METHOD FOR PRODUCING DICHLORO ADDITION PRODUCT OF ALIPHATIC OLEFIN BY PHOTOCATALYSIS UNDER VISIBLE LIGHT

Abstract

The invention provides a method for producing a dichloro addition product of an aliphatic olefin by photocatalysis under visible light. The method includes reacting an aliphatic olefin as a substrate with hydrochloric acid as a chlorine source in an organic solvent under visible light irradiation in the presence of copper chloride with visible light absorption ability as a catalyst, to obtain the dichloro addition product of the aliphatic olefin, wherein the reaction is carried out under an oxygen-containing atmosphere, the aliphatic olefin comprises a carbon-carbon double bond and a C9-C15 aliphatic chain connected to the carbon-carbon double bond by a covalent bond. In the invention, visible light is used to provide the energy and a transition metal chloride with visible light absorption ability is used to undergo light-induced electron transfer from chloride with a reaction substrate, thereby initiating an addition reaction to obtain a dichloro addition product.

Claims

1. A method for producing a dichloro addition product of an aliphatic olefin by photocatalysis under visible light, comprising steps of: reacting an aliphatic olefin as a substrate with hydrochloric acid as a chlorine source in an organic solvent under visible light irradiation in the presence of copper chloride with visible light absorption ability as a catalyst, to obtain the dichloro addition product of the aliphatic olefin, wherein the reaction is carried out under an oxygen-containing atmosphere; the aliphatic olefin comprises a carbon-carbon double bond and a C9-C15 aliphatic chain connected to the carbon-carbon double bond by a covalent bond.

2. The method according to claim 1, wherein the aliphatic olefin has a structural formula of ##STR00029## and the dichloro addition product of the aliphatic olefin has a structural formula of ##STR00030## in which R.sub.1 is selected from hydrogen, substituted or unsubstituted C7-C13 aryl, C6-C12 aryloxy, C1-C4 alkoxy, C6-C12 arylacyloxy or C6-C12 arylsulfonamido; R.sub.2 is selected from hydrogen or C1-C4 alkyl; and n=1-3.

3. The method according to claim 2, wherein the aryl is selected from phenyl, phenylhydroxyl, phthalimido or naphthyl, where the substituent on the substituted aryl is selected from C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylsulfonyl, nitro, phenyl, halo, trifluoromethyl, acetoxy, cyano or carboxyl.

4. The method according to claim 2, wherein the arylacyloxy is selected from a phthalimido-containing acyloxy group, a naphthyl-containing acyloxy group or a phenyl ring-containing acyloxy group; and the arylsulfonamido is selected from a naphthyl-containing arylsulfonamido group.

5. The method according to claim 2, wherein R.sub.2 is selected from hydrogen or methyl.

6. The method according to claim 1, wherein the reaction temperature is 23-25° C.; and the reaction time is 36-72 h.

7. The method according to claim 1, wherein the organic solvent is selected from the group consisting of petroleum ether, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, nitromethane, acetonitrile, ethyl acetate, acetone and any combination thereof.

8. The method according to claim 1, wherein the oxygen containing atmosphere is pure oxygen or air.

9. The method according to claim 1, wherein the amount of the catalyst is 20% of the molar amount of the aliphatic olefin, and the amount of hydrochloric acid is 2.5 times the molar amount of the aliphatic olefin.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] The present invention will be illustrated in further detail with reference to embodiments. The following embodiments are intended to describe the present invention, instead of limiting the scope of the present invention.

[0041] In the present invention, according to the different structures, the substrate olefin can be prepared with a starting material such as a carboxylic acid, or an alcohol, an amine, a phenol.

Example 1

[0042] ##STR00008##

[0043] 1a (0.2 mmol, 37.4 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution, and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2a (yield 85%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0044] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.90-7.88 (m, 2H), 7.78-7.75 (m, 2H), 4.57-4.51 m, 1H), 4.12-4.10 (d, J=6.8 Hz, 2H), 3.87-3.78 (m, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 167.7, 134.2, 131.6, 123.5, 57.0, 46.2, 41.8; HRMS (ESI-TOF): Anal Calcd. For C.sub.11H.sub.9.sup.35Cl.sup.35ClNO.sub.2+Na.sup.+: 279.9903, Found: 279.9916. Anal Calcd. For C.sub.11H.sub.9.sup.35Cl.sup.37ClO.sub.2+Na.sup.+: 281.9873, 281.9882; IR (neat, cm.sup.−1): b 3058, 2969, 1706, 1612, 1427, 720.

Example 2

[0045] ##STR00009##

[0046] 1b (0.2 mmol, 40.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2b (yield 77%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0047] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.87-7.85 (m, 2H), 7.75-7.73 (m, 2H), 4.13-4.07 (m, 1H), 3.97-3.87 (m, 2H), 3.86-3.81 (m, 1H), 3.73-3.68 (m, 1H), 2.49-2.41 (m, 1H), 2.15-2.04 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 168.1, 134.0, 131.9, 123.3, 58.1, 47.8, 35.0, 33.8; HRMS(ESI-TOF): Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sup.35ClNO.sub.2+Na.sup.+: 294.0059, Found: 294.0069. Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sup.37ClNO.sub.2+Na.sup.+: 296.0030, Found: 296.0038. Anal Calcd. For. C.sub.12H.sub.11.sup.37Cl.sup.37ClNO.sub.2+Na.sup.+: 298.0000, Found: 297.9995; IR (neat, cm.sup.−1): b 2996, 2853, 1692, 1609, 1442, 1402, 755.

Example 3

[0048] ##STR00010##

[0049] 1c (0.2 mmol, 51.8 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2c (yield 63%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0050] NMR (400 MHz, CDCl.sub.3) δ 7.90-7.88 (m, 2H), 7.77-7.75 (m, 2H), 4.47 (s, 2H), 4.44-4.31 (m, 2H), 4.18-4.12 (m, 1H), 3.82-3.78 (m, 1H), 3.70-3.5 m, 1H), 2.43-2.35 (m, 1H), 2.07-1.98 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 167.3, 167.0, 134.24, 131.8, 123.6, 62.1, 57.0, 48.0, 38.8, 34.0; HRMS (ESI-TOF): Anal Calcd. For C.sub.14H.sub.13.sup.35Cl.sup.35ClNO.sub.4+Na.sup.+: 352.0114, C.sub.14H.sub.13.sup.35Cl.sup.37ClNO.sub.4+Na.sup.+: 354.0084, C.sub.14H.sub.13.sup.37Cl.sup.37ClNO.sub.4+Na.sup.+: 356.0055, Found: 352.0129, 354.0079, 356.0045; IR (neat, cm.sup.−1): b 2926, 2854, 1754, 1719, 1616, 1469, 1417, 1393, 906, 725.

Example 4

[0051] ##STR00011##

[0052] 1d (0.2 mmol, 40.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2d (yield 90%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0053] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.91-7.88 (m, 2H), 7.78-7.76 (m, 2H), 4.12 (s, 2H), 3.85-3.77 (m, 1H), 1.72 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 168.1, 134.3, 131.6, 123.6, 69.6, 52.3, 46.1, 26.6; HRMS(ESI-TOF): Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sub.2NO.sub.2+Na.sup.+:294.0059, Found: 294.0082. Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sup.37ClNO.sub.2+Na.sup.+: 296.0030, Found: 296.0039. Anal Calcd. For C.sub.12H.sub.11.sup.37Cl.sub.2NO.sub.2+Na.sup.+: 298.0000, Found: 297.9984; IR (neat, cm.sup.−1): b 2937, 2860, 1719, 1605, 1394, 905, 723.

Example 5

[0054] ##STR00012##

[0055] 1e (0.2 mmol, 43.4 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2e (yield 68%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0056] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.87-7.83 (m, 2H), 7.80-7.75 (m, 2H), 4.66-4.60 (m, 1H), 4.44-4.41 (m, 2H), 3.96-383 (m, 2H), 2.52-2.44 (m, 1H), 2.17-2.09 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 163.5, 134.6, 128.8, 123.6, 74.7, 57.1, 48.6, 34.1; HRMS (ESI-TOF): Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sup.35ClNO.sub.3+Na.sup.+: 310.0008, Found: 310.0020. Anal Calcd. For. C.sub.12H11.sup.35Cl.sup.37ClNO.sub.3+Na.sup.+:311.9979, Found: 311.9953. Anal Calcd. For C.sub.12H.sub.11.sup.37Cl.sup.37ClNO.sub.3+Na.sup.+: 313.9949, Found: 313.9944; IR (neat, cm.sup.−1): ν 2955, 2924, 1726, 1609, 1467, 1186, 877.698.

Example 6

[0057] ##STR00013##

[0058] 1f (0.2 mmol, 52.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2f (yield 75%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0059] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.46 (d, J=1.4 Hz, 1H), 8.0-7.97 (m, 2H), 7.93-7.91 (d, J=7.9 Hz, 1H), 7.86-7.93 (m, 1H), 7.68-7.60 (m, 2H), 4.92-4.89 (t, J=6.3 Hz, 1H), 4.14-4.11 (m, 1H), 3.76-3.72 (m, 1H), 3.62-3.58 (m, 1H), 3.25-3.19 (m, 2H), 2.30-2.22 (m, 1H), 1.88-1.79 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 136.3, 134.8, 132.1, 129.7, 129.2, 128.9, 128.5, 127.9, 127.6, 122.1, 57.9, 48.0, 40.1, 35.1; HRMS (ESI-TOF): Anal Calcd. For C.sub.14H.sub.15.sup.35Cl.sub.2NO.sub.2S+Na.sup.+: 354.0093, Found: 354.0123. Anal Calcd. For C.sub.14H.sub.15.sup.35Cl.sup.37ClNO.sub.2S+Na.sup.+: 356.0063, Found: 356.0054. Anal Calcd. For C.sub.14H.sub.15.sup.37Cl.sub.2NO.sub.2S+Na.sup.+: 358.0034, Found: 358.0072; IR (neat, cm.sup.−1): b 3259, 3078, 2956, 2849, 1712, 1587, 1501, 1272.829.

Example 7

[0060] ##STR00014##

[0061] 1g (0.2 mmol, 45.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2g (yield 70%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0062] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.62 (s, 1H), 8.08-8.05 (m, 1H), 7.99-7.97 (d, J=8.0 Hz, 1H), 7.91-7.88 (m, 2H), 7.63-7.54 (m, 2H), 4.62-4.61 (d, J=0.9 Hz, 2H), 4.03-4.00 (d, J=11.5 Hz, 1H), 3.84-3.81 (d, J=11.4 Hz, 1H), 1.78 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 165.8, 135.7, 132.4, 131.3, 129.4, 128.5, 128.4, 127.8, 126.8, 126.6, 125.1, 68.3, 67.6, 49.9, 25.1; HRMS(ESI-TOF): Anal Calcd. For C.sub.15H.sub.14.sup.35Cl.sub.2O.sub.2+Na.sup.+: 319.0263, Found: 319.0285. Anal Calcd. For C.sub.15H.sub.14.sup.35Cl.sup.37ClO.sub.2+Na.sup.+: 321.0234, Found: 321.0214. Anal Calcd. For C.sub.15H.sub.14.sup.37Cl.sub.2O.sub.2+Na.sup.+: 323.0204, Found: 323.0243; IR (neat, cm.sup.−1): b 3062, 2930, 1719, 1631, 1457, 1279, 1194, 906, 762.

Example 8

[0063] ##STR00015##

[0064] 1h (0.2 mmol, 45.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2h (yield 82%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0065] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.60 (m, 1H), 8.05-8.03 (m, 1H), 7.96-7.94 (m, 1H), 7.88-7.86 (m, 2H), 7.61-7.52 (m, 2H), 4.66-4.52 (m, 2H), 4.34-4.28 (m, 1H), 3.89-3.73 (m, 2H), 2.61-2.53 (m, 1H), 2.23-2.14 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.4, 135.6, 132.4, 131.1, 129.3, 128.3, 128.2, 127.7, 127.1, 126.7, 125.1, 61.4, 57.5, 48.1, 34.3; HRMS (ESI-TOF): Anal Calcd. For. C.sub.15H.sub.14.sup.35Cl.sub.2O.sub.2+Na.sup.+: 319.0263, Found: 319.0291. Anal Calcd. For. C.sub.15H.sub.14.sup.35Cl.sup.37ClO.sub.2+Na.sup.+: 321.0234, Found: 321.0233. Anal Calcd. For C.sub.15H.sub.14.sup.37Cl.sub.2O.sub.2+Na.sup.+: 323.0204, Found: 323.0239; IR (neat, cm.sup.−1): ν 3062, 2963, 1714, 1631, 1467, 1226, 906, 726.

Example 9

[0066] ##STR00016##

[0067] 1i (0.2 mmol, 42.0 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2i (yield 81%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0068] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.98-7.96 (m, 2H), 7.43-7.41 (m, 2H), 4.60-4.46 (m, 2H), 4.28-4.22 (m, 1H), 3.87-3.71 (m, 2H), 2.57-2.49 (m, 1H), 2.19-2.10 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 165.4, 139.6, 130.9, 128.8, 128.3, 61.5, 57.4, 48.0, 34.2; HRMS (ESI-TOF): Anal Calcd. For C.sub.11H.sub.11.sup.35Cl.sub.3O.sub.2+Na.sup.+: 302.9717, Found: 302.9729. Anal Calcd. For C.sub.11H.sub.11.sup.35Cl.sub.2.sup.37ClO.sub.2+Na.sup.+: 304.9687, Found: 304.9677; IR (neat, cm.sup.−1): b 2963, 2853, 1717, 1594, 1488, 1402, 1267, 849.

Example 10

[0069] ##STR00017##

[0070] 1j (0.2 mmol, 44.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2j (yield 74%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0071] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.32-8.29 (m, 2H), 8.23-8.20 (m, 2H), 4.67-4.54 (m, 2H), 4.29-4.22 (m, 1H), 3.90-3.71 (m, 2H), 2.62-2.54 (m, 1H), 2.23-2.14 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 164.4, 150.6, 135.2, 130.7, 123.6, 62.3, 57.2, 47.9, 34.0; HRMS (ESI-TOF): Anal Calcd. For C.sub.11H.sub.11.sup.35Cl.sub.2NO.sub.4+Na.sup.+: 313.9957, Found: 313.9948. Anal Calcd. For C.sub.11H.sub.11.sup.35Cl.sup.37ClNO.sub.4+Na.sup.+: 315.9928; Found: 315.9956; IR (neat, cm.sup.−1): b 3117, 3057, 2964, 2850, 1719, 1598, 1519, 1439, 1275, 728.

Example 11

[0072] ##STR00018##

[0073] 1k (0.2 mmol, 35.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2k (yield 84%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0074] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.05-8.03 (m, 2H), 7.60-7.55 (m, 1H), 7.47-7.43 (m, 2H), 4.61-4.46 (m, 2H), 4.31-4.24 (m, 1H), 3.87-3.72 (m, 2H), 2.57-2.49 (m, 1H), 2.19-2.10 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.3, 133.1, 129.8, 129.6, 128.4, 61.3, 57.5, 48.1, 34.2; HRMS (ESI-TOF): Anal Calcd. For C.sub.11H.sub.12.sup.35Cl.sub.2O.sub.2+Na.sup.+: 269.0107, Found: 269.0126. Anal Calcd. For C.sub.11H.sub.12.sup.35Cl.sup.37ClO.sub.2+Na.sup.+: 271.0077, Found: 271.0193. Anal Calcd. For C.sub.11H.sub.12.sup.37Cl.sub.2O.sub.2+Na.sup.+: 273.0048, Found: 273.0060; IR (neat, cm.sup.−1): b 2962, 2926, 1716, 1602, 1452, 1268, 708.

Example 12

[0075] ##STR00019##

[0076] 11 (0.2 mmol, 38.8 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 21 (yield 80%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0077] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.08-8.03 (m, 2H), 7.15-7.09 (m, 2H), 4.60-4.46 (m, 2H), 4.29-4.23 (m, 1H), 3.88-3.71 (m, 2H), 2.57-2.49 (m, 1H), 2.19-2.10 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 165.8, 165.3, 132.2, 126.1, 115.6, 61.4, 57.4, 48.0, 34.2; HRMS(ESI-TOF): Anal Calcd. For. C.sub.11H.sub.11.sup.35Cl.sub.2FO.sub.2+Na.sup.+: 287.0012, Found: 287.0014. Anal Calcd. For C.sub.11H.sub.11.sup.35Cl.sup.37ClFO.sub.2+Na.sup.+: 288.9983, Found: 288.9964; IR (neat, cm.sup.−1): b 2963, 2928, 1716, 1603, 1508, 1411, 1387, 1267, 766.

Example 13

[0078] ##STR00020##

[0079] 1m (0.2 mmol, 38.0 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2m (yield 71%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0080] .sup.1H NMR (400 MHz, DMSO) δ 7.87-7.85 (m, 1H), 7.51-7.47 (m, 1H), 7.34-7.30 (m, 2H), 4.53-4.44 (m, 2H), 4.39-4.29 (m, 1H), 4.05-3.97 (m, 2H), 2.53 (s, 3H), 2.42-2.34 (m, 1H), 2.18-2.09 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 167.2, 140.3, 132.1, 131.8, 130.5, 129.2, 125.8, 61.1, 57.5, 48.1, 34.3, 21.7; HRMS(ESI-TOF): Anal Calcd. For. C.sub.12H.sub.14.sup.35Cl.sup.37ClO.sub.2+Na.sup.+: 285.0234, Found: 285.0240. Anal Calcd. For C.sub.12H.sub.14.sup.37Cl.sub.2O.sub.2+Na.sup.+: 287.0204, Found: 287.0184; IR (neat, cm.sup.−1): b 2964, 2929, 2855, 1717, 1602, 1576, 1489, 1249, 734.

Example 14

[0081] ##STR00021##

[0082] In (0.2 mmol, 57.6 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2n (yield 78%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0083] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.96-7.95 (m, 1H), 7.56-7.54 (m, 1H), 7.34-7.32 (m, 1H), 4.63-4.58 (m, 1H), 4.55-4.49 (m, 1H), 4.31-4.25 (m, 1H), 3.88-3.84 (m, 1H), 3.75-3.70 (m, 1H), 2.59-2.51 (m, 1H), 2.17-2.08 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 164.2, 135.6, 134.2, 132.7, 132.5, 131.3, 120.2, 62.3, 57.2, 48.0, 34.1; HRMS (ESI-TOF): Anal Calcd. For C.sub.HH.sub.10.sup.79Br.sup.35Cl.sub.3O.sub.2+Na.sup.+: 380.8822, Found: 380.8844. C.sub.11H.sub.10.sup.79Br.sup.35Cl.sub.2.sup.37ClO.sub.2+Na.sup.+: 382.8792, Found: 382.8835. C.sub.11H.sub.10.sup.79Br.sup.35Cl.sup.37Cl.sub.2O.sub.2+Na.sup.+: 384.8763, Found: 384.8815; IR (neat, cm.sup.−1): b 2964, 1733, 1600, 1460, 1238, 905, 726.

Example 15

[0084] ##STR00022##

[0085] 1o (0.2 mmol, 40.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2o (yield 80%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0086] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.32-8.27 (m, 2H), 7.88-7.86 (m, 1H), 7.64-7.60 (m, 2H), 4.65-4.52 (m, 2H), 4.31-4.25 (m, 1H), 3.90-3.86 (m, 1H), 3.78-3.74 (m, 1H), 2.60-2.52 (m, 1H), 2.23-2.14 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 164.2, 136.0, 133.5, 133.1, 131.0, 129.4, 117.7, 112.9, 62.0, 57.2, 47.9, 33.9; HRMS (ESI-TOF): Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sub.2NO.sub.2+Na.sup.+: 294.0059, Found: 294.0068. Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sup.37ClNO.sub.2+Na.sup.+: 296.0030, Found: 296.0016; IR (neat, cm.sup.−1): b 3080, 2966, 2234, 1723, 1600, 1433, 1275, 1185, 907, 818, 752.

Example 16

[0087] ##STR00023##

[0088] 1p (0.2 mmol, 48.8 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2p (yield 66%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0089] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.30 (m, 1H), 8.24-8.22 (m, 1H), 7.84-7.82 (m, 1H), 7.62-7.58 (m, 1H), 4.65-4.52 (m, 2H), 4.30-4.23 (m, 1H), 3.89-3.85 (m, 1H), 3.77-3.72 (m, 1H), 2.61-2.52 (m, 1H), 2.23-2.14 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 165.0, 132.7, 131.1 (q, J=33.0 Hz), 130.7, 129.6 (q, J=3.6 Hz), 129.1, 126.5 (q, J=3.9 Hz), 123.6 (d, J=272.5 Hz), 61.9, 57.3, 47.9, 34.1; HRMS (ESI-TOF): Anal Calcd. For C.sub.12H.sub.11.sup.35Cl.sub.2F.sub.3O.sub.2+Na.sup.+: 336.9980, Found: 336.9987; IR (neat, cm.sup.−1): b 2968, 1724, 1618, 1248, 1126, 907, 756, 693.

Example 17

[0090] ##STR00024##

[0091] 1q (0.2 mmol, 41.2 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2q (yield 74%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0092] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.00-7.98 (m, 2H), 6.94-6.91 (m, 2H), 4.57-4.42 (m, 2H), 4.30-4.24 (m, 1H), 3.87-3.83 (m, 4H), 3.76-3.72 (m, 1H), 2.55-2.47 (m, 1H), 2.17-2.09 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.0, 163.5, 131.6, 122.2, 113.6, 60.9, 57.5, 55.4, 48.1, 34.3; HRMS (ESI-TOF): Anal Calcd. For C.sub.12H.sub.14.sup.35Cl.sub.2O.sub.3+Na.sup.+: 299.0212, Found: 299.0224. Anal Calcd. For C.sub.12H.sub.14.sup.35Cl.sup.37ClO.sub.3+Na.sup.+: 301.0183, Found: 301.0200; IR (neat, cm.sup.−1): b 2965, 2841, 1708, 1606, 1512, 1458, 1423, 1254, 1167, 907, 847, 727.

Example 18

[0093] ##STR00025##

[0094] 1r (0.2 mmol, 50.4 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2r (yield 65%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0095] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.85-7.83 (m, 1H), 7.53-749 (m, 1H), 7.42-7.29 (m, 7H), 4.27-4.21 (m, 1H), 4.18-4.12 (m, 1H), 3.53-3.43 (m, 2H), 3.42-3.35 (m, 1H), 1.94-1.86 (m, 1H), 1.74-1.65 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 168.5, 142.1, 141.6, 131.3, 130.6, 130.6, 130.0, 128.2, 127.2, 127.1, 61.1, 57.0, 48.3, 33.9; HRMS (ESI-TOF): Anal Calcd. For C.sub.17H.sub.16.sup.35Cl.sub.2O.sub.2+Na.sup.+:345.0420, Found: 345.0403. Anal Calcd. For C.sub.17H.sub.16.sup.35Cl.sup.37ClO.sub.2+Na.sup.+:347.0390, Found: 347.0357. C.sub.17H.sub.16.sup.37Cl.sub.2O.sub.2+Na.sup.+: 349.0361, Found: 349.0322; IR (neat, cm.sup.−1): b 3063, 2963, 1716, 1598, 1489, 1242, 1048, 907, 700.

Example 19

[0096] ##STR00026##

[0097] 1s (0.2 mmol, 60.4 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2s (yield 57%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0098] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.00-7.98 (m, 1H), 7.80-7.77 (m, 1H), 7.43-7.39 (m, 1H), 7.18-7.14 (m, 1H), 4.63-4.57 (m, 1H), 4.51-4.47 (m, 1H), 4.36-4.30 (m, 1H), 3.87-3.83 (m, 1H), 3.76-3.71 (m, 1H), 2.59-2.51 (m, 1H), 2.17-2.08 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.2, 141.2, 134.9, 132.7, 130.9, 127.9, 93.9, 62.0, 57.4, 48.1, 34.1; HRMS(ESI-TOF): Anal Calcd. For C.sub.11H.sub.11.sup.35Cl.sub.2IO.sub.2+Na.sup.+:394.9073, Found: 394.9082. Anal Calcd. For C.sub.11H.sub.11.sup.35Cl.sup.37ClIO.sub.2+Na.sup.+: 396.9043, Found: 396.9060. Anal Calcd. For C.sub.11H.sub.11.sup.37Cl.sub.2IO.sub.2+Na.sup.+: 398.9014, Found: 398.9048; IR (neat, cm.sup.−1): b 2963, 1725, 1583, 1429, 1247, 907, 729.

Example 20

[0099] ##STR00027##

[0100] 1t (0.2 mmol, 50.8 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution, and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2t (yield 61%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0101] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.24-8.22 (m, 1H), 8.05-8.03 (m, 1H), 4.66-4.53 (m, 2H), 4.32-4.26 (m, 1H), 3.90-3.86 (m, 1H), 3.79-3.74 (m, 1H), 3.11 (s, 3H), 2.57-2.52 (m, 1H), 2.24-2.15 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 164.5, 144.3, 134.4, 130.4, 127.4, 62.0, 57.2, 47.9, 44.1, 33.9; HRMS (ESI-TOF): Anal Calcd. For C.sub.12H.sub.14.sup.35Cl.sub.2O.sub.4S+Na.sup.+: 346.9882, Found: 346.9879. Anal Calcd. For C.sub.12H.sub.14.sup.35Cl.sup.37ClO.sub.4S.sub.2+Na.sup.+: 348.9853, Found: 348.9814, C.sub.12H.sub.14.sup.37Cl.sub.2O.sub.4S+Na.sup.+: 350.9823, Found: 350.9812; IR (neat, cm.sup.−1): b 2967, 1725, 1600, 1401, 1271, 906, 724.

Example 21

[0102] ##STR00028##

[0103] 1u (0.2 mmol, 56.0 mg), CuCl.sub.2 (0.04 mmol, 5.4 mg), acetonitrile MeCN (0.5 mL), and HCl (0.5 mmol, 41 μL) were added to a test tube. Then the system was irradiated for 72 h with a 38 W white LED light with stirring in the air at room temperature. The reaction system was quenched with a saturated sodium sulfite solution, and extracted 3 times with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the residue was adsorbed on silica gel, and purified by simple column chromatography to obtain the product 2u (yield 73%). The main test data of the prepared product is shown below. It can be known through analysis that the actually synthesized product is consistent with the theoretical analysis.

[0104] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.08-8.06 (m, 1H), 7.79-7.76 (m, 2H), 7.66-7.62 (m, 1H), 7.60-7.55 (m, 2H), 7.47-7.43 (m, 2H), 7.39-7.37 (m, 1H), 4.31-4.17 (m, 2H), 3.92-3.86 (m, 1H), 3.65-3.61 (m, 1H), 3.57-3.52 (m, 1H), 2.15-2.07 (m, 1H), 1.86-1.78 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 196.6, 165.6, 141.4, 136.7, 133.3, 132.4, 130.2, 129.6, 129.4, 128.7, 128.5, 127.5, 61.8, 57.1, 48.2, 33.8; HRMS (ESI-TOF): Anal Calcd. For. C.sub.18H.sub.16.sup.35Cl.sub.2O.sub.3+Na.sup.+: 373.0369, Found: 373.0335. Anal Calcd. For C.sub.18H.sub.16.sup.35Cl.sup.37ClO.sub.3+Na.sup.+: 375.0339, Found: 375.0316. Anal Calcd. For C.sub.18H.sub.16.sup.37Cl.sub.2O.sub.3+Na.sup.+: 377.0310, Found: 377.0309; IR (neat, cm.sup.−1): b 3065, 2964, 1719, 1617, 1597, 1275, 908, 767.

[0105] In the above examples of the present invention, the white LED light can also be replaced with visible light sources of other colors.

[0106] While preferred embodiments of the present invention have been described above, the present invention is not limited thereto. It should be appreciated that some improvements and variations can be made by those skilled in the art without departing from the technical principles of the present invention, which are also contemplated to be within the scope of the present invention.