Synthesis Of Non-chlorobenzyl Alcohol And Its Derivatives

Benzyl alcohol is an important synthetic pharmaceutical intermediates and fragrances, is widely used in cosmetics, dyeing, paints and inks and other fields. Nowadays benzyl alcohol was synthesized by the hydrolysis of benzyl chloride in the presence of alkali, but with trace chloride ion and impact the use of medicine. In this study, benzyl alcohol was synthesized by liquid phase oxidation of toluene without chloride ion. 4-((4-chlorobenzyl)oxy)-N,N-diethylbut-2-yn-1-amine such as benzyl alcohol derivative were useful synthons in organic synthesis, they were found in a wide range of medicines, natural products, organic materials. Research towards their synthetic has vital significance in organic synthesis.The detail of this thesis were listed as follows:In this study, toluene as the raw material, Ceric ammonium nitrate as the oxidizing agent, prepared by the oxidation reaction of the middle product benzyl acetate,then prepared by the hydrolysis of the target product, benzyl alcohol. The optimum conditions of benzyl acetate were: when toluene was 5 mmol, the solvent was glacial acetic acid, n(toluene) : n(sodium acetate) : n(Ceric ammonium nitrate) = 1:1:2, the amount of Ce O2 was 3% weight of toluene, the reaction temperature was 118 ℃, reaction time 10 h. In the above conditions, the product yield was 78.9%. The yield of benzyl alcohol from benzyl acetate via hydrolysis was 96%.The total yield of benzyl alcohol was 75.7%. The structure of benzyl acetate and benzyl alcohol was identified by IR, GC-MS and 1H NMR.4-chlorobenzyl propargyl ether was synthesized by etherification reaction. The optimum reaction conditions for synthesis of 4-chlorobenzyl propargyl ether were: when 4-Chlorobenzyl alcohol was 5 mmol, the amount of Tetrabutylammonium bromide was 15% weight of 4-Chlorobenzyl alcohol, n(4-Chlorobenzyl alcohol) : n(3-Bromo-1-propyne) = 1:1.1, the solvent was toluene and 20% aqueous sodium hydroxide, the reaction temperature was 50 ℃, reaction time 2 h. In the above conditions, the product yield was 98.4%. Phenyl propargyl ether 、 benzyl propargyl ether 、 3-methyl- phenyl propargyl ether 、2-prop-2-ynoxybenzaldehyde was synthesized by etherification reaction of phenol、benzyl alcohol 、 m-cresol 、 salicylaldehyde and 3-Bromo-1-propyne using the optimum reaction conditions of 4-chlorobenzyl propargyl ether. In the above conditions, the product yield was 99.2%、98.2%、97.3% and 95.7%.The structure of the product was identified by IR, GC-MS and 1H NMR.The whole process was not only short and efficient, but stable and easy to post-processing.The self-made 4-chlorobenzyl propargyl ether was used to synthesize the final product 4-((4-chlorobenzyl)oxy)-N,N-diethylbut-2-yn-1-amine through Mannich reaction. The structure of the product was identified by IR, GC-MS and 1H NMR. By single factor and orthogonal experiments, optimal reaction conditions were as follows: when4-chlorobenzyl propargyl ether was 1 mmol, n(4-chlorobenzyl propargyl ether) : n(paraformaldehyde) : n(triethylamine) =1:1:2,dioxane was the solvent, the amount of Cu Cl was 25% weight of 4-chlorobenzyl propargyl ether, the reaction temperature was 80 ℃, reaction time was 6 h. The yield of 4-((4-chlorobenzyl)oxy)-N,N-diethylbut-2-yn-1-amine was 75.6%.