氨基醇杂多酸类离子液体催化环酮的Baeyer-Villiger氧化反应

doi:10.7503/cjcu20190618

摘要/Abstract

摘要：

合成了一系列氨基醇杂多酸类离子液体, 并将其用于催化环酮的Baeyer-Villiger氧化反应. 以2-庚基环戊酮为模板底物, H₂O₂为氧化剂, 探究了此类氨基醇杂多酸类离子液体的催化活性, 筛选出催化活性最高的催化剂为[Pro-ps]H₂PW₁₂O₄₀, 最佳反应条件: n(2-庚基环戊酮)∶n(催化剂)∶n(H₂O₂)=1∶0.03∶4, 反应温度40 ℃, 反应时间8 h, 无溶剂. 在最佳条件下, 2-庚基环戊酮的转化率为98.19%, 产物δ-十二内酯的选择性可达82.84%. 水相中的离子液体[Pro-ps]H₂PW₁₂O₄₀经干燥后可以重复使用. 经过5次循环使用后催化活性未见明显下降. [Pro-ps]H₂PW₁₂O₄₀还可用于催化其它多种环酮的Baeyer-Villiger氧化反应, 结果表明, 该催化剂具有良好的重复使用性和底物普适性.

关键词: 氨基醇离子液体, 杂多酸, Baeyer-Villiger氧化, 环酮, 内酯

Abstract:

A series of amino alcohol heteropolyacid ionic liquids was synthesized and used to catalyze the Baeyer-Villiger oxidation of cycloketones. 2-Heptylcyclopentanone was used as a template substrate and H₂O₂ was used as an oxidant. The catalytic activity of such amino alcohol heteropoly acid ionic liquids was investigated. The catalyst with the highest catalytic activity was [Pro-ps]H₂PW₁₂O₄₀. The obtained optimum reaction conditions were n(2-heptylcyclopentanone)∶ n(catalyst)∶ n(H₂O₂)=1∶ 0.03 ∶ 4 at 40 ℃ for 8 h by solvent free. Under the optimum conditions, the conversion rate of 2-heptylcyclopentanone was 98.19%, and the selectivity of δ-dodelactone was up to 82.84%. After simple treatment, the ionic liquid [Pro-ps]H₂PW₁₂O₄₀ could be reused, and the catalytic activity did not decrease significantly after five cycles. [Pro-ps]H₂PW₁₂O₄₀ could also be used to catalyze the Baeyer-Villiger oxidation of various cyclic ketones. The results showed that the catalyst had good reusability and substrate adaptability.

Key words: Amino alcohol ionic liquid, Heteropoly acids, Baeyer-Villiger oxidation, Cyclic ketone, Lactone

中图分类号:

O643
O621

TrendMD:

高崇,于凤丽,解从霞,于世涛. 氨基醇杂多酸类离子液体催化环酮的Baeyer-Villiger氧化反应. 高等学校化学学报, 2020, 41(5): 1101.

GAO Chong,YU Fengli,XIE Congxia,YU Shitao. Baeyer-Villiger Oxidation of Cyclic Ketones Catalyzed by Amino Alcohol Heteropoly Acid Ionic Liquid ^†. Chem. J. Chinese Universities, 2020, 41(5): 1101.

图/表 9

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Entry	Catalyst	Acid strength^b/mV	Conversion(%)	Yield(%)	Selectivity(%)
1	—	—	1.18	—	—
2	Pro	—	1.51	—	—
3	[Pro-H]H₂PMo₁₂O₄₀	633	68.23	14.07	20.62
4	[Pro-H]H₃SiW₁₂O₄₀	680	85.31	45.74	53.62
5	[Pro-H]H₂PW₁₂O₄₀	724	95.56	61.25	64.09
6	[Leu-H]H₂PW₁₂O₄₀	677	85.34	42.54	49.84
7	[Val-H]H₂PW₁₂O₄₀	684	89.34	50.75	56.80
8	[Phe-H]H₂PW₁₂O₄₀	625	53.81	24.12	44.82
9	[Pro-H]₂HPW₁₂O₄₀	698	89.25	52.78	59.14
10	[Pro-H]₃PW₁₂O₄₀	641	64.58	31.07	48.11
11	[Pro-ps]H₂PW₁₂O₄₀	742	96.18	67.58	70.26
12	[Pro-ps]H₂PMo₁₂O₄₀	646	73.41	27.98	38.12
13	[Pro-ps]H₃SiW₁₂O₄₀	694	88.64	49.11	55.40
14	[Leu-ps] H₂PW₁₂O₄₀	706	89.08	50.17	56.32
15	[Val-ps] H₂PW₁₂O₄₀	695	91.48	56.75	62.03
16	[Phe-ps] H₂PW₁₂O₄₀	651	67.47	32.45	48.10
17	H₃PW₁₂O₄₀	814	90.65	47.57	52.47

Entry	Catalyst	Acid strength^b/mV	Conversion(%)	Yield(%)	Selectivity(%)
1	—	—	1.18	—	—
2	Pro	—	1.51	—	—
3	[Pro-H]H₂PMo₁₂O₄₀	633	68.23	14.07	20.62
4	[Pro-H]H₃SiW₁₂O₄₀	680	85.31	45.74	53.62
5	[Pro-H]H₂PW₁₂O₄₀	724	95.56	61.25	64.09
6	[Leu-H]H₂PW₁₂O₄₀	677	85.34	42.54	49.84
7	[Val-H]H₂PW₁₂O₄₀	684	89.34	50.75	56.80
8	[Phe-H]H₂PW₁₂O₄₀	625	53.81	24.12	44.82
9	[Pro-H]₂HPW₁₂O₄₀	698	89.25	52.78	59.14
10	[Pro-H]₃PW₁₂O₄₀	641	64.58	31.07	48.11
11	[Pro-ps]H₂PW₁₂O₄₀	742	96.18	67.58	70.26
12	[Pro-ps]H₂PMo₁₂O₄₀	646	73.41	27.98	38.12
13	[Pro-ps]H₃SiW₁₂O₄₀	694	88.64	49.11	55.40
14	[Leu-ps] H₂PW₁₂O₄₀	706	89.08	50.17	56.32
15	[Val-ps] H₂PW₁₂O₄₀	695	91.48	56.75	62.03
16	[Phe-ps] H₂PW₁₂O₄₀	651	67.47	32.45	48.10
17	H₃PW₁₂O₄₀	814	90.65	47.57	52.47

Entry	Conversion(%)	Yield(%)	Selectivity^b(%)
1	97.91	91.18	93.12
2	98.49	88.97	90.33
3	95.19	80.38	84.44
4	93.87	75.42	80.35
5	66.98	45.35	67.71
6	64.17	41.09	64.03
7	58.86	35.67	60.60
8	41.56	23.54	56.64
9	97.64	93.14	95.39
10	98.49	91.83	93.23
11	91.31	81.56	89.32
12	95.28	88.04	92.40

Entry	Conversion(%)	Yield(%)	Selectivity^b(%)
1	97.91	91.18	93.12
2	98.49	88.97	90.33
3	95.19	80.38	84.44
4	93.87	75.42	80.35
5	66.98	45.35	67.71
6	64.17	41.09	64.03
7	58.86	35.67	60.60
8	41.56	23.54	56.64
9	97.64	93.14	95.39
10	98.49	91.83	93.23
11	91.31	81.56	89.32
12	95.28	88.04	92.40