Baeyer-Villiger Oxidation of Cyclic Ketones Catalyzed by Amino Alcohol Heteropoly Acid Ionic Liquid †

doi:10.7503/cjcu20190618

Abstract

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

CLC Number:

O643
O621

TrendMD:

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

Figures/Tables 9

References 27

[1]	Xu H., Jiang J. G., Yang B. T., Wu H. H., Wu P., Catal. Commun., 2014,55, 83—86 doi: 10.3310/hta14550-02 URL pmid: 21208548
[2]	Mallin H., Wulf H., Bornscheuer U. T., Enzyme Microb. Tech., 2013,53(4), 283—287 doi: 10.1016/j.enzmictec.2013.01.007 URL pmid: 23931695
[3]	Sever R. R., Root T. W., J. Phys. Chem. B, 2003,107(38), 10521—10530 doi: 10.1021/jp0343335 URL
[4]	Pillai U. R., Sahle-Demessie E., J. Mol. Catal. A: Chem., 2003,191(1), 93—100 doi: 10.1016/S1381-1169(02)00347-3 URL
[5]	Clark J. H., Pure Appl. Chem., 2001,73, 103—111 doi: 10.1351/pac200173010103 URL
[6]	Szpakolski K. B., Latham K., Rix C. J., Jonathan M., White., Inorg. Chim. Acta, 2011,376(1), 628—633
[7]	Yang Z. W., Niu L. Y., Jia X. J., Kang Q. X., Ma Z. H., Lei Z. Q., Catal. Commun., 2011,12(9), 798—802 doi: 10.1016/j.catcom.2011.01.028 URL
[8]	Michelin R. A., Sgarbossa P., Scarso A., Strukul G., Coord. Chem. Rev., 2010,254(5/6), 646—660 doi: 10.1016/j.ccr.2009.09.014 URL
[9]	Timofeeva M. N., Appl. Catal. A: Gen., 2004,256(1/2), 19—35 doi: 10.1016/S0926-860X(03)00386-7 URL
[10]	Kourasi M., Wills R. G. A., Shah A. A., Walsh F. C., Electrochim. Acta, 2014,127, 454—466 doi: 10.1016/j.electacta.2014.02.006 URL
[11]	Misono M., Ono I., Koyano G., Aoshima A., Pure Appl . Chem., 2000,72(7), 1305—1311
[12]	Robles-Dutenhefner P. A., Silva K. A. D., Siddiqui M. R. H., Kozhevnikov L. V., Gusevskaya E. V., J. Mol. Catal. A: Chem., 2001,175(1), 33—42 doi: 10.1016/S1381-1169(01)00217-5 URL
[13]	Kozhevnikov I. V., Cheminform, 2004,35(21), 3—18
[14]	Kozhevnikova E. F., Quartararo J., Kozhevnikov I. V., Appl. Catal. A: Gen., 2003,245(1), 69—78 doi: 10.1016/S0926-860X(02)00618-X URL
[15]	Watanabe R. I., Suzuki T., Okuhara T., Catal. Today, 2001,66(1), 123—130 doi: 10.1016/S0920-5861(00)00612-X URL
[16]	Yu F. L., Xie P. H., Zhu G. Q., Yuan B., Xie C. X., Yu S. T., Chem. J. Chinese Universities, 2016,37(12), 2184—2190
	( 于凤丽, 谢盼辉, 朱国强, 袁冰, 解从霞, 于世涛 . 高等学校化学学报, 2016,37(12), 2184—2190)
[17]	Zhang J. S., Yu F. L., Tao R. Q., Yuan B., Xie C. X., Yu S. T., Chem. J. Chinese Universities, 2017,38(12), 2248—2254
	( 张金帅, 于凤丽, 陶仁清, 袁冰, 解从霞, 于世涛 . 高等学校化学学报, 2017,38(12), 2248—2254)
[18]	Yu F. L., Wang Q. Y., Li G. X., Yuan B., Xie C. X., Yu S. T., Chem. J. Chinese Universities, 2017,38(1), 80—84
	( 于凤丽, 王庆玉, 李桂晓, 袁冰, 解从霞, 于世涛 . 高等学校化学学报, 2017,38(1), 80—84)
[19]	Zhang Z. S., Kang N., Wang J. Y., Sui H., He L., Li X. G., Chem. Eng. Sci., 2018,181, 264—271 doi: 10.1016/j.ces.2018.02.023 URL
[20]	Tao G. H., He L., Sun N., Kou Y., Chem. Commun., 2005,36(28), 3562—3564
[21]	Fukumoto K., Yoshizawa M., Ohno H ., J. Am. Chem. Soc., 2005,127(8), 2398—2399 doi: 10.1021/ja043451i URL pmid: 15724987
[22]	Vo-Thanh G., Pegot B., Aupoix A., Curr. Org. Synth, 2012,9, 53—64
[23]	Ou W. H., Huang Z. Z., Green Chem., 2006,8(8), 731—734 doi: 10.1039/b604801c URL
[24]	Thanh G. V., Pegot B., André L., Eur. J. Org. Chem., 2004,5, 1112—1116
[25]	Wasserscheid P., Bosmann A., Bolm C., Chem. Commun, 2002,7(3), 200—201
[26]	Shi J. H., Pan G., Front. Chem. China, 2009,4(2), 132—135 doi: 10.1007/s11458-009-0032-9 URL
[27]	Vazquez P., Pizzio L., Cáceres C., J. Mol. Catal. A: Chem., 2000,161(1/2), 223—232 doi: 10.1016/S1381-1169(00)00346-0 URL

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