CH2
Figure C20048000490800808
A1.127    CF3     CH2
Figure C20048000490800809
A1.128    CF2Cl   CH2
Figure C200480004908008010
A1.129    CHF2    CH2
Figure C200480004908008011
A1.130    CF3     CH2OCH2CH2
Figure C200480004908008012
A1.131    CF2Cl   CH2OCH2CH2
Figure C200480004908008013
A1.132    CHF2    CH2OCH2CH2
Figure C200480004908008014
A1.133    CF3     CH2
Figure C200480004908008015
Comp.     R4       -R1-        -X1-R2
no.
A1.134    CF2Cl    CH2
A1.135    CHF2     CH2
Figure C20048000490800812
A1.136    CF3      CH2OCH2CH2
Figure C20048000490800813
A1.137    CF2Cl    CH2OCH2CH2
Figure C20048000490800814
A1.138    CHF2     CH2OCH2CH2
Figure C20048000490800815
A1.139    CF3      CH2
Figure C20048000490800816
A1.140    CF2Cl    CH2
A1.141    CHF2     CH2
A1.142    CF3      CH2OCH2CH2
Figure C20048000490800819
A1.143    CF2Cl    CH2OCH2CH2
Figure C200480004908008110
A1.144    CHF2     CH2OCH2CH2
Figure C200480004908008111
A1.145    CF3      CH2
Figure C200480004908008112
A1.146    CF2Cl    CH2
Figure C200480004908008113
A1.147    CHF2     CH2
Figure C200480004908008114
A1.148    CF3      CH2OCH2CH2
Figure C200480004908008115
A1.149    CF2Cl    CH2OCH2CH2
Figure C200480004908008116
Comp.     R4      -R1-        -X1-R2
no.
A1.150    CHF2    CH2OCH2CH2
Figure C20048000490800821
A1.151    CF3     CH2
Figure C20048000490800822
A1.152    CF2Cl   CH2
Figure C20048000490800823
A1.153    CHF2    CH2
Figure C20048000490800824
A1.154    CF3     CH2OCH2CH2
Figure C20048000490800825
A1.155    CF2Cl   CH2OCH2CH2
Figure C20048000490800826
A1.156    CHF2    CH2OCH2CH2
A1.157    CF3     CH2
Figure C20048000490800828
A1.158    CF2Cl   CH2
A1.159    CHF2    CH2
Figure C200480004908008210
A1.160    CF3     CH2OCH2CH2
Figure C200480004908008211
A1.161    CF2Cl   CH2OCH2CH2
Figure C200480004908008212
A1.162    CHF2    CH2OCH2CH2
Figure C200480004908008213
Comp.     R4      -R1-    -X1-R2
no.
A1.163    CF3     CH2
Figure C20048000490800831
A1.164    CF2Cl   CH2
A1.165    CHF2    CH2
Figure C20048000490800833
A1.166    CF3     CH2OCH2CH2
Figure C20048000490800834
A1.167    CF2Cl   CH2OCH2CH2
Figure C20048000490800835
A1.168    CHF2    CH2OCH2CH2
Figure C20048000490800836
A1.169    CF3     CH2
Figure C20048000490800837
A1.170    CF2Cl   CH2
Figure C20048000490800838
A1.171    CHF2    CH2
Figure C20048000490800839
A1.172    CF3     CH2OCH2CH2
Figure C200480004908008310
A1.173    CF2Cl   CH2OCH2CH2
Figure C200480004908008311
Comp.    R4       -R1-         -X1-R2
no.
A1.174    CHF2   CH2OCH2CH2
Figure C20048000490800841
A1.175    CF3    CH2
Figure C20048000490800842
A1.176    CF2Cl  CH2
Figure C20048000490800843
A1.177    CHF2   CH2
Figure C20048000490800844
A1.178    CF3    CH2OCH2CH2
Figure C20048000490800845
A1.179    CF2Cl  CH2OCH2CH2
Figure C20048000490800846
A1.180    CHF2   CH2OCH2CH2
Figure C20048000490800847
A1.181    CF3    CH2
A1.182    CF2Cl  CH2
A1.183    CHF2   CH2
Figure C200480004908008410
A1.184    CF3    CH2OCH2CH2
Figure C200480004908008411
Comp.     R4      -R1-         -X1-R2
no.
A1.185    CF2Cl   CH2OCH2CH2
Figure C20048000490800851
A1.186    CHF2    CH2OCH2CH2
Figure C20048000490800852
A1.187    CF3     CH2
Figure C20048000490800853
A1.188    CF2Cl   CH2
Figure C20048000490800854
A1.189    CHF2    CH2
Figure C20048000490800855
A1.190    CF3     CH2OCH2CH2
Figure C20048000490800856
A1.191    CF2Cl   CH2OCH2CH2
A1.192    CHF2    CH2OCH2CH2
Figure C20048000490800858
A1.193    CF3     CH2
A1.194    CF2Cl   CH2
Figure C200480004908008510
A1.195    CHF2    CH2
A1.196    CF3     CH2OCH2CH2
Figure C200480004908008512
A1.197    CF2Cl   CH2OCH2CH2
Figure C200480004908008513
A1.198    CHF2    CH2OCH2CH2
Figure C200480004908008514
Comp.     R4     -R1-    -X1-R2
no.
A1.199    CF3    CH2
A1.200    CF2Cl  CH2
Figure C20048000490800862
A1.201    CHF2   CH2
Figure C20048000490800863
A1.202    CF3    CH2
Figure C20048000490800864
A1.203    CF2Cl  CH2
Figure C20048000490800865
A1.204    CHF2   CH2
Figure C20048000490800866
A1.205    CF3    CH2OCH2CH2
A1.206    CF2Cl  CH2OCH2CH2
Figure C20048000490800868
A1.207    CHF2   CH2OCH2CH2
Figure C20048000490800869
A1.208    CF3    CH2
Figure C200480004908008610
A1.209    CF3    CH2
Figure C200480004908008611
Comp.     R4     -R1-        -X1-R2
no.
A1.210    CHF2   CH2
Figure C20048000490800871
A1.211    CF3    CH2
Figure C20048000490800872
A1.212    CHF2   CH2
Figure C20048000490800873
A1.213    CF3    CH2
Figure C20048000490800874
A1.214    CF2Cl  CH2
Figure C20048000490800875
A1.215    CHF2   CH2
Figure C20048000490800876
A1.216    CF3    CH2OCH2CH2
Figure C20048000490800877
A1.217    CF2Cl  CH2OCH2CH2
Figure C20048000490800878
A1.218    CHF2   CH2OCH2CH2
Figure C20048000490800879
A1.219    CF3    CH2
A1.220    CF3    CH2OCH2CH2
Figure C200480004908008711
A1.221    CF3    CH2
Figure C200480004908008712
Comp.     R4      -R1-    -X1-R2
no.
A1.222    CF3     CH2
Figure C20048000490800881
A1.223    CF3     CH2
Figure C20048000490800882
A1.224    CF3     CH2
A1.225    CClF2   CH2
Figure C20048000490800884
A1.226    CClF2   CH2
Figure C20048000490800885
A1.227    CClF2   CH2
Figure C20048000490800886
A1.228    CClF2   CH2
Figure C20048000490800887
A1.229    CClF2   CH2
Figure C20048000490800888
A1.230    CHF2    CH2
A1.231    CHF2    CH2
Figure C200480004908008810
A1.232    CHF2    CH2
Figure C200480004908008811
A1.233    CHF2    CH2
A1.234    CHF2    CH2
Figure C200480004908008813
A1.235    CF3     CH2
Figure C200480004908008814
Comp.     R4     -R1-    -X1-R2
no.
A1.236    CHF2   CH2
Figure C20048000490800891
A1.237    CF3    CH2
Figure C20048000490800892
A1.238    CHF2   CH2
Figure C20048000490800893
A1.240    CF3    CH2
Figure C20048000490800894
A1.241    CHF2   CH2
Figure C20048000490800895
A1.242    CF3    CH2
Figure C20048000490800896
A1.243    CF3    CH2
Figure C20048000490800897
A1.244    CF3    CH2
Figure C20048000490800898
A1.245    CF3    CH2
Figure C20048000490800899

Claims (2)

1.式I化合物的制备方法：
Figure C2004800049080002C1
其中
R是C1-C6烷基；
R05是氢，C1-C3烷基，C1-C3卤代烷基或C1-C3烷基-C1-C3烷氧基；
R1是C1-C6亚烷基；
R4是C1-C4卤代烷基；
X1是氧或硫；
R2是氢或C1-C8烷基；
该方法包括使式II化合物
Figure C2004800049080002C2
其中R3是C1-C8烷基或C3-C6环烷基，以及R4和R05如式I中所定义，与式III化合物
Figure C2004800049080002C3
其中R，R1，R2和X1如式I中所定义，
在质子源的存在下于惰性溶剂中反应。
2.式IIIa化合物：
Figure C2004800049080003C1
其中R如权利要求1中对式I所定义。
CNB2004800049084A 2003-03-07 2004-03-05 取代的烟酸酯的制备方法 Expired - Lifetime CN100357273C (zh)

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