A method for the synthesis of substituted benzoylurea insect growth regulator, which comprises the following steps: 1) fluoride: two chlorobenzonitrile 1M, 450 - 1.5 ~ 550 orders of anhydrous potassium fluoride mixture of 2.0M, solvent, A catalyst in the reaction kettle, heating at 200 DEG C for 8 to 10 hours, filtering, will the filtrate obtained two Fluorobenzonitrile fractionation, and recovering solvent; the solvent sulfolane; the catalyst is a mixture of four A Butyl Ammonium Chloride and three methyl octyl ammonium chloride, wherein four Butyl Ammonium Chloride the weight percentage is 40 ~ 60wt%; the dosage of catalyst A two chlorobenzonitrile weight 1 ~ 3wt%; 2) hydrolysis: Step 1) obtained two Fluorobenzonitrile 1M, B catalyst into reactor, Stirring drops in excess of hydrogen peroxide, reaction temperature maintained at 40 degrees, after finishing dropping, and then maintained at this temperature for 1 hours, the negative pressure to exclude the unreacted hydrogen peroxide, centrifuge dry reactants, get two fluorobenzamide cake; the catalyst B for sodium hydroxide, sodium carbonate, sodium bicarbonate or in a or in the weight ratio of 1 to 1 of the two; the catalyst dosage is two B Fluorobenzonitrile weight 1 ~ 3wt%; 3) 2) two steps: esterification fluorobenzamide cake was dissolved in a solvent, with excessive phosgene, heated to reflux for 4 hours, the two generation of benzoyl fluorobenzene isocyanate; the obtained product can be directly used without purification of the next step; the solvent is toluene; 4) plus: Step 3) obtained two fliurobenzoyloxy Lsocyanate soluble in toluene, aniline, and substituted catalyst C added Moore, at 100 to 110 DEG C 4 ~ 6 hours, which substituted benzoylurea insect growth regulator; the substituted aniline as 4 chloro aniline, 3 - two, 5 chloro - 4 - (1, 1. 2, 2 - four f) ethoxy aniline or 4 - (2 - 4 - three chlorine fluoride methylphenoxy) - 2 - Fluoroaniline; the catalyst is three C triethylamine or / and triethanolamine; the catalyst dosage is two C fliurobenzoyloxy lsocyanate weight 1 ~ 3wt%.
【技术实现步骤摘要】
本专利技术涉及一种取代苯甲酰脲类昆虫生长调节剂的合成方法,具体的说是涉及氟铃脲、氟虫脲和除虫脲的合成方法。
技术介绍
苯甲酰基脲类化合物是通过抑制昆虫几丁质的合成来起作用的一类有效的杀虫杀螨剂,或称之为昆虫生长调节剂。其中最为常见的有美国DOW ELAN公司在1987年开发的氟铃脲(hexaflumuron)、氟虫脲、除虫脲等。这类化合物的合成大多是以2,6-二氟苯甲腈为起始原料,经氟化、水解酯化、加成而得到取代苯甲酰脲类化合物,如其反应式如下1)氟化 2)水解 3)酯化 4)加成 其中, 于登博等人在农药vol.39 No.3 2000中所述的除虫脲的合成,即是采用上述方法制得。但是此法的步骤2)的水解是采用90%的浓硫酸,因而对反应设备要求苛刻,需防酸材质所制备,潜在的危险性较大;步骤3)的酯化是使用草酰氯,成本高;得到的产物需分离提纯,步骤繁琐。对于步骤1),CN85100467A中公开了由氯代苯腈制备氟代苯腈的方法,虽然较一般方法提高了产率,可以达到86%,但仍不是很高;而且该法使用全氟烷基氧杂羧酸衍生物作为催化剂,这类开环醚类的催化剂的制备繁琐,不利于工业生产。对于步骤3),赵永华在农药vol.40 No.11 2001中所述的氟铃脲的合成中,采用草酰氯将2,6-二氟苯甲酰胺酯化,此法成本高,得到的异酯在室温下不够稳定,为此,作者曾尝试使用便宜的光气代替草酰氯,但是反应难以进行。陈英奇在化学反应工程与工艺vol.10 No.1 1994.12中所述的氟虫脲的合成中,步骤3)的酯化是使用草酰氯,成本高;其使用二氯甲烷作为溶剂,使得到的产物——异酯为 ...
【技术保护点】
【技术特征摘要】
1.一种取代苯甲酰脲类昆虫生长调节剂的合成方法,其包括如下步骤1)氟化将二氯苯腈1M、450-550目无水氟化钾1.5~2.0M、溶剂、催化剂A的混合物在反应釜中,于200℃加热8~10小时,过滤,将滤液分馏,得到二氟苯腈,并回收溶剂;所述溶剂为环丁砜;所述催化剂A为四丁基氯化铵和甲基三辛基氯化铵的混合物,其中四丁基氯化铵所占重量百分比为40~60wt%;所述催化剂A用量为二氯苯腈重量的1~3wt%;2)水解将步骤1)得到的二氟苯腈1M、催化剂B加入反应釜中,边搅拌边滴入过量的过氧化氢,保持反应温度在40℃,滴加完毕后,再在此温度保持1小时,负压排除未反应的过氧化氢,离心机甩干反应物,得到二氟苯甲酰胺滤饼;所述催化剂B为氢氧化...
【专利技术属性】
技术研发人员:曾益良,宋建军,张平南,秦小薇,栗心贞,陈志祥,
申请(专利权)人:中国科学院动物研究所,
类型:发明
国别省市:
还没有人留言评论。发表了对其他浏览者有用的留言会获得科技券。