5-氯-1-氧代-2,3-二氢茚-2-甲酸甲酯的合成研究

Synthesis of 5-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester

5-氯-1-氧代-2,3-二氢茚-2-甲酸甲酯(Ⅲ)是合成高效低毒杀虫剂茚虫威的关键中间体.本文对Ⅲ的合成方法进行了改进,以氯苯为起始原料,在无水三氯化铝催化下,与3-氯丙酰氯发生傅克酰基化反应制得3,4'-二氯苯丙酮(Ⅰ),Ⅰ在浓硫酸作用下环合制得5-氯-2,3-二氢-1-茚酮(Ⅱ),Ⅱ与氢化钠和碳酸二甲酯缩合制得Ⅲ,总收率53%.其化学结构通过1HNMR得到确证.Ⅱ的不加入惰性溶剂方法减小了反应釜体积,降低了设备成本.Ⅲ采用重结晶提纯方法相比柱色谱分离更适合工业化生产.

5-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester（Ⅲ） is the key intermediate of pesticide Indoxacarb.An improved method for synthesis of Ⅲ was introduced.3,4＇-dichloropropiophenone was preparated by reation of 3-chloropropionyl chloride with chlorobenzene in the aluminium chloride catalyst.Subsequently,3,4＇-dichloropropiophenone reacted with sulfuric acid to form 5-chloro-2,3-dihydro-1H-inden-1-one.The 5-chloro-2,3-dihy dro-1-oxo-1H-indene-2-carboxylic acid methyl ester was obtained finally by reaction of 5-chloro-2,3-dihydro-1H-inden-1-one with dimethyl carbonate and sodium hydride.The target compound could be obtained in 53% yield.The product was confirmed by1HNMR.Removing inert solvent method of Ⅱreduced the reaction kettle volume and equipment cost.We argue that the recrystallization method of Ⅲ is more suitable than column chromatography separation for industrial production.