对氯苯甲醇绿色催化氧化合成对氯苯甲醛
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山东省自然科学青年基金(No. ZR2020QB168)


Green catalytic oxidation of p-chlorobenzyl alcohol to p-chlorobenzaldehyde
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    摘要:

    介绍了一种重要精细化工中间体对氯苯甲醛的绿色合成方法。以对氯苯甲醇为原料,过氧化氢作氧化剂,铜盐作催化剂,通过催化氧化合成对氯苯甲醛。分别考察了铜盐种类及用量、过氧化氢用量及滴加时长和反应温度对收率的影响。得到最佳反应条件为:乙酸铜作催化剂,投料摩尔比n(乙酸铜)∶n(对氯苯甲醇)∶n(过氧化氢) = 1∶100∶300,水作溶剂,96 ℃反应2 h后,转化率为93.1%,生成对氯苯甲醛的选择性为97.7%,最终收率高达91.0%。将含催化剂水相进行循环利用,发现循环5次后,对氯苯甲醛的收率仍可达85%以上。该方法氧化剂绿色环保,催化剂及溶剂可多次循环利用,且不产生废酸,适用于工业生产。

    Abstract:

    A green synthesis method of p-chlorobenzaldehyde, an important fine chemical intermediate, was reported. p-Chlorobenzaldehyde was achieved through the catalytic oxidation of p-chlorobenzyl alcohol. Hydrogen peroxide and copper salt were used as oxidant and catalyst, respectively. The effects of the type and amount of copper salt, the amount of hydrogen peroxide, the dropping time and the reaction temperature on the yield of p-chlorobenzaldehyde were investigated. The optimum reaction conditions were obtained as follows: copper acetate was used as the catalyst, n[Cu(OAc)2] : n(p-chlorobenzyl alcohol) : n(H2O2) = 1 : 100 : 300, water as the solvent, reaction temperature and time were 96 ℃ and 2 h, respectively. The conversion rate was 93.1%, the selectivity for generating p-chlorobenzaldehyde was 97.7%, and the yield was up to 91.0%. The catalyst-containing water phase was recycled, and the yield could still reach above 85% after 5 cycles. The method has the advantages of green and environmentally friendly oxidant, recyclable catalyst and solvent, no waste acid production, which is suitable for industrial production.

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杨丰科,袁世申,张永富,牛鹏程,茹雨晴,高巍伟.对氯苯甲醇绿色催化氧化合成对氯苯甲醛[J].精细化工,2022,39(3):0

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  • 收稿日期:2021-08-25
  • 最后修改日期:2021-11-03
  • 录用日期:2021-11-08
  • 在线发布日期: 2022-01-11
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