CN1297429A - 制备杀虫剂中间体的方法 - Google Patents
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Abstract
本发明涉及制备式(Ⅰ)化合物的方法,其中R1、R2和W如说明书中所定义。
Description
本发明涉及用于制备杀虫剂的中间体(尤其是2-(芳基肼基)丁二腈化合物和3-(芳基亚肼基)丙腈衍生物)的新的制备方法。
欧洲专利出版物No.0295117和0234119描述了有杀虫活性的苯基吡唑化合物以及用于其合成过程的5-氨基-1-芳基-3-氰基吡唑中间体化合物的制备。
已知制备这些化合物有各种方法。本发明试图提供改进的或更经济的方法来制备杀虫剂和用于制备该杀虫剂的中间体化合物。
德国专利出版物No.3612940公开了5-氨基-1-芳基吡唑衍生物的制备，该衍生物具有下列通式：其中Ar代表取代的苯基或吡啶基，它能用作制备具有除草或杀虫性能的化合物的中间体，通过芳基肼盐酸盐与下式的甲酰丙腈钠盐(NaOCH=CH-CN)反应产生具有下列通式的腙：
Ar-NH-N=CH-CH2-CN其中Ar如上所定义；然后，它在碱存在下环化。
然而，可能希望获得纯形式的腙化合物用于将其进一步转变成杀虫剂。已知的步骤可能会导致形成的腙被环化的5-氨基-1-芳基吡唑产物所污染。
本申请者已经惊奇地发现了一种制备腙化合物而不发生环化的新方法。然后，腙化合物可用来提供一种制备5-氨基-1-芳基吡唑化合物的新方法，或者用于一新方法中，该方法涉及氰化物的加成来提供2-(芳基肼基)丁二腈衍生物，该衍生物可进一步加工而提供重要的5-氨基-1-芳基-3-氰基吡唑化合物，该化合物是制备杀虫剂的有价值的中间体。
美国专利No.4,824,960描述了5-氨基-1-芳基吡唑衍生物的制备，该衍生物具有以下通式：其中Ar代表了取代的苯基或吡啶基，它可用作制备具有除草或杀虫性能的化合物的中间体，在第一阶段，在稀释剂和任选的催化剂存在下通过下式的芳基肼：
Ar-NH-NH2其中Ar如上文所定义，和下式的丙烯腈：
NC-CH=CH2
反应，获得具有下式的3-芳基肼基丙腈化合物：
Ar-NH-NH-CH2-CH2-CN其中Ar如上文所定义，然后在第二个加工阶段氧化和环化。
然而，如果为了获得3-芳基亚肼基丙腈(它可被进一步加工来提供重要的5-氨基-1-芳基-3-氰基吡唑化合物(在制备杀虫剂过程中的有价值的中间体))，希望将上述3-芳基肼基丙腈(而不环化成5-氨基-1-芳基吡唑)氧化，则必须采用不同的方法。
因此，本发明提供了一种制备下式(Ⅰ)化合物的方法(A)：
其中W表示氮或-CR3；R1代表卤素、卤烷基(较佳的是三氟甲基)、卤代烷氧基(较佳的是三氟甲氧基)、R4S(O)n、或-SF5；
R2代表氢或卤素(例如氯或溴)；
R3代表卤素(例如氯或溴)；
R4代表烷基或卤烷基；和n代表0、1或2；该方法包括使下式(Ⅱ)化合物
其中R5和R6独立代表烷基，或一起代表含有两个或三个碳原子的亚烷基链，和下式(Ⅲ)的芳基肼化合物的酸加成盐反应：
其中R1、R2和W如上所述。式(Ⅰ)化合物可能以顺反异构体混合物形式存在，或作为单独的异构体形式存在。
除非在本说明书中另有特指，“烷基”指具有1-6个(较佳的1-3个)碳原子的直链或支链烷基。除非另有特指，“卤烷基”和“卤代烷氧基”是具有1-6个(较佳的1-3个)碳原子的被一个或多个选自氟、氯或溴的卤原子取代的直链或支链烷基或烷氧基。
通常，式(Ⅱ)中的R5和R6代表相同的烷基，较佳的是甲基或乙基。
式(Ⅲ)化合物的酸加成盐宜为从强酸如无机酸(例如硫酸或较佳的是盐酸)形成的盐。该盐通常是预先形成的，但也可任选地原位生成。反应可在水存在下在极性或非极性溶剂中进行。极性溶剂的例子包括水；醇，如甲醇或乙醇；腈，如乙腈；N-甲基吡咯烷酮或亚砜，如二甲基亚砜。非极性溶剂的例子包括：氯化的烃类，较佳的是四氯化碳；和烃类，如环己烷。反应温度通常在20℃至100℃，较佳的在50℃至90℃。通常采用等摩尔量的式(Ⅱ)和(Ⅲ)化合物。可以存在的水的用量为催化量至过量。
在式(Ⅰ)、(Ⅲ)以及下文描述的式子中，较佳的符号数值如下：
R1代表卤烷基(较佳的是三氟甲基)、卤代烷氧基(较佳的是三氟甲氧基)或-SF5；
W代表-CR3；R3代表卤素。
最佳的式(Ⅰ)化合物是3-(2,6-二氯-4-三氟甲基苯基亚肼基)丙腈。
另一个较佳的式(Ⅰ)化合物是3-(2-氯-4-三氟甲基苯基亚肼基)丙腈。
式(Ⅱ)和(Ⅲ)的化合物是文献中通常所知道的。
本发明方法的特点是具有许多优点。因此，该方法是设法从易获得的原料来获得高产率的式(Ⅰ)3-芳基亚肼基-丙腈化合物。另外，该反应的进行非常简单，而且成本非常低，产物的分离非常简单。另外，获得式(Ⅰ)化合物时不会发生大量的环化。
本发明的另一特征是提供制备式(Ⅰ)化合物的方法(B)，其中W、R1和R2如上所定义，该方法包括使式(Ⅳ)化合物：
其中R7代表烷基(较佳的是甲基或乙基)，与式(Ⅲ)化合物(其中R1、R2和W如上所定义)反应。通常采用的反应条件与上述通过式(Ⅱ)化合物和式(Ⅲ)化合物的酸加成盐反应来制备式(Ⅰ)化合物的那些条件相同。
式(Ⅳ)化合物通常是文献中已知的。
本发明的另一特征是提供制备式(Ⅰ)(其中W、R1和R2如上所定义)的方法(C)，该方法包括氧化式(Ⅴ)化合物：
其中R1、R2和W如上所定义。
用于上述反应形成式(Ⅰ)化合物的合适的氧化剂包括：醌如苯醌、过氧化物如过氧化氢、次卤素盐如次氯酸钠；或宜为金属盐或氧化物，例如氯化铜或氧化汞。氧化反应通常在溶剂中进行。适用的溶剂包括：卤化或非卤化的芳族烃，如甲苯或氯苯；腈，如乙腈；或酰胺，如N,N-二甲基甲酰胺。反应温度通常在大约20℃至150℃，较佳的在约50℃至约100℃。
氧化剂与式(Ⅴ)化合物的摩尔比通常在0.01∶1至5∶1，较佳的为1∶1至3∶1。
本发明的另一个特征是提供制备式(Ⅵ)化合物的方法：
其中R1、R2和W如上所定义；该方法包括使式(Ⅰ)化合物(其中R1、R2和W如上所定义)和氰化氢源反应。式(Ⅵ)化合物可以R型或S型或其混合物形式存在。
当反应在任选地在碱(例如吡啶)存在下进行时，氰化氢源可以是氰化氢气体本身；但是它最好是在酸存在下从氰化物金属盐(通常是氰化物碱金属盐，例如氰化钠或氰化钾)原位制得(以避免直接使用氰化氢)。合适的酸包括：有机酸，如脂族羧酸，例如乙酸；或卤代的脂族羧酸，例如氯乙酸或三氟乙酸；磺酸，例如苯磺酸、4-甲苯磺酸或甲磺酸；或无机酸，如盐酸或硫酸。
氰化氢(可原位产生)的另一个来源是，在20℃至100℃的温度下，较佳的30℃至60℃的温度下，在水中的三甲基甲硅烷基氰化物，或三甲基甲硅烷基氰化物和路易斯酸的混合物，该路易斯酸例如是在诸如二氯甲烷或四氢呋喃溶剂中的四氯化锡(Ⅳ)。反应宜在加压下进行，这样能提高反应速度。
从式(Ⅰ)化合物制备式(Ⅵ)化合物可以在极性或非极性溶剂中进行。可采用的极性溶剂的例子包括：水；醇，如甲醇或乙醇；N,N二甲基甲酰胺；二甲基亚砜；或链烷酸，如乙酸。非极性溶剂的例子包括：烃，如己烷；或醚，如四氢呋喃；二噁烷或或二烷基醚，如乙醚；或腈，如乙腈。当在酸存在下使用氰化物金属盐时，较佳的溶剂是水或水和能与水混溶的溶剂的混合物。可以采用等摩尔量或过量的氰化物源，通常采用1至4摩尔的当量。反应温度通常在0℃至100℃，较佳的在20℃至50℃。
最佳的式(Ⅵ)化合物是2-(2,6二氯-4-三氟甲基苯基肼基)丁二腈。
另一较佳的式(Ⅵ)化合物是2-(2-氯-4-三氟甲基苯基肼基)丁二腈。
本发明的另一特征是，方法(A)和(D)可以组合起来，从式(Ⅲ)化合物制备式(Ⅵ)化合物。
本发明的另一特征是，方法(B)和(D)可以组合起来，从式(Ⅲ)化合物制备式(Ⅵ)化合物。
本发明的另一特征是，方法(C)和(D)可以组合起来，从式(Ⅴ)化合物制备式(Ⅵ)化合物。
本发明的另一特征是，上述方法(C)和(D)的组合可以与另一方法步骤(E)组合，该方法(E)包括使式(Ⅲ)芳基肼化合物(其中R1、R2和W如上所定义)与下式(Ⅶ)的丙烯腈：
NC-CH=CH2(Ⅶ)
反应，得到如上所述的式(Ⅴ)化合物。
式(Ⅶ)化合物为已知化合物。
用本发明方法(A)、(B)或(C)获得的式(Ⅰ)化合物可用于根据下述反应方案制备有杀虫活性的式(Ⅷ)5-氨基-1-芳基吡唑衍生物：
其中R1、R2和W如上所定义。
本发明方法(D)获得的式(Ⅵ)化合物特别可用于制备有杀虫活性的式(Ⅸ)5-氨基-1-芳基-3-氰基吡唑衍生物，该衍生物按照下述反应方案从式(X)和式(Ⅺ)的中间体化合物获得：
其中R1、R2和W如上所定义。
式(Ⅹ)化合物可通过式(Ⅵ)化合物氧化而制得。用于该反应的合适的氧化剂包括：醌如苯醌、过氧化物如过氧化氢、次卤素盐如次氯酸钠；或在空气存在下的金属盐氢氧化物，如氢氧化钠，或宜为金属盐或金属氧化物，例如氯化铜或氧化汞。反应通常在溶剂下进行。适用的溶剂包括：卤化或非卤化的芳族烃，如甲苯或氯苯；腈，如乙腈；或酰胺，如N,N-二甲基甲酰胺。反应温度通常在大约20℃至150℃，较佳的在约50℃至约100℃。氧化剂与式(Ⅵ)化合物的摩尔比通常在0.01∶1至5∶1之间，较佳的在1∶1至3∶1之间。
式(Ⅺ)化合物可以根据已知的方法从式(Ⅹ)化合物制得。
下列非限制性实施例描述了本发明。NMR谱用氘代氯仿作为溶剂来记录。
实施例1
从3,3二甲氧基丙腈制备3-(2,6-二氯-4-三氟甲基苯基亚肼基)丙腈
将氯化氢气体鼓泡入2,6-二氯-4-三氟甲基苯基肼的乙醚溶液，过滤获得定产率的盐酸盐，制得2,6-二氯-4-三氟甲基苯基肼氯化氢。在上述含2,6-二氯-4-三氟甲基苯基肼盐酸盐(0.349克)的水(5毫升)溶液中加入四氯化碳(5毫升)和3,3-二甲氧基丙腈(141微升)，75℃加热10小时。用二氯甲烷萃取出冷却的混合物，用水洗涤，用硫酸镁干燥并蒸发，得到0.358克主题化合物(NMR 3.37(d,2H)，7.03(t,1H)，7.5(s,2H)，7.75(s,1H))。得率为98％。
实施例2
从3,3-二甲氧基丙腈制备3-(2,6-二氯-4-三氟甲基苯基亚肼基)丙腈
在惰性气体下将2,6-二氯-4-三氟甲基苯基肼(1.8克)和盐酸(4毫升，2N，1当量)的混合物加热至80℃。一次加入3,3-二甲氧基丙腈(912微升，1当量)80℃加热该混合物2小时，冷却，用二氯甲烷萃取，用水洗涤，硫酸镁干燥并蒸发。在硅胶上色谱纯化残余物，并用二氯甲烷洗脱，得到1.4克主题化合物(NMR3.37(d,2H)，7.03(t,1H)，7.5(s,2H)，7.75(s,1H))。得率为59％。
实施例3
从3-甲氧基-丙烯腈制备3-(2,6-二氯-4-三氟甲基苯基亚肼基)丙腈
按照实施例1进行，只是用3-甲氧基-丙烯腈代替3,3-二甲氧基丙腈，在硅胶上色谱纯化以及用二氯甲烷洗脱后，获得主题化合物(NMR 3.37(d,wH)，7.03(t,1H)，7.5(s,2H)，7.75(s,1H))。得率为63％。
实施例4
2-(2,6-二氯-4-三氟甲基苯基肼基)丁二腈的制备
在密封的管内依次加入2-(2,6-二氯-4-三氟甲基苯基亚肼基)丁二腈(0.296克，1毫摩尔)，氰化钠(0.196克，4当量)，水(1毫升)和乙酸(5毫升)。20℃反应40小时后，将该混合物加入饱和的碳酸氢钠溶液中，用二氯甲烷萃取，用水洗涤，硫酸镁干燥并蒸发，得到的混合物含有40％所需主题化合物(NMR 3.1(m,2H)，4.5(m,1H)，5.89(m,1H)，6.94(d,1H)，7.71(s,2H))，还有60％的未改变的原料腙。
实施例5
从3-(2,6-二氯-4-三氟甲基苯基肼基)丙腈制备3-(2,6-二氯-4-三氟甲基苯基亚肼基)丙腈
在含3-(2,6-二氯-4-三氟甲基苯基肼基)丙腈(0.591克，2毫摩尔)的氯苯溶液中，一次加入氯化铜(0.673克，2.5当量)，65℃加热该混合物50分钟。判断反应完全，然后冷却，用水洗涤，用硫酸镁干燥，蒸发并在硅胶上色谱分离，得到3-(2,6-二氯-4-三氟甲基苯基亚肼基)丙腈(NMR 3.37(d,2H)，7.03(t,1H)，7.5(s,2H)，7.75(s,1H))(得率为35％)，以及3-(2,6-二氯-4-三氟甲基苯基偶氮)丙腈(NMR 3.0(t,2H)，4.6(t,2H)，7.6(s,2H))(得率为60％)。
实施例6
2-(2,6-二氯-4-三氟甲基苯基肼基)丁二腈的制备
将2-(2,6-二氯-4-三氟甲基苯基亚肼基)丁二腈(0.296克，1毫摩尔)、氰化钠(0.196克，当量)、水(1毫升)和乙酸(5毫升)依次加入管中，将管密封并于20℃反应40小时。将混合物加入饱和碳酸氢钠溶液中，用二氯甲烷萃取，用水洗涤，用硫酸镁干燥并蒸发，得到一混合物，该混合物含有40％所需的主题化合物(NMR3.1(m,2H)，4.5(m,1H)，5.89(m,1H)，6.94(d,1H)，7.71(s,2H))以及60％未改变的原料腙。
参照例
ⅰ)2-(2,6-二氯-4-三氟甲基苯基亚肼基)丁二腈的制备
使2-(2,6-二氯-4-三氟甲基苯基肼基)丁二腈(0.323克)和氯化铜(0.175克)的混合物在氯苯中于60℃加热6小时。过滤并蒸发后，获得主题化合物与5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)吡唑为7∶1的混合物。在硅胶上进行柱色谱层析，用二氯甲烷洗脱，得到纯的主题化合物，获得的是顺式和反式异构体的混合物(NMR(反式异构体)3.6(s,2H)，7.57(s,2H)，8.82(s,1H，可与D2O交换)，NMR(顺式异构体)3.56(s,2H)，7.59(s,2H)，8.27(s,1H，可与D2O交换)。
ⅱ)5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)吡唑的制备
在0℃下，在含有上述2-(2,6-二氯-4-三氟甲基苯基亚肼基)丁二腈(0.077克)的乙醇(1毫升)和水(0.2毫升)的混合物中加入氨(20微升含8％氨气的水溶液)。10分钟后，用二氯甲烷萃取混合物并蒸发，得到5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)吡唑(0.076克，得率为97％)。纯度为98％(用HPLC测得)。
Claims (17)
1．一种制备式(Ⅰ)化合物的方法：
其中W代表氮或-CR3；
R1代表卤素，卤烷基、宜为三氟甲基，卤代烷氧基、宜为三氟甲氧基，R4S(O)n-或-SF5；
R2代表氢或卤素，如氯或溴；
R3代表卤素，如氯或溴；
R4代表烷基或卤烷基；和
n代表0、1或2；该方法包括：
(A)使式(Ⅱ)化合物其中R5和R6独立代表烷基或一起代表含有两个或三个碳原子的亚烷基链，与式(Ⅲ)的芳基肼化合物的酸加成盐反应：
其中R1、R2和W如上所定义；或
(B)使式(Ⅳ)化合物其中R7代表烷基，宜为甲基或乙基，和式(Ⅲ)的芳基肼化合物的酸加成盐反应，其中R1、R2和W如上所定义；或
(C)氧化式(V)化合物：
其中R1、R2和W如上所定义。
2．根据权利要求1(A)所述的方法，其中R5和R6各自代表甲基或乙基。
3．根据权利要求1(A)或1(B)所述的方法，其中式(Ⅲ)化合物的酸加成盐是从强酸形成的盐。
4．根据权利要求1(A)、1(B)、2或3所述的方法，其中存在水。
5．根据权利要求1(C)所述的方法，其中氧化剂是金属盐或金属氧化物。
6．根据权利要求1(C)或5所述的方法，该方法在溶剂中进行。
7．根据权利要求1(C)、5或6所述的方法，其中氧化剂与式(Ⅴ)化合物的摩尔比为0.01∶1至5∶1，较佳的为1∶1至3∶1。
8．一种制备式(Ⅵ)化合物的方法：其中R1、R2和W如权利要求1所定义；该方法包括使式(Ⅰ)化合物，其中R1、R2和W如权利要求1所定义，与氰化氢源反应。
9．根据权利要求8所述的方法，其中在酸存在下从氰化物金属盐制得氰化氢。
10．根据权利要求8或9所述的方法，该方法在加压下进行。
11．根据权利要求8所述的方法，其中用权利要求1(A)的方法制备式(Ⅰ)化合物。
12．根据权利要求8所述的方法，其中用权利要求1(B)的方法制备式(Ⅰ)化合物。
13．根据权利要求8至12任一项所述的方法，其中氧化式(Ⅵ)的化合物，并任选地与碱反应来制备式(Ⅹ)或式(Ⅺ)的化合物：
其中W、R1和R2如权利要求1所定义。
14．根据权利要求1(C)所述的方法，然后使式(Ⅰ)化合物与氰化氢源反应，制得式(Ⅵ)化合物，其中R1、R2和W如权利要求1所定义。
15．根据权利要求1(C)、5、67或14所述的方法，其中通过使式(Ⅲ)化合物，其中R1、R2和W如权利要求1所定义，与式(Ⅶ)的丙烯腈
NC-CH=CH2 (Ⅶ)
反应来制得式(Ⅴ)化合物。
16．根据前述任一项权利要求所述的方法，其中R1代表卤烷基、较佳的是三氟甲基，卤代烷氧基、较佳的是三氟甲氧基，或-SF5；
W代表-CR3；R3代表卤素。
17．根据前述任一项权利要求所述的方法，其中R1代表三氟甲基，W代表-CR3，R2和R3代表氯。
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| EP19980420069 EP0952144B1 (en) | 1998-04-20 | 1998-04-20 | Processes for preparing pesticidal intermediates |
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| EP98420070.9 | 1998-04-20 | ||
| EP98420070A EP0952145B1 (en) | 1998-04-20 | 1998-04-20 | Process for preparing pesticidal intermediates |
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| WO2014163933A1 (en) * | 2013-03-13 | 2014-10-09 | Dow Agrosciences Llc | Process for preparation of triaryl pesticide intermediate |
| US9108932B2 (en) | 2013-03-13 | 2015-08-18 | Dow Agrosciences Llc | Preparation of haloalkoxyarylhydrazines and intermediates therefrom |
| US9102655B2 (en) | 2013-10-17 | 2015-08-11 | Dow Agrosciences Llc | Processes for the preparation of pesticidal compounds |
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