Visible-light-induced Selective Oxidation of Alcohols

doi:10.7503/cjcu20190652

Abstract

Abstract:

Selective oxidation of alcohols to aldehydes or ketones has been regarded as one of the most important oxidation reactions in the chemical industry. Establishing a green and mild synthesis method is the main purpose of this research. In this work， 2-chloroanthraquinone is used to selectively oxidize primary and secon-dary alcohols to corresponding carbonyl compounds under the driving of visible light， without additional heavy metals and auxiliary additives. Air or oxygen as the oxidant avoids the stoichiometric use of traditional oxidants， reduces waste release and toxicity， and makes the reaction system simple and easy to purify. The results show that the reaction has a moderate to excellent conversion and selectivity， and is suitable for a series of substrates， providing a new economic， environmentally friendly and sustainable way for the synthesis of benzyl oxygenates.

Key words: Benzyl oxidation, Photocatalytic, Dye, 2-Chloroanthraquinone

CLC Number:

O621.3

ZHOU Jinlong, LIU Xiaolong, FU Yao. Visible-light-induced Selective Oxidation of Alcohols[J]. Chemical Journal of Chinese Universities, 2020, 41(11): 2435-2441.

Figures/Tables 2

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Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
2a	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	192.38, 136.33, 134.52, 129.63, 128.47
2b	7.76(d, J=8.1 Hz, 2H), 7.32(d, J=7.8 Hz, 2H), 2.41(s, 3H)	191.91, 145.61, 134.26, 129.85, 129.71, 21.83
2c	9.89(s, 1H), 7.95—7.52(m, 2H), 7.14—6.69(m, 2H), 3.89(s, 3H)	190.79, 164.63, 131.99, 130.01, 114.33, 55.59
2d	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	190.29, 154.32, 131.97, 125.29, 111.09, 40.12
2e	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	190.79, 140.95, 134.75, 130.89, 129.45
2f	10.14(s, 2H), 8.04(m, 4H)	191.58, 140.18, 130.27
2g	9.81(s, 1H), 7.41(dd, J=1.9 Hz, 2H), 7.36(d, J=1.9 Hz, 1H), 6.94(d, J=8.2 Hz, 1H), 3.92(s, 3H), 3.90(s, 3H)	190.86, 154.50, 149.64,130.16, 126.83, 110.44, 108.99, 56.18, 56.01
2h	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	189.76, 137.94, 135.08, 132.52, 130.61, 129.39, 127.28
2i	10.78(s, 1H), 9.41(d, J=9.4 Hz, 1H), 8.43(d, J=7.9 Hz, 1H), 8.27(ddd, J=18.1, 9.6, 5.6 Hz, 5H), 8.14—7.99(m, 2H)	193.06, 135.55, 131.38, 131.10, 130.97, 130.84, 130.72, 130.45, 127.44, 127.21, 127.06, 126.85, 126.58, 124.69, 124.56, 124.09, 123.04
2j	10.10(s, 1H), 9.07(d, J=2.0 Hz, 1H), 8.82—8.84(q, 1H), 8.15—8.18(m, 1H),7.46—7.50(q, 1H)	190.64, 154.63, 151.91,135.72, 131.44, 124.02
Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
2k	9.87(s, 2H), 7.35(s, 2H)	179.19, 154.23, 119.26
2l	9.91(d, J=1.3 Hz, 1H), 7.85—7.64(m, 2H), 7.19(dd, J=4.9, 3.8 Hz, 1H)	183.04, 144.10, 136.39, 135.18, 128.40
2m	7.80(ddd, J=7.3, 2.9, 1.6 Hz, 4H), 7.61—7.53(m, 2H), 7.50—7.40(m, 4H)	196.73, 137.64, 132.43, 130.07, 128.30
2n	7.91(d, J=8.5 Hz, 2H), 7.45(d, J=8.5 Hz, 2H),2.60(s, 3H)	196.71, 139.52, 135.45, 129.72, 128.86, 26.54
2o	7.54(dd, J=1.5, 2.0 Hz, 1H), 7.36—7.42(m, 2H),7.31(td, J=7.5, 1.5 Hz, 1H), 2.64(s, 3H)	200.43, 139.16, 131.93, 131.20, 130.60, 129.31, 126.92, 30.57
2p	7.91(t, J=1.8 Hz, 1H),7.81—7.84(m, 1H),7.52—7.55(m, 1H),7.41(t, J=7.7 Hz, 1H), 2.59(s, 3H)	196.58, 138.61, 134.91, 132.91, 129.86, 128.34, 126.31, 26.53
2q	7.96(dt, J=8.6, 1.7 Hz, 2H), 7.59—7.51(m, 1H), 7.49—7.39(m, 2H), 2.60(s, 3H)	198.13, 137.17, 133.10, 128.58, 128.31, 26.60
2r	8.74(d, J=8.6 Hz, 1H), 7.92(ddd, J=25.7, 23.8, 8.2 Hz, 3H), 7.69—7.41(m, 3H), 2.74(s, 3H)	201.84, 135.51, 134.01, 133.04, 130.18, 128.67, 128.43, 128.07, 126.46, 126.04, 124.35, 30.00
2s	8.69(ddd, J=4.8, 1.6, 0.9 Hz, 1H), 8.05(dt, J=7.9, 1.1 Hz, 1H), 7.83(td, J=7.7, 1.7 Hz, 1H), 7.47(ddd, J=7.6, 4.8, 1.3 Hz, 1H), 2.73(s, 3H)	200.10, 153.62, 148.98, 136.82, 127.06, 121.63, 25.76
2t	7.77(d, J=7.7 Hz, 1H), 7.58(dd, J=7.4, 1.1 Hz, 1H), 7.50—7.44(m, 1H), 7.38(dd, J=10.9, 3.9 Hz, 1H), 3.23—3.06(m, 2H), 2.78—2.60(m, 2H)	207.05, 155.16, 137.13, 134.60, 127.30, 126.71, 123.76, 36.24, 25.82
2u	7.70(dd, J=3.8, 1.1 Hz, 1H), 7.64(dd, J=5.0, 1.1 Hz, 1H), 7.13(dd, J=5.0, 3.8 Hz, 1H), 2.62—2.49(m, 3H)	190.71, 144.61, 133.76, 132.45, 128.11, 26.93

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
2a	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	192.38, 136.33, 134.52, 129.63, 128.47
2b	7.76(d, J=8.1 Hz, 2H), 7.32(d, J=7.8 Hz, 2H), 2.41(s, 3H)	191.91, 145.61, 134.26, 129.85, 129.71, 21.83
2c	9.89(s, 1H), 7.95—7.52(m, 2H), 7.14—6.69(m, 2H), 3.89(s, 3H)	190.79, 164.63, 131.99, 130.01, 114.33, 55.59
2d	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	190.29, 154.32, 131.97, 125.29, 111.09, 40.12
2e	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	190.79, 140.95, 134.75, 130.89, 129.45
2f	10.14(s, 2H), 8.04(m, 4H)	191.58, 140.18, 130.27
2g	9.81(s, 1H), 7.41(dd, J=1.9 Hz, 2H), 7.36(d, J=1.9 Hz, 1H), 6.94(d, J=8.2 Hz, 1H), 3.92(s, 3H), 3.90(s, 3H)	190.86, 154.50, 149.64,130.16, 126.83, 110.44, 108.99, 56.18, 56.01
2h	10.02(s, 1H), 7.89(ddd, J=7.0, 2.9, 1.6 Hz, 2H), 7.66—7.59(m, 1H), 7.56—7.50(m, 2H)	189.76, 137.94, 135.08, 132.52, 130.61, 129.39, 127.28
2i	10.78(s, 1H), 9.41(d, J=9.4 Hz, 1H), 8.43(d, J=7.9 Hz, 1H), 8.27(ddd, J=18.1, 9.6, 5.6 Hz, 5H), 8.14—7.99(m, 2H)	193.06, 135.55, 131.38, 131.10, 130.97, 130.84, 130.72, 130.45, 127.44, 127.21, 127.06, 126.85, 126.58, 124.69, 124.56, 124.09, 123.04
2j	10.10(s, 1H), 9.07(d, J=2.0 Hz, 1H), 8.82—8.84(q, 1H), 8.15—8.18(m, 1H),7.46—7.50(q, 1H)	190.64, 154.63, 151.91,135.72, 131.44, 124.02
Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
2k	9.87(s, 2H), 7.35(s, 2H)	179.19, 154.23, 119.26
2l	9.91(d, J=1.3 Hz, 1H), 7.85—7.64(m, 2H), 7.19(dd, J=4.9, 3.8 Hz, 1H)	183.04, 144.10, 136.39, 135.18, 128.40
2m	7.80(ddd, J=7.3, 2.9, 1.6 Hz, 4H), 7.61—7.53(m, 2H), 7.50—7.40(m, 4H)	196.73, 137.64, 132.43, 130.07, 128.30
2n	7.91(d, J=8.5 Hz, 2H), 7.45(d, J=8.5 Hz, 2H),2.60(s, 3H)	196.71, 139.52, 135.45, 129.72, 128.86, 26.54
2o	7.54(dd, J=1.5, 2.0 Hz, 1H), 7.36—7.42(m, 2H),7.31(td, J=7.5, 1.5 Hz, 1H), 2.64(s, 3H)	200.43, 139.16, 131.93, 131.20, 130.60, 129.31, 126.92, 30.57
2p	7.91(t, J=1.8 Hz, 1H),7.81—7.84(m, 1H),7.52—7.55(m, 1H),7.41(t, J=7.7 Hz, 1H), 2.59(s, 3H)	196.58, 138.61, 134.91, 132.91, 129.86, 128.34, 126.31, 26.53
2q	7.96(dt, J=8.6, 1.7 Hz, 2H), 7.59—7.51(m, 1H), 7.49—7.39(m, 2H), 2.60(s, 3H)	198.13, 137.17, 133.10, 128.58, 128.31, 26.60
2r	8.74(d, J=8.6 Hz, 1H), 7.92(ddd, J=25.7, 23.8, 8.2 Hz, 3H), 7.69—7.41(m, 3H), 2.74(s, 3H)	201.84, 135.51, 134.01, 133.04, 130.18, 128.67, 128.43, 128.07, 126.46, 126.04, 124.35, 30.00
2s	8.69(ddd, J=4.8, 1.6, 0.9 Hz, 1H), 8.05(dt, J=7.9, 1.1 Hz, 1H), 7.83(td, J=7.7, 1.7 Hz, 1H), 7.47(ddd, J=7.6, 4.8, 1.3 Hz, 1H), 2.73(s, 3H)	200.10, 153.62, 148.98, 136.82, 127.06, 121.63, 25.76
2t	7.77(d, J=7.7 Hz, 1H), 7.58(dd, J=7.4, 1.1 Hz, 1H), 7.50—7.44(m, 1H), 7.38(dd, J=10.9, 3.9 Hz, 1H), 3.23—3.06(m, 2H), 2.78—2.60(m, 2H)	207.05, 155.16, 137.13, 134.60, 127.30, 126.71, 123.76, 36.24, 25.82
2u	7.70(dd, J=3.8, 1.1 Hz, 1H), 7.64(dd, J=5.0, 1.1 Hz, 1H), 7.13(dd, J=5.0, 3.8 Hz, 1H), 2.62—2.49(m, 3H)	190.71, 144.61, 133.76, 132.45, 128.11, 26.93

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