CN102816112B - Method for preparing pesticide nitenpyram - Google Patents

Method for preparing pesticide nitenpyram Download PDF

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CN102816112B
CN102816112B CN 201210341712 CN201210341712A CN102816112B CN 102816112 B CN102816112 B CN 102816112B CN 201210341712 CN201210341712 CN 201210341712 CN 201210341712 A CN201210341712 A CN 201210341712A CN 102816112 B CN102816112 B CN 102816112B
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reaction
chloro
nitenpyram
ethyl
give
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CN102816112A (en )
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曾挺
陈华
陈共华
潘光飞
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浙江禾本科技有限公司
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Abstract

本发明涉及杀虫剂的合成方法,尤其是一种烯啶虫胺的制备方法。 The present invention relates to a method for the synthesis of pesticides, in particular a method for preparation of nitenpyram. 其特征在于:一是以1,1,2-三氯乙烷为起始原料,经消除反应和催化硝化反应,直接合成中间体1,1,1-三氯-2-硝基乙烷;二是以2-氯-5-氯甲基吡啶为起始原料,以水为溶剂,采用相转移催化技术,经N-烷基化反应得到中间体N-乙基-2-氯-5-吡啶甲基胺;三是将两者中间体混合,用低毒的二氯甲烷为溶剂,在同一反应锅中进行缩合和甲胺基化反应,再经萃取、脱溶、结晶而得到烯啶虫胺。 Wherein: one as a starting material to 1,1,2-trichloroethane, and the elimination reaction catalyzed by nitration reaction, the direct synthesis of Intermediate 1,1,1-trichloro-2-nitroethane; Second, 2-chloro-5-chloromethyl-pyridine as a starting material, water as solvent, phase transfer catalysis, by N- alkylation reaction to give the intermediate N- ethyl-2-chloro-5- picolylamine; Third mixing two intermediates, low toxicity with methylene chloride as the solvent, and condensation reactions in the same methylamino 11:50 and then was extracted, desolventized, and crystallized to give nitenpyram clothianidin. 其目的是为了提供一种收率和纯度高,工艺流程短的杀虫剂烯啶虫胺制备方法。 Its purpose is to provide one kind of high yield and purity, short process insecticides nitenpyram preparing amines. 与现有技术相比具有总收率高,成本低,产品纯度高,环境污染少,利于工业化生产等优点。 The prior art having a high total yield compared to low cost, high product purity, less environmental pollution, etc. industrially advantageous.

Description

一种杀虫剂烯啶虫胺的制备方法 A method for preparing insecticides nitenpyram

技术领域 FIELD

[0001] 本发明涉及杀虫剂的合成方法,尤其是一种以1,I, 2-三氯乙烷和2-氯氯甲基吡啶为主要原料的烯啶虫胺的制备方法。 [0001] The present invention relates to a method for the synthesis of pesticides, in particular a 1, I, 2- trichloroethane, and chloro-2-chloro-methylpyridine is prepared nitenpyram the main raw material.

背景技术 Background technique

[0002] 烯啶虫胺是继吡虫啉之后的新一代烟碱类杀虫剂,其分子结构式为: [0002] Nitenpyram is the second generation neonicotinoid insecticide imidacloprid, its molecular formula is:

[0003] [0003]

Figure CN102816112BD00041

[0004] 它是国内最新推广的代替高毒有机磷农药的新品种,具有独特的化学和生物性质,对害虫的突触受体具有神经阻断作用,对各种蚜虫、粉虱、水稻叶蝉和蓟马等显示有卓越的活性,具有高效、低毒、对环境安全、高内吸性、无交互抗性、对作物无药害等优点,广泛用于防治水稻、果树、蔬菜和茶叶上的多种作物害虫。 [0004] It is to replace the newest promotion of highly toxic organophosphorus pesticides new varieties have unique chemical and biological properties of neural synaptic receptor blocking effect of pests of all kinds of aphids, whiteflies, leaf rice cicadas and thrips showed excellent activity, high efficiency, low toxicity, environmental safety, a high absorption property, no cross-resistance, no phytotoxicity to crops, etc., it is widely used in the control of rice, fruit trees, vegetables and tea, a variety of crop pests. 特别是该产品对灰飞虱及褐飞虱有绝杀作用,用药后10分钟左右见效,速效性明显,持效期可达14天,效果优于啶虫脒、吡虫啉等同类药品。 In particular, the product of the small brown planthopper and brown planthopper has the role of lore, about 10 minutes after administration effective, quick result obviously, the persistence of up to 14 days, better than acetamiprid, imidacloprid and other similar drugs. 该产品是1989年由日本武田公司开发成功,并获有相关专利,如:EP302389,GB228003, US5935981, US5849768, US5364989, US4028379, US4347250, US5175301 等。 The product was developed in 1989 by the Japanese company Takeda success, and was related patents, such as: EP302389, GB228003, US5935981, US5849768, US5364989, US4028379, US4347250, US5175301 and so on. 国内对该产品研究报道较晚,2002年以来曾发表过三篇论文,如2002年王党生在《农药》杂志上首先发表了题为《烯啶虫胺的合成路线》,介绍了国内外烯啶虫胺的合成路线。 The domestic product reported late, since 2002, has published three papers, such as the king of the party born in 2002 in the journal "pesticide" first published a report entitled "synthetic routes nitenpyram" and introduced at home and abroad nitenpyram Scheme amine.

[0005] 本申请人为了开发此杀虫剂烯啶虫胺产品,曾采用文献记载的制备技术方法进行小试。 [0005] The present applicant to develop pesticides nitenpyram this product was prepared using the method described in the literature techniques small test. ①以硝基甲烷和二硫化碳为原料,先制备1,1_ 二甲硫基-2-硝基乙烯,再与2-氯-5-氯甲基吡唳为原料合成得到中间体N-乙基-2-氯-5-吡唳甲基胺反应。 ① The nitromethane and carbon disulfide as raw materials, is first prepared 1,1_-dimethoxy-2- nitroethylene, with 2-chloro-5-chloromethyl-pyridine was synthesized by Li to give the intermediate N- ethyl - chloro-5-methyl-pyrazol Li amine. 在试验中碰到许多问题:中间体1,1-二甲硫基-2-硝基乙烯制备工艺复杂,并有毒且有难闻臭味,存在有工艺流程复杂、操作不安全、污染环境、成本高等缺点;②采用文献记载技术,用工业盐酸和硝酸制备I,I,1- 二氯_2_硝基乙烧,再与N-乙基-2-氯-5-吡唳甲基胺反应的路线中,硝化过程酸过量太多,废酸难处理,环境污染严重。 Many of the problems encountered in the experiments: the intermediate 1,1-dimethoxy-2- nitroethylene complicated preparation process, and an unpleasant smell and toxic, there is a complex process, unsafe operation, environmental pollution, high cost; ② literature described techniques, with hydrochloric acid and nitric industrial preparation of I, I, 1- dichloro _2_ nitro burn acetate, and then with N- ethyl-2-chloro-5-pyrazol Li methylamine route reaction, excess acid nitrification process too much waste acid intractable, serious environmental pollution. 中间体N-乙基-2-氯-5-吡啶甲基胺的制备过程中,用了大量的溶剂,而收率不高,回收溶剂处理困难,成本高,对环境造成较大的污染。 Preparation of Intermediate N- ethyl-2-chloro-5-pyridylmethyl amine, with a large amount of solvent, and the yield is not high, the solvent recovery process is difficult, costly, cause greater environmental pollution.

发明内容 SUMMARY

[0006] 本发明的目的是提供一种收率和纯度高,工艺流程短的杀虫剂烯啶虫胺制备方法。 [0006] The object of the present invention is to provide a high yield and purity, short process insecticides nitenpyram preparing amines.

[0007] 为了达到上述目的,本发明采用以下技术解决方案:一种杀虫剂烯啶虫胺的制备方法,其特征在于其按以下合成工艺路线进行:[0008] (I)消除反应,以1,1,2_三氯乙烷为起始原料,与氢氧化钠溶液反应,于_15°C~ [0007] To achieve the above object, the present invention employs the following technical solutions: A method for preparing insecticides nitenpyram, characterized in that it is carried out in the following synthesis route: [0008] (I) elimination reaction to 1,1,2_ trichloroethane as a starting material, the reaction with sodium hydroxide solution, at _15 ° C ~

100°C下进行消除反应,得到偏二氯乙烯,其反应方程式: 100 ° C for an elimination reaction, to give vinylidene chloride, the reaction equation:

Figure CN102816112BD00051

[0010] (2)硝化反应,所述的偏二氯乙烯在催化剂Al存在下,与盐酸和硝酸进行硝化反应,反应结束后经分离纯化得到1,1,1_三氯-2-硝基乙烷,其反应方程式: [0010] (2) the nitration reaction, the vinylidene chloride in the presence of a catalyst Al, nitrification reaction with hydrochloric acid and nitric acid, after the reaction to give 2-nitro-trichloro 1,1,1_ was purified by ethane, reaction equation:

[0011] [0011]

Figure CN102816112BD00052

[0012] 所述的催化剂Al为下列之一:①ZSM25分子筛,②(62沸石分子筛,③SAP0211分子筛,④NH4Y型分子筛,⑤ReY分子筛,⑥SSY分子筛; [0012] The catalyst Al is one of the following: ①ZSM25 molecular sieves, ② (62 Zeolite, ③SAP0211 sieve, ④NH4Y zeolite, ⑤ReY sieve, ⑥SSY sieve;

[0013] (3) N-乙基化反应,以2-氯-5-氯甲基吡啶起始原料,以水做溶剂,在-10~50°C下,与乙胺在相转移催化剂A2的作用下反应,反应产物经过脱溶,碱洗,蒸馏得到所述的中间体N-乙基-2-氯-5-吡啶甲基胺,其反应方程式: [0013] (3) N- ethyl reaction with 2-chloro-5-chloromethyl-pyridine starting materials, water as solvent, at -10 ~ 50 ° C, and a phase transfer catalyst A2 ethylamine the role of the reaction, the reaction product was desolventized, alkali washing, distillation of the intermediate N- ethyl-2-chloro-5-pyridylmethyl amine, the reaction equation:

Figure CN102816112BD00053

[0015] 所述的催化齐A2为下列之一:①四甲基氢氧化铵,②四乙基氢氧化铵、③三甲基苄基氢氧化铵,④三乙基苄基氯化铵,⑤四丁基溴化铵,⑥十六烷基三甲基溴化铵; Catalytic [0015] The homogeneous A2 is one of the following: ① tetramethylammonium hydroxide, tetraethylammonium hydroxide ②, ③ ammonium hydroxide, trimethylbenzylammonium, triethylbenzylammonium chloride ④, tetrabutylammonium bromide ⑤, ⑥ cetyl trimethyl ammonium bromide;

[0016] (4)缩合反应,所述的N-乙基-2-氯-5-吡啶甲基胺与所述的1,I,1-三氯-2-硝基乙烷在二氯甲烷溶剂中,加入缚酸剂,在相转移催化剂A3作用下,-10~50°C下,反应得到缩合物1_氯-N-{(6-氯吡卩定-3-)甲基} -N-乙基-2-硝基乙烯胺,其反应方程式: [0016] (4) condensation reaction of the ethyl-2-chloro-5-pyridin-N- methylamine with said 1, I, 1- trichloro-2-nitroethane in dichloromethane solvent, acid binding agent is added, the effect of the A3 phase transfer catalyst, at -10 ~ 50 ° C, the reaction to give a condensate 1_-chloro -N - {(6- chloro-pyridine -3- given Jie) methyl} - N- ethyl-2-nitroethylene-amine, reaction equation:

[0017].CH2NHC2H5 ?2H5 [0017] .CH2NHC2H5? 2H5

Figure CN102816112BD00054

[0018] 所述的催化剂A3为下列之一:①四甲基氢氧化铵,②四乙基氢氧化铵、③三甲基苄基氢氧化铵,④三乙基苄基氯化铵,⑤四丁基溴化铵,⑥十六烷基三甲基溴化铵; [0018] The catalyst A3 is one of the following: ① ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide ②, ③ trimethylbenzylammonium, triethylbenzylammonium chloride ④, ⑤ tetrabutylammonium bromide, ⑥ cetyl trimethyl ammonium bromide;

[0019] 所述的缚酸剂为下列之一:①Na2CO3,②K2CO3,③NaHCO3,④KHCO3,⑤NaOH,©K0H ; The acid-binding agents [0019] according to one of the following: ①Na2CO3, ②K2CO3, ③NaHCO3, ④KHCO3, ⑤NaOH, © K0H;

[0020] (5)甲胺基化反应,所述甲胺基化反应与所述的缩合反应在同一反应锅中进行,在所述缩合反应完成后,得到缩合物1_氯-N-{(6-氯吡卩定-3-)甲基}_N_乙基-2-硝基乙烯胺,随后在-10~50°C下,滴加甲胺水溶液,反应产物经萃取、脱溶、重结晶得到烯啶虫胺,其反应方程式: [0020] (5) A group of reaction, the reaction with the amine A condensation reaction is carried out in the same reaction pot, after completion of the condensation reaction to give a condensate chloro -N- {1_ (6-chloro-pyrazol -3- given Jie) methyl} _N_ ethyl-2-nitro-vinylamine, and then at -10 ~ 50 ° C, aqueous methylamine was added dropwise, the reaction product was extracted, desolventized, recrystallization nitenpyram, reaction equation:

[0021] [0021]

Figure CN102816112BD00061

[0022] 本发明为了提高硝化反应的反应产物1,1,1-三氯-2-硝基乙烷中间体含量和收率,对合成技术方案进行进一步设置: [0022] In order to improve the reaction product of the present invention, the nitration reaction intermediate 1,1,1-trichloro-2-nitroethane content and yield of the synthesis scheme is further provided:

[0023] 所述硝化反应按以下步骤进行:在2000L的搪瓷反应釜中,加入412.5Kg31 %所述工业盐酸、324Kg68%所述工业浓硝酸和7.5kg所述SAP0-211分子筛催化剂Al,剧烈搅拌下,控制好反应温度,5~6小时内,均匀滴入所述偏二氯乙烯315Kg ;滴毕,继续保温反应3小时;反应结束,静置分层,取下层油层,用300Kg水洗涤一次,得到534Kgl,l,l-三氯-2-硝基乙烷,含量≥90%,收率≥ 85%以上。 [0023] The nitration reaction is performed in the following steps: 2000L enamel reactor was added the 412.5Kg31% industrial hydrochloric acid, the industrial 324Kg68% concentrated nitric acid and 7.5kg of the molecular sieve catalyst SAP0-211 Al, vigorously stirred under control the reaction temperature within 5 to 6 hours, the uniformly added dropwise 315 kg vinylidene chloride; dropwise, incubation was continued for 3 hours; the reaction was completed, standing layer, and the lower layer oil, washed once with water 300Kg to give 534Kgl, l, l- trichloro-2-nitroethane, the content of ≥90%, the yield of ≥ 85%.

[0024] 本发明为了使N-乙基化反应能够提高中间体纯度和收率,纯化过程无毒,减少环境污染,对合成技术方案进行进一步设置: [0024] In order that the present invention is N- ethyl reaction intermediates can be improved purity and yield, non-toxic purification process, to reduce environmental pollution, is provided for further synthesis scheme:

[0025] 所述N-乙基化反应按以下步骤进行:在2000L的搪瓷反应釜中,以水做溶剂,加入289.2Kg70%的所述乙胺水溶液、5Kg的所述四丁基溴化铵催化剂A2,搅拌,调节好反应的温度,缓慢将304.5Kg95.9%的所述2-氯-5-氯甲基吡啶加入反应爸,控制好温度,加毕,继续保温反应I小时;反应结束,蒸馏回收过量的乙胺水溶液,加入30%氢氧化钠溶液240Kg,静置分层,取油层,得到318Kg N-乙基-2-氯-5-吡啶甲基胺粗品,含量≥95%;减压蒸馏,取馏分162~164°C / -0.095Mpa,得到浅黄色液体285Kg,含量≥99%。 [0025] The N- ethylation reaction is carried out as follows: in the 2000L enamel reactor, with water as solvent, was added an aqueous solution of the amine of 289.2Kg70%, 5Kg of the tetrabutylammonium bromide the catalyst A2, stirring, adjusting the temperature of the reaction well, the slowly 304.5Kg95.9% of 2-chloro-5-chloromethyl-pyridine to the reaction, dad, control the temperature, plus complete, incubation was continued for I hr reaction; the reaction , recovered by distillation of excess ethylamine aqueous solution, 30% sodium hydroxide solution 240Kg, standing layer, from the oil obtained 318Kg N- chloro-5-ethyl-2-picolylamine crude content ≥95%; distillation under reduced pressure, taken fraction 162 ~ 164 ° C / -0.095Mpa, to give a pale yellow liquid 285kg, the content of ≥99%.

[0026] 本发明与现有技术相比具有以下优点: [0026] The present invention and the prior art has the following advantages:

[0027] 本发明以1,1,2_三氯乙烷为起始原料,经消除反应和催化硝化反应,采用催化硝化技术,大大提高了反应的含量和收率,直接合成得到含量达90 %以上的1,1,1-三氯-2-硝基乙烷;采用相转移催化技术,以水来代替日本武田公司所用的有毒有污染的乙腈为溶剂,来完成2-氯-5-氯甲基吡啶的乙胺化反应及其纯化程序,得到高纯度(99% )的N-乙基-2-氯-5-吡啶甲基胺;过量的乙胺通过降膜吸收塔,可重复套用,减少了环境污染。 [0027] In the present invention 1,1,2_ trichloroethane as a starting material, and by elimination reaction catalyzed nitration, catalytic nitration techniques, greatly improves the content and yield of the reaction, the content of the direct synthesis of 90 to give % or more of 1,1,1-trichloro-2-nitroethane; phase transfer catalysis, water companies instead of Takeda contaminated with toxic acetonitrile as solvent, 2-chloro-done chloromethylpyridine ethylamine reaction and purification procedure to obtain a high purity (99%) of N- chloro-5-ethyl-2-picolylamine; excess ethylamine by falling film absorber may be repeated apply reduce environmental pollution. 此步反应的收率由文献报道的85%提高至92%。 This reaction step yields increased from 85% to 92% reported in the literature.

[0028] 本发明将1,1,1- 二氣_2_硝基乙烧同N-乙基_2_氣_5_吡唳甲基胺混合,用低毒的二氯甲烷代替文献报道的高毒氯仿为反应介质,在温和条件下进行缩合和消除反应,并在同一反应锅中不经分离直接进行相转移甲胺基化反应,再经萃取、脱溶、结晶而得到纯度达97%以上的烯啶虫胺。 [0028] The present invention is 1,1,1-nitro-B burning the second gas _2_ methylamine mixed with Li-pyrazol-ethyl-N- _5_ _2_ gas, instead of the reported toxicity with dichloromethane purity highly toxic and chloroform as reaction medium, carried out under mild reaction conditions and the elimination of condensation, and without isolation directly in the same reaction pot methylamino phase transfer reaction, and then extracted, desolventized, crystalline 97 % or more of nitenpyram. 总收率高,成本低,产品纯度高,利于工业化生产。 The total yield, low cost, high product purity, suitable for industrial production.

附图说明 BRIEF DESCRIPTION

[0029] 图1为本实施例烯啶虫胺合成工艺流程方框图。 [0029] Synthesis process flow block diagram of FIG. 1 nitenpyram present embodiment.

具体实施方式 detailed description

[0030] 下面结合附图和实施例对本发明作进一步详细说明。 Drawings and embodiments of the present invention will be further described in detail [0030] below in conjunction.

[0031] 如图1所示,本实施例按以下合成工艺路线和步骤进行: [0031] As shown in FIG 1, the present embodiment will be following the synthetic routes and process steps:

[0032] (I)消除反应,其反应方程式为:, [0032] (I) elimination reaction, the reaction equation is:,

[0033] [0033]

Figure CN102816112BD00071

[0034] 所述消除反应按以下步骤进行:在2000L的搪瓷反应釜中,加入450Kgl,I, 2_三氯乙烷,加热到一定的温度,在剧烈搅拌下,均匀地滴加30%氢氧化钠溶液450Kg,滴加时间约为5小时。 [0034] The elimination reaction is performed in the following steps: 2000L enamel reactor was added 450Kgl, I, 2_ trichloroethane, is heated to a certain temperature, under vigorous stirring, dropwise addition of 30% hydrogen uniformly sodium hydroxide solution 450Kg, dropwise addition time is about 5 hours. 反应期间,产物偏二氯乙烯从蒸馏柱顶逸出,柱顶温度在32~40°C,经过冷凝管冷凝后进入接收罐。 During the reaction, the vinylidene chloride product from the distillation column top to escape, at a head temperature of 32 ~ 40 ° C, after condenser is condensed into a receiving tank. 滴毕,继续保温反应直到基本没有产物逸出。 Dropwise, incubation was continued until the reaction product is substantially no escape. 再缓慢升温到一定的温度70V反应I~2小时,至无产物馏出来为止。 And then slowly warmed to a temperature 70V reaction I ~ 2 hours until no product was distilled out of date. 得到315Kg(≥98% )无色透明液体产物偏二氯乙烯。 To give 315Kg (≥98%) as a colorless transparent liquid product vinylidene chloride.

[0035] 所述消除反应经6批次中试,中试结果如下: [0035] The elimination reaction was 6 batch test, test results were as follows:

[0036] [0036]

Figure CN102816112BD00072

[0037] 由上表可知,消除反应制备偏二氯乙烯的最高收率为97.3%,最低为96.7%,平均收率为97.1%,平均含量为98.3 %。 [0037] The above table shows that elimination reaction of vinylidene chloride prepared the highest yield of 97.3%, a minimum of 96.7%, an average yield of 97.1%, an average content of 98.3%.

[0038] (2)硝化反应,其反应方程式为: [0038] (2) the nitration reaction, the reaction equation is:

[0039] [0039]

Figure CN102816112BD00073

[0040] 所述硝化反应按以下步骤进行:在2000L的搪瓷反应釜中,加入412.5Kg31%工业盐酸、324Kg68%工业浓硝酸和7.5kg SAP0211分子筛催化剂Al,剧烈搅拌下,控制好反应的温度,5~6小时内,均匀滴入第一步所得的315Kg偏二氯乙烯,滴毕,继续保温反应3小时。 [0040] The nitration reaction is performed in the following steps: 2000L enamel reactor was added 412.5Kg31% industrial hydrochloric acid, 324Kg68% concentrated nitric acid and 7.5kg SAP0211 industrial molecular sieve catalyst Al, with vigorous stirring, a good control of the reaction temperature, within 5 to 6 hours, resulting in the first step was added dropwise homogeneous 315Kg vinylidene chloride, dropwise, the reaction was continued for 3 hours. 反应结束,静置分层,取下层油层,用300Kg水洗涤一次,得到534Kgl,1,1-三氯_2_硝基乙烷0含量> 90%。 The reaction end, standing layer, and the lower layer oil, washed once with water 300Kg give 534Kgl, 1,1- trichloro-nitroethane _2_ 0 content of> 90%.

[0041] 在该步骤的硝化反应中,所述SAP0211分子筛催化剂Al的作用是提高分子重排的选择性,减少副产物。 [0041] The nitration in this step, the Al SAP0211 molecular sieve catalyst is to enhance the selectivity of molecular rearrangement, reduction of by-products. 下列物质:①ZSM25分子筛,②(62沸石分子筛、③NH4Y型分子筛,④ReY分子筛和⑤SSY分子筛也有类似的特性,也可做该硝化反应的催化剂Al。 The following materials: ①ZSM25 molecular sieves, ② (62 Zeolite, ③NH4Y zeolite, ④ReY ⑤SSY zeolite molecular sieves, and have similar characteristics, but also do the nitration reaction catalyst Al.

[0042] 所述硝化反应经6批次中试,中试结果如下: [0042] The nitration reaction was 6 batch test, test results were as follows:

[0043] [0043]

Figure CN102816112BD00074
Figure CN102816112BD00081

[0044] 由上表可知,硝化反应制备1,1,1-三氯-2-硝基乙烷的最高收率为85.9%,最低为84.8 %,平均收率为85.4%,平均含量为90.5 %。 [0044] The above table shows that the preparation of 1,1,1-trichloro-2-nitroethane nitration highest yield of 85.9%, a minimum of 84.8%, an average yield of 85.4%, an average content of 90.5 %.

[0045] ⑶N-乙基化反应,其反应方程式为: [0045] ⑶N- ethyl reaction, the reaction equation is:

Figure CN102816112BD00082

[0047] 所述N-乙基化反应按以下步骤进行:在2000L的搪瓷反应釜中,以水做溶剂,加入289.2Kg70%的乙胺水溶液和5Kg三乙基苄基氯化铵催化剂A2,搅拌调节好反应的温度,缓慢将304.5Kg95.9%的2-氯-5-氯甲基吡啶加入反应釜中,加毕,继续保温反应I小时,反应结束,蒸馏回收过量的乙胺水溶液。 [0047] The N- ethylation reaction is carried out as follows: in the 2000L enamel reactor, with water as solvent, was added 289.2Kg70% aqueous ethylamine solution and triethyl benzyl ammonium chloride 5Kg catalyst A2, regulate the temperature of the reaction was stirred and slowly 304.5Kg95.9% of 2-chloro-5-chloromethyl-pyridine added to the kettle, plus complete, incubation was continued for I hr reaction, the reaction was completed, the excess aqueous ethylamine solution recovered by distillation. 加入30%的氢氧化钠溶液240Kg,静置分层,取油层,得到318Kg褐色液体产物,含量94.5%。 30% sodium hydroxide solution was added 240Kg, standing layer, from the oil obtained 318Kg brown liquid product, content 94.5%. 经减压蒸馏,取馏分162~164°C / -0.095Mpa,得到浅黄色液体285Kg,含量≥99%。 By distillation under reduced pressure, taken fraction 162 ~ 164 ° C / -0.095Mpa, to give a pale yellow liquid 285kg, the content of ≥99%.

[0048] 在所述N-乙基化反应中,所述四丁基溴化铵催化剂A2的作用是使反应物料处于均相体系中。 [0048] ethyl N- in the reaction, the action of tetrabutylammonium bromide catalyst A2 is to make the reaction mass in a homogeneous system. 下列物质:四甲基氢氧化铵、四乙基氢氧化铵、三甲基苄基氢氧化铵、三乙基苄基氯化铵和十六烷基三甲基溴化铵也有相似的性质,也可作为该N-烷基化反应的相转移催化剂。 The following materials: tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, triethyl benzyl ammonium chloride and cetyl trimethyl ammonium bromide has similar properties, as a phase transfer catalyst may be the N- alkylation reaction.

[0049] 所述N-乙基化反应经6批次中试,中试结果如下: [0049] The reaction for 6-ethyl-N- batch test, test results were as follows:

Figure CN102816112BD00083

[0051] 由上表可知,N-乙基化反应制备N_(6_氯-3-吡唳甲基)_N_乙胺的最闻收率为92.9%,最低为91.7%,平均收率为92.4%,平均含量为99.2%。 [0051] From the above table can be seen, N- ethyl-prepared reaction N_ (6_ chloro-3-methyl-pyrazol Li) ethylamine most _N_ smell yield 92.9%, 91.7% minimum, and an average yield 92.4%, with an average content of 99.2%.

[0052] (4)缩合反应和甲胺基化反应,其反应方程式分别为: [0052] (4) A condensation reaction of amine reaction, are reaction equation:

[0053] [0053]

Figure CN102816112BD00091

[0054] 所述甲胺基化反应与所述的缩合反应在同一反应锅中进行。 [0054] The reaction with the amine A condensation reaction performed in the same reaction pot.

[0055] 所述缩合反应和甲胺基化反应按以下步骤进行:在1000L的搪瓷反应釜中,加5Kg四丁基溴化铵催化剂A3、64Kg碳酸钠缚酸剂、480Kg 二氯甲烷溶剂,控制好反应温度,加入1,1,1- 二氯-2-硝基乙烧65.4Kg,随后,滴加N- (6-氯-3-吡唳甲基)-N-乙胺52Kg, 2~3小时滴完。 The [0055] reaction and the condensation reaction methylamino perform the following steps: in the 1000L enamel reactor, add tetrabutylammonium bromide catalyst 5Kg A3,64Kg carbonate acid-binding agent, 480kg solvent was methylene chloride, good control of the reaction temperature, 1,1,1-dichloro-2-nitro-b burning 65.4Kg, then added dropwise N- (6- chloro-3-methyl-pyrazol Li) -N- ethylamine 52Kg, 2 to 3 hours dropwise. 滴毕,滴加46.5Kg40%的甲胺水溶液,2~3小时滴完。 Dropwise, 46.5Kg40% aqueous solution of methylamine, 2 to 3 hours dropwise. 滴毕,在此温度下继续保温搅拌I小时。 Dropwise, with stirring and incubation was continued at this temperature for I h. 然后,升温回流反应2小时。 Then, the reaction was warmed to reflux for 2 hours. 反应结束降温静置分层,水层用220Kg 二氯甲烷萃取,合并有机层。 Cooling the reaction was separated out and the aqueous layer was extracted with 220Kg dichloromethane, the organic layers were combined. 回收二氯甲烷,先常压,然后再减压,得到粗品83.lKg,加入IOOKg甲醇进行重结晶,过滤,烘干得到72Kg烯啶虫胺原药,含量> 97%。 Methylene chloride was recovered, to atmospheric pressure, then under reduced pressure to give a crude product 83.lKg, added IOOKg recrystallized from methanol, filtered and dried to obtain 72Kg nitenpyram original drug content of> 97%.

[0056] 在所述缩合反应和甲胺基化反应中,所述四丁基溴化铵催化剂A3的作用是使反应物料处于均相体系中。 [0056] In the condensation reaction and the reaction of the amine A, the action of tetrabutylammonium bromide catalyst A3 is that the reaction mass in a homogeneous system. 下列物质:四甲基氢氧化铵、四乙基氢氧化铵、三甲基苄基氢氧化铵、三乙基苄基氯化铵和十六烷基三甲基溴化铵也有相似的性质,可作为该缩合反应的相转移催化剂。 The following materials: tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, triethyl benzyl ammonium chloride and cetyl trimethyl ammonium bromide has similar properties, It may be used as phase transfer catalyst the condensation reaction.

[0057] 在所述缩合反应和甲胺基化反应中,所述碳酸钠缚酸剂的作用是中和反应生成的氯化氢。 [0057] In the condensation reaction and the reaction of the amine A, the effect of sodium carbonate acid binding agent is hydrogen chloride generated in the neutralization reaction. 因此,所述的缚酸剂还可以为下列之一:碳酸钾,碳酸氢钾,碳酸氢钠,氢氧化钠和 Thus, the acid binding agent may also be one of the following: potassium carbonate, potassium bicarbonate, sodium bicarbonate, sodium hydroxide and

氢氧化钾。 Potassium hydroxide.

[0058] 所述缩合反应和甲胺基化反应经6批次中试,中试结果如下: [0058] The condensation reaction of the amine and the reaction was 6 A batch test, test results were as follows:

[0059] [0059]

Figure CN102816112BD00092

[0060] 由上表可知,缩合反应与甲胺基化反应一锅法制备烯啶虫胺的最高收率为86.8%,最低为84.1%,平均收率为85.5%,平均含量为97.3%。 [0060] The above table shows that the condensation reaction is reacted with methylamino Preparation pot nitenpyram highest yield of 86.8%, a minimum of 84.1%, and an average yield of 85.5%, an average content of 97.3%.

[0061] 以2-氯-5-氯甲基吡啶计,烯啶虫胺合成总收率为79%。 [0061] 2-chloro-5-chloromethyl-pyridine meter, nitenpyram overall synthesis yield was 79%.

Claims (2)

  1. 1.一种杀虫剂烯啶虫胺的制备方法,其特征在于其按以下合成工艺路线进行: (1)消除反应,以1,1,2-三氯乙烷为起始原料,与氢氧化钠溶液反应,于-15°c~100°C下进行消除反应,得到偏二氯乙烯,其反应方程式: A method of preparing an insecticide nitenpyram, characterized in that it is carried out according to the following synthesis routes: (1) elimination reaction to 1,1,2-trichloroethane as a starting material, hydrogen sodium hydroxide solution the reaction was carried out at -15 ° c ~ 100 ° C elimination reaction, to give vinylidene chloride, the reaction equation:
    Figure CN102816112BC00021
    (2)硝化反应,所述的偏二氯乙烯在催化剂Al存在下,与盐酸和硝酸进行硝化反应,反应结束后经分离纯化得到1,1,1-三氯-2-硝基乙烷,其反应方程式: (2) the nitration reaction, the vinylidene chloride in the presence of a catalyst Al, nitrification reaction with nitric acid and hydrochloric acid, to give 1,1,1-trichloro-2-nitroethane was isolated and purified after the reaction, reaction equation:
    Figure CN102816112BC00022
    所述的催化剂Al为下列之一:①ZSM25分子筛,②β2沸石分子筛,③SAP0211分子筛,④NH4Y型分子筛,⑤ReY分子筛,⑥SSY分子筛; (3)N-乙基化反应,以2-氯-5-氯甲基吡啶起始原料,以水做溶剂,在-10~50°C下,与乙胺在相转移催化剂A2的作用下反应,反应产物经过脱溶,碱洗,蒸馏得到所述的中间体N-乙基-2-氯-5-吡啶甲基胺,其反应方程式: Al catalyst according to one of the following: ①ZSM25 molecular sieves, ②β2 zeolite molecular sieve, ③SAP0211 sieve, ④NH4Y zeolite, ⑤ReY sieve, ⑥SSY sieve; (3) N- ethyl reaction with 2-chloro-5-chloromethyl- pyridine starting materials, water as solvent, at -10 ~ 50 ° C, and triethylamine phase transfer catalyst under reaction A2, the reaction product was desolventized, alkali washing, distillation of the intermediate N- ethyl-2-chloro-5-pyridyl methyl amine, reaction equation:
    Figure CN102816112BC00023
    所述的催化剂A2为下列之一:①四甲基氢氧化铵、②四乙基氢氧化铵,③三甲基苄基氢氧化铵,④三乙基苄基氯化铵,⑤四丁基溴化铵,⑥十六烷基三甲基溴化铵; (4)缩合反应,所述的N-乙基-2-氯-5-吡啶甲基胺与所述的I,I,1-三氯-2-硝基乙烷在二氯甲烷溶剂中,加入缚酸剂,在相转移催化剂A3作用下,-10~50°C下,反应得到缩合物1-氯-N- {(6-氯吡啶-3-)甲基} -N-乙基-2-硝基乙烯胺,其反应方程式: The catalyst A2 is one of the following: ① tetramethylammonium hydroxide, tetraethylammonium hydroxide ②, ③ ammonium hydroxide, trimethylbenzylammonium, triethylbenzylammonium chloride ④, ⑤ tetrabutylammonium ammonium bromide, ⑥ cetyl trimethyl ammonium bromide; (4) condensation reaction of the ethyl-2-chloro-5-pyridin-N- methylamine with said I, I, 1- trichloro-2-nitroethane in a methylene chloride solvent, acid binding agent is added, the effect of the A3 phase transfer catalyst, at -10 ~ 50 ° C, a condensate obtained by reacting 1-chloro -N- {(6 - pyridin-3-chloro) methyl} -N- ethyl-2-nitroethylene-amine, reaction equation:
    Figure CN102816112BC00024
    所述的催化剂A3为下列之一:①四甲基氢氧化铵,②四乙基氢氧化铵、③三甲基苄基氢氧化铵,④三乙基苄基氯化铵,⑤四丁基溴化铵,⑥十六烷基三甲基溴化铵; 所述的缚酸剂为下列之一:①Na2CO3,②K2CO3,③NaHCO3,④KHCO3,⑤NaOH,⑥KOH ; (5)甲胺基化反应,所述甲胺基化反应与所述的缩合反应在同一反应锅中进行,在所述缩合反应完成后,得到缩合物1-氯-N-{(6-氯吡卩定-3-)甲基}-N_乙基-2-硝基乙烯胺,随后在-10~50°C下,滴加甲胺水溶液,反应产物经萃取、脱溶、重结晶得到烯啶虫胺,其反应方程式: The catalyst A3 is one of the following: ① tetramethylammonium hydroxide, tetraethylammonium hydroxide ②, ③ ammonium hydroxide, trimethylbenzylammonium, triethylbenzylammonium chloride ④, ⑤ tetrabutylammonium ammonium bromide, ⑥ cetyl trimethyl ammonium bromide; acid binding agent according to one of the following: ①Na2CO3, ②K2CO3, ③NaHCO3, ④KHCO3, ⑤NaOH, ⑥KOH; (5) methylamino reaction, the a group of reaction with said condensation reaction is carried out in the same reaction pot, after completion of the condensation reaction to give a condensate of 1-chloro -N - {(6- chloro-pyridine -3- given Jie) methyl} -N_ ethyl-2-nitro-vinylamine, and then at -10 ~ 50 ° C, aqueous methylamine was added dropwise, the reaction product was extracted, desolventized, recrystallized nitenpyram, reaction equation:
    Figure CN102816112BC00031
  2. 2.根据权利要求1所述的一种杀虫剂烯啶虫胺的制备方法,其特征在于所述硝化反应按以下步骤进行:在2000L的搪瓷反应釜中,加入412.5Kg31%所述工业盐酸、324Kg68%所述工业浓硝酸和7.5kg所述SAP0-211分子筛催化剂Al,剧烈搅拌下,控制好反应温度,5~6小时内,均匀滴入所述偏二氯乙烯315Kg ;滴毕,继续保温反应3小时;反应结束,静置分层,取下层油层,用300Kg水洗涤一次,得到534Kgl,l,l-三氯_2_硝基乙烷,含量≥90%,收率≥85%以上; 所述N-乙基化反应按以下步骤进行:在2000L的搪瓷反应釜中,以水做溶剂,加入289.2Kg70%的所述乙胺水溶液、5Kg的所述四丁基溴化铵催化剂A2,搅拌,调节好反应的温度,缓慢将304.5Kg95.9%的所述2-氯_5_氯甲基吡啶加入反应釜,控制好温度,加毕,继续保温反应I小时;反应结束,蒸馏回收过量的乙胺水溶液,加入30%的氢氧化钠溶液240Kg,静 The method for preparing a pesticide nitenpyram according to claim 1, characterized in that the nitration reaction is carried out according to the following steps: 2000L enamel reactor was added the 412.5Kg31% industrial hydrochloric acid the industrial 324Kg68% concentrated nitric acid and 7.5kg of the molecular sieve catalyst SAP0-211 Al, under vigorous stirring, control the reaction temperature within 5 to 6 hours, the uniformly added dropwise 315 kg vinylidene chloride; dropwise, continued incubated for 3 hours; the reaction was completed, standing stratified reservoir and the lower layer washed once with water 300Kg give 534Kgl, l, l- trichloro _2_ nitroethane, content ≥90%, ≥85% yield above; the N- ethylation reaction is carried out as follows: in the 2000L enamel reactor, with water as solvent, was added an aqueous solution of the amine of 289.2Kg70%, 5Kg of the tetrabutylammonium bromide catalyst A2, stirring, adjusting the temperature of the reaction well, the slowly 304.5Kg95.9% of 2-chloro-chloromethylpyridine _5_ added to the kettle, controlling the temperature, plus complete, incubation was continued for I hr reaction; the reaction was completed, recovered by distillation of excess ethylamine aqueous solution, 30% sodium hydroxide solution 240Kg, static 置分层,取油层,得到318Kg N-乙基_2_氯-5-吡啶甲基胺粗品,含量≥95%;减压蒸馏,取馏分162~164°C / -0.095Mpa,得到浅黄色液体285Kg,含量≥99%。 For delamination, from the oil obtained 318Kg N- chloro-5-ethyl-picolylamine _2_ crude content ≥95%; distillation under reduced pressure, taken fraction 162 ~ 164 ° C / -0.095Mpa, to give a pale yellow liquid 285Kg, the content of ≥99%.
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