CN1142134C - 杀虫剂中间体的制备方法 - Google Patents

杀虫剂中间体的制备方法 Download PDF

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CN1142134C
CN1142134C CNB008057605A CN00805760A CN1142134C CN 1142134 C CN1142134 C CN 1142134C CN B008057605 A CNB008057605 A CN B008057605A CN 00805760 A CN00805760 A CN 00805760A CN 1142134 C CN1142134 C CN 1142134C
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J·E·安塞尔
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G·佩林一雅内
M·万格斯蒂
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P·韦斯普劳梅
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Abstract

本发明涉及制备式(I)化合物的方法，式(I)中R1、R2和W的定义如说明书所述。

Description

杀虫剂中间体的制备方法
本发明涉及用于制备杀虫剂的中间体(具体为某些芳胺化合物和芳肼衍生物)的新制备方法。
公布的欧洲专利No.0295117和0234119描述了在其合成中使用的具有杀虫活性的苯基吡唑化合物和5-氨基-1-芳基-3-氰基吡唑中间体化合物的制备。
这些化合物的各种制备方法是已知的。而本发明致力于提供这些杀虫剂和用来制备它们的中间体化合物的改进的或更经济的制备方法。4-三氟甲基苯胺、2-氯-4-三氟甲基苯胺和2，6-二氯-4-三氟甲基苯胺是用于合成具有杀虫活性的苯基吡唑化合物的有价值的化合物。已知有多种方法制备这些化合物。但是，它们的工艺成本高，而且所述化合物很难制备，需要多步合成工序。例如，公开的美国专利№4096185描述了在Hastelloy容器中，在氟化钾和氯化亚铜存在下，由4-氯三氟甲苯与氨在200℃反应制备4-三氟甲基苯胺。仍然需求开发可获得这些化合物的新方法。
本发明的申请人意外地发现了制备某些取代的芳胺和芳肼的新方法，由此提供了制备重要化合物5-氨基-1-芳基-3-氰基吡唑的新方法，它是制备杀虫剂的有价值的中间体。
由此，本发明提供制备式(I)化合物或它的酸加成盐的方法(A)：
Figure C0080576000041
其中R1是卤代烷基(优选三氟甲基)、卤代烷氧基(优选三氟甲氧基)或-SF5；
W是N或CR3；和
R2和R3各是氢或氯；
该方法包括式(II)化合物或它的酸加成盐与金属或金属化合物(例如金属盐)在还原条件下的氢解：某些式(I)和(II)的化合物是新的，因此构成本发明的特征。
在本发明中除非另有说明，“卤代烷基”和“卤代烷氧基”分别是具有1-3个碳原子的被一个或多个选自氟、氯和溴的卤原子取代的直链或支链烷基或烷氧基。
本发明中所称的酸加成盐优选是由强酸例如无机酸形成的盐，例如硫酸或盐酸。
氢解可以使用选自如下的金属或金属盐实施：任选存在有铁、锰、钴、铜、锌或铬的拉尼镍(一种镍-铝合金)，氯化亚锡，存在有乙酸的锌，和钼(III)盐。反应也可以在氢气存在下，使用拉尼镍、铂或钯(它们可以承载在炭或其他惰性材料上)实施。当反应在氢气下进行时，通常使用的压力为2-20巴(优选5-10巴)。氢解优选使用拉尼镍进行。
反应通常在溶剂内进行，所述溶剂可以选自醇例如甲醇或乙醇、醚和芳烃(甲醇和乙醇是优选的溶剂)。
反应温度通常为20-150℃，优选20-90℃，更优选50-80℃。虽然当反应在氢气气氛下进行时，通常较少的催化剂量给出令人满意的结果，但是催化剂的使用量通常为0.01-3摩尔当量(优选0.05-2摩尔当量)。
在式(I)和(II)和在下述各式中，R1优选表示三氟甲基、三氟甲氧基或-SF5，更优选三氟甲基。
尤其优选的式(I)化合物是2，6-二氯-4-三氟甲基苯胺、2-氯-4-三氟甲基苯胺和4-三氟甲基苯胺。方法(A)寻求能够以高产率从容易得到的原料得到式(I)的芳胺化合物。此外，该反应还能够简便地和经济地实施，而且能够直接得到分离产物。该方法的另一个优点是式(I)的化合物可以在适中的温度和压力下制备，而现有技术的方法需要高温。
如果需要，式(I)的化合物可以由结晶纯化，例如从石油醚中结晶，以脱除可能少量存在的不要的异构体产物。另外，在合成过程的较后阶段结晶也是有效的。
式(II)的化合物能够由方法(B)获得，其中式(III)的化合物与肼或其酸加成盐或其源物质反应：
Figure C0080576000061
式(III)的化合物是已知的，可以由已知方法制备。
根据本发明的另一个特征，方法(A)能够与方法(B)结合，以从式(III)的化合物制备式(I)的化合物。
优选在方法(B)中使用水合肼。
当使用肼的酸加成盐时，任选存在一种碱例如三烷基胺(例如三乙胺)。
尤其优选的式(II)的化合物是2，6-二氯-4-三氟甲基苯肼、2-氯-4-三氟甲基苯肼和4-三氟甲基苯肼。
方法(B)可以在选自下述溶剂的溶剂中进行：环醚或脂肪醚，例如四氢呋喃、1，4-二噁烷或1，2-二甲氧基乙烷，N-甲基吡咯烷酮，二甲基亚砜，N，N-二甲基甲酰胺，丁撑砜，N，N，N’，N’-四甲脲，可以被一个或多个烷基或氯原子取代的芳烃例如氯苯或二甲苯，醇例如异丙醇，和吡啶。优选的溶剂包括吡啶、四氢呋喃、N，N，N’，N’-四甲脲和1，4-二噁烷(尤其优选吡啶和四氢呋喃)。对于每克式(III)的化合物，溶剂的使用量通常为1-10ml(优选4-8ml)。
方法(B)通常在高压釜或其他密封容器内进行。通常使用的压力为1-8巴(优选2-6巴)。
方法(B)的反应温度通常为50-250℃，优选120-180℃。反应温度最优选120-150℃，这时容器的腐蚀和产物的热分解最小。
反应通常使用1-20摩尔当量(优选4-8摩尔当量)的肼原料进行。
方法(B)中可以任选使用催化剂，使用催化剂时，通常选自碱金属和碱土金属氟化物，例如氟化钾。催化剂的使用量通常为0.05-2摩尔当量(优选0.5-1摩尔当量)。反应也可以在铜或铜盐存在下进行，优选氯化铜(I)。
根据本发明的另一个特征，方法(A)或组合的方法(A)和(B)给出式(I)的化合物，它通过在有机溶剂存在下用强酸处理而形成的盐的沉淀进行纯化。
当本发明的方法(A)和(B)的组合用来制备和反应重要的中间体2-氯-4-三氟甲基苯肼时尤其有价值，因为方法(B)以高产率进行，并与本发明的其他方法一同提供有效获得重要的杀虫苯基吡唑化合物的方法。但是2-氯-4-三氟甲基苯肼的制备除了所要求的异构体，还常常形成少量不要的2-氯-5-三氟甲基苯肼污染物。发现该混合物可直接用于下述方法(A)中，随后再纯化。2-氯-4-三氟甲基苯胺的纯化可以通过有机溶剂存在下用强酸形成的盐(优选盐酸盐)沉淀实现。盐酸盐可以使用氯化氢气体或含水的盐酸得到。溶剂通常是醇优选乙醇，或卤代芳族化合物，优选氯苯，或其混合物。该工序能由所要求的异构体以2-氯-4-三氟甲基苯胺盐酸盐形式沉淀，从而以高产率和高纯度有效地脱除不要的2-氯-5-三氟甲基苯胺异构体。
根据本发明的优选特征，方法(A)或组合的方法(A)和(B)，其中R1是三氟甲基，W是CR3，R2是氯，R3是氢，可制成式(I)的化合物，它通过有机溶剂存在下用强酸处理而形成的盐的沉淀而得以纯化。
此外，当方法(B)用来制备4-三氟甲基苯肼时，其中反应物(4-氯三氟甲苯)特别不活泼，反应过程中具有优良的区域选择性。另外，发现使用催化剂可提高反应速率。在该情形下，没有产物异构体存在，因此，当该方法与后面的步骤结合时，就可提供更有用的获得重要的杀虫剂苯基吡唑化合物的方法。
如上所述，本发明的一个特别的优点是，它能有效地制备式(I)的化合物，其中R2和R3的一个或两个表示氢原子。
根据本发明的优选特征，方法(A)或组合的方法(A)和(B)后随方法(C)，方法(C)包括式(I)的化合物(其中W是N或CR3，R2和R3中的一个或两个表示氢原子)与氯化剂反应，以置换R2和R3表示的该氢原子或每个氢原子，并形成相应的式(I)化合物，其中R2和R3各表示氯原子。根据已知工艺，氯化可以使用氯气或磺酰氯在惰性溶剂例如卤代烃(如二氯甲烷)中进行。
根据本发明的又一个特征，方法(A)或组合的方法(A)和(B)，方法(A)和(C)，或(A)、(B)和(C)，能够与进一步的加工步骤(D)结合，在加工步骤(D)中，式(I)的化合物重氮化，形成式(IV)的化合物：
Figure C0080576000081
其中X是阴离子，通常为硫酸氢根或氯离子，它与式(V)的化合物反应：
Figure C0080576000082
其中R4是C1-6烷基，而且任选与碱反应，形成式(VI)的化合物：
Figure C0080576000083
其中R1、R2和W的定义如上所述。
本发明的上述制备式(VI)化合物的方法与上述使式(III)化合物转化成式(II)和(I)化合物的反应步骤结合，可提供一种有利的新合成路线。
根据本发明的再一个特征，组合的方法(A)和(D)，(A)、(C)和(D)，(A)、(B)和(D)，或(A)、(B)、(C)和(D)，能够与进一步的加工步骤(E)结合，制备式(VII)的化合物：
其中R是烷基或卤代烷基，n是0、1或2。尤其优选的式(VII)化合物是5-氨基-1-(2，6-二氯-4-三氟甲基苯基)-3-氰基-4-三氟甲基亚磺酰吡唑(fipronil)和5-氨基-1-(2，6-二氯-4-三氟甲基苯基)-3-氰基-4-乙基亚磺酰吡唑(ethiprole)。该方法步骤(E)是已知的，例如如公开的欧洲专利№0295117和0374061和公开的美国专利№5814652所述。
由本发明方法(A)获得的式(I)化合物尤其适用于制备具有杀虫活性的式(VII)的5-氨基-1-芳基-3-氰基吡唑衍生物，它例如根据下述反应过程，从式(VI)的中间体化合物得到：
                           1.重氮化其中R1、R2、R3和R4的定义如上所述。
下面非限制性实施例可说明本发明。每种示出的产物都与已经提到的化合物样品一致。
实施例1
4-三氟甲基苯胺的制备
将拉尼镍(2g)加入到4-三氟甲基苯肼(1g)的甲醇(5ml)溶液中，并回流加热1小时。过滤冷却的混合物，并蒸发，制成标题化合物，产率100％。
实施例2
2-氯-4-三氟甲基苯胺的制备
重复实施例1的步骤，但是使用2-氯-4-三氟甲基苯肼，制成标题化合物，产率100％。
实施例3
4-三氟甲基苯胺的制备
重复实施例1的步骤，但是在甲醇中(8-10ml，对于每mmole 4-三氟甲基苯肼)使用催化量的拉尼镍，在氢气(5巴)气氛下20℃搅拌2小时。过滤混合物并蒸发，制成纯的标题化合物，产率75％(未优化)。
也以同样的方式，以类似的结果制备了：
2-氯-4-三氟甲基苯胺；和
2，6-二氯-4-三氟甲基苯胺。
实施例4
4-三氟甲基苯肼的制备
4-氯三氟甲苯(1.08g)、水合肼(1.8g，6摩尔当量)和吡啶(5ml)在高压釜(用氩气净化)中180℃加热6小时。冷却混合物，轻轻倒出过量的肼，减压蒸发有机相。从石油醚中结晶残留物，形成标题化合物，产率为20％。这说明利用了20％原料，反应的进行具有高选择性。
实施例5
使用氟化钾作为催化剂制备4-三氟甲基苯肼
重复实施例4的步骤，但是加入氟化钾(0.8摩尔当量)，制成标题化合物，产率30％。这说明利用了30％原料，反应的进行具有高选择性。
重复上述反应，但是使用N，N，N’，N’-四甲脲作为溶剂，制成标题化合物，产率40％。这说明利用了40％原料，反应的进行具有高选择性。
实施例6
使用氟化钾和氯化铜(I)作为催化剂制备4-三氟甲基苯肼
重复实施例4的步骤，但是加入氟化钾(0.1摩尔当量)和氯化铜(I)(0.1摩尔当量)，制成标题化合物，产率14％。这说明利用了14％原料，反应的进行具有高选择性。
实施例7
2-氯-4-三氟甲基苯肼的制备
重复实施例4的步骤，但是使用3，4-二氯三氟甲苯。后处理后，分离出标题化合物，产率为95％。这说明100％原料都被利用，反应的进行具有高选择性和高产率。重复上述反应，但是使用各种其他溶剂。得到下述的标题化合物的产率：
  溶剂     产率％
  四氢呋喃     90
  1，4-二噁烷     93
  N，N，N’，N’-四甲脲     72
实施例8
从3，4-二氯三氟甲苯开始两步制备2-氯-4-三氟甲基苯胺并纯化
(a)3，4-二氯三氟甲苯(48g)、水合肼(65g)和吡啶(240g)在高压釜中4巴压力下，搅拌并150℃加热6小时。用氢氧化钠溶液淬灭冷却的混合物，减压蒸发有机层。将残留物溶解于乙醚中，洗涤(水)，并蒸发乙醚，制成2-氯-4-三氟甲基苯肼和2-氯-5-三氟甲基苯肼的95/5混合物(36g)。
(b)将拉尼镍(0.7g)加入到氢化反应器内的上述异构体混合物(35.85g)的乙醇溶液中，在50℃、氢气气氛5巴压力下达5小时。冷却混合物，过滤并蒸发，制成2-氯-4-三氟甲基苯胺和2-氯-5-三氟甲基苯胺的95/5混合物(33.1g)。在0.5小时内向上述混合物的乙醇和氯苯溶液中加入氯化氢气体，冷却至0℃，过滤，制成2-氯-4-三氟甲基苯胺盐酸盐(33.5g)，纯度大于99％。从3，4-二氯三氟甲苯计算的总产率为85％。

Claims (10)

1.一种制备式(I)化合物或它的酸加成盐的方法：
其中R1是卤代烷基、卤代烷氧基或-SF5；
W是N或CR3；和
R2和R3各是氢或氯；
该方法包括使式(II)化合物或它的酸加成盐与金属或金属化合物在还原条件下氢解：
Figure C0080576000022
2.如权利要求1所述的方法，其中所述的氢解使用拉尼镍进行。
3.如权利要求1或2所述的方法，其中所述的式(II)化合物由式(III)化合物与肼或其酸加成盐或其源物质的反应制得：
Figure C0080576000023
其中R1、R2和W的定义如上所述。
4.如权利要求3所述的方法，其中使用水合肼。
5.如权利要求1或2所述的方法，其中所述的式(I)化合物进一步通过在有机溶剂存在下用强酸处理形成盐的沉淀而得以纯化。
6.如权利要求5所述的方法，其中所述的盐是盐酸盐，溶剂是醇或卤代芳族化合物。
7.如权利要求1或2所述的方法，其中所述的R1是三氟甲基，W是CR3，R2是氯，R3是氢。
8.如权利要求1或2所述的方法，其中在所述的方法之后再使式(I)的化合物与氯化剂反应，式(I)中R2和R3中的一个或两个表示氢原子，以置换R2和R3表示的该氢原子或每个氢原子，形成相应的式(I)化合物，其中R2和R3各是氯原子。
9.如权利要求1或2所述的方法，其中所述的R1是三氟甲基、三氟甲氧基或-SF5。
10.如权利要求9所述的方法，其中所述的R1是三氟甲基。
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