CN1103759C - 杀虫剂中间体的制备方法 - Google Patents
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Abstract
本发明涉及具有分子式(I)的化合物的制备方法，其中W、R2、R3、R5和R6的定义如说明书，该化合物作为合成具有杀虫活性的化合物的中间体很有用。
Description
本发明涉及杀虫剂中间体的制备方法，并涉及新型2-芳基亚肼基丁二腈化合物，和涉及2-芳基肼基丁二腈化合物。
公布的欧洲专利No.0295117和0234119描述了在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。然而，现在需求的是提供这些化合物及其中间体化合物的改进的制备方法。
已知芳基肼在极性的质子溶剂例如醇中与缺电子烯烃例如丙烯腈发生迈克尔加成反应，然后在碱性介质中发生氧化，给出5-氨基-1-芳基吡唑，在例如美国专利No.4824960中有所描述。然而，本发明申请人未找到报道肼与富马腈反应的任何资料。N，N’-二芳基肼氧化成偶氮化合物是已知的，仅在一个氮原子上被取代的N-烷基肼和N-芳基肼也氧化成偶氮化合物，但它们通常不稳定，分解成氮气和碳氢化合物(见J.March著，Advanced Organic Chemistry，第三版，1062页)。Y.H.Kim和Y.Choi在发表于Tetrahedron Letter 1996年第37卷8771-4页的文章中描述了环戊烯存在下钯催化的α-肼基腈的脱氢作用，生成腙基氰化物。然而，本发明申请人尚未了解到任何其他有关肼氧化生成腙的信息。此外，Kim和Choi的描述局限于未取代的苯基肼的衍生物，而且未作出可实现富马腈的肼衍生物的氧化的任何提示。
本发明的第一个目标是提供5-氨基-1-芳基-3-氰基吡唑杀虫剂中间体的方便的制备方法，而且获得的产品产率高、纯度高。
本发明的另一个目标是提供2-芳基亚肼基丁二腈化合物的制备方法，该化合物可用于制备5-氨基-1-芳基-3-氰基吡唑杀虫剂中间体。
本发明的又一个目标是提供2-芳基肼基丁二腈化合物的制备方法。
本发明的再一个目标是提供在具有杀虫活性化合物的制备中使用的新型中间体。
本发明的这些和其他目标将由下面的说明书显而易见，并可通过本发明全部或部分地得以实现。
本发明的一个方面提供了由分子式为(II)的化合物的成环作用来制备分子式为(I)的化合物的方法，如下面反应图解Sc1所示：
其中W是氮或-CR4；R2、R4、R5、R6独立地选自氢、卤素、烷基、卤代烷基、烷氧基、卤代烷氧基、R7S(O)n-、硝基、氰基、和-SF5； R3的定义同R2，或是由1-5个选自卤素、烷基、卤代烷基、烷氧基、卤代烷氧基、R7S(O)n-、硝基、氰基、和-SF5的基团所任意取代的苯基，这些基团可以是相同的或是不同；R7是烷基或卤代烷基；n是0、1或2。
除非在本说明书中另有规定，“烷基”指有1-6个碳原子(优选1-3个)的直链或支链烷基。除非另有说明，“卤代烷基”和“卤代烷氧基”分别是被一个或多个选自氟、氯、溴的卤素原子所取代的有1-6个碳原子(优选1-3个)的直链或支链的烷基、烷氧基。
优选的分子式为(I)的化合物具有一个或多个的下列特点：R2是卤素或氢；R3表示卤素、卤代烷基(优选三氟甲基)、卤代烷氧基(优选三氟甲氧基)、R7S(O)p-、-SF5或是由1-3个选自三氟甲基、三氟甲氧基、二氟甲基、-S(O)nCF3、二氯氟甲基、氯二氟甲基、氯二氟甲氧基、二氯氟甲氧基和卤素基团取代的苯基，这些基团可以是相同的或是不同；R4是卤素；R5和R6是氢。
尤其优选的分子式为(I)的化合物具有一个或多个的下列特点：-W表示-CR4，R4是卤素；R3表示卤代烷基、卤代烷氧基、或-SF5；R5和R6表示氢。
最优选的分子式为(I)的化合物是5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑。
上述获得分子式为(I)的化合物的反应Sc1通常是在碱存在的条件下进行，碱可以是有机的或无机的。合适的有机碱的例子是胺，例如三乙胺或吡啶。合适的无机碱的例子是碱、或碱土金属氢氧化物、乙酸盐、碳酸盐、或碳酸氢盐例如氢氧化钠或碳酸钠、或优选氨(含水的或气态的)。通常分子式为(I)的化合物与碱的摩尔比范围从大约1∶10到大约10∶1。反应也可以在相转移催化剂存在的条件下进行，例如季胺盐如氯化苄基三甲铵、氯化三辛酰甲铵、氯化四甲铵、溴化四-正-丙铵、氯化正-十二烷基三甲铵、氯化四-正-丁铵、和溴化正-十四烷基三甲铵。此反应通常在溶剂中进行，合适的溶剂包括醇(优选乙醇)、或非水-溶混的溶剂，尤其是卤代的碳氢化合物例如二氯乙烷或二氯甲烷，当使用相转移催化剂时非溶混溶剂是合适的。也可以选择水用作共溶剂。反应温度通常为大约-20-50℃，优选大约0-20℃。
根据本发明的另一个特征，本发明还提供通过分子式为(III)的化合物的氧化而制备分子式为(II)的化合物的方法，如下面反应图解Sc2所示：
其中W、R2、R3、R5和R6的定义如上。
优选的分子式为(II)的化合物对W、R2、R3、R5和R6的定义与上述分子式为(I)的化合物的所作定义相同。最优选的分子式为(II)的化合物是2-(2，6-二氯-4-三氟甲基-苯亚肼基)丁二腈。
获得的分子式为(II)的化合物可以是顺式和反式异构体的混合物，所有这样的形式都包括在本发明的范围内。
对于上述形成分子式为(II)的化合物的反应图解Sc2所合适的氧化剂包括醌例如苯醌、过氧化物例如过氧化氢、次卤酸盐例如次氯酸钠、或空气存在下的碱金属氢氧化物例如氢氧化钠、或优选金属的盐或金属氧化物例如二氯化铜或氧化汞。此反应通常在溶剂中进行。适用的溶剂包括芳香卤代或非卤代碳氢化合物例如甲苯或氯苯、腈例如乙腈、或酰胺例如N，N-二甲基甲酰胺。反应温度通常大约20-150℃，优选大约50-100℃。
根据本发明的又一个特征，本发明提供通过将分子式为(IV)的化合物、其烯醇、或其烯醇盐与分子式为(V)的重氮盐进行反应来制备分子式为(II)的化合物的方法，如下面反应图解Sc3所示：
这里W、R2、R3、R5和R6的含义与上述反应图解Sc1中所定义的一样，X通常是无机酸的阴离子基团例如硫酸氢根或氯根。
化合物(IV)通常是烯醇盐的形式，优选碱金属盐，例如烯醇钾或烯醇钠。
上述由分子式为(IV)的化合物与分子式为(V)的化合物进行反应形成分子式为(II)的化合物的反应图解Sc3是通过偶联和去甲酰化发生的。当使用的化合物(IV)是金属的烯醇盐时，反应通常是在无机酸例如硫酸和盐酸充分过量的情况下进行(重氮化反应在同一个容器内进行时，无机酸通常是存在的)，将金属的烯醇盐转变成游离烯醇。通常使用溶剂例如乙酸、水、卤代碳氢化合物例如二氯甲烷或二氯乙烷、卤代芳香化合物例如氯苯、乙腈、N，N-二甲基甲酰胺、或优选醇例如乙醇。反应也可以在一种缓冲剂例如乙酸钠存在的条件下进行。在偶联阶段之后，通常加入一种弱碱例如氢氧化铵溶液以产生弱碱性溶液使反应完成，例如pH值大约为8。反应温度通常大约-20-50℃，优选大约0-20℃。
上述分子式为(V)的重氮盐通常是就地将分子式为(Va)的化合物：
重氮化而制成，其中W、R2、R3、R5和R6的含义与上述定义的一样，采用文献中已知的条件，通常使用1摩尔当量的亚硝酸钠和无机酸例如盐酸或硫酸。
根据本发明的再一个特征，也可以将分子式为(VI)的化合物与分子式为(V)的重氮盐进行反应来制备分子式为(II)的化合物，分子式为(V)的重氮盐中W、R2、R3、R5、R6和X的定义如上所述，分子式为(II)化合物中W、R2、R3、R5和R6含义与上述反应图解Sc1所定义的相同，分子式为(VI)的化合物中：
Ra是烷基，优选乙基。
采用的反应条件与上述反应图解Sc3中描述的相同。
根据本发明的又再一个特征，上述分子式为(III)的化合物可以通过分子式为(VII)的芳基肼与分子式为(VIII)的化合物的反应来制备，如下面反应图解Sc4所示：
其中W、R2、R3、R5和R6的含义与上述反应图解Sc1所定义的相同。
分子式为(VIII)的化合物是已知的，可以以顺式异构体马来腈或优选反式异构体富马腈的形式使用。也可以使用两个异构体的混合物。分子式为(VII)的芳基肼是已知的，或可以由已知的方法制备。
优选的分子式为(III)的化合物的W、R2、R3、R5和R6与上述分子式为(I)的化合物所优选的相同。最优选的分子式为(III)的化合物是2-(2，6-二氯-4-三氟甲基苯肼基)丁二腈。
上述生成分子式为(III)的化合物的反应可以在多种溶剂中进行，优选极性溶剂，例如醇。极性的质子惰性溶剂例如N-甲基吡咯烷酮、N,N-二甲基甲酰胺、或二甲亚砜是尤其优选的。优选的另一个方面是在没有溶剂情况下加热分子式为(VII)和(VIII)的化合物的混合物而使反应进行。
催化剂例如四-烷基铵盐如N-苄基三甲基氢氧化铵、或丙氨酸也可以在反应中使用。
反应温度通常约为20-150℃，优选大约80-100℃。
此反应可以在分子式为(VIII)的化合物与分子式为(VII)的化合物两者摩尔比约1∶10--10∶1的条件下进行，优选大约1∶1--5∶1，尤其优选大约1.1∶1。
上述分子式为(II)和(III)的化合物是新型的，因而构成本发明的再一个特征。
下列非限制性实施例用以说明本发明。采用氘代氯仿为溶剂，记录NMR谱图。Hplc是指高效液体色谱，m.p.是指熔点。
实施例1
5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑(反应图解Sc1)的制备
氨(20微升8％氨的水溶液)在0℃加入到2-(2，6-二氯-4-三氟甲基苯亚肼基)丁二腈(0.077克)与乙醇(1毫升)和水(0.2毫升)的混合物中，10分钟后将混合物萃取(二氯甲烷)并蒸发，得到本标题化合物(0.076克，97％产率)，纯度98％(由Hplc得到)。
实施例2
5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑(反应图解Sc1)的制备
2-(2，6-二氯-4-三氟甲基苯亚肼基)丁二腈(1.0克)和碳酸氢钠(40毫升饱和的水溶液)和二氯甲烷(915毫升)在20℃、pH值为9的条件下搅拌3小时。加入碳酸钠溶液直至pH值为11，并连续搅拌一个过夜。加入少量的氢氧化钠溶液使pH值达12，3小时后再加入少量的Aliquat336(商标，三辛酰基甲基氯化铵)，2小时后反应结束。洗涤二氯甲烷的萃取物(水和盐水)，干燥(硫酸钠)并蒸发，得到本标题的化合物。
实施例3
2-(2，6-二氯-4-三氟甲基苯亚肼基)丁二腈(反应图解Sc2)的制备
2-(2，6-二氯-4-三氟甲基苯肼基)丁二腈(0.323克)和二氯化铜(0.175克)的混合物在氯苯中于60℃加热6小时，过滤并蒸发后，得到本标题化合物和5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑的比例为7∶1的混合物，经硅胶柱色谱用二氯甲烷洗脱，给出纯的本标题化合物，得到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，可用D2O交换)，NMR(顺式异构体)3.56(s，2H)、7.59(s，2H)、8.27(s，1H，可用D2O交换)。
实施例4
2-(2，6-二氯-4-三氟甲基苯亚肼基)丁二腈(反应图解Sc3)的制备
亚硝酸钠(3.9克)加入到搅拌的浓硫酸(12.8毫升)中，在80℃下加热直至溶解。在30℃加入乙酸(25毫升)。在20℃、10分钟以上的时间内加入2,6-二氯-4-三氟甲基苯基苯胺(10.0克)和乙酸(25毫升)的混合物，温度维持在25℃以下。混合物在55℃下加热50分钟，再加入亚硝酸钠(0.65克)和乙酸(10毫升)，20分钟之后加热到70℃，并加入硫酸(2.8毫升)。20分钟之后，冷却的混合物在10℃下加入到2-羟基亚甲基丁二腈的钾盐(7.6克)和乙酸钠(35.6克)在水和乙酸(70毫升)中的混合物中。在1小时内升温到20℃，之后加入二氯甲烷，再加入氢氧化铵溶液(210毫升)使pH值达8。分离有机相，洗涤(水和盐水)，干燥(硫酸钠)并蒸发，给出本主题的红棕色固态化合物(18.1克)。从己烷/叔丁基甲基醚中重结晶得到本标题的纯化合物(6.85克)，熔点80-82℃，NMR3.6(s,2H)、7.66(s,2H)、9.03(s，lH，可用D2O交换)。
实施例5
2-(2，6-二氯-4-三氟甲基苯肼基)丁二腈(反应图解Sc4)的制备
2,6-二氯-4-三氟甲基苯肼(1.0克)和富马腈(1.0克)在二甲亚砜(10毫升)中的混合物于100℃加热7小时。冷却的混合物用水稀释并萃取(乙醚)，蒸发并从二氯甲烷/已烷中结晶，给出本标题的化合物(0.828克，63％)，熔点101-102℃。
实施例6
2-(苯肼基)丁二腈(反应图解Sc4)的制备
苯肼(4.29克)和富马腈(3.1克)的混合物，其中苯肼用作溶剂，该混合物在75-80℃加热20小时，用快速硅胶色谱纯化，并从二氯甲烷/已烷中结晶，给出本标题的化合物(3.29克，45％)，熔点97-98℃。
虽然本发明是根据各种优选的实施例进行说明的，熟练的技术人员将会意识到可以在不脱离本发明精神下进行各种改变、替换、省略、和变化。因此，本发明的保护范围仅由下面的权利要求书所限定，包括本发明的等价物。
Claims (9)
1.分子式为(I)的化合物的制备方法，
其中W是氮或-CR4；
R2、R4、R5和R6独立地选自氢、卤素、C1-6烷基、C1-6卤代烷基、C1-6烷氧基、C1-6卤代烷氧基、R7S(O)n-、硝基、氰基和-SF5；
R3是氢、卤素、C1-6烷基、C1-6卤代烷基、C1-6烷氧基、C1-6卤代烷氧基、R7S(O)n-、硝基、氰基、-SF5，或是由1-5个选自卤素、C1-6烷基、C1-6卤代烷基、C1-6烷氧基、C1-6卤代烷氧基、R7S(O)n-、硝基、氰基和-SF5的基团所取代的苯基，这些基团可相同或不同；
R7是C1-6烷基或C1-6卤代烷基；
n是0、1或2；
所述制备方法包括使分子式为(II)的化合物：
在碱存在下环化，其中W、R2、R3、R5和R6的定义如上。
2.如权利要求1所述的方法，其中碱与分子式为(II)的化合物的摩尔比范围是约1∶10到10∶1。
3.具有分子式(II)的化合物：
其中W、R2、R3、R5和R6的定义如权利要求1。
4.如权利要求3所述的化合物，其中：
R2是卤素或氢；
R3表示卤素、C1-6卤代烷基、C1-6卤代烷氧基、R7S(O)p-、-SF5或是由1-3个选自三氟甲基、三氟甲氧基、二氟甲基、-S(O)nCF3、二氯氟甲基、氯二氟甲基、氯二氟甲氧基、二氯氟甲氧基和卤素的基团所取代的苯基，这些基团可相同或不同；
R4是卤素；
R5和R6是氢。
5.制备如权利要求3所定义的分子式为(II)的化合物的方法，该方法包括使用氧化剂，使具有分子式(III)的化合物：
氧化，其中W、R2、R3、R5和R6的定义如权利要求3。
6.如权利要求5所述的方法，其中氧化剂选自醌、过氧化物、次卤酸盐、空气存在下的碱金属氢氧化物、金属盐和金属氧化物。
7.制备如权利要求3所定义的分子式为(II)的化合物的方法，该方法包括使具有分子式(IV)的化合物：的烯醇盐与具有分子式(V)的重氮盐：进行反应，其中W、R2、R3、R5和R6的定义如权利要求3，X是硫酸氢根或氯根。
8.具有分子式(III)的化合物：其中W、R2、R3、R5和R6的定义如权利要求1。
9.如权利要求8所述的化合物，其中：
R2是卤素或氢；
R3表示卤素、C1-6卤代烷基、C1-6卤代烷氧基、R7S(O)p-、-SF5或是由1-3个选自三氟甲基、三氟甲氧基、二氟甲基、-S(O)nCF3、二氯氟甲基、氯二氟甲基、氯二氟甲氧基、二氯氟甲氧基和卤素的基团所取代的苯基，这些基团可相同或不同；
R4是卤素；
R5和R6是氢。
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| FR2789387B1 (fr) | 1999-02-04 | 2001-09-14 | Aventis Cropscience Sa | Nouveau procede de preparation d'intermediaires pesticides |
| DE10142665B4 (de) | 2001-08-31 | 2004-05-06 | Aventis Pharma Deutschland Gmbh | C2-Disubstituierte Indan-1-one und ihre Derivate |
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| WO2015058024A1 (en) | 2013-10-17 | 2015-04-23 | Dow Agrosciences Llc | Processes for the preparation of pesticidal compounds |
| CN106117145A (zh) * | 2016-07-12 | 2016-11-16 | 潍坊鑫诺化工有限公司 | 5‑氨基‑1‑（2,6‑二氯‑4‑三氟甲基苯基）‑3‑氰基吡唑的制备方法 |
| CN110325036B (zh) | 2016-12-29 | 2021-10-26 | 美国陶氏益农公司 | 用于制备杀虫化合物的方法 |
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