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四丁基溴化铵相转移催化中间体2-甲基-2-(4-吗啉基)-1-(4-氯苯基)-1-丙酮(Ⅳ)与质量分数为20%的甲硫醇钠水溶液的芳甲硫醚化反应合成光引发剂2-甲基-1-[4-(甲硫基)苯基)-2-(4-吗啉基)-1-丙酮(TPMK)是目前TPMK合成工艺中的关键反应步骤，但在该反应中存在相转移催化效率不稳定、四丁基溴化铵耗量大、后处理中因四丁基溴化铵回收难度大导致的生产废水中含大量季铵盐类有机污染物、废水处理费用增加以及对TPMK产品纯度的影响等问题。为了克服这些弊端，偶极非质子溶剂N-甲基吡咯烷酮(NMP)和二甲亚砜(DMSO)被筛选出来取代四丁基溴化铵而介入该反应中，增强反应介质对阴离子CH_3S~-亲核试剂的去溶剂化效应、促成中间体Ⅳ分别在NMP-H_2O和DMSO-H_2O中与甲硫醇钠的高效芳甲硫醚化反应合成光引发剂TPMK。在优化反应条件基础上，获得了不采用催化剂、中间体Ⅳ与甲硫醇钠芳甲硫醚化反应的最佳反应条件及结果参数为：水在反应介质NMP-H_2O和DMSO-H_2O中的体积分数φ(%)为28%、甲硫醇钠相对于中间体Ⅳ的物质的量分数χ(%)为64%、反应温度为116～120℃,反应转化率在2 h内达100%,产物光引发剂TPMK的收率达97%,GC纯度达98.9%,为避免使用四丁基溴化铵、改进目前光引发剂TPMK合成工艺提供了科学依据。
Abstract：The key step in the current synthesis process of the photoinitiator, 1-(4-methylthiophenyl)-2-methyl-2-morpholinopropan-1-one(TPMK),is the aryl-methylthiolation of 1-(4-chlorophenyl)-2-methyl-2-morpholinopropan-1-one(Ⅳ) with aqueous solution of sodium methanethiolate with a mass fraction of 20% under liquid-liquid phase-transfer catalysis(PTC) catalyzed by tetrabutylammonium bromide.However, in this reaction, there are problems, such as the unstable phase transfer catalysis efficiency, the high consumption of tetrabutylammonium bromide with its difficulty in recovery, which lead to a large amount of quaternary ammonium salt as organic pollutants in the production wastewater with wastewater treatment costs increased as well as the side-effect on the purity of TPMK.In order to overcome these disadvantages, dipolar aprotic solvents, N-methylpyrrolidone(NMP) and dimethyl sulfoxide(DMSO) were selected to replace tetrabutylammonium bromide and introduced into in the reaction to enhance the desolvation effect of the reaction medium on anionic nucleophile CH_3S~- for prompting the higly efficient aryl-methylthiolation of intermediate Ⅳ with sodium methanethiolate in NMP-H_2O and DMSO-H_2O,respectively.Based on optimizing the reaction conditions, the reaction parameters for the higly efficient aryl-methylthiolation of intermediate Ⅳ with sodium methanethiolate without any catalyst were obtained as follows: the volume fraction of water in NMP-H_2O and DMSO-H_2O φ(%) as 28%,the substance fraction of sodium methanethiolate relative to intermediate Ⅳ χ(%) is 64%,the reaction temperature is 116～120 ℃,and the conversion of intermediate Ⅳ reached 100% within 2 h with the yield of the photoinitiator TPMK is 97% and the GC purity is 98.9%.It provided a scientific basis for avoiding the use of tetrabutylammonium bromide and improving the synthesis process of TPMK.
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基本信息:
DOI：10.13822/j.cnki.hxsj.2025.0010
中图分类号:TQ314.241;O621.256.4
引用信息:
[1]罗勇波,程格.高效芳甲硫醚化反应合成光引发剂TPMK[J].化学试剂,2025,47(06):97-102.DOI:10.13822/j.cnki.hxsj.2025.0010.
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