CN1915977A - 氯氟虫腈及其制备和用途 - Google Patents

氯氟虫腈及其制备和用途 Download PDF

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CN1915977A
CN1915977A CN 200510095913 CN200510095913A CN1915977A CN 1915977 A CN1915977 A CN 1915977A CN 200510095913 CN200510095913 CN 200510095913 CN 200510095913 A CN200510095913 A CN 200510095913A CN 1915977 A CN1915977 A CN 1915977A
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CN1915977B (zh
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李坚
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GUANGDONG LIWEI CHEMICAL INDUSTRY Co Ltd
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Abstract

本发明涉及一种氯氟虫腈及其制备方法和其在杀虫剂中的应用，氟虫腈原药经与三氯乙醛进行加成反应，生成新的低毒化农药氯氟虫腈。本发明提供的新化合物既保留原氟虫腈的杀虫活性和杀虫谱，又降低了原氟虫腈对鱼、虾等水生动物的高毒性，而且制备工艺简单，生产成本低于氟虫腈。

Description

氯氟虫腈及其制备和用途
                      技术领域
本发明涉及一种氯氟虫腈及其制备和用途，特别涉及一种原有的氟虫腈农药经与三氯乙醛进行加成反应，生成新的对鱼、虾等水生动物毒性较低的农药。
                      背景技术
氟虫腈是由法国罗纳——普朗克公司开发，现有许多公司正在生产的含氟吡唑类广谱性杀虫剂，又名锐劲特，其化学名称：5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑，结构式：
Figure A20051009591300031
相对分子量437.2
氟虫腈活性高，应用范围广，对半翅目、缨翅目、鞘翅目、鳞翅目等害虫及菊酯类、氨基甲酸酯类杀虫剂已产生抗性的害虫显示极高敏感性。可用于水稻、棉花、蔬菜、大豆、油菜、烟叶、马铃薯、茶叶、高粱、玉米、果树、森林、公共卫生、畜牧业等，是今后中国农药工业重点发展的杀虫剂品种。但是，该品种也存在着2个主要的缺点：(1)生产成本相对较高；(2)尤其是对鱼、虾等水生动物毒性很高，易造成对鱼、虾等水生动物的药害，一定程度限止了氟虫腈的应用和发展。
                      发明内容
本发明的目的是提供一种新的化合物，既可完整保留氟虫腈分子结构，又因为通过进一步的化学反应，合成出的新化合物氯氟虫腈基本保留原有氟虫腈的杀虫活性和杀虫谱，且降低了生产成本，尤其是降低了原有氟虫腈对鱼、虾等水生动物的高毒性。
氯氟虫腈具有下列结构：
相对分子量：584.5
产品中还含有少量下列结构式的化合物：
Figure A20051009591300042
相对分子量：566.5
化学反应方程式如下：
Figure A20051009591300043
将原料氟虫腈和三氯乙醛一次性投入反应瓶中，慢慢升至迴流温度，搅拌反应36小时，在0℃结晶48小时，过滤、烘干制得上述两种化合物的混合物，然后通过重结晶分离两种化合物。
化合物I和化合物II都可用作于杀虫剂。
本发明提供的化合物比原有氟虫腈的生产成本降低15％以上。一般说来，以氟虫腈为原料制成的新的氟虫腈衍生物，其生产成本高于原料氟虫腈，但是选用三氯乙醛为原料与氟虫腈加成反应合成出的氯氟虫腈，有三个特点：a)原子利用率为100％，不产生新的废水、废气、废渣；b)反应收率≥98％，工艺过程十分简单；c)氯氟虫腈的分子量比氟虫腈的分子量大25％。此三个特点的组合，使氯氟虫腈的生产成本低于氟虫腈。
本发明提供的化合物基本上保留了原有氟虫腈的杀虫谱和杀虫活性。
                氯氟虫腈对菜青虫生物活性测定结果
  药剂名称   倍数(ppm)   总虫数(头)   死虫数(头)   死亡率
  氯氟虫腈   20   30   30   100.0
  4   30   30   100.0
  0.8   30   29   98.0
  0.16   30   23   76.6
  0.04   30   3   10.0
  氟虫腈   4   30   30   100.0
  0.16   30   30   100.0
  0.04   30   14   46.7
  CK   30   0   0.0
                      氟虫腈对二化螟生物活性测定结果
  药剂名称  倍数(ppm)   总虫数(头)   死虫数(头)   死亡率(％)
氯氟虫腈   10   30   30   100.0
  2   30   30   100.0
  0.4   30   22   73.3
  0.08   30   3   10.0
  氟虫腈   2   30   30   100.0
  0.4   30   30   100.0
  0.08   30   14   46.7
  CK   30   0   0.0
以上试验的菜青虫为三龄幼虫，二化螟为二龄幼虫，菜青虫采用甘兰叶浸药饲喂法，计算72小时死亡率；二化螟采用试管稻苗浸药法，计算72小时死亡率。
本发明提供的化合物降低了氟虫腈的毒性，尤其是降低了氟虫腈对鱼、虾等水生动物的高毒性。
氯氟虫腈原药径口、经皮试验为低毒，急性经口LD50为雄性大鼠大于506mg/kg，雌性大鼠大于502mg/kg，经皮LD50大于2050mg/L；对斑马鱼为中低毒，鱼毒LD50(96小时)：6.76mg/L；试验显示，氯氟虫腈对鳞翅目等多种害虫具有较高的活性，特别是对水稻、蔬菜等方面的害虫活性呈现了与氟虫腈相当的效力，氯氟虫腈对鱼的毒性为中低毒级，这为其在水稻、蔬菜等作物上的应用，开辟了更广阔的空间。
                      具体实施方式
将100克含量为95％的氟虫腈原药投入500ml三口烧瓶中，加入400ml含量为96％的三氯乙醛，启动搅拌，缓缓升温至迴流温度98℃，连续搅拌反应36小时，降温至0℃，结晶48小时，过滤、烘干，得氯氟虫腈固体107克，产品为混合物，其中(I)化合物92％，(II)化合物4％，总含量≥96％，然后将过滤母液蒸去三氯乙醛，烘干，又得氯氟虫腈固体25克，产品为混合物，含(I)化合物86％，(II)化合物6％，总含量≥92％，分子收率大于98％。

Claims (4)

1、氯氟虫腈是具有下列结构的化合物：
Figure A2005100959130002C1
2、根据权利要求1所述化合物的制备方法，其特征于：选用三氯乙醛与氟虫腈原药进行加成反应。
3、以权利要求1中(I)化合物或(II)化合物为活性成分的杀虫剂，其特征在于该杀虫剂中含有(I)化合物或(II)化合物。
4、根据权利要求1所述化合物的可直接用作于杀虫剂。
CN2005100959137A 2005-08-18 2005-08-18 氯氟虫腈及其制备和用途 Expired - Fee Related CN1915977B (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206184A (zh) * 2010-03-29 2011-10-05 南开大学 3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑衍生物杀虫剂

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1204123C (zh) * 2002-07-30 2005-06-01 王正权 N－苯基吡唑衍生物杀虫剂

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206184A (zh) * 2010-03-29 2011-10-05 南开大学 3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑衍生物杀虫剂
WO2011120312A1 (zh) * 2010-03-29 2011-10-06 南开大学 3-氰基-1-(2,6-二氯-4-三氟甲基苯基)吡唑衍生物杀虫剂
CN102206184B (zh) * 2010-03-29 2013-07-10 南开大学 3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑衍生物杀虫剂

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