[(10-磺基-3-甲基-二苯基脲亚甲基)-三甲基]十二烷基苯磺酸铵的合成

Synthesis of [(10-Sulfonic group-3-methyl-biphenyl urea methano) trimethyl ammonium] Dodecyl Benzene Sulfonate

以邻甲基苯胺为原料 ,经氯甲基化 ,两次缩合 ,季铵化和复分解 5步反应合成了一种季铵盐型植物生长调节剂 :[(10 磺基 3 甲基 二苯基脲亚甲基 ) 三甲基 ]十二烷基苯磺酸铵。邻甲基苯胺在浓盐酸中用多聚甲醛进行氯甲基化 ,n(邻甲基苯胺 )∶n(多聚甲醛 ) =11∶30 ,在 5 0℃通入HCl气体 ,反应 6h ,得到 2 甲基 4 氯甲基苯胺 (Ⅰ ) ,产率 78%。中间产物Ⅰ与尿素溶于浓盐酸 ,在 96℃反应 2h ,得到淡黄绿色反应液 (Ⅱ ) ,再将对 氨基苯磺酸直接加入Ⅱ中 ,在 12 0℃反应 3h ,得淡黄色晶体 (Ⅲ ) ,产率 2 5 %。然后将Ⅲ用少量盐酸溶解 ,在 6 0℃滴加质量分数为 30 %的三甲胺水溶液 ,当 pH =6时 ,再升温 70℃ ,反应 2h ,得到 [(10 磺基 3 甲基 二苯脲亚甲基 ) 三甲基 ]氯化铵 (Ⅳ ) ,产率 92 %。中间产物Ⅳ与十二烷基苯磺酸钠 (LAS)以n(Ⅳ )∶n(LAS) =1∶1的量比溶于水中 ,在 96℃反应 1h ,得到最终产物 (Ⅴ ) ,产率 90 %。用w(Ⅴ ) =0 0 2 %的水溶液喷施小麦 1次 ,使小麦增产 4 %。

Sulfonic group 3 methyl biphenyl urea methano) trimethyl ammonium] dodecyl benzene sulfonate used as a plant growth regulator was synthesized by five steps reaction.The chloromethylation of ο methylaniline with paraformaldehyde in conc.hydrochloric acid in mole ratio n(ο methylaniline)∶ n (paraformaldehyde)=11∶30 was proceeded.Gaseous HCl was passed in at 50 ℃ for 6 h to get 2 methyl 4 chloromethylaniline(Ⅰ) in 78% yield.The intemediate (Ⅰ) reacted with urea in hydrochloric acid at 96 ℃ for 2 h and p aminobenzene monosulfonic acid was added in it,at 120 ℃ reacted for 3 h to get 2 methyl 4 chloromethyl 4′ sulfonic group biphenyl (Ⅲ),in 25% yield.Then aqueous trimethylamine was dropped at 60 ℃ and reacted for 2 h to get [(10 sulfonic group 3 methyl biphenyl urea methano)trimethyl ammonium] chloride(Ⅳ),in 92% yield.The intermediate(Ⅳ) reacted with sodium dodecyl benzene sulfonate(LAS) in mole ratio n (Ⅳ)∶ n (LAS)=1∶1 at 96 ℃ for 1 h to get [(10 sulfonic group 3 methyl biphenyl urea methano)trimethyl ammonium] dodecyl benzene sulfonate(Ⅴ), in 90%yield.By spraying once 0.02% aqueous solution of (Ⅴ),the yield of wheat was increased by 4%.