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首先以廉价易得的非金属硒作催化剂,CO替代剧毒光气作羰基化试剂,O2作氧化剂,通过硒催化苯胺与醇“一锅煮”的氧化羰基化反应制得苯氨基甲酸酯;然后在HCl/ZnCl_2催化下再与甲醛缩合制得二苯甲烷二氨基甲酸酯.两反应的目标产物收率从中等到良好,底物普遍适用性广.CO利用率及原子经济性高,且避免了剧毒光气的使用.催化剂硒具有相转移催化作用,便于回收且能循环使用.合成方法清洁、经济、高效.提出了可能的反应机理.
First, cheap and readily available non-metallic selenium as catalyst, CO instead of highly toxic phosgene for carbonylation reagent, O2 as an oxidant, selenium catalyzed aniline and alcohol “one-pot ” oxidative carbonylation reaction to obtain phenyl carbamate ; Then, it was condensed with formaldehyde under the HCl / ZnCl 2 catalysis to produce diphenylmethane dicarbamate. The yield of the target products of the two reactions was moderate to good, and the substrate was widely applicable. The CO utilization rate and atom economy were high, And avoids the use of highly poisonous phosgene.The catalyst selenium has the function of phase transfer catalysis, which is easy to recover and can be recycled, and the synthesis method is clean, economical and efficient, and the possible reaction mechanism is proposed.