Method for preparing deuterated aromatic hydrocarbon by catalyzing aryl thianthrene salt with visible light

Abstract

The invention belongs to the field of organic synthesis, and relates to a preparation method of deuterated aromatic hydrocarbon. According to the method, the aryl thianthrene salt is used as a raw material under the condition of irradiation of visible light at room temperature, deuterated chloroform is used as a deuterium source, and a photocatalyst 2, 3, 4, 5, 6-penta (9-carbazolyl)-cyanophenyl 5CzBN is used as a photocatalyst, so that the preparation of the deuterated aromatic hydrocarbon is realized. The method is mild in condition, cheap and easily available in raw materials, simple and convenient to operate, high in yield and free of metal participation, a preliminary experiment result shows that the method can be used for deuteration of various drug molecule skeleton structures, conversion of drug molecules from C-H bonds to C-D bonds is effectively achieved, and a material basis is provided for research on pharmacokinetics of deuterated drug molecules and improvement of drug effects.

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 technology plays an important role in drug and pesticide chemistry research. In the pharmaceutical field, isotope labeling is widely used to study the metabolic process of active drugs and identify specific metabolites. Deuterium atoms are currently the most mainstream isotope labeling method, especially playing a key role in studying the isotope effect of basic reaction kinetics. Deuterium-labeled compounds are similar to hydrogen isotopes and have almost the same physical properties, but due to different molecular weights, they are often used as internal standards for liquid chromatography-mass spectrometry (LC-MS) analysis in environmental and human sample studies. In addition, deuterated compounds show significant improvements in drug metabolism and pharmacological properties while maintaining the chemical structure and physical properties of unlabeled compounds, so they have attracted much attention in new drug research and development. In 2017, the FDA approved the first deuterated drug Austedo for the treatment of diseases such as Huntington's disease, which marked an important step forward for deuterated compounds in clinical practice. Deuterated aromatics are widely used in organic synthesis, medicinal chemistry and materials science. The application with publication number CN112281182A discloses a method for preparing deuterated aromatics under electrochemical conditions, which uses heavy water as a deuterium source, triphenylamine and triphenylphosphine as sacrificial reagents, and the reaction substrate can be bromoaromatics, chloroaromatics or iodoaromatics; the types of deuterated aromatics obtained are limited, and the electrochemical preparation cost is high. It can be seen that the traditional method for preparing deuterated aromatics usually requires high temperature and pressure or expensive reagents, and the reaction conditions are harsh and the cost is high.

[0003] In recent years, photocatalysis has attracted much attention due to its mild reaction conditions and efficient catalytic performance. Although visible light catalysis is a rapidly developing field, compared with traditional free radical initiators, photocatalysis has the advantages of mild reaction conditions, good functional group compatibility and no need to use toxic initiators. However, the current methods for preparing deuterated aromatics using photocatalysis still have certain 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 aryl thianthrene salts under visible light catalysis.

[0005] The technical solution of the present invention is achieved in this way:

[0006] A method for preparing deuterated aromatic hydrocarbons by catalyzing aryl thianthrene salts with 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 aryl thianthrene salt, deuterated chloroform, and water are sequentially added to a Schlenk reaction tube, and irradiated with 20-40W 427nm blue light for 3-12 hours at room temperature. After the reaction is completed, a saturated sodium chloride solution and dichloromethane are added for extraction, and the organic phase is collected. The obtained crude product is purified by silica gel column chromatography to obtain deuterated aromatic hydrocarbons;

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

[0010]

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

[0012] Furthermore, Ar is

[0013] Any of;

[0014] 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.

[0015] The photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile, abbreviated as 5CzBN, has the following structural formula:

[0016]

[0017] 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.

[0018] The volume ratio of deuterated chloroform to water is 1:1.

[0019] The present invention has the following beneficial effects:

[0020] The method for preparing deuterated aromatic hydrocarbons by photocatalytic arylthianthrene salts provided by the present invention has the advantages of low energy consumption, high conversion rate and environmental protection, is suitable for large-scale industrial production, and provides a new efficient and economical way for the synthesis of deuterated aromatic hydrocarbons. The method has mild conditions, cheap and readily available raw materials, simple operation, high yield, and no metal involvement. 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 CH bonds to CD bonds, and providing a reliable experimental means for studying the pharmacokinetics of drug molecules and improving drug efficacy. DETAILED DESCRIPTION

[0021] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the 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.

[0022] Unless otherwise specified, the experimental methods used in the following experimental examples are all conventional methods; the materials and reagents used are reagents and materials that can be obtained from commercial channels unless otherwise specified.

[0023] Example 1

[0024] The preparation method of deuterated biphenyl comprises the following steps:

[0025] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), a biphenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W427nm blue light at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 80%.

[0026]

[0027] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (24.9 mg, 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).

[0028] Example 2

[0029] The preparation method of deuterated tert-butylbiphenyl comprises the following steps:

[0030] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), tert-butyl biphenyl thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated tert-butyl biphenyl with a yield of 65%.

[0031]

[0032] 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.

[0033] Example 3

[0034] The preparation method of deuterated methyl biphenyl is as follows: a magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), a methyl biphenyl thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) are sequentially added to a Schlenk reaction tube, and irradiated with 40W 427nm blue light for 6 hours at room temperature. After the reaction is completed, a saturated sodium chloride solution and dichloromethane are added for extraction, and the organic phase is collected. The obtained crude product is purified by silica gel column chromatography to obtain deuterated methyl biphenyl, and the yield is 81%.

[0035]

[0036] 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.

[0037] Example 4

[0038] The preparation method of deuterated bromobiphenyl comprises the following steps:

[0039] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), a bromobiphenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated bromobiphenyl with a yield of 63%.

[0040]

[0041] 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.

[0042] Example 5

[0043] The preparation method of aldehyde deuterated biphenyl comprises the following steps:

[0044] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), an aldehyde biphenyl thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain aldehyde deuterated biphenyl with a yield of 91%.

[0045]

[0046] 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; found 206.0818.

[0047] Example 6

[0048] The preparation method of deuterated cyanobiphenyl comprises the following steps:

[0049] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), a cyanobiphenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain cyanodeuterated biphenyl with a yield of 83%.

[0050]

[0051] 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.

[0052] Example 7

[0053] The preparation method of ester-deuterated biphenyl comprises the following steps:

[0054] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), an ester-biphenyl thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 ester-deuterated biphenyl with a yield of 85%.

[0055]

[0056] 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.

[0057] Example 8

[0058] The preparation method of ketone-substituted deuterated biphenyl comprises the following steps:

[0059] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), a ketobiphenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 keto-substituted deuterated biphenyl with a yield of 73%.

[0060]

[0061] 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;Found 198.0990.

[0062] Example 9

[0063] The preparation method of methoxy-substituted deuterated biphenyl comprises the following steps:

[0064] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), a methoxy-substituted biphenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 methoxy-substituted deuterated biphenyl with a yield of 88%.

[0065]

[0066] 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.

[0067] Example 10

[0068] The preparation method of 3-bromo-1,1'-biphenyl-4'-d comprises the following steps:

[0069] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 3-bromo-substituted biphenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 81%.

[0070]

[0071] 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.

[0072] Embodiment 11

[0073] The preparation method of 1,1'-diphenyl-2-d comprises the following steps:

[0074] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 2-phenyl substituted phenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and irradiated with 40W 427nm blue light for 6 hours at room temperature. After the reaction was completed, 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 with a yield of 63%.

[0075]

[0076] 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).

[0077] Example 12

[0078] The preparation method of 1,1'-diphenyl-3-d comprises the following steps:

[0079] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 3-phenyl substituted phenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 77%.

[0080]

[0081] 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.

[0082] Embodiment 13

[0083] The preparation method of 2-fluoro-6-(phenoxy-4-d)benzonitrile comprises the following steps:

[0084] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 2-fluoro-6-(phenoxy)benzonitrile thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 79%.

[0085]

[0086] Purification by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1, v / v) afforded the title compound as a white solid (33.8 mg, 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.

[0087] Embodiment 14

[0088] The preparation method of 4-(phenoxy-4-d)benzonitrile comprises the following steps:

[0089] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 4-(phenoxy)benzonitrile thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 40%.

[0090]

[0091] 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.

[0092] Embodiment 15

[0093] The preparation method of phenyl-4-d benzoate comprises the following steps:

[0094] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), phenylbenzoate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 80%.

[0095]

[0096] 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.

[0097] Example 16

[0098] The preparation method of 1-(phenyl-4-d)pyrrolidin-2-one comprises the following steps:

[0099] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 1-(phenyl)pyrrolidin-2-one thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 77%.

[0100]

[0101] 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.

[0102] Embodiment 17

[0103] The preparation method of 2,4-dimethylbenzoate-5-d comprises the following steps:

[0104] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 2,4-dimethylbenzoate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 52%.

[0105]

[0106] 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.

[0107] Embodiment 18

[0108] The preparation method of 2-methoxybenzaldehyde-5-d comprises the following steps:

[0109] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 2-methoxybenzaldehyde thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 42%.

[0110]

[0111] 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.

[0112] Embodiment 19

[0113] The preparation method of (R)-4-((phenyl-4-d)methyl)-3-propionyloxypyrrolidin-2-one comprises the following steps:

[0114] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), (R)-4-(phenyl)methyl)-3-propionyloxypyrrolidin-2-one thianthrene salt (0.2mmol) and deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain (R)-4-((phenyl-4-d)methyl)-3-propionyloxypyrrolidin-2-one with a yield of 91%.

[0115]

[0116] 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.

[0117] Embodiment 20

[0118] The preparation method of methyl 2,3-dihydrobenzo[b][1,4]dioxane-5-carboxylate-7-d comprises the following steps:

[0119] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), methyl 2,3-dihydrobenzo[b][1,4]dioxane-5-carboxylate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 2,3-dihydrobenzo[b][1,4]dioxane-5-carboxylate-7-d with a yield of 32%.

[0120]

[0121] 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.

[0122] Embodiment 21

[0123] The preparation method of 6-methylchromen-4-one-8-d comprises the following steps:

[0124] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 6-methylchromen-4-one thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were sequentially added to a Schlenk reaction tube, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain 6-methylchromen-4-one-8-d with a yield of 51%.

[0125]

[0126] 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.

[0127] Embodiment 22

[0128] The preparation method of 9H-amino-9-ketone-2-d comprises the following steps:

[0129] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 9H-amino-9-ketone thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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-ketone-2-d with a yield of 50%.

[0130]

[0131] 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.

[0132] Embodiment 23

[0133] The preparation method of 3-chloro-6-methyldibenzo[c,f][1,2]thiazin-11(6H)-one-9-d 5,5-dioxide comprises the following steps:

[0134] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 3-chloro-6-methyldibenzo[c,f][1,2]thiazin-11(6H)-one thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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-chloro-6-methyldibenzo[c,f][1,2]thiazin-11(6H)-one-9-d 5,5-dioxide with a yield of 32%.

[0135]

[0136] 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.

[0137] Embodiment 24

[0138] The preparation method of 9-p-toluenesulfonyl-9H-carbazole-3-d comprises the following steps:

[0139] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 9-toluenesulfonyl-9H-carbazole thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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-toluenesulfonyl-9H-carbazole-3-d with a yield of 65%.

[0140]

[0141] 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.

[0142] Embodiment 25

[0143] The preparation method of dibenzo[b,d]furan-2-d comprises the following steps:

[0144] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), dibenzo[b,d]furanthrenthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 65%.

[0145]

[0146] 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.

[0147] Embodiment 26

[0148] The preparation method of methyl ([1,1'-biphenyl]-4-carbonyl-4'-d)-L-proline ester comprises the following steps:

[0149] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), methyl([1,1'-biphenyl]-4-carbonyl-4'-d)-L-proline ester thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 51%.

[0150]

[0151] 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.

[0152] Embodiment 27

[0153] The preparation method of (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl[1,1'-biphenyl]-4-carboxylate-4'-d comprises the following steps:

[0154] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl[1,1'-biphenyl]-4-carboxylate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 51%.

[0155]

[0156] 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.

[0157] Embodiment 28

[0158] 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:

[0159] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane-2-yl[1,1'-biphenyl]-4-carboxylate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane-2-yl[1,1'-biphenyl]-4-carboxylate-4'-d with a yield of 62%.

[0160]

[0161] 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.

[0162] Embodiment 29

[0163] The preparation method of 2-isopropyl-5-methylphenyl-4-d benzoate comprises the following steps:

[0164] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), 2-isopropyl-5-methylphenylthianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 88%.

[0165]

[0166] 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.

[0167] Embodiment 30

[0168] The preparation method of [1,1'-biphenyl]-4-yl-4'-d-dodecanoate comprises the following steps:

[0169] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), [1,1'-biphenyl]-4-yl-4'-d dodecanoate thianthrene salt (0.2mmol) and deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain [1,1'-biphenyl]-4-yl-4'-d dodecanoate with a yield of 52%.

[0170]

[0171] 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.

[0172] Embodiment 31

[0173] The preparation method of [1,1'-biphenyl]-4-yl-4'-d 2-propyl valerate comprises the following steps:

[0174] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), [1,1'-biphenyl]-4-yl-4'-d 2-propyl valerate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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-propyl valerate with a yield of 79%.

[0175]

[0176] 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.

[0177] Embodiment 32

[0178] The preparation method of [1,1'-biphenyl]-4-yl-4'-d 2-(4-isobutylphenyl) propionate comprises the following steps:

[0179] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), [1,1'-biphenyl]-4-yl-2-(4-isobutylphenyl) propionate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a 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 with a yield of 64%.

[0180]

[0181] 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

[0182] Embodiment 33

[0183] The preparation method of phenyl-4-d 2-(3-benzoylphenyl) propionate comprises the following steps:

[0184] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), phenyl-2-(3-benzoylphenyl) propionate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 44%.

[0185]

[0186] 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 NMRδ7.29(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 + Found 354.1208.

[0187] Embodiment 34

[0188] The preparation method of [1,1'-biphenyl]-4-yl-4'-d 4-(N,N-dipropylsulfonamide)benzoate comprises the following steps:

[0189] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), [1,1'-biphenyl]-4-yl-4-(N,N-dipropylsulfonamide)benzoate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 4-(N,N-dipropylsulfonamide)benzoate with a yield of 51%.

[0190]

[0191] 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.

[0192] Embodiment 35

[0193] The preparation method of deuterated boscalid comprises the following steps:

[0194] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), a boscalid thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated boscalid with a yield of 60%.

[0195]

[0196] 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.

[0197] Embodiment 36

[0198] The preparation method of deuterated ether pyrethrin comprises the following steps:

[0199] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), thiothrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and irradiated with 40W427nm blue light for 6 hours at room temperature. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated thiothrene with a yield of 60%.

[0200]

[0201] 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.

[0202] Embodiment 37

[0203] The preparation method of deuterated pyriproxyfen is as follows:

[0204] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), pyriproxyfenthianthrene salt (0.2mmol), deuterated chloroform (1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and 40W427nm blue light was irradiated at room temperature for 6 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated pyriproxyfen with a yield of 60%.

[0205]

[0206] 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.

[0207] Embodiment 38

[0208] The preparation method of deuterated benzbromarone comprises the following steps:

[0209] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), benzbromarone thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and irradiated with 40W427nm blue light for 6 hours at room temperature. After the reaction was completed, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated benzbromarone with a yield of 80%.

[0210]

[0211] 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

[0212] Embodiment 39

[0213] The preparation method of deuterated fenofibrate comprises the following steps:

[0214] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), fenofibrate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and irradiated with 40W427nm blue light for 6 hours at room temperature. After the reaction was completed, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated fenofibrate with a yield of 59%.

[0215]

[0216] 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.

[0217] Embodiment 40

[0218] The preparation method of deuterated fenbufen methyl ester comprises the following steps:

[0219] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), fenbufen methyl thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated fenbufen methyl ester with a yield of 51%.

[0220]

[0221] 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.

[0222] Embodiment 41

[0223] The preparation method of deuterated indomethacin methyl ester comprises the following steps:

[0224] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), indomethacin methyl thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated indomethacin methyl ester with a yield of 51%.

[0225]

[0226] 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.

[0227] Embodiment 42

[0228] The preparation method of deuterated isoxic acid methyl ester comprises the following steps:

[0229] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.01mmol), methyl isoxalate thianthrene salt (0.2mmol), deuterated chloroform (63mmol, 1mL), and water (1mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 40W 427nm blue light irradiation at room temperature for 6 hours. After the reaction was completed, 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 with a yield of 51%.

[0230]

[0231] 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.

[0232] Embodiment 43

[0233] The preparation method of deuterated biphenyl comprises the following steps:

[0234] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.002mmol), a biphenylthianthrene salt (0.2mmol), deuterated chloroform (65mmol, 1.03mL), and water (1.03mL) were added to a Schlenk reaction tube in sequence, and the reaction was carried out under 30W 427nm blue light irradiation at room temperature for 12 hours. After the reaction was completed, a saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated biphenyl with a yield of 30%.

[0235]

[0236] 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).

[0237] Embodiment 44

[0238] The preparation method of deuterated tert-butylbiphenyl comprises the following steps:

[0239] A magnetic stirrer, a photocatalyst 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile (0.02mmol), tert-butyl biphenyl thianthrene salt (0.2mmol), deuterated chloroform (10mmol, 0.16mL), and water (0.16mL) were added to a Schlenk reaction tube in sequence, and irradiated with 20W 427nm blue light for 3 hours at room temperature. After the reaction was completed, saturated sodium chloride solution and dichloromethane were added for extraction, and the organic phase was collected. The obtained crude product was purified by silica gel column chromatography to obtain deuterated tert-butyl biphenyl with a yield of 45%.

[0240]

[0241] 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.

[0242] 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing deuterated aromatic hydrocarbons by catalyzing aryl thianthrene salts under visible light, characterized in that: The steps are: (1) The raw materials arylthianthrene salt and deuterated chloroform are reacted in aqueous solution under the catalysis of 2,3,4,5,6-penta(9-carbazolyl)-benzonitrile at room temperature under visible light conditions until completion; (2) The reactant in step (1) is extracted and the organic phase is collected, which is then purified by silica gel column chromatography to obtain deuterated aromatic hydrocarbons.

2. The method for preparing deuterated aromatic hydrocarbons by using aryl thianthrene salts catalyzed by visible light according to claim 1, characterized in that: The structural formula of the arylthianthrene salt is: ； Wherein Ar is an aromatic ring or an aromatic heterocyclic ring; R is any one of hydrogen, alkyl, methoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, keto, cyano, ester, N,N-dipropylsulfonamide and p-toluenesulfonyl.

3. The method for preparing deuterated aromatic hydrocarbons using aryl thianthrene salts catalyzed by visible light according to claim 2, 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.

4. The method for preparing deuterated aromatic hydrocarbons using aryl thianthrene salts catalyzed by visible light according to claim 3, characterized in that: The visible light is 427nm blue light irradiation.

5. The method for preparing deuterated aromatic hydrocarbons using aryl thianthrene salts catalyzed by visible light according to claim 3, characterized in that: The light intensity of the 427nm blue light is 20W-40W.

6. The method for preparing deuterated aromatic hydrocarbons using aryl thianthrene salts catalyzed by visible light according to claim 5, characterized in that: The reaction time is 3-12 hours.

7. The method for preparing deuterated aromatic hydrocarbons using aryl thianthrene salts catalyzed by visible light according to claim 6, characterized in that: The reagents used for extraction in step (2) are saturated sodium chloride solution and dichloromethane.

8. The method for preparing deuterated aromatic hydrocarbons by catalyzing aryl thianthrene salts using visible light according to any one of claims 1 to 7, characterized in that: The structural formula of the deuterated aromatic hydrocarbon is: ； Wherein: Ar is an aromatic ring or an aromatic heterocyclic ring; R is any one of hydrogen, alkyl, methoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, keto, cyano, ester, N,N-dipropylsulfonamide and p-toluenesulfonyl.

9. The method for preparing deuterated aromatic hydrocarbons using aryl thianthrene salts catalyzed by visible light according to claim 8, characterized in that: The structural formula of the deuterated aromatic hydrocarbon is: ； Where: Ar is , , , , , , , , , , , , , , , , , , , , , , and Any of .

10. The method for preparing deuterated aromatic hydrocarbons using aryl thianthrene salts catalyzed by visible light according to claim 7, characterized in that: The R is any one of methyl, ethyl, methoxy, tert-butyl, isopropyl, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, keto, cyano, 2-propylvalerate, proline ester, carboxylate, benzoate, dodecanoate, N,N-dipropylsulfonamide and p-toluenesulfonyl.

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