A method for preparing deuterated aromatic hydrocarbons by catalyzing arylthianthrene salts using visible light

Abstract

The present invention belongs to the field of organic synthesis and relates to a method for preparing deuterated aromatic hydrocarbons. The present invention proposes a method for preparing deuterated aromatic hydrocarbons by using visible light catalyzed arylthianthrene salts: arylthianthrene salts are used as raw materials under conditions of visible light irradiation at room temperature, deuterated chloroform is a deuterium source, and photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile 5CzBN is a photocatalyst, thereby achieving the preparation of deuterated aromatic hydrocarbons. The method has mild conditions, cheap and easy-to-obtain raw materials, simple operation, high yield, and no metal participation. Preliminary experimental results show that the method can be used for the deuteration of the skeleton structure of various drug molecules, effectively realizing the conversion of drug molecules from C-H bonds to C-D bonds, and providing a material basis for studying the pharmacokinetics of deuterated drug molecules and improving drug efficacy.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis and relates to a method for preparing deuterated aromatic hydrocarbons. Background Art

[0002] Isotope labeling plays a crucial role in drug and pesticide chemistry research. In the pharmaceutical field, isotope labeling is widely used to study the metabolic processes of active drugs and identify specific metabolites. Deuterium is currently the most popular isotope labeling method, playing a key role in studying isotope effects in fundamental reaction kinetics. Deuterium-labeled compounds are similar to hydrogen isotopes and have nearly identical physical properties, but due to differences in molecular weight, they are often used as internal standards in liquid chromatography-mass spectrometry (LC-MS) analysis in environmental and human sample studies. Furthermore, deuterated compounds exhibit significant improvements in pharmacokinetic and pharmacological properties while maintaining the chemical structure and physical properties of the unlabeled compounds, making them a popular target for new drug development. In 2017, the FDA approved the first deuterated drug, Austedo, for the treatment of Huntington's disease and other conditions, marking a significant step forward in the clinical application of deuterated compounds. Deuterated aromatic hydrocarbons are widely used in organic synthesis, medicinal chemistry, and materials science. Application Publication No. CN112281182A discloses a method for preparing deuterated aromatic hydrocarbons under electrochemical conditions. This method uses heavy water as a deuterium source, triphenylamine and triphenylphosphine as sacrificial reagents, and the reaction substrates can be bromoaryl, chloroaryl, or iodoaryl. The types of deuterated aromatic hydrocarbons produced are limited, and the electrochemical preparation cost is high. Traditional methods for preparing deuterated aromatic hydrocarbons typically require high temperatures and pressures or expensive reagents, resulting in harsh reaction conditions and high costs.

[0003] In recent years, photocatalysis has garnered significant attention due to its mild reaction conditions and efficient catalytic performance. While visible light catalysis is a rapidly developing field, it offers advantages over traditional free radical initiators, such as mild reaction conditions, good functional group compatibility, and the absence of toxic initiators. However, current methods for preparing deuterated aromatics using photocatalysis still have limitations. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a method for preparing deuterated aromatic hydrocarbons by using arylthianthrene salts under visible light catalysis.

[0005] The technical solution of the present invention is achieved as follows:

[0006] A method for preparing deuterated aromatic hydrocarbons by catalyzing arylthianthrene salts using visible light, the reaction equation is:

[0007]

[0008] The preparation steps are as follows: a magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile, an arylthianthrene salt, deuterated chloroform, and water are sequentially added to a Schlenk reaction tube and irradiated with 20-40W 427nm blue light at room temperature for 3-12 hours. After the reaction is complete, saturated sodium chloride solution and dichloromethane are added for extraction, and the organic phase is collected. The resulting crude product is purified by silica gel column chromatography to obtain the deuterated aromatic hydrocarbon.

[0009] The structural formula of the arylthianthrene salt is as follows:

[0010]

[0011] Wherein Ar is an aromatic ring or heterocyclic ring substituted with any of various substituents such as hydrogen, alkyl, methoxy, fluorine, chlorine, bromine, trifluoromethyl, cyano, ester, N,N-dipropylsulfonamide and p-toluenesulfonyl.

[0012] Furthermore, Ar is Any of;

[0013] Preferably, R is any one of hydrogen, methyl, ethyl, methoxy, tert-butyl, isopropyl, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, keto, cyano, 2-propyl valerate, proline ester, carboxylate, benzoate, dodecanoate, N,N-dipropylsulfonamide and p-toluenesulfonyl.

[0014] The photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile, abbreviated as 5CzBN, has the following structural formula:

[0015]

[0016] The molar ratio of the arylthianthrene salt, deuterated chloroform and 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile is 1:10-65:0.01-0.1.

[0017] The volume ratio of the deuterated chloroform to water is 1:1.

[0018] The present invention has the following beneficial effects:

[0019] The method provided by the present invention for preparing deuterated aromatic hydrocarbons using photocatalytic arylthianthrene salts has the advantages of low energy consumption, high conversion rate, and environmental friendliness. It is suitable for large-scale industrial production and provides a new, efficient and economical route for the synthesis of deuterated aromatic hydrocarbons. The method is mild, uses inexpensive and readily available raw materials, is simple to operate, has high yields, and is metal-free. Preliminary experimental results indicate that the method can be used to deuterate the backbone structures of various drug molecules, effectively converting C-H bonds to CD bonds in drug molecules, providing a reliable experimental method for studying the pharmacokinetics of drug molecules and improving their efficacy. DETAILED DESCRIPTION

[0020] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Unless otherwise specified, the experimental methods used in the following experimental examples are conventional methods; the materials and reagents used are commercially available reagents and materials unless otherwise specified.

[0022] Example 1

[0023] The preparation method of deuterated biphenyl comprises the following steps:

[0024] A magnetic stirrer, photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), biphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 40W 427nm blue light at room temperature for 6 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated biphenyl in an 80% yield.

[0025]

[0026] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (24.9mg, 80% yield). 1H NMR (600MHz, Chloroform-d) δ7.64–7.59 (m, 4H), 7.46 (dt, J = 7.9, 3.7Hz, 4H), 7.38–7.35 (m, 1H). 13 CNMR (151MHz, Chloroform-d) δ 141.4, 128.9, 128.8, 127.4, 127.3, 127.1 (t, J = 24.4MHz).

[0027] Example 2

[0028] The preparation method of deuterated tert-butylbiphenyl comprises the following steps:

[0029] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), tert-butylbiphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated tert-butylbiphenyl in a 65% yield.

[0030]

[0031] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (27.3mg, 65% yield).mp58.0–58.3℃; 1 HNMR(600MHz,Chloroform-d)δ7.61–7.56(m,2H),7.53(dd,J=8.2,1.5Hz,2H),7.48–7.45(m,2H),7.43–7.39(m,2H),1.36(s,9H). 2 H NMR(92MHz,CH2Cl2)δ7.37(s,1D). 13 CNMR(151MHz,Chloroform-d)δ150.4,141.2,138.5,128.7,127.2,127.0,126.7(d,J=24.3Hz),125.9,34.7,31.5.HRMS(APCI-TOF)m / z:[M+H] +Calcd for C 16 H 18 D + 212.1544;Found 212.1580.

[0032] Example 3

[0033] The preparation method of deuterated methylbiphenyl comprises the following steps: a magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), a methylbiphenyl thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) are sequentially added to a Schlenk reaction tube. The reaction is then irradiated with 40W 427nm blue light at room temperature for 6 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane are added for extraction, and the organic phase is collected. The resulting crude product is purified by silica gel column chromatography to obtain deuterated methylbiphenyl in an 81% yield.

[0034]

[0035] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (27.4mg, 81% yield). 1 H NMR (600MHz, Chloroform-d) δ7.59–7.56(m,2H),7.50–7.47(m,2H),7.41(d,J=7.9Hz,2H),7.26–7.23(m,2H),2.39(s,3H). 13 C NMR (151MHz, Chloroform-d) δ141.3, 138.5, 137.1, 129.6, 128.7, 127.14, 127.11, 126.8 (t, J = 24.0Hz), 21.2.

[0036] Example 4

[0037] The preparation method of deuterated bromobiphenyl comprises the following steps:

[0038] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), a bromobiphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated bromobiphenyl in a 63% yield.

[0039]

[0040] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (29.3 mg, 63% yield). 1 H NMR (600MHz, Chloroform-d) δ7.59–7.55(m,4H),7.49–7.44(m,4H). 13 C NMR (151MHz, Chloroform-d) δ140.3, 140.2, 132.0, 128.92, 128.88, 127.5 (t, J = 24.0Hz), 127.1, 121.7.

[0041] Example 5

[0042] The preparation method of aldehyde-deuterated biphenyl comprises the following steps:

[0043] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), an aldehyde-deuterated biphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain the aldehyde-deuterated biphenyl in a 91% yield.

[0044]

[0045] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (33.2mg, 91% yield).mp100.4–100.9℃; 1 H NMR (600MHz, Chloroform-d) δ10.06 (s, 1H), 7.96 (d, J = 8.3Hz, 2H), 7.76 (d, J = 8.3Hz, 2H), 7.64 (d, J = 8.2Hz, 2H), 7.48 (d, J = 8.1Hz, 2H). 2 HNMR(92MHz,CH2Cl2)δ7.45(s,1D). 13 C NMR(151MHz,Chloroform-d)δ192.0,147.3,139.8,135.3,130.4,129.0,128.3(t,J=24.0Hz),127.8,127.5.HRMS(ESI-TOF)m / z:[M+H] + Calcdfor C 13 H 10 DO + 206.0867;found206.0818.

[0046] Example 6

[0047] The preparation method of deuterated cyanobiphenyl comprises the following steps:

[0048] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), cyanobiphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain cyanodeuterated biphenyl in an 83% yield.

[0049]

[0050] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (29.9mg, 83% yield).mp94.3–94.6℃; 1 HNMR(400MHz,Chloroform-d)δ7.69(q,J=8.5Hz,4H),7.60–7.55(m,2H),7.48(d,J=8.1Hz,2H). 2 H NMR(92MHz,CH2Cl2)δ7.41(s,1D). 13 C NMR(151MHz,Chloroform-d)δ145.8,139.3,132.7,129.1,128.5(t,J=24.7Hz),127.9,127.4,119.1,111.0.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 13 H9DN + 181.0871; found 181.0868.

[0051] Example 7

[0052] The preparation method of ester-deuterated biphenyl comprises the following steps:

[0053] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), an ester-deuterated biphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain the ester-deuterated biphenyl in an 85% yield.

[0054]

[0055] Purification by column chromatography on silica gel(petroleum ether / ethyl acetate=100:1,v / v) afforded the title compound as a white solid(36.1mg,85%).mp122.0–122.4℃; 1 HNMR(400MHz,Chloroform-d)δ8.16–8.08(m,2H),7.71–7.65(m,2H),7.65–7.61(m,2H),7.51–7.44(m,2H),3.94(s,3H). 2 H NMR(92MHz,CH2Cl2)δ7.37(s,1D). 13 C NMR(151MHz,Chloroform-d)δ167.0,145.7,140.0,130.1,128.9,128.8,127.9(t,J=24.3Hz),127.3,127.1,52.1.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 14 H 12 DO2 + 214.0973; found 214.0964.

[0056] Example 8

[0057] The preparation method of ketone-substituted deuterated biphenyl comprises the following steps:

[0058] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), a ketobiphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain the keto-substituted deuterated biphenyl in a 73% yield.

[0059]

[0060] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless solid (28.6mg, 73% yield).mp124.6–124.9℃; 1 H NMR (600MHz, Chloroform-d) δ8.03(d,J=8.4Hz,2H),7.69(d,J=8.4Hz,2H),7.63(d,J=8.2Hz,2H),7.47(d,J=7.9Hz,2H),2.64(s,3H). 2 H NMR (92MHz, CH2Cl2) δ7.45 (s, 1D). 13 C NMR(151MHz,Chloroform-d)δ197.8,145.8,139.9,135.9,128.9,128.9,128.0(t,J=24.9Hz),127.3,127.2,26.7.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 14 H 12 DO + 198.1024;Found198.0990.

[0061] Example 9

[0062] The preparation method of methoxy-substituted deuterated biphenyl comprises the following steps:

[0063] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), a methoxy-substituted biphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain the methoxy-substituted deuterated biphenyl in an 88% yield.

[0064]

[0065] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a yellow oil (32.5mg, 88% yield). 1 H NMR (400MHz, Chloroform-d) δ7.52(dt,J=8.1,1.0Hz,2H),7.43–7.36(m,2H),7.31(q,J=4.4Hz,3H),6.97(d,J=8.7Hz,1H),3.79(s,3H). 2 H NMR(92MHz,CH2Cl2)δ7.07(s,1D). 13 C NMR(101MHz,Chloroform-d)δ156.6,138.7,130.9,129.7,128.6,128.1,127.0,120.6(t,J=24.0Hz),111.3,55.7.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 13 H 12 DO + 186.1024; found 186.1039.

[0066] Example 10

[0067] The preparation method of 3-bromo-1,1'-biphenyl-4'-d is as follows:

[0068] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), a 3-bromo-substituted biphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 3-bromo-1,1'-biphenyl-4'-d in 81% yield.

[0069]

[0070] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (40.1mg, 81% yield). 1 H NMR(600MHz,Chloroform-d)δ7.73(t,J=1.9Hz,1H),7.56–7.52(m,2H),7.50(dt,J =7.8,1.3Hz,1H),7.51–7.48(m,1H),7.43(d,J=8.1Hz,2H),7.29(t,J=7.8Hz,1H). 13 C NMR (151MHz, Chloroform-d) δ 143.5, 139.9, 130.38, 130.35, 130.3, 128.9, 127.7 (t, J = 24.3Hz), 127.2, 125.9, 123.0.

[0071] Example 11

[0072] The preparation method of 1,1'-diphenyl-2-d is as follows:

[0073] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), a 2-phenyl-substituted phenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 1,1'-diphenyl-2-d in a 63% yield.

[0074]

[0075] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (19.4mg, 63% yield). 1H NMR (600MHz, Chloroform-d) δ7.63 (dd, J=8.2, 1.4Hz, 3H), 7.55–7.43 (m, 4H), 7.38 (td, J=7.4, 1.3Hz, 2H). 13 C NMR (151MHz, Chloroform-d) δ141.4, 141.3, 128.9, 128.8, 127.4, 127.3, 127.0 (t, J = 24.0Hz).

[0076] Example 12

[0077] The preparation method of 1,1'-diphenyl-3-d is as follows:

[0078] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), a 3-phenyl-substituted phenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 1,1'-diphenyl-3-d in a 77% yield.

[0079]

[0080] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (23.9mg, 77% yield). 1 H NMR (600MHz, Chloroform-d) δ7.75–7.53(m,4H),7.53–7.44(m,3H),7.41–7.29(m,2H). 13 C NMR (151MHz, Chloroform-d) δ141.4, 128.9, 128.6 (t, J = 24.1Hz), 127.4, 127.31, 127.28, 127.2.

[0081] Example 13

[0082] The preparation method of 2-fluoro-6-(phenoxy-4-d)benzonitrile comprises the following steps:

[0083] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 2-fluoro-6-(phenoxy)benzonitrile thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube and irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 2-fluoro-6-(phenoxy-4-d)benzonitrile in a yield of 79%.

[0084]

[0085] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (33.8mg, 79% yield). 1 H NMR (600MHz, Chloroform-d) δ7.42(dd,J=7.3,4.2Hz,3H),7.11(d,J=8.4Hz,2H),6.88(t,J=8.4Hz,1H),6.60(d,J=8.6Hz,1H). 13 C NMR(151MHz,Chloroform-d)δ164.1(d,J=259.7Hz),161.1(d,J=4.5Hz),154.5,134.8(d,J=10.4Hz),1 30.2, 125.4 (t, J = 24.0Hz), 120.4, 111.8 (d, J = 3.2Hz), 111.1, 109.6 (d, J = 19.6Hz), 93.6 (d, J = 18.1Hz). 19 F NMR(376MHz,Chloroform-d)δ-104.8.

[0086] Example 14

[0087] The preparation method of 4-(phenoxy-4-d)benzonitrile comprises the following steps:

[0088] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 4-(phenoxy)benzonitrile thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube and irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 4-(phenoxy-4-d)benzonitrile in a 40% yield.

[0089]

[0090] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless oil (15.5mg, 40% yield). 1 H NMR (600MHz, Chloroform-d) δ7.63–7.57(m,2H),7.41(d,J=8.4Hz,2H),7.09–7.04(m,2H),7.00(d,J=2.0Hz,2H). 13 C NMR (151MHz, Chloroform-d) δ161.8, 155.0, 134.3, 130.3, 125.0 (t, J = 24.2Hz), 120.5, 119.0, 118.0, 106.0.

[0091] Example 15

[0092] The preparation method of phenyl-4-d benzoate comprises the following steps:

[0093] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), phenylbenzoate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain phenyl-4-d-benzoate in 80% yield.

[0094]

[0095] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (32.0mg, 80% yield).mp74.8–75.1℃; 1 HNMR(600MHz,Chloroform-d)δ8.23–8.16(m,2H),7.65–7.60(m,1H),7.50(t,J=7.8Hz,2H),7.45–7.37(m,2H),7.24–7.19(m,2H). 2 H NMR (92MHz, CH2Cl2) δ7.35 (s, 1D). 13 CNMR(151MHz,Chloroform-d)δ165.3,151.1,133.7,130.3,129.5,128.7,125.7(t,J=24.2Hz),121.8.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 13 H9DO2Na + 222.0636; found 222.0655.

[0096] Example 16

[0097] The preparation method of 1-(phenyl-4-d)pyrrolidin-2-one comprises the following steps:

[0098] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 1-(phenyl)pyrrolidin-2-one thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 1-(phenyl-4-d)pyrrolidin-2-one in a 77% yield.

[0099]

[0100] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a yellow oil (23.9mg, 77% yield). 1 H NMR (600MHz, Chloroform-d) δ7.64–7.59(m,2H),7.36(d,J=8.2Hz,2H),3.86(t,J=7.0Hz,2H),2.61(t,J=8.1Hz,2H),2.18–2.13(m,2H). 13 C NMR (151MHz, Chloroform-d) δ174.2, 139.4, 128.7, 124.2 (t, J = 24.0Hz), 120.0, 48.8, 32.8, 18.0.

[0101] Example 17

[0102] The preparation method of 2,4-dimethylbenzoate-5-d comprises the following steps:

[0103] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 2,4-dimethylbenzoate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 2,4-dimethylbenzoate-5-d in a 52% yield.

[0104]

[0105] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a colorless oil (17.2mg, 52% yield). 1H NMR (600MHz, Chloroform-d) δ7.83(s,1H),7.05(s,1H),3.87(s,3H),2.57(s,3H),2.35(s,3H). 13 C NMR (151MHz, Chloroform-d) δ168.1, 142.5, 140.5, 132.6, 130.8, 126.7, 126.3 (t, J = 24.0Hz), 51.8, 21.9, 21.4.

[0106] Example 18

[0107] The preparation method of 2-methoxybenzaldehyde-5-d comprises the following steps:

[0108] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 2-methoxybenzaldehyde thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 2-methoxybenzaldehyde-5-d in a 42% yield.

[0109]

[0110] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a colorless solid (11.6 mg, 42% yield). 1 H NMR (400MHz, Chloroform-d) δ10.47(s,1H),7.83(dt,J=2.0,1.1Hz,1H),7.55(ddt,J=8.4,2.1,1.1Hz,1H),6.99(d,J=8.5Hz,1H),3.93(s,3H). 13 C NMR (101MHz, Chloroform-d) δ190.0, 162.0, 136.0, 128.6, 125.0, 120.3 (t, J = 24.0Hz), 111.7, 55.8.

[0111] Example 19

[0112] The preparation method of (R)-4-((phenyl-4-d)methyl)-3-propionyloxypyrrolidin-2-one comprises the following steps:

[0113] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), (R)-4-(phenyl)methyl)-3-propionyloxypyrrolidin-2-one thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain (R)-4-((phenyl-4-d)methyl)-3-propionyloxypyrrolidin-2-one in a 91% yield.

[0114]

[0115] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a white solid (42.4mg, 91% yield). 1 H NMR(400MHz,Chloroform-d)δ7.33(d,J=7.8Hz,2H),7.21(d,J=7.9Hz,2H),4.67(ddd,J=7.3,6.3,3.6Hz,1H),4.38–3.9 8(m,2H),3.30(dd,J=13.4,3.3Hz,1H),2.96(dq,J=9.9,7.3Hz,2H),2.77(dd,J=13.4,9.6Hz,1H),1.20(t,J=7.3Hz,3H). 13 C NMR (151MHz, Chloroform-d) δ174.2, 153.7, 135.5, 129.6, 129.0, 127.2 (t, J = 24.6Hz), 66.3, 55.3, 38.1, 29.4, 8.5.

[0116] Example 20

[0117] The preparation method of methyl 2,3-dihydrobenzo[b][1,4]dioxane-5-carboxylate-7-d comprises the following steps:

[0118] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), methyl 2,3-dihydrobenzo[b][1,4]dioxolane-5-carboxylate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to afford methyl 2,3-dihydrobenzo[b][1,4]dioxolane-5-carboxylate-7-d in a 32% yield.

[0119]

[0120] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a white solid (42.4mg, 32% yield).mp87.5-87.9℃; 1 H NMR (600MHz, Chloroform-d) δ7.39(d,J=1.6Hz,1H),7.02(d,J=1.7Hz,1H),4.42–4.34(m,2H),4.32–4.22(m,2H),3.88(s,3H). 2 H NMR(92MHz,CH2Cl2)δ6.88(s,1D). 13 C NMR(151MHz,Chloroform-d)δ166.0,144.09,144.07,123.6,121.2,120.3(t,J=24.3Hz),120.0,64.6,63.9,52.0.HRMS(ESI-TOF)m / z:[M+Na] + Calcdfor C 10 H9DNaO4 + 218.0534; Found 218.0536.

[0121] Example 21

[0122] The preparation method of 6-methylchromen-4-one-8-d comprises the following steps:

[0123] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 6-methylchromen-4-one thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were sequentially added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 6-methylchromen-4-one-8-d in a 51% yield.

[0124]

[0125] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a colorless oil (16.6mg, 51% yield). 1 H NMR (600MHz, Chloroform-d) δ7.69(dd,J=2.4,0.9Hz,1H),7.28(dd,J=2.3Hz,1H),4.50(dd,J=6.8,6.0Hz,2H),2.79(dd,J=6.9,6.0Hz,2H),2.30(s,3H). 2 H NMR(92MHz,CH2Cl2)δ6.90(s,1D). 13 CNMR(151MHz,Chloroform-d)δ192.2,160.1,137.1,131.0,126.8,121.1,117.6(t,J=24.7Hz),67.2,38.0,20.6.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 10 H 10 DO2 + 164.0816; Found 164.0816.

[0126] Example 22

[0127] The preparation method of 9H-amino-9-ketone-2-d is as follows:

[0128] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 9H-amino-9-ketothianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 9H-amino-9-keto-2-d in a 50% yield.

[0129]

[0130] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (19.6 mg, 50% yield). 1 H NMR (400MHz, Chloroform-d) δ8.53–8.17(m,2H),7.85–7.68(m,2H),7.48(dd,J=8.5,2.6Hz,2H),7.37(td,J=7.5,2.4Hz,1H). 13 C NMR (151MHz, Chloroform-d) δ 177.3, 156.3, 134.9, 134.8 126.9, 126.8, 124.0, 123.8 (t, J = 24.0Hz), 122.0, 118.1.

[0131] Example 23

[0132] A method for preparing 3-chloro-6-methyldibenzo[c,f][1,2]thiazin-11(6H)-one-9-d 5,5-dioxide comprises the following steps:

[0133] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 3-chloro-6-methyldibenzo[c,f][1,2]thiazin-11(6H)-one thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, the reaction was extracted with saturated sodium chloride solution and dichloromethane, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 3-chloro-6-methyldibenzo[c,f][1,2]thiazin-11(6H)-one-9-d 5,5-dioxide in a 32% yield.

[0134]

[0135] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a yellow solid (19.8mg, 32% yield).mp165.2–167.1℃; 1 H NMR(600MHz,Chloroform-d)δ8.30(d,J=1.6Hz,1H),7.97–7.89(m,2H),7.75–7.57(m,2H),7.35(d,J=8.1Hz,1H),3.36(s,3H). 2 HNMR(92MHz,CH2Cl2)δ7.43(s,1D). 13 CNMR(151MHz,Chloroform-d)δ189.6,141.5,138.8,138.5,135.0,134.6,133.4,1 32.2,131.1,126.1(t,J=24.8Hz),125.6,124.8,39.2.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 14 H9DClNO3SNa + 331.0025; Found 331.0040.

[0136] Example 24

[0137] The preparation method of 9-p-toluenesulfonyl-9H-carbazole-3-d comprises the following steps:

[0138] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 9-(p-toluenesulfonyl)-9H-carbazole thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 9-(p-toluenesulfonyl)-9H-carbazole-3-d in a 65% yield.

[0139]

[0140] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=5:1, v / v) afforded the title compound as a white solid (22.0mg, 65% yield). 1 H NMR(600MHz,Chloroform-d)δ8.33(d,J=8.4Hz,2H),7.92–7.86(m,2H),7.69(d,J=8.4Hz,2 H),7.48(dt,J=7.2,3.6Hz,2H),7.35(t,J=7.5Hz,1H),7.08(d,J=8.2Hz,2H),2.24(s,3H). 13 C NMR (151MHz, Chloroform-d) δ 144.8, 138.4, 135.1, 129.6, 127.4, 127.3, 126.5, 126.4, 123.9, 123.4 (t, J = 24.2Hz), 120.0, 119.9, 115.2, 21.47.

[0141] Example 25

[0142] The preparation method of dibenzo[b,d]furan-2-d comprises the following steps:

[0143] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), dibenzo[b,d]furan-thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain dibenzo[b,d]furan-2-d in a 65% yield.

[0144]

[0145] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (22.0mg, 65% yield). 1 H NMR (600MHz, Chloroform-d) δ7.88(d,J=6.7Hz,2H),7.50(d,J=8.1Hz,2H),7.37(d,J=7.2Hz,2H),7.26(d,J=7.2Hz,1H). 13 C NMR (151MHz, Chloroform-d) δ156.2,127.1,127.0,124.2,122.7,122.6,120.6,120.3,111.7,111.6.

[0146] Example 26

[0147] The preparation method of methyl ([1,1'-biphenyl]-4-carbonyl-4'-d)-L-proline ester comprises the following steps:

[0148] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), methyl ([1,1'-biphenyl]-4-carbonyl-4'-d)-L-proline ester thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain methyl ([1,1'-biphenyl]-4-carbonyl-4'-d)-L-proline ester in a 51% yield.

[0149]

[0150] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (31.6mg, 51% yield).mp130.0–130.4℃; 1 H NMR(600MHz,Chloroform-d)δ7.66(d,J=8.2Hz,2H),7.64–7.59(m,4H),7.45(d,J=8.0Hz,2H),4.70(dd,J=8.4,5.1Hz,1H ),3.79(s,3H),3.73(dd,J=10.4,6.6Hz,1H),3.64–3.59(m,1H),2.39–2.29(m,1H),2.08–1.97(m,2H),1.95–1.87(m,1H). 2 H NMR (92MHz, CH2Cl2) δ7.30 (s, 1D). 13 C NMR(151MHz,Chloroform-d)δ173.1,169.8,143.4,140.6,135.2,129.1,127.8(t,J=24.8Hz),127.3,59.6,52.6,50.3,29.7,25.8.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 19 H 18 DNNaO3 + 333.1320; Found 333.1331.

[0151] Example 27

[0152] The preparation method of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl[1,1'-biphenyl]-4-carboxylate-4'-d comprises the following steps:

[0153] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl[1,1'-biphenyl]-4-carboxylate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl[1,1'-biphenyl]-4-carboxylate-4'-d in a 51% yield.

[0154]

[0155] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless solid (52.3mg, 78% yield).mp74.0–74.4℃; 1 H NMR(400MHz,Chloroform-d)δ8.11(d,J=8.4Hz,2H),7.69–7.57(m,4H),7.49–7.42(m,2H),4.96(td,J=10.9,4.4Hz,1H),2.23–2.07(m ,1H),1.99(pd,J=7.0,2.7Hz,1H),1.79–1.69(m,2H),1.62–1.51(m,2H),1.20–1.06(m,2H),0.99–0.88(m,7H),0.81(d,J=6.9Hz,3H). 2 H NMR (92MHz, CH2Cl2) δ7.33 (s, 1D). 13 C NMR (151 MHz, Chloroform-d) 13 CNMR(151MHz,Chloroform-d)δ167.0,145.9,140.5,130.4,130.0,129.2,128.1(t,J=24.8Hz),12 7.6,127.4,80.9,49.5,48.3,45.4,37.3,28.5,27.8,20.1,19.3,14.0.HRMS(ESI-TOF)m / z:[M+Na]+ Calcd for C 23 H 27 DNaO2 + 360.2044; Found 360.2048.

[0156] Example 28

[0157] The preparation method of (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane-2-yl[1,1'-biphenyl]-4-carboxylate-4'-d comprises the following steps:

[0158] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl[1,1'-biphenyl]-4-carboxylate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, the reaction was extracted with saturated sodium chloride solution and dichloromethane, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl[1,1'-biphenyl]-4-carboxylate-4'-d in a 62% yield.

[0159]

[0160] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless solid (41.6mg, 62% yield).mp124.4–124.7℃; 1H NMR(600MHz,Chloroform-d)δ8.13(d,J=8.3Hz,2H),7.69–7.65(m,2H),7.63–7.61(m,2H),7.46(d ,J=7.9Hz,2H),5.15(ddd,J=9.9,3.4,2.1Hz,1H),2.58–2.39(m,1H),2.17(ddd,J=13.4,9.5,4.5H z,1H),1.82(tq,J=12.2,4.2Hz,1H),1.75(t,J=4.5Hz,1H),1.43(tdd,J=12.4,4.6,2.2Hz,1H),1. 33(ddd,J=12.7,9.5,4.5Hz,1H),1.15(dd,J=13.9,3.5Hz,1H),0.98(s,3H),0.93(d,J=5.1Hz,6H). 2 H NMR(92MHz,CH2Cl2)δ7.23(s,1D). 13 C NMR(151MHz,Chloroform-d)δ166.8,145.7,140.3,130.2,129.8,128.9,127.9(t,J=23.8Hz),127 .4,127.2,80.7,49.3,48.0,45.2,37.1,28.3,27.6,19.9,19.0,13.8.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 23 H 25 DNaO2 + 358.1888; Found 358.1890.

[0161] Example 29

[0162] The preparation method of 2-isopropyl-5-methylphenyl-4-d benzoate comprises the following steps:

[0163] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), 2-isopropyl-5-methylphenylthianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain 2-isopropyl-5-methylphenyl-4-d-benzoate in an 88% yield.

[0164]

[0165] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless oil (44.7mg, 88% yield). 1 H NMR(600MHz,DMSO-d6)δ8.20–8.11(m,2H),7.80–7.72(m,1H),7.62(t,J=7.7Hz,2H),7 .29(s,1H),7.00(s,1H),2.95(hept,J=6.9Hz,1H),2.30(s,3H),1.15(d,J=6.9Hz,6H). 2 H NMR(92MHz,CH2Cl2)δ7.13(s,1D). 13 C NMR(151MHz,DMSO-d6)δ165.2,148.3,137.1,136.7,134.5,130.1,129.6,129.3, 127.3(t,J=24.8Hz),126.8,123.4,27.4,23.3,20.7.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 17 H 17 DNaO2 + 278.1262; Found 278.1280.

[0166] Example 30

[0167] The preparation method of [1,1'-biphenyl]-4-yl-4'-d-dodecanoate comprises the following steps:

[0168] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), [1,1'-biphenyl]-4-yl-4'-d-dodecanoate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain [1,1'-biphenyl]-4-yl-4'-d-dodecanoate in a 52% yield.

[0169]

[0170] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless solid (36.7mg, 52% yield).mp68.2–68.4℃; 1 H NMR(600MHz,Chloroform-d)δ7.59(dd,J=12.3,8.4Hz,4H),7.44(d,J=8.3Hz,2H),7.17(d,J=8.6Hz,2H) ,2.59(t,J=7.5Hz,2H),1.84–1.72(m,2H),1.48–1.41(m,2H),1.40–1.21(m,14H),0.91(t,J=7.0Hz,3H). 2 H NMR (92MHz, CH2Cl2) δ7.33 (s, 1D). 13 C NMR(151MHz,Chloroform-d)δ172.4,150.2,140.4,138.9,128.7,128.1,127.1,121.9, 34.5,31.9,29.6,29.5,29.4,29.3,29.2,25.0,22.7,14.1.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 24 H 31 DO2Na + 376.2357; Found 376.2361.

[0171] Example 31

[0172] The preparation method of [1,1'-biphenyl]-4-yl-4'-d 2-propyl valerate comprises the following steps:

[0173] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), [1,1'-biphenyl]-4-yl-4'-d 2-propylpentanoate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain [1,1'-biphenyl]-4-yl-4'-d 2-propylpentanoate in a 79% yield.

[0174]

[0175] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless solid (47.0mg, 79% yield).mp47.3–47.7℃; 1 H NMR(600MHz,Chloroform-d)δ7.59(dd,J=12.2,8.4Hz,4H),7.45(d,J=7.7Hz,2H),7.16(dd,J=8.5,1.7Hz ,2H),2.68–2.59(m,1H),1.89–1.75(m,2H),1.66–1.54(m,2H),1.51–1.41(m,4H),1.00(t,J=7.3Hz,6H). 2 H NMR (92MHz, CH2Cl2) δ7.40 (s, 1D). 13 CNMR(151MHz,Chloroform-d)δ175.2,150.4,140.6,139.0,128.8,128.3,127.2 ,127.1(t,J=23.6Hz),122.0,45.6,34.8,20.9,14.2.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 20 H 23 DO2Na + 320.1731; Found 320.1730.

[0176] Example 32

[0177] The preparation method of [1,1'-biphenyl]-4-yl-4'-d 2-(4-isobutylphenyl) propionate comprises the following steps:

[0178] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), [1,1'-biphenyl]-4-yl-2-(4-isobutylphenyl) propionate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain [1,1'-biphenyl]-4-yl-4'-d 2-(4-isobutylphenyl) propionate in a 64% yield.

[0179]

[0180] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless solid (45.8mg, 64% yield).mp76.9–77.2℃; 1 H NMR(600MHz,Chloroform-d)δ7.53(d,J=7.6Hz,4H),7.41(d,J=7.9Hz,2H),7.31(d,J=7.9Hz,2H),7.15(d,J=7.9Hz,2H),7.07(d,J= 8.5Hz, 2H), 3.95 (q, J = 7.1Hz, 1H), 2.48 (d, J = 7.2Hz, 2H), 1.87 (dt, J = 13.5, 6.8Hz, 1H), 1.62 (d, J = 7.2Hz, 3H), 0.91 (d, J = 6.6Hz, 6H). 2 HNMR(92MHz,CH2Cl2)δ7.27(s,1D). 13 CNMR(151MHz,Chloroform-d)δ173.3,150.3,140.9,140.4,138.9,137.3,129.5,128.7 ,128.1,127.2,127.1,121.7,45.3,45.1,30.2,22.4,18.6.HRMS(ESI-TOF)m / z:[M+Na] +Calcd for C 25 H 25 DO2Na + 382.1888; Found 382.1961

[0181] Example 33

[0182] The preparation method of phenyl-4-d 2-(3-benzoylphenyl) propionate comprises the following steps:

[0183] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), phenyl-2-(3-benzoylphenyl) propionate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain phenyl-4-d2-(3-benzoylphenyl) propionate in a 44% yield.

[0184]

[0185] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a colorless oil (42.3mg, 44% yield). 1 H NMR(600MHz,Chloroform-d)δ7.87(t,J=1.8Hz,1H),7.84–7.81(m,2H),7.74(dt,J=7.7,1.4Hz,1H),7.65(dt,J=7.8,1.5Hz,1 H),7.61–7.58(m,1H),7.53–7.45(m,3H),7.38–7.33(m,2H),7.05–6.99(m,2H),4.06(q,J=7.2Hz,1H),1.67(d,J=7.2Hz,3H). 2 H NMR δ7.29 (s, 1D). 13C NMR(151MHz,Chloroform-d)δ196.5,172.7,150.8,140.5,138.3,137.6,132.7,131.6,130.2,1 29.4,129.3,128.9,128.5,125.7(t,J=24.2Hz),121.4,45.7,18.6.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 22 H 17 DO3Na + 354.1208; Found 354.1208.

[0186] Example 34

[0187] The preparation method of [1,1'-biphenyl]-4-yl-4'-d 4-(N,N-dipropylsulfonamide)benzoate comprises the following steps:

[0188] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), [1,1'-biphenyl]-4-yl-4-(N,N-dipropylsulfonamide)benzoate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, the reaction was extracted with saturated sodium chloride solution and dichloromethane, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain [1,1'-biphenyl]-4-yl-4'-d 4-(N,N-dipropylsulfonamide)benzoate in a 51% yield.

[0189]

[0190] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a white solid (31.6mg, 51% yield).mp146.0–146.3℃; 1HNMR(600MHz,Chloroform-d)δ8.38–8.32(m,2H),8.02–7.94(m,2H),7.72–7.64(m,2H),7.64–7.58(m, 2H),7.50–7.43(m,2H),7.38–7.28(m,2H),3.84–2.89(m,4H),1.62–1.54(m,4H),0.90(t,J=7.4Hz,6H). 2 H NMR (92MHz, CH2Cl2) δ7.33 (s, 1D). 13 C NMR(151MHz,Chloroform-d)δ164.0,150.2,145.1,140.3,139.5,132.9,130.9,128.8,128.4,127.3,121.9,50.1,22.1,11.3.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 25 H 26 DNO4SNa + 461.1616; Found 461.1579.

[0191] Example 35

[0192] The preparation method of deuterated boscalid comprises the following steps:

[0193] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), boscalid thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated boscalid in a 60% yield.

[0194]

[0195] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a yellow solid (41.2mg, 60% yield). 1H NMR (400MHz, Chloroform-d) δ8.49–8.33(m,2H),8.17(s,1H),8.11(dd,J=7.685,1.981Hz,1H),7.55–7.39(m,3H),7.36–7.28(m,3H),7.30–7.22(m,1H). 13 C NMR(151MHz,Chloroform-d)δ162.6,151.3,146.8,140.1,136.4,134.5,134.4 ,132.5,131.2,130.9,130.2,129.4,128.8,125.2(t,J=24.8Hz),123.0,122.4.

[0196] Example 36

[0197] The preparation method of deuterated ether pyrethrin comprises the following steps:

[0198] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), ethathrin thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 40W 427nm blue light at room temperature for 6 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated ethathrin in a 60% yield.

[0199]

[0200] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a colorless oil (22.6mg, 60% yield). 1H NMR(400MHz,Chloroform-d)δ7.39–7.33(m,2H),7.31–7.25(m,3H),7.16–7.09(m,1H),7.02(dddd,J=10.4,7.6,1.8,1.1Hz,3 H),6.97–6.89(m,2H),6.86–6.81(m,1H),4.46(s,2H),4.02(q,J=7.0Hz,2H),3.43(s,2H),1.41(t,J=7.0Hz,3H),1.33(s,6H). 13 C NMR(151MHz,Chloroform-d)δ157.5,157.3,157.10 141.2,139.1,129.8,129.7,127.2,127.1,123.4,122.1,119.1,117.8,117. 7,114.14,114.10,113.8(t,J=24.2Hz),80.5,72.9,63.5,38.7,26.3,15.1.

[0201] Example 37

[0202] The preparation method of deuterated pyriproxyfen is as follows:

[0203] A magnetic stirrer, photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), pyriproxyfen thianthrene salt (0.2 mmol), deuterated chloroform (1 mL), and water (1 mL) were added to a Schlenk reaction tube and irradiated with 40W 427nm blue light at room temperature for 6 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated pyriproxyfen with a yield of 60%.

[0204]

[0205] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a colorless oil (38.1mg, 60% yield). 1H NMR(600MHz,Chloroform-d)δ8.25–8.00(m,1H),7.57(ddd,J=8.3,7.1,2.0Hz,1H),7.30(d,J=8.2Hz,2H),7.04–6.91(m,6H),6. 86(ddd,J=7.1,5.1,1.0Hz,1H),6.75(dd,J=8.2,1.1Hz,1H),5.69–5.47(m,1H),4.26–4.04(m,2H),1.50(dd,J=6.4,1.1Hz,3H). 13 C NMR(151MHz,Chloroform-d)δ163.3,158.6,155.4,150.4,146.9,138.8,129. 6,122.3(t,J=24.2Hz),120.9,117.7,116.9,115.9,111.8,71.2,69.4,17.1.

[0206] Example 38

[0207] The preparation method of deuterated benzbromarone comprises the following steps:

[0208] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), benzbromarone thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 40W 427nm blue light at room temperature for 6 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated benzbromarone in 80% yield.

[0209]

[0210] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a yellow oil (55.2mg, 80% yield). 1H NMR(600MHz,Chloroform-d)δ7.32(qd,J=8.0,7.0,1.7Hz,4H),7.29–7.23(m,1H),7.12(dd,J=7.8,1.7Hz,1H),6.94(ddd,J=8.3,3.7,1.7Hz,1H),6 .55(dd,J=22.7,8.2Hz,1H),5.19(ddd,J=8.7,3.9,1.6Hz,1H),3.83–3.5 3(m,2H),3.08(q,J=1.5Hz,3H),2.34(d,J=5.1Hz,3H),2.31–2.12(m,2H). 2 H NMR(92MHz,CH2Cl2)δ6.82(s,1D). 13 C NMR (151MHz, Chloroform-d) δ156.93 (q, J = 35.8Hz), δ156.86 (q, J = 35.7Hz), 155.6, 155. 4,130.8,130.7,128.9,128.8,128.0,127.9,126.91,126.86,126.6,126.5,125.7,125.5 ,120.4(t,J=24.3Hz),120.3(t,J=24.2Hz),116.6(q,J=287.3Hz),116.5(q,J=287.8Hz) ,112.7,112.4,47.1,46.7(q,J=3.3Hz),37.6,35.6,35.3(q,J=3.9Hz),34.7,16.5,16.4. 19 F NMR(565MHz,Chloroform-d)δ-69.0,-69

[0211] Example 39

[0212] The preparation method of deuterated fenofibrate comprises the following steps:

[0213] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), fenofibrate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 40W 427nm blue light at room temperature for 6 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated fenofibrate in a 59% yield.

[0214]

[0215] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a colorless oil (41.6mg, 59% yield). 1 H NMR (600MHz, Chloroform-d) δ7.96–7.65 (m, 4H), 7.45 (d, J = 8.0Hz, 2H), 7.06–6.76 (m, 2H), 5.08 (p, J = 6.3Hz, 1H), 1.65 (s, 6H), 1.19 (d, J = 6.3Hz, 6H). 2 H NMR (92MHz, CH2Cl2) δ7.60 (s, 1D). 13 CNMR(151MHz,Chloroform-d)δ195.6,173.3,159.7,138.3,132.2,131.7(t,J=24.0Hz) ,131.3,130.7,129.8,128.2,117.3,79.5,69.4,25.5,21.6HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 20 H 21 DNaO4 + 350.1473; Found 350.1454.

[0216] Example 40

[0217] The preparation method of deuterated fenbufen methyl ester comprises the following steps:

[0218] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), fenbufen methyl thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated fenbufen methyl ester in a 51% yield.

[0219]

[0220] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a white solid (27.5mg, 51% yield), mp95.4–96.2℃. 1 H NMR(400MHz,Chloroform-d)δ8.06(d,J=8.5Hz,2H),7.72–7.67(m,2H),7.65–7.60( m,2H),7.50–7.46(m,2H),3.72(s,3H),3.36(t,J=6.6Hz,2H),2.80(t,J=6.6Hz,2H). 2 H NMR(92MHz,CH2Cl2)δ7.43(s,1D). 13 C NMR(101MHz,Chloroform-d)δ197.8,173.5,146.1,140.0,135.3,129.0,128.8,127.4,52.0,33.6,28.2.HRMS(ESI-TOF)m / z:[M+Na] + Calcd for C 17 H 15 DO3Na + 292.1054; Found 292.1051.

[0221] Example 41

[0222] The preparation method of deuterated indomethacin methyl ester comprises the following steps:

[0223] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), indomethacin methyl thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated indomethacin methyl ester in a 51% yield.

[0224]

[0225] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a white solid (29.9 mg, 41% yield). 1 H NMR (400MHz, Chloroform-d) δ7.75–7.63(m,2H),7.54–7.43(m,2H),6.96(s,1H),6.86(s,1H),3.84(s,3H),3.71(s,3H),3.67(s,2H),2.39(s,3H). 13 C NMR (101MHz, Chloroform-d) δ168.4,156.1,139.4,136.1,134.0,131.3,130.8,129.2,115.0,112.6,101.4,55.8,52.3,30.3,13.5.

[0226] Example 42

[0227] The preparation method of deuterated isoxic acid methyl ester comprises the following steps:

[0228] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01 mmol), methyl isoxalate thianthrene salt (0.2 mmol), deuterated chloroform (63 mmol, 1 mL), and water (1 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 427 nm blue light at 40 W for 6 hours at room temperature. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated methyl isoxalate in a 51% yield.

[0229]

[0230] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=10:1, v / v) afforded the title compound as a yellow oil (37.7mg, 67% yield). 1H NMR(600MHz,Chloroform-d)δ8.11(d,J=2.5Hz,1H),7.89(dd,J=7.8,1.3Hz,1H),7.55(td,J=7.5,1.4Hz,1H),7.47 (td,J=7.6,1.3Hz,1H),7.42(d,J=2.5Hz,1H),7.36(dd,J=7.5,1.2Hz,1H),5.18(s,2H),3.70(s,3H),3.65(s,2H). 2 H NMR(92MHz,CH2Cl2)δ7.07(s,1D). 13 C NMR(151MHz,Chloroform-d)δ190.9,172.0,160.6,140.6,136.3,135.7,132. 9,132.6,129.6,129.4,127.9,125.3,120.9(t,J=24.0Hz),73.8,52.2,40.2.

[0231] Example 43

[0232] The preparation method of deuterated biphenyl comprises the following steps:

[0233] A magnetic stirrer, photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.002 mmol), biphenylthianthrene salt (0.2 mmol), deuterated chloroform (65 mmol, 1.03 mL), and water (1.03 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 30W 427nm blue light at room temperature for 12 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated biphenyl in a 30% yield.

[0234]

[0235] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (24.9mg, 80% yield). 1 H NMR (600MHz, Chloroform-d) δ7.64–7.59 (m, 4H), 7.46 (dt, J = 7.9, 3.7Hz, 4H), 7.38–7.35 (m, 1H). 13CNMR (151MHz, Chloroform-d) δ 141.4, 128.9, 128.8, 127.4, 127.3, 127.1 (t, J = 24.4MHz).

[0236] Example 44

[0237] The preparation method of deuterated tert-butylbiphenyl comprises the following steps:

[0238] A magnetic stirrer, the photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.02 mmol), tert-butylbiphenylthianthrene salt (0.2 mmol), deuterated chloroform (10 mmol, 0.16 mL), and water (0.16 mL) were added to a Schlenk reaction tube. The reaction was irradiated with 20W 427nm blue light at room temperature for 3 hours. After completion of the reaction, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The crude product was purified by silica gel column chromatography to obtain deuterated tert-butylbiphenyl in a 45% yield.

[0239]

[0240] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (27.3mg, 65% yield).mp58.0–58.3℃; 1 HNMR(600MHz,Chloroform-d)δ7.61–7.56(m,2H),7.53(dd,J=8.2,1.5Hz,2H),7.48–7.45(m,2H),7.43–7.39(m,2H),1.36(s,9H). 2 H NMR(92MHz,CH2Cl2)δ7.37(s,1D). 13 CNMR(151MHz,Chloroform-d)δ150.4,141.2,138.5,128.7,127.2,127.0,126.7(d,J=24.3Hz),125.9,34.7,31.5.HRMS(APCI-TOF)m / z:[M+H] + Calcd for C 16 H 18 D + 212.1544;Found 212.1580.

[0241] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing deuterated aromatic hydrocarbons by catalyzing arylthianthrene salts using visible light, characterized in that: The steps are: (1) The raw materials, arylthianthrene salt and deuterated chloroform, react in aqueous solution under the catalysis of 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile and under visible light conditions at room temperature until complete reaction; (2) The reactant in step (1) is extracted and the organic phase is collected, and then purified by silica gel column chromatography to obtain deuterated aromatic hydrocarbons; The structural formula of the arylthianthrene salt is: ; Where Ar is 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 and Any of; R is any one of methyl, ethyl, methoxy, tert-butyl, isopropyl, fluorine, chlorine, bromine, trifluoromethyl, cyano, 2-propylvalerate, proline ester, benzoate, dodecanoate, N,N-dipropylsulfonamide and p-toluenesulfonyl; The visible light is 427nm blue light irradiation.

2. The method for preparing deuterated aromatic hydrocarbons using arylthianthrene salts catalyzed by visible light according to claim 1, characterized in that: The molar ratio of the arylthianthrene salt, deuterated chloroform and 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile is 1: 10-65:0.01-0.

1.

3. The method for preparing deuterated aromatic hydrocarbons using arylthianthrene salts under visible light catalysis according to claim 2, characterized in that: The light intensity of the 427nm blue light is 20W-40W.

4. The method for preparing deuterated aromatic hydrocarbons using arylthianthrene salts catalyzed by visible light according to claim 3, characterized in that: The reaction time is 3-12 hours.

5. The method for preparing deuterated aromatic hydrocarbons using arylthianthrene salts catalyzed by visible light according to claim 4, characterized in that: The extraction reagents used in step (2) are saturated sodium chloride solution and dichloromethane.

6. The method for preparing deuterated aromatic hydrocarbons using arylthianthrene salts catalyzed by visible light according to any one of claims 1 to 5, characterized in that: The structural formula of the deuterated aromatic hydrocarbon is: ; Where: Ar is 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 and Any of; R is any one of methyl, ethyl, methoxy, tert-butyl, isopropyl, fluorine, chlorine, bromine, trifluoromethyl, cyano, 2-propylvalerate, proline ester, benzoate, dodecanoate, N,N-dipropylsulfonamide and p-toluenesulfonyl.

Images