Synthesis Of Isonitriles And Amination-Aromatization Of 2-Cyclohexenones Promoted By Molecular Iodine

The paper consists of two parts, the first part is the method to preparate isocyanide using triphenyl phosphine with iodine. Many marine natural products contain Isocyanide radicals. Isocyanide is able to involve in a number of important reactions, like multicomponent reactions, metal-catalyzed isocyanide insertions and polymerizations and so on. Isocyanide is therefore a very important class of compounds in organic chemistry. There are many methods for preparation isocyanide, the most widely used is the dehydration of substituted formamide. Traditional dehydrating agent have some disadvantages. Such as phosgene, expensive and toxic; Sulfuryl chloride, low toxicity, but these reagents are mainly used for dehydration of N-alkyl-substituted formamides rather than the N-aryl-substituted counterparts.; A system of phosphoryl trichloride/organic base is most common used. However, phosphoryl trichloride is known as one of specific controlled hazardous substances under a serial of legal regulations in China8 and Japan. Therefore, using accessible materials, gentle, low-toxicity method for preparing isocyanide is of great significance.we used triphenylphosphine and iodine as dehydrating agent, achieved better results. The system conditions are mild, convenient, efficient and cost-effective and can be adapted to the substrate containing acid or alkali-sensitive functional groups.The Second part is the direct amination/aromatization of 2-cyclohexenones promoted by iodine. Aromatic amine compounds is an important target molecules in organic synthesis, which are widely used in many fields, such as pharmaceuticals, pesticides, photographic, agricultural chemicals, paints, electronics materials and natural products. Many methods for synthesis the aromatic amines, such as: the reduction of Nitro, metal-catalyzed C-N coupling and Michael-addition reactions. But these methods are more or less inadequate: such as environmental pollution, producing a large amount of metal wastes or hazardous gases; Green synthesis typically require expensive metal catalysts or harsh reaction conditions, high cost; Substrate limitation, need electron-withdrawing group or a good leaving group. Therefore, the development of metal-free, convenient, efficient methods for aromatic amines are meaningful.In this paper we prepared amines through amination-aromatization with the easy getting cyclohexene-one in the presence of molecular iodine. It is a mild, metal-free preparation of aromatic amine method.