CN1100760C - 杂芳族羧酸的芳基酰胺的制备方法 - Google Patents

杂芳族羧酸的芳基酰胺的制备方法 Download PDF

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CN1100760C
CN1100760C CN97109948A CN97109948A CN1100760C CN 1100760 C CN1100760 C CN 1100760C CN 97109948 A CN97109948 A CN 97109948A CN 97109948 A CN97109948 A CN 97109948A CN 1100760 C CN1100760 C CN 1100760C
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diphenyl phosphine
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J·P·鲁道特
G·卡尔伯马体
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Guangzhou Nansha Lonza Co., Ltd.
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Abstract

描述了一种式I所示杂芳族羧酸的芳族酰胺的制备方法：其中An分别是氮或CRn(n＝1-5)，条件是环成员中至少有一个是氮，并且两个氮原子不直接相互连接；如果存在R1-R5，则其分别是氢，C1-4的烷基或芳基，取代基R1-R5中有一个是通式为-OR的基团，其中R是任选取代的芳族或杂芳族基团；R6是氢或C1-4的烷基；R7是任选取代的芳族或杂芳族基团。在二膦合钯配合物的存在下该酰胺由相应的杂芳族卤化物，相应的芳族胺和一氧化碳制得。这类化合物是重要的除草剂。

Description

杂芳族羧酸的芳基酰胺的制备方法
本发明涉及在催化剂和碱的存在下，通过杂芳族卤化物与一氧化碳和芳族胺类反应，制备杂芳族羧酸的芳基酰胺的方法。还涉及通过杂芳族二卤化物与芳族或杂芳族羟基化合物反应，得到被(杂)芳氧基取代的杂芳族一卤化物，再使这些化合物在催化剂和碱的存在下与一氧化碳和芳族胺类反应，制备在杂芳环上带有芳氧基或杂芳氧基取代基的杂芳族羧酸的芳基酰胺的方法。
可按照本发明制备的酰胺具有下列通式：
Figure C9710994800041
其中：A1是氮或CR1，
  A2是氮或CR2，
  A3是氮或CR3，
  A4是氮或CR4，
  A5是氮或CR5，
条件是环成员A1-A5中至少有一个是氮，并且两个氮原子不直接相互连接；
R1-R5(如果存在)分别是氢，C1-4的烷基或芳基，取代基R1-R5中有一个是通式为-OR的基团，其中R是任选取代的芳族或杂芳族基团；
R6是氢或C1-4的烷基；
R7是任选取代的芳族或杂芳族基团。
所述酰胺主要包括吡啶、嘧啶、吡嗪和1，3，5-三嗪羧酸的芳基酰胺。
许多这种结构的化合物(特别是那些取代基R1-R5中的一个是与环氮原子相邻的芳氧基(-OR))是重要的除草剂(参见WO-A 94/27974，EP-A0 053 011，EP-A0 447 004)。这些已知的化合物常从相应的羧酸或羧酸衍生物(酸的氯化物类，酯类，腈类)合成，不过这样做常难以获得并且成本较高。
因此，本发明的目的是提供一种基于更容易获得离析物的替代方法。
本发明目的可由权利要求1和13中所述的方法实现。
业已发现在碱的存在下，下列通式的卤化物：
其中A1-A5如上所限定，X是氯，溴或碘，
与一氧化碳和下列通式的伯胺或仲胺直接反应：
                     R6-NH-R7  III，
其中，R6和R7如上所限定，
可有效生成几乎定量产率的要求的产物(I)，所用的催化剂为以下列通式的二膦为配体的钯配合物：
                   R8R9P-[CH2]n-PR10R11     IV
在所述通式IV中，R8至R11分别为苯基或取代的苯基，n为3或4。
在本文中，C1-4的烷基应理解成是指具有高达4个碳原子的任何直链或支链的伯，仲或叔烷基。在本文中，芳族的或杂芳族的基团应理解成特别是指单环或多环体系，例如苯基，萘基，联苯基，蒽基，呋喃基，吡咯基，吡唑基，苯硫基，吡啶基，吲哚基或喹啉基。这些基团可带有一个或多个相同或不同的取代基，例如低级烷基如甲基；卤代烷基如三氟甲基；低级烷氧基如甲氧基；或低级烷硫基或烷磺酰基如甲硫基或乙磺酰基。取代的苯基应理解成特别指如下的基团，如对氟苯基、对甲氧基苯基、对甲苯基或对三氟甲基苯。
用作原料的卤化物(II)是已知的化合物或可按类似于已知化合物的方法被制成。许多这种化合物公开在例如US-A 4254125和EP-A 0001187中。
其中的-OR基团与环氮原子相邻的碳原子连接的卤化物(II)用下述方法很易制备：使具有通式(V)的二卤化物
Figure C9710994800052
其中A1至A5的定义如上所述，条件是与环氮原子相邻的碳原子上的R1至R5基团中的一个基团被Z取代，Z为氯、溴或碘，X独立地为氯、溴或碘，与反应具有通式(VI)的芳族或杂芳族羟基化合物反应
R-OH                                   VI
其中R的定义如上所述。包括本反应和随后的以上述方法进行的与一氧化碳和胺(III)反应的两步方法是本发明的另一个主题，下述的较好实例也可采用两步方法。
本发明方法特别适用于制备其中的A2是氮并与其它环成员形成吡啶环的式(I)酰胺。R1是式-OR基团并且R如上所限定的式(I)酰胺是优选的。
其它优选的式(I)酰胺是那些A1是氮并与其它环成员形成吡啶环的酰胺；
是那些A1和A5是氮并与其它环成员形成嘧啶环的酰胺；
是那些A1和A4是氮并与其它环成员形成吡嗪环的酰胺；
以及是那些A1，A3和A5是氮并与其它环成员形成1，3，5-三嗪环的酰胺。
在最后四类中，那些R2是式-OR的基团，R如上所限定的酰胺依次是最优选的。其它优选的酰胺(I)是那些其中的R是任选取代的苯基的酰胺。这特别适合于R1或R2是式-OR基团的上述含吡啶，嘧啶，吡嗪或1，3，5-三嗪环的酰胺。其它优选的酰胺是那些其中的R6是氢，R7是任选取代的苯基的酰胺。
优选的卤化物(II)是氯化物(X＝Cl)。
通过细分的单质钯(如活性碳上的钯)，Pd(II)盐(如氯化物或乙酸盐)或合适的Pd(II)配合物(如二氯二(三苯膦)合钯(II))与二膦反应的方法可方便地就地形成催化活性的二膦合钯配合物。按卤化物的量计，钯的用量优选为0.02-0.2摩尔％Pd(II)，或者0.5-2摩尔％Pd(0)(以钯炭的形式)，每种情况都以卤化物(II)计。二膦的用量最好是过量的(按Pd计)，优选为0.2-5摩尔％(也按卤化物(II)计)。
所使用的溶剂可以是相对非极性的，如甲苯或二甲苯，或者是极性的，如乙腈，四氢呋喃或N，N-二甲基乙酰胺。
所使用的碱最好是相对较弱的碱。在所用溶剂中该碱不需要是可溶的。合适的碱的例子有碳酸盐，如碳酸钠或碳酸钾；乙酸盐如乙酸钠。使用乙酸钠可获得特别好的结果。
反应温度最好为80-250℃。
一氧化碳的压力最好为1-50巴。
下列实施例将说明本发明方法是如何实施的。
实施例1
2-氯-6-[3-(三氟甲基)苯氧基]吡啶
将17.45g(690mmol)氢化钠(95％)悬浮在420ml N.N-二甲基乙酰胺中。在15℃、2小时内滴加106.7g(658mmol)3-(三氟甲基)苯酚。在氮气氛中，于2.5小时内将生成的苯酚盐溶液滴入162.4g(1.097mol)2，6-二氯吡啶在330ml N，N-二甲基乙酰胺中的溶液内，加热至90℃。再反应3小时后，将混合物冷却至室温，滤去氯化钠沉淀，浓缩滤液。用甲苯和0.1N盐酸提取残留物，有机相用氯化钠饱和溶液洗涤并浓缩。在真空中蒸馏油状残留物(约200g)。
产量：151.5g(84％)无色油状物，纯度(气相色谱法)99.8％。
n20 D＝1.5267。
MS；m/z：273/275；238；39。
1H NMR(CDCl3)：δ＝6.84(d，J＝7.8Hz，1H)；7.07(d，J＝7.8Hz，1H)；7.35(m，1H)；
                   7.42(m，1H)；7.45-7.52(m，2H)；7.65(t，J＝7.8Hz，1H)。
13C NMR(CDCl3)：δ＝109.88(CH)；118.16(CH)；119.24(CH)；121.67(CH)；
                    123.74(CF3)；124.50(CH)；130.24(CH)；132.21(CCF3)；
                    141.77(CH)；149.12(C)；153.89(C)；162.28(C)。
实施例2
3-氯-2-[3-(三氟甲基)苯氧基]吡啶
在氮气氛中，用戊烷洗涤7.68g氢化钠悬浮液(约50％在矿物油中)，随后加入100ml N，N-二甲基甲酰胺。在室温，于30分钟内滴入21.92g(135mmol)3-(三氟甲基)苯酚。在氮气氛中，于2小时内将生成的苯酚盐溶液滴入20.1g(136mmol)2，3-二氯吡啶在80ml N，N-二甲基甲酰胺中的溶液内，加热至120℃。反应3小时后，将混合物冷却至室温，滤去氯化钠沉淀，浓缩滤液。用甲苯和0.1N盐酸萃取残留物，有机相用氯化钠饱和溶液洗涤并浓缩。在真空中蒸馏油状残留物。
产量：24.75g(67％)无色油状物，纯度(气相色谱法)99.7％。
沸点18毫巴＝145-148℃。
n20 D＝1.5282。
MS；m/z：273/275。
1H NMR(CDCl3)：δ＝6.99(m，1H)；7.36(d，1H)；7.45-7.53(m.3H)；
                   7.77(d，1H)；8.02(d，1H)。
13C NMR(CDCl3)：δ＝118.66(CH)；119.44(C)；119.98(CH)；121.75(CH)；
                    123.78(CF3)；124.94(CH)；130.13(CH)；132.16(CCF3)；
                    139.65(CH)；145.20(CH)；153.88(C)；158.51(C)。
实施例3
N-(4-氟苯基)-6-[3-(三氟甲基)苯氧基]吡啶-2-酰胺
在室温，将6.84g(25mmol)2-氯-6-[3-(三氟甲基)苯氧基]吡啶(纯度99.5％，根据实施例1制得)，4.17g(37.5mmol)4-氟苯胺，2.92g(27.5mmol)碳酸钠，0.27g(0.25mmol)钯/活性碳(10％Pd)和0.32g(0.75mmol)1，4-二(二苯膦)丁烷(IV，n＝4，R8＝R9＝R10＝R11＝苯基)在25ml二甲苯中的混合物放入一个高压釜中。用惰性气体吹洗该高压釜，随后以5巴的压力导入一氧化碳，接着将温度升至200℃。将一氧化碳的压力升至14.5巴并在200℃将混合物搅拌16小时。冷却至室温并减压后，用50ml二甲苯和50ml水处理反应混合物并过滤。用25ml二甲苯萃取水相，并用30ml水洗涤合并的有机相。用气相色谱法测定溶解的产物的组成，发现具有92.1％标题化合物(酰胺)，1.9％离析物和6.0％副产物(3.1％由苯胺直接取代Cl形成的仲胺，2.9％由氢解形成的2-[3-(三氟甲基)苯氧基]吡啶)。溶剂蒸馏后，得到黄色固态粗产物(8.63g)。在甲基环己烷中重结晶纯化粗产物。
产量：6.3g(67％)无色晶体
熔点＝104-105℃
MS；m/z：376(M+)，238
1H NMR(CDCl3)：δ＝6.99-7.04(m，2H)；7.17(d，J＝8.4Hz，1H)；7.40(m，1H)；
                   7.46-7.51(m，2H)；7.55-7.63(m，3H)；7.93(t，J＝7.8Hz，1H)；
                   8.03(d，J＝7.8Hz，1H)；9.24(br.m，1H)。
实施例4
N-(4-氟苯基)-6-[3-(三氟甲基)苯氧基]吡啶-2-酰胺
使用相同于实施例3所述的步骤，但所不同的是用17.5mg(25μmol)二氯二(三苯基膦)-钯(II)代替钯/活性碳。一氧化碳的压力为12.8巴，温度为150℃，反应时间为17.7h。用气相色谱法测定在二甲苯相中溶解产物的组成。发现具有96.0％标题化合物(酰胺)和4.0％副产物(2.3％仲胺，1.7％氢解产物)。
实施例5
N-(4-氟苯基)-6-[3-(三氟甲基)苯氧基]吡啶-2-酰胺
使用相同于实施例4所述的步骤，但所不同的是用相同摩尔数的1，3-二(二苯膦)丙烷(IV，n＝3，R8＝R9＝R10＝R11＝苯基)代替1，4-二(二苯膦)丁烷。一氧化碳的压力为16巴，反应时间为21.6h。用气相色谱法测定在二甲苯相中溶解产物的组成。发现具有98.9％标题化合物(酰胺)，0.1％离析物和1.0％副产物(0.3％仲胺和0.7％氢解产物)。
实施例6
N-(2，4-二氟苯基)-2-[3-(三氟甲基)苯氧基]吡啶-3-酰胺(DifLufenicam)
类似于实施例4，使6.84g(25mmol)3-氯-2-[3-(三氟甲基)苯氧基]吡啶(根据实施例2制得)，4.84g(37.5mmol)2，4-二氟苯胺，2.92g(27.5mmol)碳酸钠，17.5mg(25μmol)二氯二(三苯膦)合钯(II)以及0.32g(0.75mmol)1，4-二(二苯膦)丁烷在25ml二甲苯中的混合物在15巴的一氧化碳压力下于190-195℃反应19小时。转化率约80％。如实施例3处理混合物，得到6g黄色晶状固态粗产物，在50ml甲基环己烷中对其进行重结晶纯化。
产量：3.25g(33％)白色固体
熔点：157-159℃
MS；m/z：394(M+)，266(100％)
1H NMR(CDCl3)：δ＝6.89-6.96(m，2H)；7.26(m，1H)；7.46(m，
                   1H)；7.54-7.63(m，3H)；8.28(dd，1H)；8.52
                   (m，1H)；8.71(dd，1H)；9.97(br.s，1H)。
比较例1
使用相同于实施例4所述的步骤，但所不同的是用相同摩尔数的三苯膦代替1，4-二(二苯膦)丁烷。在压力为15巴的一氧化碳中反应15.5小时后。用气相色谱法测定在二甲苯相中溶解产物的组成。发现仅有43.2％所需的产物和56.8％未转化的离析物。
比较例2
使用相同于实施例4所述的步骤，但所不同的是用相同摩尔数的三正丁基膦代替1，4-二(二苯膦)丁烷。在压力为14巴的一氧化碳中反应15小时后，用气相色谱法测定在二甲苯相中溶解产物的组成。发现仅有痕量(0.4％)所需的产物和96.8％未转化的离析物。
比较例3
使用相同于实施例4所述的步骤，但所不同的是用相同摩尔数的1，2-二(二苯膦基)乙烷代替1，4-二(二苯膦)丁烷，在压力为14.7巴的一氧化碳中反应20.2小时后。用气相色谱法测定在二甲苯相中溶解产物的组成。发现仅有痕量(2.2％)所需的产物和97.7％未转化的离析物。

Claims (19)

1.制备具有下列通式的酰胺的方法：
Figure C9710994800021
其中：A1是氮或CR1，
      A2是氮或CR2，
      A3是氮或CR3，
      A4是氮或CR4，
      A5是氮或CR5，
条件是环成员A1-A5中至少有一个是氮，并且两个氮原子不直接相互连接；
R1-R5，如果存在，分别是氢，C1-4的烷基或芳基，取代基R1-R5中有一个是通式为-OR的基团，其中R是任选地被一个或多个相同或不相同的低级烷基、卤代烷基、低级烷氧基、低级烷硫基或低级烷磺酰基取代的芳族或杂芳族基团；
R6是氢或C1-4的烷基；
R7是任选地被一个或多个相同或不相同的低级烷基、卤代烷基、低级烷氧基、低级烷硫基或低级烷磺酰基取代的芳族或杂芳族基团，
其特征在于在下列通式的二膦为配体的钯配合物的存在下并使用一种碱：
               R8R9P-[CH2]n-PR10R11     IV
在所述通式IV中，R8至R11分别为苯基或被一个或多个相同或不相同的低级烷基、卤代烷基、低级烷氧基、低级烷硫基或低级烷磺酰基取代的苯基，n为3或4，
使下列通式的卤化物：
Figure C9710994800022
其中A1-A5如上所限定，X是氯，溴或碘，
与一氧化碳和下列通式的胺反应：
                             R6-NH-R7 III，
其中，R6和R7如上所限定。
2.如权利要求1所述的方法，其特征在于A2是氮，并且是吡啶环的一部分。
3.如权利要求2所述的方法，其特征在于R1是式-OR基团，R如权利要求1所定义。
4.如权利要求1所述的方法，其特征在于A1是氮，并且是吡啶环的一部分。
5.如权利要求1所述的方法，其特征在于A1和A5是氮，并且是嘧啶环的一部分。
6.如权利要求1所述的方法，其特征在于A1和A4是氮，并且是吡嗪环的一部分。
7.如权利要求1所述的方法，其特征在于A1，A3和A5是氮。
8.如权利要求4，5，6或7所述的方法，其特征在于R2是式-OR基团，R如权利要求1所定义。
9.如权利要求3所述的方法，其特征在于R是任选地被一个或多个相同或不相同的低级烷基、卤代烷基、低级烷氧基、低级烷硫基或低级烷磺酰基取代的苯基。
10.如权利要求8所述的方法，其特征在于R是任选取代的苯基。
11.如权利要求1-7、9和10中任何一项所述的方法，其特征在于R6是氢，R7是任选地被一个或多个相同或不相同的低级烷基、卤代烷基、低级烷氧基、低级烷硫基或低级烷磺酰基取代的苯基。
12.如权利要求8所述的方法，其特征在于R6是氢，R7是任选取代的苯基。
13.如权利要求1-7、9、10和12中任何一项所述的方法，其特征在于X是氯。
14.如权利要求8所述的方法，其特征在于X是氯。
15.如权利要求11所述的方法，其特征在于X是氯。
16.如权利要求1-7、9、10、12、14和15中任何一项所述的方法，其特征在于所使用的二膦(IV)是1，3-二(二苯膦)丙烷或1，4-二(二苯膦)丁烷。
17.如权利要求8所述的方法，其特征在于所使用的二膦(IV)是1，3-二(二苯膦)丙烷或1，4-二(二苯膦)丁烷。
18.如权利要求11所述的方法，其特征在于所使用的二膦(IV)是1，3-二(二苯膦)丙烷或1，4-二(二苯膦)丁烷。
19.如权利要求13所述的方法，其特征在于所使用的二膦(IV)是1，3-二(二苯膦)丙烷或1，4-二(二苯膦)丁烷。
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KR970065520A (ko) 1997-10-13
NO971386L (no) 1997-09-29
PL319172A1 (en) 1997-09-29
EP0802189A2 (de) 1997-10-22
CA2200898C (en) 2007-03-06
KR100673348B1 (ko) 2007-05-14
HUP9700666A3 (en) 1999-09-28
PL189843B1 (pl) 2005-09-30
EP0802189A3 (de) 1999-01-13
NO971386D0 (no) 1997-03-24
CZ294344B6 (cs) 2004-12-15
PT802189E (pt) 2004-07-30
HUP9700666A2 (en) 1997-12-29
JPH1017552A (ja) 1998-01-20
ATE262511T1 (de) 2004-04-15
EP0802189B1 (de) 2004-03-24

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