CN1139919A - 经钯催化的交叉偶联反应制备芳基乙酸酯的方法 - Google Patents

经钯催化的交叉偶联反应制备芳基乙酸酯的方法 Download PDF

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CN1139919A
CN1139919A CN95191390A CN95191390A CN1139919A CN 1139919 A CN1139919 A CN 1139919A CN 95191390 A CN95191390 A CN 95191390A CN 95191390 A CN95191390 A CN 95191390A CN 1139919 A CN1139919 A CN 1139919A
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H·兹格勒
D·尼夫
W·斯图兹
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Abstract

制备式I的2-甲氧基亚氨基-2-芳基乙酸酯的方法，式中，R为C1-C12烷基，该法包括通式II的适宜取代的硼酸或其三聚形式III(II与III处于平衡状态)，在Pd催化剂存在下与式IV的甲氧基亚氨基乙酸酯反应，式中，R为C1-C12烷基，X为离去基。根据本发明另一方法变种，原则上分裂成两个反应物的基团可改变位置。该法不仅可用于苯基衍生物，而且也可用于大环体系(萘环系、吡啶环系、杂环系)。

Description

经钯催化的交叉偶联反应制备芳基乙酸酯的方法
本发明涉及一种用以下步骤制备式I未取代的或环取代的2-甲氧亚氨基-2-芳基乙酸酯的新方法
Figure A9519139000071
式中，在芳环中存在一个可被N(吡啶基)取代的CH基，环的四个价键中的两个(四个价键打算表示可能的取代基)在相邻位置可能表示稠合的未取代的或取代的五元或六元环，它可含有1～3个选自N，S和O的相同或不同杂原子，以及R为C1-C12烷基，
A)通式II的适宜结构的硼酸
Figure A9519139000072
或其三聚形式III，
Figure A9519139000073
II与III处于平衡状态，在钯催化剂存在下，与通式IV的甲氧亚氨基乙酸酯反应
Figure A9519139000074
式中，R为C1-C12烷基，X为离去基，反之亦然。
B)式X的甲氧亚氨基乙酸酯
Figure A9519139000081
式中R和R8为C1-C12烷基或-B(OR8)2优选为下式基团，在钯催化剂存在下与通式X1的卤代苯基化合物反应，
Figure A9519139000083
如希望，它可被取代，其中Y为Br或I，苯环中的四个价键表示I提到的可能取代基。
术语离去基指离核基团。例子是卤素(如氯、溴或碘)或磺酸根〔-O-SO2(C1-C4)烷基、-O-SO2-C6H5、-O-SO2-C6H4-CH3、-O-SO2-CF3等〕。
原则上钯催化剂可按希望选择。可使用金属钯或Pd/C。优选的例子是以下化合物：Pd(II)(OAc)2、(φ3P)2Pd(II)(OAc)2、(φ3P)2Pd(II)Cl2、(φ3P)4Pd(0)、双〔1，2-双(二苯基膦基)乙烷〕钯(0)、二氯〔1，1′-双(二苯基膦基)二茂铁〕钯(II)、二氯〔1，3-双(二苯基膦基)丙烷〕Pd(II)、二氯〔1，4-双(二苯基膦基)丁烷〕Pd(II)、二氯〔1，2-双(二苯基膦基)乙烷〕Pd(II)、二氯双(三苯基膦)Pd(II)。这一系列钯催化剂非限制的。特别优选式IV和X的化合物，其中R＝CH3〔φ表示苯基〕。
更确切地说，本发明涉及一种由适宜结构的硼酸IIa制备式Ia的有杀微生物/杀虫活性的化合物的方法式中，R为C1-C12烷基，U、V、W和Z规定如下：
Z为卤素、硝基、氰基、未取代的或取代的烷基、未取代的或取代的环烷基、未取代的或取代的芳烷基、未取代的或取代的芳氧烷基、未取代的或取代的芳硫烷基、未取代的或取代的杂芳烷基、未取代的或取代的杂芳氧烷基、未取代的或取代的杂芳硫烷基、未取代的或取代的链烯基、未取代的或取代的芳链烯基、未取代的或取代的芳氧链烯基、未取代的或取代的芳硫链烯基、未取代的或取代的杂芳链烯基、未取代的或取代的杂芳氧链烯基、未取代的或取代的杂芳硫链烯基、未取代的或取代的炔基、未取代的或取代的芳炔基、未取代的或取代的杂芳炔基、未取代的或取代的芳基、未取代的或取代的杂芳基、未取代的或取代的芳偶氮基、未取代的或取代的酰氨基、-OR12、-SR13、-SOR14、-SO2R15、-COOR16、-CONR17R18、-COR19、-CR20＝NR21、-N＝CR22R23、-CR24＝N-OR25、-CR25R26-O-N＝CR27R28、-CH2-OCOR39或-NR37R38，其中R12～R28和R38和R39是相同的或不同的，为氢、未取代的或取代的C1-C6烷基、未取代的或取代的C1-C6链烯基、未取代的或取代的C1-C6炔基、未取代的或取代的C3-C6环烷基、未取代的或取代的环烷基烷基、未取代的或取代的芳基、未取代的或取代的杂芳基、未取代的或取代的芳烷基、未取代的或取代的杂芳烷基、未取代的或取代的芳氧烷基、未取代的或取代的芳硫烷基或者未取代的或取代的杂芳硫烷基以及R37为氢或C1-C4烷基，以及其中U、V和W为相同的或不同的，为氢或Z规定的基团中的一个，或者其中苯环相邻位置中Z、U、V和W中的两个与这些位置的碳原子一起构成未取代的或取代的五元或六元芳族环或环脂族环，它们稠合成芳环，可含有或不含1～3个杂原子(N、S、O)。
优选制备这样的式Ia化合物，其中Z为-A-R1和相邻芳基的-A-是O或-C≡C-、-CR30＝CR31-、-CHR31-CHR30-、-CHR31O-、-OCHR31-、-CO-O-、-CONR30-、-CHR31S-、-CR31＝N-、-CHR31-OCO-、-CHR31ON＝CR30-、-CR31＝N-O-、-N＝CR30-、-N＝N-或-CHR30-、R1为未取代的或取代的烷基、未取代的或取代的链烯基、未取代的或取代的炔基、未取代的或取代的芳烷基、未取代的或取代的杂芳烷基、未取代的或取代的芳氧烷基、未取代的或取代的杂芳氧烷基或杂芳硫烷基或者未取代的或取代的芳基或者未取代的或取代的杂芳基，以及R30和R31是相同的或不同的，为直链或支链C1-C4烷基或氢。
所制备的特别优选的式Ia化合物是这样的化合物，其中-A-为-O-、-CH2-O-、-O-CH2-、-CH2ON＝CR2-、-CH2-、-CH2-CH2-、-CH＝CH-或-C≡C以及R1为未取代的或取代的芳基或者未取代的或取代的杂芳基，R2为氢、C1-C4烷基、C3-C6环烷基、CF3、C1-C4烷氧基、C1-C4烷硫基或C1-C4烷氧基-C1-C2烷基，或者R1和R2与它们连接的碳原子一起构成未取代的或取代的四至七元碳环，碳环可含有也可不含氧或硫原子，它们也可有未取代的或取代的稠合苯环。
反应在碱存在下，在情性溶剂或溶剂混合物中进行，溶剂如烃类如己烷、苯、甲苯或二甲苯、醚类如乙醚、二甲氧基乙烷或四氢呋喃，腈类如乙腈，胺类如二甲基甲酰胺或卤代烃如四氯化碳等。碱如碱金属化合物或碱土金属化合物如锂、钠、钾、镁、钙和钡的氢氧化物、氧化物和碳酸盐(固体形式或水溶液形式)。还有其他氧化物如ZnO、Al2O3、Ag2O等(固体形式或水溶液形式)。其他碱的例子是胺类如三乙胺，吡啶、哌啶和4-甲基氨基吡啶。
反应温度优选为0℃至溶剂沸点温度。
在许多情况下，优选使用(φ3P)4Pd(0)作催化剂，甲苯、二甲氧基乙烷、四氢呋喃或二甲基甲酰胺作溶剂，三乙胺、氢氧化钠或氢氧化钾溶液、碳酸钠或碳酸钾或碳酸氢钠或碳酸氢钾水溶液作碱，反应温度为60℃至反应混合物的回流温度。
本发明新的合成方法的特征是步骤简单，与以前公开的制备式I化合物的方法相比，它得到高产率式I和/或Ia的化合物，得到高纯度产物，有相当大的制备优点。
显然，在反应过程中，其他取代基对芳基反应物II或XI的影响是次要的。关键因素是在Pd和/或Pd盐存在下取代基-B(OH)2或-B(OR8)2和-X或-Y易于从特定的反应物中分裂出来的倾向。
通式II或III的化合物的制备用已知的方法进行(参见R.Koster，in Houber-Weyl，Volume13/3a，PP.616-652)。有易于分裂的离去基团的式XI化合物从文献中已知，并已充分公开。
制备式I的甲氧基亚氨基苯基乙酸酯衍生物的方法在EP-A-253123、EP-B-254426、EP-299694、EP-336211、EP-354571、EP-363818、EP-A-525516、EP-A-460575、EP-A-463488、EP-A-554767和另一些发表物中公开。
通式IV和式X的甲氧基亚氨基乙酸酯是新的化合物，是本发明的组成部分。它们用以下方法制备，
a)通式V的甲氧基酰胺与卤化剂，如三氯氧化磷、三溴氧化磷、五氯化磷、五溴化磷、亚硫酰氯、亚硫酰溴、光气、三苯基膦/四氯化碳和三苯基膦/四溴化碳进行反应。
Figure A9519139000111
优选的试剂是三氯氧化磷和三溴氧化磷。
反应在惰性溶剂中(如甲苯、二甲氧基乙烷、二甲基甲酰胺、1，2-二氯乙烷等)，在室温至溶剂沸点温度之间进行。优选使用过量的卤化剂作溶剂，反应温度优选为溶剂的沸点温度。
另外，式IV的化合物的制备可在类似由酰胺制备亚氨基卤化物的条件下进行(参见Bonnett in Patai′s“The Chemistry of theCarbon-Nitrogen Double Bond”，pp.597-662(IntersciencePublishers，New York，1970))。
X为碘的式IV化合物优选在催化量FeCl3存在下，在丙酮或非极性溶剂中，通过用碘化钠的卤素交换，由式IV相应的化合物制备，其中X为氯或溴(参见Miller and Nunn；TetrahedronLett.2691(1974))。
X为磺酰基的式IV化合物的制备通过化合物V与相应的磺酰卤反应来进行。式IV的化合物也可用以下方法制备：
b)通式VI的甲氧基亚氨基乙酸酯与卤化剂如氯或溴反应。
Figure A9519139000121
反应在稀释剂中，在0℃至稀释剂沸点范围内，优选在0-30℃下进行。式V的化合物是已知的(EP465986)或可用已知的方法制备。
在式XI化合物中磺酸根作为离去基Y可通过相应的酚(Y＝OH)与磺酰卤(特别是磺酰氯)反应来制得，特别是当在苯环中存在活化基团时。
式VI的化合物是已知的(DE3405327(1985))或可用类似的方法制备。
此外，本发明的新方法有以下特征：
a)硼酸衍生物如芳基硼酸衍生物的应用，作为反应组分它们是简单的和易得的；
b)α-溴-邻-甲苯硼酸的易得性(高产率)(Torssell，Ark.Kemi.10,507,509(1957)；Snyder etal.，J.Am.Chem.Soc.80,835and3611(1958))，它可用作制备通式IIa化合物的中间体，其中Z例如是取代的烷基、未取代的或取代的芳氧烷基、未取代的或取代的芳硫烷基、未取代的或取代的杂芳氧烷基、未取代的或取代的杂芳硫烷基、-CR25R26-ON＝CR27R28或-CH2OCOR39以及U，V和W为如上规定的。
制备实施例实施例1
将0.8g2-(邻-甲苯氧基甲基)苯硼酸、0.8g溴甲氧基亚氨基乙酸甲酯、0.38g(三苯基膦)钯、5ml 1M碳酸钠溶液和15ml甲苯的混合物在剧烈搅拌下，在惰性气气氛下回流6hr。将混合物冷却后，加入17ml水，然后用乙酸乙酯萃取两次。将合并的萃取液在硫酸钠上干燥，溶液在真空中浓缩，残留物在硅胶上色谱法纯化，用乙醚/己烷混合物(1∶2％体积比)作冲洗剂。用这一方法得到0.4gα-甲氧基亚氨基-2-(邻-甲苯氧基甲基)苯基乙酸酯白色结晶，熔点99-100℃。
实施例2(中间体的制备)
Figure A9519139000132
在氮气气氛下，在搅拌下将20ml 1.6M正丁基锂己烷溶液滴加到冷却到-75℃的8.0g1-溴-2-(邻-甲苯氧基甲基)苯于50ml四氢呋喃的溶液中，其速率使温度不超过-70℃。再过1hr后，在-75℃下滴加入5.4ml硼酸三乙酯。搅拌3hr以上后，加入5ml饱和氯化铵溶液，然后取出冷却浴。在室温下，加入100ml 1N Hcl溶液，用乙醚萃取分离出的油两次。用水洗涤合并的萃取物，然后在硫酸钠上干燥。在蒸馏除去溶剂后留下的白色固体通过溶于2N氢氧化钠水溶液来纯化，用乙醚萃取溶液两次，然后用浓盐酸溶液酸化萃取物。过滤出沉淀物并干燥，得到4.1g2-(邻-甲苯氧基甲基)苯硼酸白色粉末，熔点170-171℃。实施例3(中间体的制备)
将4.9gα-溴甲苯硼酸、2.16g邻甲酚、6.4g碳酸钾、0.1g碘化钾、2.5ml水和25ml乙腈的混合物在回流下搅拌16hr。将混合物冷却和过滤，将滤液真空浓缩，用1N盐酸酸化并用乙酸乙酯萃取两次。合并和干燥的萃取物在真空下浓缩，残留物在硅胶上色谱法纯化，用乙醚/己烷(1∶1体积)混合物作冲洗剂。用这一方法，得到1g2-(邻-甲苯氧基甲基)苯硼酸，其1H-NMR谱与实施例2的硼酸相同。
实施例4(中间体的制备)
Figure A9519139000142
将26.6gN-甲氧基草氨酸甲酯和0.5二甲基甲酰胺于100ml三氯氧化磷中的混合物回流18hr。蒸馏除去过量的三氯氧化磷以后，将残留物倒入冰水中，然后用乙醚萃取分离出的黄色油两次。用水洗涤合并的萃取物并在硫酸钠上干燥，用蒸馏除去溶剂。用这一方法得到24.6g氯甲氧基亚氨基乙酸甲酯浅黄色结晶，熔点43-44℃。
用三溴氧化磷类似制得溴甲氧基亚氨基乙酸甲酯(浅黄色结晶，熔点49-51℃)。
实施例5(中间体的制备)
Figure A9519139000143
将氯气在10-15℃下通入2.9g甲氧基亚氨基乙酸甲酯和20ml水的混合物中1hr。然后将混合物在25-30℃下搅拌5hr，用二氯甲烷萃取。将有机相在硫酸钠上干燥。蒸馏除去溶剂后，得到2.4g氯甲氧基亚氨基乙酸甲酯浅黄色结晶，熔点43-44℃。
实施例6
下式化合物的制备
将1.58g苯基硼酸和1.52g2-氯-2-甲氧基亚氨基乙酸甲酯溶于15ml甲苯和4ml乙醇的混合物中，然后在搅拌下加入0.27g双(三苯基膦)氧化钯(II)和7.5ml 1M Na2CO3溶液，最初的黄色悬浮液变成红色。将混合物在室温下搅拌0.5hr，然后在45℃搅拌1hr，在50℃再搅拌1hr。将混合物冷却到室温后，加入20ml水，分离出甲苯相。用40ml乙酸乙酯萃取水相两次，在Hyflo上过滤合并的有机萃取物。用20ml水洗涤滤液，在Na2SO4上干燥，然后蒸发浓缩。得到1.7g红-褐色油，在硅胶柱上纯化，用乙醚/己烷(1∶4)作冲洗剂。产率0.65g(理论值的43.9％)。
可用类似上述实施例的方法，由硼酸IIb和氯甲氧基亚氨基乙酸甲酯或溴甲氧基亚氨基乙酸甲酯在Pd催化剂存在下制备肟醚VII。
表1：式lIb的中间体
Figure A9519139000152
实施例    Z                 物理数据1       2-甲苯氧基甲基    熔点170-171℃2       苄基3       苯乙基4       -CH＝CH-C6H55       -C≡C-C6H56       苯氧基7       苯氧甲基8       苄氧基9       2，5-二甲基苯氧甲基10      4-〔6-(2-氰基苯氧基)嘧啶氧基〕
上述表1式IIb的中间体是本发明的另一目的。
表2
可用类似实施例的方法，由硼酸IIc和式IV的甲氧基亚氨基乙酸酯在Pd催化剂存在下制备肟醚VIII，肟醚VIII在溶点和/或MS(M+(强度％；基峰)方面有特点：
Figure A9519139000171
实施例  R2       R1                        物理数据11    CH3       β-萘基                    熔点97-98℃12    CH3       α，α，α-三氟间甲苯基    408(＜0.5)；18613    CH3       3，4-二氯苯基              熔点103-105℃14    CH3       2-噻吩基                   346(2)；11615    CH3       2-吡啶基                   熔点82-84℃*16   CH3       3-氯丙基甲氧苯基           410(8)；11617    CH3       4-氯苯基                   343(2)；11618    丙基       苯基                       368(＜0.5)；11619    CH3       4-甲氧苯基                 370(10)；11620    CH3       3，4，5-三甲氧苯基         430(49)；11621    CH3       2-呋喃基                   熔点95-97℃22    CH3       3-溴苯基                   389(0.5)；116→23  CH3       3-氰基苯基                 熔点103-104℃24    CH3       3-三氟甲基苄基             422(4)；11625    CH3       4-硝基苯基                 354(1)；11626    CH3       3-硝基苯基                 354(0.5)；11627    CF3       苯基                       222(4)；11628    CH3CH2-  苯基                       323(2)；11629    异丙基     苯基                       368(1)；11630    CF3       3-溴苯基                   252(2)；116实施例    R2              R1                      物理数据31      CF3          4-甲苯基                 222(6)；11632      CH3          2-苯并呋喃基             熔点110-112℃33      CH3          3，5-二(三氟甲基)        熔点76-78℃
                    苯基34      CH3          4-氟苯基                熔点89-90℃35      CH3O-CH2-  β-萘基                  420(4)；4536      环丙基        苯基                     355(3)；11637      CH3          1-苯氧乙基               291(63)；11638      CH3          3，4-亚甲二氧苯基        384(12)；11639      CF3          3-三氟甲基苯基           240(3)；116→40      CH3          3-氟苯基                 熔点84-85℃→41      环丙基        3，4-亚甲二氧苯基        熔点69-72℃*42      CH3          4-溴苯基                 熔点78℃→43      CH3          6-(1，4-苯并二噁烷基)    熔点103-106℃→44      环丙基        6-(1，4-苯并二噁烷基)    424(20)；116→45      CH3          3，4-(二氟亚甲二氧基)    熔点88-89℃
                    苯基*46      CH3          3-甲氧苯基               熔点96-97℃→47      CH3          3-炔丙氧苯基             394(2)；116*48      CH3          4-氰基苯基               熔点80-81℃→49      CH3          4-甲氧基-3-(甲硫甲基)    熔点74-78℃
                     苯基→50      CH3       
Figure A9519139000181
熔点130-132℃*51      CH3       
Figure A9519139000182
熔点180-113℃→52      CH3          苯基                     熔点69-71℃→53      CH3          3，5-二氯苯基            熔点90-93℃→54      CH3          3-氟甲基苯基             425(1)；116→55      环丙基        4-氯苯基                 熔点78-84℃实施例    R2       R1                        物理数据→56      环丙基    3-氯苯基                   400(2)；116→57      环丙基    4-氟苯基                   熔点64-65℃*58      环丙基    3-氟-4-甲氧苯基            414(17)；116→59      环丙基    3-氟甲基苯基               434(2)；116→60      环丙基    4-溴苯基                   熔点93℃→61      CH3      3-氯苯基                   熔点79-81℃→62      CH3      3-烯丙氧苯基               熔点54-55℃→63      CH3S     3，4-亚甲二氧基苯基        416(53)；116*64      CH3      2-氯苯基                   343(3)：M-OCH3；116*65      CH3      3-(氯二氟甲氧基)苯基       440(＜1)；116*66      CH3      3-甲苯基                   熔点99-101℃*67      CH3      4-甲氧基-2，3，5，6-       熔点88-91℃
                四氟苯基*68      CH3      4-甲硫基-2，3，5，6-       熔点84-87℃
                四氟苯基→69      CH3CH2  3，4-二氟亚甲二氧基苯基    熔点52-55℃→70      CH3      2-(5-氯噻吩基)             382(10)；116→71      正丙基    3，4-二氟亚甲二氧基苯基    熔点102-105℃*72      CH3      4-乙氧基-3-甲氧苯基        熔点110-111℃*73      H          苯基                       熔点82-83℃*74      H          4-氯苯基                   熔点158-159℃→75      CH3S     苯基                       372(4)；116*76      CH3O     苯基                       356(2，5)；116*77      CH3      4-环丙基甲氧苯基           熔点98-99℃*78      CH3CH2  3-硝基苯基                 熔点95-96℃→79      CH3O     4-氯苯基                   390(2)；116→80      CH3S     4-氯苯基                   406(2)；116→81      CH3S     3-三氟甲基苯基             440(1)；116*82      CH3O     3-三氟甲基苯基             424(0.6)；116→83      CH3      4-氟-3-三氟甲基            熔点60-63℃实施例    R2         R1                                      物理数据
                  苯基→84      CH3       4-二氟甲氧基苯基                      熔点82-83℃→85      CH3CH2   2-噻吩基                              熔点80-84℃→86      CH3       6-甲氧基-2-萘基                       熔点118-119℃*87      CH3       4-三氟甲基苯基                         熔点71℃→88      CH3       3，4-亚丙二氧基苯基                   熔点97-100℃→89      CH3       
Figure A9519139000201
熔点103-104℃*90      CH3       3-二氟甲氧基苯基                       熔点68-69℃*91     
Figure A9519139000202
                               熔点 108-110℃*92 
Figure A9519139000203
                                  熔点92-94℃*93        
Figure A9519139000204
                   熔点108-110℃*94                                    熔点98-101℃*95         
Figure A9519139000206
                    熔点89-92℃*96                             熔点124-127℃ 实施例    R2       R1                  物理数据97                    熔点82-86℃98    
Figure A9519139000212
              118-120℃99                     熔点97-104℃100    
Figure A9519139000214
          熔点386(13)；116
上述表2式IIc的中间体是本发明的另一目的，特别是其中R1为一直到三取代的苯环，R2也可以是甲基、乙基、三氟甲基、环丙基、甲氧基或甲硫基的那些中间体。

Claims (23)

1.一种制备式I化合物的方法，式中，在芳环中存在一个可被N(吡啶基)取代的CH基，环的四个价键中的两个，四个价键打算表示可能的取代基，在相邻位置可能表示稠合的未取代的或取代的五元或六元环，它可含有1～3个选自N，S和O的相同或不同杂原子，以及R为C1-C12烷基，
A)通式II的适宜结构的硼酸
Figure A9519139000022
或其三聚形式III，
Figure A9519139000023
II与III处于平衡状态，在钯催化剂存在下，与通式IV的甲氧亚氨基乙酸酯反应
Figure A9519139000024
式中，R为C1-C12烷基，X为离去基，反之亦然，
B)式X的甲氧亚氨基乙酸酯
Figure A9519139000025
式中R和R8为C1-C12烷基或-B(OR8)2优选为下式基团，在钯催化剂存在下与通式XI的卤代苯基化合物反应，
Figure A9519139000032
如希望，它可被取代，其中Y为Br或I，苯环中的四个价键表示I中提到的可能取代基。
2.一种根据权利要求1制备式Ia化合物的方法，该法包括使用适宜结构的硼酸IIa式中，R为C1-C12烷基，U、V、W和Z规定如下：
Z为卤素、硝基、氰基、未取代的或取代的烷基、未取代的或取代的环烷基、未取代的或取代的芳烷基、未取代的或取代的芳氧烷基、未取代的或取代的芳硫烷基、未取代的或取代的杂芳烷基、未取代的或取代的杂芳氧烷基、未取代的或取代的杂芳硫烷基、未取代的或取代的链烯基、未取代的或取代的芳链烯基、未取代的或取代的芳氧链烯基、未取代的或取代的芳硫链烯基、未取代的或取代的杂芳链烯基、未取代的或取代的杂芳氧链烯基、未取代的或取代的杂芳硫链烯基、未取代的或取代的炔基、未取代的或取代的芳炔基、未取代的或取代的杂芳炔基、未取代的或取代的芳基、未取代的或取代的杂芳基、未取代的或取代的芳偶氮基、未取代的或取代的酰氨基、-OR12、-SR13、-SOR14、-SO2R15、-COOR16、-CONR17R18、-COR19、-CR20＝NR21、-N＝CR22R23、-CR24＝N-OR25、-CR25R26-O-N＝CR27R28、-CH2-OCOR39或-NR37R38，其中R12～R28和R38和R39是相同的或不同的，为氢、未取代的或取代的C1-C6烷基、未取代的或取代的C1-C6链烯基、未取代的或取代的C1-C6炔基、未取代的或取代的C3-C6环烷基、未取代的或取代的环烷基烷基、未取代的或取代的芳基、未取代的或取代的杂芳基、未取代的或取代的芳烷基、未取代的或取代的杂芳烷基、未取代的或取代的芳氧烷基、未取代的或取代的芳硫烷基或者未取代的或取代的杂芳硫烷基以及R37为氢或C1-C4烷基，以及其中U、V和W为相同的或不同的，为氢或Z规定的基团中的一个，或者其中苯环相邻位置中Z、U、V和W中的两个与这些位置的碳原子一起构成未取代的或取代的五元或六元芳族环或环脂族环，它们稠合成芳环，可含有或不含1～3个杂原子(N、S、O)。
3.根据权利要求1的方法，其中Pd催化剂选自Pd(II)(OAc)2、(φ3P)2Pd(II)(OAc)2、(φ3P)2Pd(II)Cl2、(φ3P)4Pd(0)、双〔1，2-双(二苯基膦基)乙烷〕钯(0)、二氯〔1，1′-双(二苯基膦基)二茂铁〕钯(II)、二氯〔1，3-双(二苯基膦基)丙烷〕Pd(II)、二氯〔1，4-双(二苯基膦基)丁烷]Pd(II)、二氯〔1，2-双(二苯基膦基)乙烷〕Pd(II)二氯双(三苯基膦)Pd(II)。
4.根据权利要求3的方法，其中Pd催化剂为四(三苯基膦)钯(0)。
5.根据权利要求1的方法，其中离去基团是卤素或磺酸根。
6.根据权利要求1的方法，其中该法在溶剂或溶剂混合物存在下进行。
7.根据权利要求1的方法，其中反应在碱存在下进行。
8.根据权利要求7的方法，其中碱是胺。
9.根据权利要求7的方法，其中碱是碳酸钠或碳酸钾或碳酸氢钠或碳酸氢钾。
10.根据权利要求6的方法，其中反应在0℃至溶剂的沸点温度下进行。
11.根据权利要求2的方法，其中Z为-A-R1和相邻芳基的-A-是O或-C≡C-、-CR30＝CR31-、-CHR31-CHR30-、-CHR31O-、-OCHR31-、-CO-O-、-CONR30-、-CHR31S-、-CR31＝N-、-CHR31-OCO-、-CHR31ON＝CR30-、-CR31＝N-O-、-N＝CR30-、-N＝N-或-CHR30-、R1为未取代的或取代的烷基、未取代的或取代的链烯基、未取代的或取代的炔基、未取代的或取代的芳烷基、未取代的或取代的杂芳烷基、未取代的或取代的芳氧烷基、未取代的或取代的杂芳氧烷基或杂芳硫烷基或者未取代的或取代的芳基或者未取代的或取代的杂芳基，以及R30和R31是相同的或不同的，为直链或支链C1-C4烷基或氢。
12.根据权利要求11的方法，其中-A-为-O-、-CH2-O-、-O-CH2-、-CH2ON＝CR2-、-CH2-、-CH2-CH2-、CH＝CH-或-C≡C以及R1为未取代的或取代的芳基或者未取代的或取代的杂芳基，R2为氢、C1-C4烷基、C3-C6环烷基、CF3、C1-C4烷氧基、C1-C4烷硫基或C1-C4烷氧基-C1-C2烷基，或者R1和R2与它们连接的碳原子一起构成未取代的或取代的四至七元碳环，碳环可含有也可不含氧或硫原子，它们也可有未取代的或取代的稠合苯环。
13.一种式IIb的硼酸
Figure A9519139000051
式中，Z为2-甲苯氧基甲基、苄基、苯乙基、-CH＝CH-C6H5、-C≡C-C6H5、苯氧基、苯氧基甲基、苄氧基、2，5-二甲基苯氧甲基或4-〔6-(2-氰基-苯氧基)嘧唑氧基〕。
14.一种式IIc 的硼酸，其中R1为至多三取代的苯环，R2为CH3、C2H5、CF3、环丙基、CH3O或CH3S。
15.权利要求2中定义的硼酸IIa作为制备权利要求2的式Ia化合物的中间体的应用。
16.权利要求13的硼酸IIb作为制备式VII化合物的中间体的应用。
17.权利要求14的硼酸IIc作为制备式VIII化合物的中间体的应用。
18.一种式IV的化合物式中，R为C1-C12烷基，X为离去基团。
19.一种根据权利要求18的下式的化合物。
20.一种用权利要求1的方法制备的式I的化合物。
21.一种用权利要求1的方法制备的式Ia的化合物。
22.一种用权利要求1的方法制备的式VII的化合物。
23.一种用权利要求1的方法制备的式VIII的化合物。
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CN115836049A (zh) * 2020-07-08 2023-03-21 巴斯夫欧洲公司 嗜球果伞素类型化合物防除在线粒体细胞色素b蛋白中含有赋予对Qo抑制剂VI的耐受性的氨基酸替代F129L的植物病原性真菌的用途

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CN108250102B (zh) * 2018-02-01 2020-11-10 青岛润农化工有限公司 一种（e）-2-甲氧基亚胺-2-（邻甲苯基）乙酸甲酯的制备方法
CN115836049A (zh) * 2020-07-08 2023-03-21 巴斯夫欧洲公司 嗜球果伞素类型化合物防除在线粒体细胞色素b蛋白中含有赋予对Qo抑制剂VI的耐受性的氨基酸替代F129L的植物病原性真菌的用途

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