Friedel-Crafts酰基化反应合成α-氯代芳香酮类化合物
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摘要
2`-氯苯乙酮及它的衍生物是一种重要的有机合成中间体，在医药、农药、塑料、液晶等工业生产上有着重要的应用。苯乙酮衍生物的不对称还原合成手性醇，制备手性药物是现在研究的热点。Friedel-Crafts酰基化反应是一类重要的基础有机反应，是合成芳香酮的主要反应。本论文研究的目的就是为实验室制备2`-氯苯乙酮及它的衍生物，作为进行手性拆分研究的底物。
首先以氯苯为反应物研究了合成单取代2`-氯苯乙酮衍生物的各种反应条件，并得到了优化的反应条件和工艺：无水三氯化铝作催化剂；溶剂为二硫化碳；温度为15-20℃；物料配比:n(无水三氯化铝):n(氯乙酰氯):n(氯苯)=1.8:1.2:1.0；反应时间为4h。在优化的反应条件和工艺下合成了以下芳香酮：2`-氯苯乙酮、2`-氯-4-氟苯乙酮、2`,4-二氯苯乙酮、2`-氯4-溴苯乙酮、2`-氯-4甲基苯乙酮、2`-氯-4-乙基苯乙酮、2`-氯-4-甲氧基苯乙酮、2`-氯-4-苯基苯乙酮。
以间二氯苯为反应物研究了合成双取代2`-氯苯乙酮衍生物的各种反应条件，并得到了优化的反应条件和工艺：无水三氯化铝作催化剂；反应温度为50-55℃；物料配比为n(氯乙酰氯)／n(间二氯苯)=1.2，n(无水三氯化铝)／n(间二氯苯)=1.7；反应时间为4h。在优化的反应条件和工艺下合成了以下芳香酮：2`-氯-2,4-二氟苯乙酮、2`,2,4-三氯苯乙酮、2`-氯-2,4-二甲基苯乙酮、2`,3,4-三氯苯乙酮、2`-氯-3,4-二甲基苯乙酮。
此外还合成了3-氯-1-苯丙酮和3-氯-1-(α-噻吩)丙酮，获得了高纯度产物和，收率也很高，其中3-氯-1-苯丙酮经不对称还原得到的R-3-氯-1-苯丙醇是合成R-托莫西汀的起始原料，S-3-氯-1-苯丙醇是合成S-氟西汀的起始原料，3-氯-1-(α-噻吩)丙酮是合成度洛西汀的起始原料。
所有合成产物都进行了红外谱图的结构鉴定并的大了确认，并且测定了熔点和溶解性。
2-chloroacetophenone and its derivatives are important intermediates in organic synthesis, applied in various areas of the fine chemical industry, such as pharmaceutical, pesticide, plastic, liquid crystals. Asymmetric reduction of acetophenone derivatives preparing chiral aromatic alcohol has become a new focus of study. Friedel-Crafts acylation is important and fundamental organic reactions for preparing aromatic ketones. The aim of this work is to prepare 2-chloroacetophenone derivatives.
Studying acylation of chlorobenzene preparing 2,4-dichloroacetophenone, an optimum processing condition of the synthesis of mono-substituted 2 -acetophenone derivatives was obtained. By the reaction of mono-substituted benzene, chloroacetyl chloride and aluminum chloride anhydrous in mole ratio of 1:1.2:1.8 with carbon disulfide as solvent at 15-20℃ for about 4h, we prepared 2-chloroacetophenone, 2-chloro-4-fluroacetophenone, 2 ,4-dichloroacetophenone, 2 -chloro-4-bromoaceto-phenone, 2-chloro-4-methylacetophenone, 2-chloro-4-ethylacetophenone, 2-chlo-ro-4-methoxyacetophenone, 2 -chloro-4-phenylacetophenone.
Studying acylation of 1,3-dichlorobenzene preparing 2,2,4-trichloro-acetophenone, an optimum processing condition of the synthesis of di-substituted 2 -acetophenone derivatives was obtained. By the reaction of di-substituted benzene, chloroacetyl chloride and aluminium chloride anhydrous in mole ratio of 1:1.2:1.7 without solvent at 50-55℃ for about 4h, we prepared 2,2,4-trichloroacetophenone, 2 -chloro-2,4-difluroacetophenone, 2 ,3,4-trichloroacetophenone, 2 -chloro-2,4-dime-thylacetophenone, 2-chloro-3,4-dimethylacetophenone,.
3-chloro-l-phenylacetone and 3-chloro-l-(α -thiophene)acetone were prepared, The yield and the purity of the products were high.
All of these compounds were identified by IR, their melt point and solubility were measured.
首先以氯苯为反应物研究了合成单取代2`-氯苯乙酮衍生物的各种反应条件，并得到了优化的反应条件和工艺：无水三氯化铝作催化剂；溶剂为二硫化碳；温度为15-20℃；物料配比:n(无水三氯化铝):n(氯乙酰氯):n(氯苯)=1.8:1.2:1.0；反应时间为4h。在优化的反应条件和工艺下合成了以下芳香酮：2`-氯苯乙酮、2`-氯-4-氟苯乙酮、2`,4-二氯苯乙酮、2`-氯4-溴苯乙酮、2`-氯-4甲基苯乙酮、2`-氯-4-乙基苯乙酮、2`-氯-4-甲氧基苯乙酮、2`-氯-4-苯基苯乙酮。
以间二氯苯为反应物研究了合成双取代2`-氯苯乙酮衍生物的各种反应条件，并得到了优化的反应条件和工艺：无水三氯化铝作催化剂；反应温度为50-55℃；物料配比为n(氯乙酰氯)／n(间二氯苯)=1.2，n(无水三氯化铝)／n(间二氯苯)=1.7；反应时间为4h。在优化的反应条件和工艺下合成了以下芳香酮：2`-氯-2,4-二氟苯乙酮、2`,2,4-三氯苯乙酮、2`-氯-2,4-二甲基苯乙酮、2`,3,4-三氯苯乙酮、2`-氯-3,4-二甲基苯乙酮。
此外还合成了3-氯-1-苯丙酮和3-氯-1-(α-噻吩)丙酮，获得了高纯度产物和，收率也很高，其中3-氯-1-苯丙酮经不对称还原得到的R-3-氯-1-苯丙醇是合成R-托莫西汀的起始原料，S-3-氯-1-苯丙醇是合成S-氟西汀的起始原料，3-氯-1-(α-噻吩)丙酮是合成度洛西汀的起始原料。
所有合成产物都进行了红外谱图的结构鉴定并的大了确认，并且测定了熔点和溶解性。
2-chloroacetophenone and its derivatives are important intermediates in organic synthesis, applied in various areas of the fine chemical industry, such as pharmaceutical, pesticide, plastic, liquid crystals. Asymmetric reduction of acetophenone derivatives preparing chiral aromatic alcohol has become a new focus of study. Friedel-Crafts acylation is important and fundamental organic reactions for preparing aromatic ketones. The aim of this work is to prepare 2-chloroacetophenone derivatives.
Studying acylation of chlorobenzene preparing 2,4-dichloroacetophenone, an optimum processing condition of the synthesis of mono-substituted 2 -acetophenone derivatives was obtained. By the reaction of mono-substituted benzene, chloroacetyl chloride and aluminum chloride anhydrous in mole ratio of 1:1.2:1.8 with carbon disulfide as solvent at 15-20℃ for about 4h, we prepared 2-chloroacetophenone, 2-chloro-4-fluroacetophenone, 2 ,4-dichloroacetophenone, 2 -chloro-4-bromoaceto-phenone, 2-chloro-4-methylacetophenone, 2-chloro-4-ethylacetophenone, 2-chlo-ro-4-methoxyacetophenone, 2 -chloro-4-phenylacetophenone.
Studying acylation of 1,3-dichlorobenzene preparing 2,2,4-trichloro-acetophenone, an optimum processing condition of the synthesis of di-substituted 2 -acetophenone derivatives was obtained. By the reaction of di-substituted benzene, chloroacetyl chloride and aluminium chloride anhydrous in mole ratio of 1:1.2:1.7 without solvent at 50-55℃ for about 4h, we prepared 2,2,4-trichloroacetophenone, 2 -chloro-2,4-difluroacetophenone, 2 ,3,4-trichloroacetophenone, 2 -chloro-2,4-dime-thylacetophenone, 2-chloro-3,4-dimethylacetophenone,.
3-chloro-l-phenylacetone and 3-chloro-l-(α -thiophene)acetone were prepared, The yield and the purity of the products were high.
All of these compounds were identified by IR, their melt point and solubility were measured.
引文
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