3-乙/芳酰乙酰基吲哚的水相合成

doi:10.6023/cjoc201904002

摘要/Abstract

探讨了4-十二烷基苯磺酸（DBSA）催化的β-乙硫基-β-吲哚基-α，β-不饱和酮（1）的水相水解反应，实现了3-乙/芳酰乙酰基吲哚（2）的水相合成.研究表明，在回流和10 mol% DBSA存在下，1有效地发生水相水解反应，高产率合成产物2.

关键词: 水相反应, 水解反应, 3-乙酰乙酰基吲哚, β-乙硫基-β-吲哚基-α, β-不饱和酮

4-Dodecylbenzenesulfonic acid (DBSA) catalyzed hydrolysis reaction of β-ethylthio-β-indolyl-α, β-unsaturated ketones (1) in water to yield 3-ethanoyl/aroylacetylindoles (2) was studied. It showed that the hydrolysis of 1 in water smoothly occurred in the presence of 10 mol% DBSA in reflux water, and 2 was obtained in excellent yield.

Key words: aqueous reaction, hydrolysis reaction, 3-acetoacetylindole, β-ethylthio-β-indolyl-α, β-unsaturated ketone

引用此文

胡小宇, 于海丰, 王文举, 姜思傲, 刘奇, 何洁. 3-乙/芳酰乙酰基吲哚的水相合成[J]. 有机化学, 2019, 39(11): 3183-3189.

Hu Xiaoyu, Yu Haifeng, Wang Wenju, Jiang Siao, Liu Qi, He Jie. Synthesis of 3-Ethanoyl/Aroylacetylindoles in Water[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3183-3189.

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图/表 6


Entry	DBSA/mol%	T/℃	Time/h	Yield^b/%
1	0	Reflux	20	0
2	20	Reflux	6	95
3	15	Reflux	8	94
4	10	Reflux	9	95
5	7.5	Reflux	15	90
6	7.5	Reflux	20	92
7	10	90	9	88
8	10	90	17	92

表 1. 反应条件优化a

Table 1. Screening of reaction conditions

表 2. 2的水相合成a

Table 1. Synthesis of 2 in water

图 1. 烯醇式结构2

Figure 1. Proposed enol structures of 2

图 2. 在B3LYP-D3/6-31G*水平下优化得到的2hA~2lB分子的几何结构

Figure 2. Optimized geometric structures of the 2hA~2lB based on B3LYP-D3/6-31G * level

Item	Single-point energy/eV	Free energy/Hartree
2hA	－19273.19	－708.09621
2hB	－19273.28	－708.09695
2lA	－24489.64	－899.74782
2lB	－24489.69	－899.75220

表 3. 在M06-2x/6-311G*水平下计算的2hA~2lB分子的能量

Table 3. Calculated energies of 2hA~2lB based on M06-2x/6- 311G* level

Run	t/h	Yield/%
1	10	94
2	13	92
3	20	83
4	30	70

表 4. 水循环实验

Table 4. Cycle experiment of water

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