Study On Synthesis Of Alkyl Chlorides By Use Of Hydrochloride

Alkyl chlorides are important intermediates for organic chemical industry. A large number of drugs, pesticides, dyes and chemicals are made from alkyl chlorides. Preparation of alkyl chlorides by use of hydrochloride, not only made use of hydrochloride, but also obtained some important intermediates. On the basis of consulting a large of literatures and comparing the different routes synthesizing alkyl chlorides, the methods of preparing alkyl chlorides by chloridizing the corresponding alcohols were studied in this paper. The catalysts and the reaction conditions for the chloridizing were studied and optimized, which offered the fundamental datas to make synthesis process industrialization.A constant chloridizing apparatus was designed. The apparatus included separation system, distillation system, extraction system, adsorption system. As the difference between the characteristic of the reagent and product, had choosed the appropriate apparatus to chloridizing.By investigating the effects of the catalyst and other factors, The reaction conditions of chloriding butyl alcohol were studied. The optimized conditions were: 200mL butyl alchol, 20g strongly basic resin, 200mL 30% hydrochloride acid, in the self-prepared apparatus, hydrochloride was bubbled into the apparatus, after 7 hours, crude products was obtained, then by distillation, obtained the product which the purtity was 99.5%. The total yield was 81.8%. The catalyst was repeat used five times.By investigating the effects of the catalyst, water and other factors, The reaction conditions of chloriding 1-octanol were studied. The optimized conditions were: 100mL 1-octanol, 16g strongly basic resin and 1g phase transfer catalyst tetrabutyl ammonium bromide, 100 mL 30 % hydrochloride acid, in the self-prepared apparatus, hydrochloride was bubbled into the apparatus, after 6 hours, crude product was obtained. As the result of ASPEN simulated, the crude product couldn't be separatedby simple distillation, so had adopted two difference technology to deal with, one was be treated with sulfuric acid, the other was treated with thionyl chloride. The total yield respectively was 70.0%, 90.0%.By investigating the effects of the catalyst, reaction time, temperature and other factors, The reaction conditions of chloriding cyclohexanol were studied. The optimized conditions were: 100mL cyclohexanol, 16g strongly basic resin, 100mL 30% hydrochloride acid, at 80 ℃ , hydrochloride was bubbled into the apparatus, after 6 hours, crude product was obtained, then by distillation, obtained the product which the purtity was 99.5%. The total yield was 87.7%. The catalyst can be repeat used.By investigating the effects of the catalyst, temperature, time and other factors, the reaction conditions of chloriding tertiary butyl alcohol were studied. The optimized conditions were: 90mL butyl alchol, 10g strongly basic resin, 100mL 30% hydrochloride acid, at 20 ℃, hydrochloride was bubbled into the apparatus, after 8 hours, obtained the product which the purtity was 99.5%. The total yield was 78.1%. The catalyst can be repeat used.The technology studied in this paper, the material was easy to get, the yield was high, and the separating process was simple, which can be easy to bring into commercial process.