Preliminary Studies On The Conversion Of Benzyl Alcohols Into Benzyl Chlorides Using TCT Catalyzed By DMSO

In this paper, a mild and effective procedure for converting benzyl and allyl alcohols into the corresponding chlorides was reported. The chlorination reagent was 2,4,6-trichloro[1,3,5]triazine (TCT) and the catalyst was DMSO. The reaction is high-yielding (87%～100%), the reaction time short (1.0～3.5h) and the reaction conditions mild (20～82℃). Anhydrous acetonitrile was used as solvent. The reaction conditions were optimized according to different alcohols. When the substrates were benzyl alcohols and allylic alcohols, the reaction went smoothly at room temperature. When the substrate was 2,6-dichlorophenylmethanol, the reaction was carried out at reflux temperature. To probe the mechanism of the reaction, we used optical active alcohols as starting materials. Configuration invertions were observed in the chlorination. In addition, KI, NaN3 and tetrabutylammoniun bromide were added respectively in order to probe the reaction mechanism. The structures of the products were fully characterized by IR, 1HNMR, GC and GC-MS.A possible mechanism for the reaction was proposed and further experiments need to be carried out.