Aromatic ring hydrogen-deuterium exchange reaction catalytic system and preparation method of deuterated aromatic hydrocarbon

Abstract

The invention relates to an aromatic ring hydrogen-deuterium exchange reaction catalytic system and a preparation method of deuterated aromatic hydrocarbon, and belongs to the technical field of chemical synthesis, the aromatic ring hydrogen-deuterium exchange reaction catalytic system comprises aromatic hydrocarbon, deuterated trifluoroacetic acid and ferric perchlorate hydrate, the structural formula of the ferric perchlorate hydrate is Fe (ClO4) 3 * xH2O, x = 1-9; the method comprises the following steps: activating an aromatic ring C-H bond of aromatic hydrocarbon in weak coordinated deuterated trifluoroacetic acid by perchlorate coordinated ferric ions to obtain an aryl iron intermediate, and then carrying out mass decomposition on the C-Fe bond to obtain an aromatic hydrocarbon deuterated product. According to the present invention, the aromatic ring perdeuteration of the aromatic hydrocarbon is achieved by using the cheap and easily available ferric iron catalyst through the brand new activation mechanism, the reaction operation is simple and convenient, the catalyst is cheap and easily available, the deuteration efficiency is high, and the aromatic ring perdeuterated alkyl substituted and halogenated aromatic hydrocarbon difficult to prepare by using the traditional method can be efficiently prepared at the relatively low cost; various deuterated aromatic hydrocarbons prepared by the method have wide application value in the fields of organic chemistry research, medicine and material development.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a catalytic system for aromatic ring hydrogen-deuterium exchange reaction and a method for preparing deuterated aromatic hydrocarbons. Background Art

[0002] Deuterium is a cheap, non-radioactive hydrogen isotope. In organic molecules, carbon-deuterium bonds are stronger and harder to break than corresponding carbon-hydrogen bonds. Based on this principle, using carbon-deuterium bonds to replace corresponding carbon-hydrogen bonds can significantly improve the physical, chemical and metabolic stability of corresponding organic molecules, and therefore has a wide range of applications in drug and material development. The preparation method of deuterated compounds is currently a hot research area.

[0003] Deuterated aromatics are an important class of deuterated organic molecules with many applications in the fields of medicine and materials. At present, the most important method for preparing deuterated aromatics is the hydrogen isotope exchange reaction (HIE reaction) of aromatics. The main process is to make the aromatic ring CH bonds in the aromatics undergo hydrogen-deuterium exchange reaction with the deuterium source in the deuterated solvent under the action of a catalyst in a deuterated solvent to achieve the deuteration of the aromatics. According to the type of catalyst used, it can be divided into proton acid catalysts, super electrophilic reagent catalysts, base catalysts, and transition metal catalysts. The deuterated solvents used include acidic deuterated solvents, such as deuterated sulfuric acid, deuterated trifluoroacetic acid, etc., and neutral deuterated solvents, such as deuterated water, deuterated methanol, deuterated benzene, etc. Although great progress has been made, there are still many difficulties in the preparation of deuterated aromatics using the hydrogen isotope exchange reaction of aromatic rings:

[0004] 1) When using protonic acid catalytic conditions, the catalytic efficiency is low, usually requiring a higher equivalent amount of catalyst, and the deuteration effect on electron-withdrawing substituted aromatics such as halogenated aromatics is poor;

[0005] 2) When super-electrophiles and transition metals are used as catalysts, there are problems of difficulty in synthesizing the catalyst and high cost;

[0006] 3) Under base-catalyzed conditions, sites with greater steric hindrance on the aromatic ring, such as the ortho-CH bonds of the methyl substituent, are difficult to be deuterated, and thus fully deuterated aromatics on the aromatic ring cannot be prepared from aromatic substrates containing alkyl substituents.

[0007] In summary, there is an urgent need in the art to develop a HIE catalytic system with a new activation mechanism that can efficiently achieve full deuteration of the aromatic rings of hindered aromatics and halogenated aromatics. Summary of the invention

[0008] In order to overcome at least one of the difficulties in the current preparation of deuterated aromatic hydrocarbons by hydrogen isotope exchange reaction of aromatic rings, the present invention provides an aromatic ring hydrogen-deuterium exchange reaction catalytic system and a method for preparing deuterated aromatic hydrocarbons.

[0009] The inventors conducted a detailed study of the reaction mechanism and discovered for the first time that trivalent iron ions coordinated by weakly coordinated anions (perchlorate) can efficiently activate the C-H bonds of aromatic rings in weakly coordinated deuterated trifluoroacetic acid solvents to obtain aromatic iron intermediates, followed by proteolysis of the C-Fe bonds to obtain deuterated aromatic products. This is the first time that direct electrophilic substitution of aromatic rings by trivalent iron ions has been observed.

[0010] In the research done by predecessors before the present invention, although there are reports on adding nearly equivalent metal salts to deuterated trifluoroacetic acid for deuteration of aromatic hydrocarbons, the predecessors' cognition is that the reaction is a metal ion as a Lewis acid to induce the generation of protons, followed by the proton-promoted hydrogen-deuterium exchange process of aromatic hydrocarbons. This mechanism is essentially a traditional proton acid-promoted aromatic ring HIE reaction, which is completely different from the activation mechanism involved in the present invention. According to the principle of the present invention, combined with a large number of experimental results of the inventors, the best catalyst is ferric perchlorate hydrate coordinated by weakly coordinated anions, and this catalytic system has not been reported in previous aromatic ring hydrogen-deuterium exchange reactions.

[0011] The purpose of the present invention can be achieved by the following technical solutions:

[0012] One of the purposes of the present invention is to provide a catalytic system for aromatic ring hydrogen-deuterium exchange reaction, comprising:

[0013] Aromatics;

[0014] Deuterated trifluoroacetic acid; and

[0015] Ferric perchlorate hydrate, with the structural formula of Fe(ClO 4 ) 3 ·xH 2 O, where x = 1-9;

[0016] Among them, the trivalent iron ion coordinated by perchlorate efficiently activates the CH bond of the aromatic ring of aromatic hydrocarbons in weakly coordinated deuterated trifluoroacetic acid to obtain an aromatic iron intermediate, and then the C-Fe bond undergoes protolysis to obtain the deuterated aromatic hydrocarbon product.

[0017] Further, the aromatic hydrocarbon is selected from toluene, ethylbenzene, propylbenzene, isobutylbenzene, o-xylene, m-xylene, p-xylene, 1-ethyl-2-methylbenzene, 1-ethyl-4-methylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, mesitylene, 1,2,4-trimethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1,2,3,4,5-pentamethylbenzene, 1-fluoro -3,5-dimethylbenzene, 1-chloro-3,5-dimethylbenzene, 1-bromo-3,5-dimethylbenzene, 2-fluoro-1,3-dimethylbenzene, 2-chloro-1,3-dimethylbenzene, 2-bromo-1,3-dimethylbenzene, 2-fluoro-1,4-dimethylbenzene, 2-chloro-1,4-dimethylbenzene, 2-bromo-1,4-dimethylbenzene, 4-fluoro-1,2-dimethylbenzene, 1-chloro-2,3-dimethylbenzene, 4 -Bromo-1,2-dimethylbenzene, 1-chloro-2,3-dimethylbenzene, 1-bromo-2,3-dimethylbenzene, 1-chloro-2,4-dimethylbenzene, 1-bromo-2,4-dimethylbenzene, 2-fluoro-1,3,5-trimethylbenzene, 2-chloro-1,3,5-trimethylbenzene, 2-bromo-1,3,5-trimethylbenzene, 1-bromo-2,4,5-trimethylbenzene, 2-bromo-1,3-diisopropylbenzene, 2- Any one of bromo-1,3,5-triisopropylbenzene, 3,3',5,5'-tetramethylbiphenyl, 3,3',4,4'-tetramethylbiphenyl, 2,2',5,5'-hexamethylbiphenyl, 2,2',4,4',6,6'-hexamethylbiphenyl, 1,2-diphenylethane, 1,2-p-xylylethane, 2,2-diphenylpropane and 2,2-bis(3,4-xylyl)hexafluoropropane.

[0018] The above aromatic compounds are numbered A1-A46 in sequence, and the structural formula is as follows:

[0019]

[0020] Furthermore, the amount of the ferric perchlorate hydrate used is 0.10-0.50 equivalent relative to the aromatic hydrocarbon.

[0021] Furthermore, the amount of the ferric perchlorate hydrate used is preferably 0.1-0.2 equivalent relative to the aromatic hydrocarbon.

[0022] Furthermore, the molar ratio of the deuterated trifluoroacetic acid to the aromatic hydrocarbon substrate is (20:1)-(200:1).

[0023] Furthermore, the molar ratio of the deuterated trifluoroacetic acid to the aromatic hydrocarbon substrate is preferably (50:1)-(100:1).

[0024] The second object of the present invention is to provide a method for preparing deuterated aromatic hydrocarbons. The preparation method is based on the catalytic system as described above and comprises the following steps: adding ferric perchlorate hydrate to a mixed system of aromatic hydrocarbons and deuterated trifluoroacetic acid, separating after the reaction, and obtaining deuterated aromatic hydrocarbons.

[0025] Furthermore, the reaction temperature of the reaction is 0°C-80°C, and the reaction time is 0.5h-48h.

[0026] Furthermore, the reaction temperature of the reaction is preferably 70°C.

[0027] Furthermore, the separation step is specifically as follows: after the reaction is completed, the reaction solution is extracted with dichloromethane, the organic phase is spin-dried, and silica gel column chromatography is performed, and gradient elution with n-pentane and dichloromethane is used to separate the deuterated aromatic hydrocarbons.

[0028] The present invention has the following beneficial effects:

[0029] (1) The present invention uses a cheap and readily available trivalent iron catalyst to achieve full deuteration of aromatic rings of aromatic hydrocarbons through a completely new activation mechanism. The reaction operation is simple, the catalyst is cheap and readily available, and the deuteration efficiency is high. The present invention breaks through the limitations of the traditional protonic acid-catalyzed aromatic hydrogen-deuterium exchange reaction that is difficult to apply to electron-withdrawing halogenated aromatic hydrocarbons, the limitations of the traditional base-catalyzed reaction that is difficult to fully deuterate alkyl-substituted aromatic hydrocarbons, and the limitations of the super-electrophilic reagent and transition metal complex-catalyzed aromatic hydrocarbon deuteration method that is difficult to synthesize catalysts and has high preparation costs. A series of alkyl-substituted and halogenated aromatic hydrocarbons with full deuteration of aromatic rings that are difficult to prepare by traditional methods can be prepared at a relatively low cost and with high efficiency.

[0030] (2) The various deuterated aromatic hydrocarbons prepared by the preparation method of the present invention have wide application value in the fields of organic chemistry research, medicine and material development. DETAILED DESCRIPTION

[0031] The present invention is described in detail below in conjunction with specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0032] 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. If no specific conditions are specified, the conventional conditions or the conditions recommended by the manufacturer shall be followed. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0033] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0034] All reactions were performed under argon atmosphere. Thin layer chromatography (TLC) was performed on TLC silica gel 60F254 (Merck), and column chromatography used Huanghai 100-200 mesh silica gel. Iron (III) perchlorate hydrate was purchased from Sigma-Adrich. The molecular formula of the purchased iron (III) perchlorate hydrate crystals was marked as Fe(ClO 4 ) 3 ·xH 2 O, according to the analysis and testing of the Element Analysis and Testing Center of the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, it contains 9 crystal waters, so the molecular formula is determined to be Fe(ClO 4 ) 3 9H 2 O, the following experiments are calculated according to this molecular formula. 3 COOD) was purchased from Adamas brand.

[0035] 1 H NMR, 13 C NMR and 19 F NMR spectra were measured at 25°C using Bruker AMX-400, Agilent Av 500 or Bruker AMX 600 NMR, with cyclododecane, TMS or trifluorinated benzene as internal standards. Mass spectra were measured by HP5989A or VG Quattro MS / MS mass spectrometers, with ionization modes of EI or FI.

[0036] The general operation process of the following embodiments is as follows:

[0037] A. General process of 0.1mmol scale reaction, denoted as GP1:

[0038]

[0039] Under argon protection, the target aromatic hydrocarbon (0.1mmol, 1.0eq.), Fe(ClO 4 ) 3 9H 2 O (7.4 mg, 0.014 mmol, 0.14 eq.), cyclododecane (0.1 mmol, 1.0 eq.) were dispersed in CF 3COOD (1 mL) was added and the reaction was then stirred at room temperature or 70°C for 0.5-24 hours. The reaction was cooled to room temperature and D 2 O (2 mL), CDCl 3 (2mL×3) extraction, combined organic layers, and CDCl 3 Test hydrogen spectrum, GC low resolution and FI high resolution mass spectrum.

[0040] B. The general operation process of 1mmol scale reaction is denoted as GP2:

[0041]

[0042] Under argon protection, the target aromatic hydrocarbon (1 mmol, 1.0 eq.), Fe(ClO 4 ) 3 9H 2 O (74 mg, 0.14 mmol, 0.14 eq) was dispersed in CF 3 COOD (10 mL) was added and the reaction was then stirred at room temperature or 70 °C for 1-24 hours. The reaction was cooled to room temperature and H 2 O (10 mL), extracted with n-pentane (10 mL × 3), combined the organic layers, washed with saturated NaCl, anhydrous Na 2 SO 4 Dry, filter, rotary evaporate, separate by column chromatography, elute with n-pentane and concentrate to obtain the target compound.

[0043] Example 1

[0044] Preparation of deuterated compound B1

[0045]

[0046] The compound was prepared from toluene (0.1 mmol, 10.5 μL) and the target molecule was obtained according to the general operation procedure GP1 with an NMR yield of 92%. 1 H NMR(500MHz,Chloroform-d)δ7.27(s,0.2H),2.37(s,3H). 13 CNMR (126MHz, CDCl 3 )δ137.85,129.1-127.7(m),21.48.

[0047] HRMS(EI + )calculated for C 7 H 5 D 3 [M(3D)] + 95.0814 found 95.0811.

[0048] HRMS(EI + )calculated for C 7 H 4 D 4 [M(4D)] + 96.0877 found 96.0877.

[0049] HRMS(EI + )calculated for C 7 H 3 D 5 [M(5D)] + 97.0940 found 97.0938.

[0050] HRMS(EI + )calculated for C 87 H 2 D 6 [M(6D)] + 98.1003 found 98.0962.

[0051] M(3D)5.1%, M(4D)23.3%, M(5D)66.0%, M(6D)5.6%

[0052] Deuteriumincorporation:4.72D(HRMS),4.80D( 1 H-NMR).

[0053] Example 2

[0054] Preparation of deuterated compound B2

[0055]

[0056] The compound was prepared from ethylbenzene (0.1 mmol, 12.2 μL) and the target molecule was obtained according to the general operation procedure GP1 with an NMR yield of 99%. 1 H NMR (500MHz, Chloroform-d) δ7.29 (s, 0.22H), 7.20 (d, J = 13.3Hz, 0.18H), 2.70-2.63 (m, 2H), 1.25 (tdd, J = 7.6, 2.2, 1.2Hz, 3H). 13 C NMR (151 MHz, CDCl 3 )δ144.22,128.2-127.4(m),125.5-125.04(m),28.91,15.73.

[0057] HRMS(EI + )calculated for C 8 H 9 D[M(1D)] + 107.0845found 107.0799.

[0058] HRMS(EI + )calculated for C 8 H 8 D 2 [M(2D)] + 108.0908found 108.0875.

[0059] HRMS(EI + )calculated for C 8 H 7 D 3 [M(3D)] + 109.0971found 109.0950.

[0060] HRMS(EI + )calculated for C 8 H 6 D 4 [M(4D)] + 110.1034found 110.1023.

[0061] HRMS(EI + )calculated for C 8 H 5 D 5 [M(5D)] + 111.1096found 111.1088.

[0062] HRMS(EI + )calculated for C 8 H 4 D 6 [M(6D)] + 112.1159found 112.1129.

[0063] Deuteriumincorporation:4.15D(HRMS),4.6D( 1 H-NMR).

[0064] M(1D)4.7%, M(2D)5.4%, M(3D)11.7%, M(4D)28.6%, M(5D)45.6%, M(6D)4.0% Example 3

[0065] Preparation of deuterated compound B3

[0066]

[0067] The compound was prepared using propylbenzene as raw material (0.1 mmol, 13.9 μL) and the target molecule was obtained according to the general operation procedure GP1 with an NMR yield of 70%. 1 H NMR(500MHz,Chloroform-d)δ7.28(s,0.09H),7.19(s,0.13H),2.62-2.56(m,2H),1.72-1.59(m,2H),1.01-0.90(m,3H).

[0068] HRMS(EI + )calculated for C 9 H 9 D 3 [M(3D)] + 123.1127 found 123.1109.

[0069] HRMS(EI + )calculated for C 9 H 8 D 4 [M(4D)] + 124.1190 found 124.1177.

[0070] HRMS(EI + )calculated for C 9 H 7 D 5 [M(5D)] + 125.1253 found 125.1246.

[0071] HRMS(EI + )calculated for C 9 H 6 D 6 [M(6D)] + 126.1316 found 126.1285.

[0072] Deuteriumincorporation:4.68D(HRMS),4.78D(1 H-NMR).

[0073] M(2D)5.4%, M(3D)27.0%, M(4D)61.3%, M(5D)6.3%

[0074] Example 4

[0075] Preparation of deuterated compound B4

[0076]

[0077] The compound was prepared using isobutylbenzene as raw material (1 mmol, 157 μL). According to the general operation procedure GP2, 92 mg of the target molecule was obtained with a yield of 66%. According to the general operation procedure GP1, the NMR yield was 88%. 1 H NMR(500MHz,MethyleneChloride-d 2 )δ7.30(s,0.22H),7.19(d,J=8.8Hz,0.23H),2.51(dt,J=7.2,1.5Hz,2H),1.94-1.84(m,1H),0.94(dt,J=6.7,1.8Hz,6H). 13 C NMR (126MHz, cd 2 cl 2 )δ142.21,129.6-129.1(m),128.4-127.9(m),125.9-125.5(m),45.86,30.90,22.71.HRMS data of Xobtained from GP1:

[0078] HRMS(FI + )calculated for C 10 H 11 D 3 [M(3D)] + 137.1284 found 137.1265.

[0079] HRMS(FI + )calculated for C 10 H 10 D 4 [M(4D)] + 138.1347 found 138.1338.

[0080] HRMS(FI + )calculated for C 10 H 9D 5 [M(5D)] + 139.1409 found 139.1403.

[0081] HRMS(FI + )calculated for C 10 H 8 D 6 [M(6D)] + 140.1472 found 140.1460.

[0082] M(3D)9.3%, M(4D)32.6%, M(5D)52.1%, M(6D)6.0%

[0083] Deuteriumincorporation:4.55D(HRMS),4.55D( 1 H-NMR).

[0084] Example 5

[0085] Preparation of deuterated compound B5

[0086]

[0087] Using o-xylene as the raw material (0.1 mmol, 12 μL), according to the general operation procedure GP1, the target molecule B5 was obtained by reacting in an oil bath at 70°C for 1 h with an NMR yield of 99%. 1 H NMR (500 MHz, deuterated chloroform) δ7.13 (d, J=17.2 Hz, 0.29 H), 2.28 (s, 6 H). 13C NMR (126 MHz, CDCl3) δ136.57, 129.6-129.1 (m), 125.7-125.2 (m), 19.80.

[0088] HRMS(FI + ) Calculated value C 8 H 8 D 2 [M(2D)] + 108.0908 Measured value 108.0862.

[0089] HRMS(FI + ) Calculated value C 8 H 7 D 3 [M(3D)] + 109.0971 Measured value 109.0966.

[0090] HRMS(FI +) Calculated value C 8 H 6 D 4 [M(4D)] + 110.1034 Measured value 110.1026.

[0091] HRMS(FI + ) Calculated value C 8 H 5 D 5 [M(5D)] + 111.1096 Measured value 111.1080.

[0092] Mass spectrum abundance: M(2D) 1.8%, M(3D) 21.3%, M(4D) 71.3%, M(5D) 5.6%

[0093] Deuterium rate: 3.93D (calculated by HRMS), 3.71D (calculated by 1 H-NMR calculated).

[0094] Example 6

[0095] Preparation of deuterated compound B6

[0096]

[0097] Using m-xylene (A6) as the raw material (0.1 mmol, 12 μL), according to the general operation procedure GP1, the target molecule B6 was obtained by reacting in an oil bath at 70°C for 1 h with an NMR yield of 79%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.17 (s, 0.07H), 7.01 (d, J = 13.1 Hz, 0.2H), 2.34 (s, 6H). 13 C NMR (126 MHz, CDCl 3 )δ137.84,137.75,130.0-129.5,128.1-127.6,126.05,126.0-125.5,21.35.

[0098] HRMS(FI + ) Calculated value C 8 H 7 D 3 [M(3D)] + 109.0971 Measured value 109.0965.

[0099] HRMS(FI + ) Calculated value C 8 H 6 D 4 [M(4D)]+ 110.1034 Measured value 110.1025.

[0100] HRMS(FI + ) Calculated value C 8 H 5 D 5 [M(5D)] + 111.1096 Measured value 111.1060..

[0101] Mass spectrum abundance: M(3D) 21.2%, M(4D) 72.2%, M(5D) 6.6%

[0102] Deuterium rate: 3.85D (calculated by HRMS), 3.73D (calculated by 1 H-NMR calculated).

[0103] Example 7

[0104] Preparation of deuterated compound B7

[0105]

[0106] Using p-xylene (A7) as the raw material (0.1 mmol, 12 μL), according to the general operation procedure GP1, the target molecule B7 was obtained by reacting in an oil bath at 70°C for 1 h with an NMR yield of 90%. 1 H NMR (500 MHz, deuterated chloroform) δ7.08 (s, 0.29H), 2.33 (s, 6H). 13 C NMR (126 MHz, CDCl 3 )δ134.64,128.9-128.4(m),20.97.HRMS(FI + ) Calculated value C 8 H 7 D 3 [M(3D)] + 109.0971 Measured value 109.0956.

[0107] HRMS(FI + ) Calculated value C 8 H 6 D 4 [M(4D)] + 110.1034 Measured value 110.1026.

[0108] HRMS(FI + ) Calculated value C 8 H 5 D 5 [M(5D)] +111.1096 Measured value 111.1063..

[0109] Mass spectrum abundance: M(3D) 8.0%, M(4D) 84.1%, M(5D) 7.9%

[0110] Deuterium rate: 4.0D (calculated by HRMS), 3.71D (calculated by 1 H-NMR calculated).

[0111] Example 8

[0112] Preparation of deuterated compound B8

[0113]

[0114] The compound was prepared from 1-ethyl-2-methylbenzene (0.1 mmol, 13.5 μL) and the target molecule was obtained according to the general operation procedure GP1 with an NMR yield of 87%. 1 H NMR (600MHz, Chloroform-d) δ7.16 (s, 0.06H), 7.14 (d, J = 5.1Hz, 0.12H), 7.10 (s, 0.06H), 2.64 (q, J = 7.6Hz, 2H), 2.31 (s, 3H), 1.22 (t, J = 7.6Hz, 3H). 13 C NMR (151 MHz, CDCl 3 )δ142.35,135.79,130.0-129.5(m),127.9-127.4(m),125.9-125.2(m),26.24,19.23,14.50.

[0115] HRMS(EI + )calculated for C 9 H 10 D 2 [M(2D)] + 122.1065 found 122.1051.

[0116] HRMS(EI + )calculated for C 9 H 9 D 3 [M(3D)] + 123.1127 found 123.1120.

[0117] HRMS(EI + )calculated for C 9 H8 D 4 [M(4D)] + 124.1190 found 124.1181.

[0118] HRMS(EI + )calculated for C 9 H 7 D 5 [M(5D)] + 125.1253 found 125.1209.

[0119] Deuteriumincorporation:3.76D(HRMS),3.76D( 1 H-NMR).

[0120] M(2D)4.2%, M(3D)21.4%, M(4D)67.6%, M(5D)6.8%

[0121] Example 9

[0122] Preparation of deuterated compound B9

[0123]

[0124] The compound was prepared from 1-ethyl-4-methylbenzene (0.1 mmol, 13.9 μL) and the target molecule was obtained according to the general operation procedure GP1 with an NMR yield of 64%. 1 H NMR (600MHz, Chloroform-d) δ7.10 (s, 0.2H), 2.62 (q, J = 7.6Hz, 2H), 2.32 (s, 3H), 1.23 (t, J = 7.6Hz, 3H). 13 C NMR (151 MHz, CDCl 3 )δ141.17,134.94,129.0-128.5(m),127.8-127.3(m),28.46,21.00,15.90.

[0125] HRMS(EI + )calculated for C 9 H 10 D 2 [M(2D)] + 122.1065 found 122.1043.

[0126] HRMS(EI + )calculated for C 9H 9 D 3 [M(3D)] + 123.1127 found 123.1123.

[0127] HRMS(EI + )calculated for C 9 H 8 D 4 [M(4D)] + 124.1190 found 124.1183.

[0128] HRMS(EI + )calculated for C 9 H 7 D 5 [M(5D)] + 125.1253 found 125.1241.

[0129] HRMS(EI + )calculated for C 9 H 6 D 6 [M(6D)] + 126.1316 found 125.1206.

[0130] Deuteriumincorporation:3.85D(HRMS),3.80D( 1 H-NMR).

[0131] M(2D)5.5%, M(3D)20.4%, M(4D)59.2%, M(5D)12.5%, M(6D)2.4%

[0132] Example 10

[0133] Preparation of deuterated compound B10

[0134]

[0135] The compound was prepared using 1,3-diethylbenzene as raw material (0.1 mmol, 15.4 μL) and the target molecule was obtained according to the general operation process GP1 with an NMR yield of 93%. 1 H NMR (500MHz, Chloroform-d) δ7.22 (s, 0.05H), 7.04 (d, J = 9.3Hz, 0.17H), 2.64 (q, J = 7.6Hz, 4H), 1.25 (t, J = 7.6Hz, 6H).13 C NMR (151 MHz, CDCl 3 )δ144.22,128.2-127.1(m),125.1-124.7(m),28.88,15.75.

[0136] HRMS(EI + )calculated for C 10 H 12 D 2 [M(2D)] + 136.1221 found 136.1218.

[0137] HRMS(EI + )calculated for C 10 H 11 D 3 [M(3D)] + 137.1284 found 137.1279.

[0138] HRMS(EI + )calculated for C 10 H 10 D 4 [M(4D)] + 138.1347 found 138.1339.

[0139] HRMS(EI + )calculated for C 10 H 9 D 5 [M(5D)] + 139.1409 found 139.1486.

[0140] Deuteriumincorporation:3.84D(HRMS),3.78D( 1 H-NMR).

[0141] M(2D)3.5%, M(3D)22.0%, M(4D)66.4%, M(5D)8.1%

[0142] Embodiment 11

[0143] Preparation of deuterated compound B11

[0144]

[0145] The compound was prepared using 1,4-diethylbenzene as raw material (0.1 mmol, 15.5 μL) and the target molecule was obtained according to the general operation process GP1 with an NMR yield of 90%. 1 H NMR (600MHz, Chloroform-d) δ7.13 (s, 0.22H), 2.63 (q, J = 7.6Hz, 4H), 1.23 (t, J = 7.6Hz, 6H). 13 C NMR (151 MHz, CDCl 3 )δ141.40,127.8-127.3(m),28.46,15.81.

[0146] HRMS(EI + )calculated for C 10 H 12 D 2 [M(2D)] + 136.1221 found 136.1189.

[0147] HRMS(EI + )calculated for C 10 H 11 D 3 [M(3D)] + 137.1284 found 137.1259.

[0148] HRMS(EI + )calculated for C 10 H 10 D 4 [M(4D)] + 138.1347 found 138.1340.

[0149] HRMS(EI + )calculated for C 10 H 9 D 5 [M(5D)] + 139.1409 found 139.1378.

[0150] Deuteriumincorporation:3.92D(HRMS),3.78D( 1 H-NMR).

[0151] M(2D)5.0%, M(3D)17.9%, M(4D)64.7%, M(5D)14.9%

[0152] Example 12

[0153] Preparation of deuterated compound B12

[0154]

[0155] Using mesitylene as the raw material (1 mmol, 139 μL), according to the general operation procedure GP2, the target molecule B12 90 mg was obtained after reacting at room temperature for 12 h with an isolated yield of 73% and an NMR yield of 84%. 1 H NMR (500 MHz, deuterated chloroform) δ 6.82 (s, 0.17H), 2.29 (s, 9H). 13 C NMR (126 MHz, CDCl 3 )137.71, δ127.21-126.43(m),21.21.

[0156] HRMS(FI + ) Calculated value C 9 H 10 D 2 [M(2D)] + 122.1065, measured value 122.1055.

[0157] HRMS(FI + ) Calculated value C 9 H 9 D 3 [M(3D)] + 123.1127, measured value 123.1121.

[0158] HRMS(FI + ) Calculated value C 9 H 8 D 4 [M(4D)] + 124.1190, measured value 124.1164.

[0159] Mass spectrum abundance: M(2D) 14.7%, M(3D) 76.2%, M(4D) 9.1%

[0160] Deuterium rate: 2.94D (calculated by HRMS), 2.83D (calculated by 1 H-NMR calculation).

[0161] Embodiment 13

[0162] Preparation of deuterated compound B13

[0163]

[0164] The compound was prepared from 1,2,4-trimethylbenzene (1 mmol, 137 μL) and the target molecule B13 (114 mg) was obtained according to the general operation procedure GP2 with a yield of 93% and an NMR yield of 93%. 1 H NMR (500MHz, Chloroform-d) δ7.02 (s, 0.05H), 6.97 (s, 0.05H), 6.90 (s, 0.05H), 2.28 (s, 3H), 2.23 (d, J = 5.5Hz, 6H). 13 C NMR (126MHz, cdcl 3 )δ136.75,135.57,135.48,133.76,130.8-130.3(m),129.8-129.3(m),126.6-126.2(m),21.04,19.89,19.45.

[0165] HRMS(EI + )calculated for C 9 H 10 D 2 [M(2D)] + 122.1065 found 122.1054.

[0166] HRMS(EI + )calculated for C 9 H 9 D 3 [M(3D)] + 123.1127 found 123.1118.

[0167] HRMS(EI + )calculated for C 9 H 8 D 4 [M(4D)] + 124.1190 found 124.1151.

[0168] Deuteriumincorporation:2.95D(HRMS),2.85D( 1 H-NMR).

[0169] M(2D)13.0%, M(3D)79.3%, M(4D)7.7%

[0170] Embodiment 14

[0171] Preparation of deuterated compound B14

[0172]

[0173] Using 1,2,3,4-tetramethylbenzene as the raw material (1 mmol, 149 μL), according to the general operation procedure GP2, the target molecule B14 125 mg was obtained after reaction at room temperature for 12 h with a yield of 92%. 1 H NMR (500 MHz, deuterated chloroform) δ 6.93 (s, 0.09H), 2.28 (s, 6H), 2.21 (s, 6H). 13 C NMR (126MHz, CDCl3) δ135.03,133.94,126.96-126.35(m),20.78,15.95.

[0174] HRMS(FI + ) Calculated value C 10 H 13 D[M(1D)] + 135.1158 Measured value 135.1158.

[0175] HRMS(FI + ) Calculated value C 10 H 12 D 2 [M(2D)] + 136.1221 Measured value 136.1214.

[0176] HRMS(FI + ) Calculated value C 10 H 11 D 3 [M(3D)] + 137.1284 Measured value 148.1250.

[0177] Mass spectrum abundance: M(1D) 5.7%, M(2D) 83.7%, M(3D) 10.6%

[0178] Deuterium rate: 2.05D ​​(calculated by HRMS), 1.91D (calculated by 1 H-NMR calculated).

[0179] Embodiment 15

[0180] Preparation of deuterated compound B15

[0181]

[0182] Using 1,2,4,5-tetramethylbenzene as raw material (1 mmol, 134 mg), according to the general operation procedure GP2, the reaction was carried out at room temperature for 1 h to obtain 129 mg of the target molecule B15 with a yield of 95%. 1 H NMR (500 MHz, deuterated chloroform) δ 6.92 (s, 0.2H), 2.21 (s, 12H). 13 C NMR (126 MHz, CDCl 3 )δ133.68,131.2-130.6(m),19.15.HRMS(FI + ) Calculated value C 10 H 13 D[M(1D)] + 135.1158 Measured value 135.1155.

[0183] HRMS(FI + ) Calculated value C 10 H 12 D 2 [M(2D)] + 136.1221 Measured value 136.1218.

[0184] HRMS(FI + ) Calculated value C 10 H 11 D 3 [M(3D)] + 137.1284 Measured value 148.1253.

[0185] Mass spectrum abundance: M(1D) 10.2%, M(2D) 80.8%, M(3D) 9.0%

[0186] Deuterium rate: 1.98D (calculated by HRMS), 1.80D (calculated by 1 H-NMR calculated).

[0187] Example 16

[0188] Preparation of deuterated compound B16

[0189]

[0190] The compound was prepared from 1,2,3,4,5-pentamethylbenzene (1 mmol, 148 mg) and reacted at room temperature for 1 h according to the general operation procedure GP2 to obtain 145 mg of the target molecule B16 with an NMR yield of 97%. 1H NMR (500 MHz, deuterated chloroform) δ 6.86 (s, 0.05H), 2.26 (s, 6H), 2.23 (s, 3H), 2.20 (s, 3H). 13 C NMR (126 MHz, CDCl 3 )δ135.04,133.27,132.46,128.9-128.3,20.61,16.41,16.02.

[0191] HRMS(FI + ) Calculated value C 11 H 16 [M(0D)] + 148.1252 Measured value 148.1247.

[0192] HRMS(FI + ) Calculated value C 11 H 15 D[M(1D)] + 149.1315 Measured value 149.1308.

[0193] HRMS(FI + ) Calculated value C 11 H 14 D 2 [M(2D)] + 150.1378 Measured value 150.1340.

[0194] Mass spectrum abundance: M(0D) 5.1%, M(1D) 84.0%, M(2D) 10.9%

[0195] Deuterium rate: 1.05D (calculated according to HRMS), 0.95D (calculated according to 1 H-NMR calculation).

[0196] Embodiment 17

[0197] Preparation of deuterated compound B17

[0198]

[0199] The compound was prepared from 1-fluoro-3,5-dimethylbenzene (1 mmol, 136 μL) and the target molecule B17 (78 mg) was obtained according to the general operation procedure GP2 with a yield of 61% and an NMR yield of 81%. 1 H NMR (600MHz, Chloroform-d) δ6.76 (s, 0.05H), 6.68 (d, J = 9.8Hz, 0.11H), 2.30 (s, 6H). 13C NMR (151MHz, Chloroform-d) δ162.93 (d, J = 244.2Hz), 139.89 (d, J = 7.8Hz), 125.7-125.2 (m), 113.0-112.5 (m), 21.24.

[0200] HRMS data of X obtained from GP1:

[0201] HRMS(EI + )calculated for C 8 H 7 D 2 F[M(2D)] + 126.0814 found 126.0793.

[0202] HRMS(EI + )calculated for C 8 H 6 D 3 F[M(3D)] + 127.0877 found 127.0872.

[0203] Deuteriumincorporation:2.69D(HRMS),2.84D( 1 H-NMR).

[0204] M(2D)31.4%,M(3D)68.6%

[0205] Embodiment 18

[0206] Preparation of deuterated compound B18

[0207]

[0208] Using 1-chloro-3,5-dimethylbenzene as the raw material (1 mmol, 130 μL), according to the general operation procedure GP2, the target molecule B18 was obtained by reacting in an oil bath at 70°C for 24 h with a yield of 79%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.01 (d, J = 3.3 Hz, 0.17 H), 6.90 (d, J = 3.2 Hz, 0.09 H), 2.33 (d, J = 3.7 Hz, 6 H). 13 CNMR (126MHz,cdcl 3)δ139.53,139.44,133.71,133.62,128.3-127.8(m),126.3-125.8(m),21.05.

[0209] HRMS(EI + ) Calculated value C 8 H 7 D 2 Cl[M(2D)] + 142.0518 Measured value 142.0520.

[0210] HRMS(EI + ) Calculated value C 8 H 6 D 3 Cl[M(3D)] + 143.0581 Measured value 143.0573.

[0211] HRMS(EI + ) Calculated value C 8 H 5 D 4 Cl[M(4D)] + 144.0644 Measured value 144.0615.

[0212] Mass spectrum abundance: M(2D) 17.8%, M(3D) 67.8%, M(4D) 14.4%

[0213] Deuterium rate: 2.97D (calculated by HRMS), 2.74D (calculated by 1 H-NMR calculated).

[0214] Embodiment 19

[0215] Preparation of deuterated compound B19

[0216]

[0217] The compound was prepared from 1-bromo-3,5-dimethylbenzene (1 mmol, 136 μL) and the target molecule B19 (153 mg) was obtained according to the general operation procedure GP2 with a yield of 81% and an NMR yield of 91%. 1 H NMR (500MHz, Chloroform-d) δ7.15 (s, 0.11H), 6.92 (s, 0.06H), 2.30 (d, J = 2.2Hz, 6H). 13 C NMR (126MHz, cdcl 3 )δ139.77,129.2-128.3(m),121.95,21.05.

[0218] HRMS(EI + )calculated for C 8 H 7 D 2 Br[M(2D)] + 186.0013 found 186.0017.

[0219] HRMS(EI + )calculated for C 8 H 6 D 3 Br[M(3D)] + 187.0076 found 187.0072.

[0220] Deuteriumincorporation:2.84D(HRMS),2.83D( 1 H-NMR).

[0221] M(2D)15.3%,M(3D)84.7%

[0222] Embodiment 20

[0223] Preparation of deuterated compound B20

[0224]

[0225] Using 2-fluoro-1,3-dimethylbenzene as the raw material (1 mmol, 124 μL), according to the general operation procedure GP2, the target molecule B20 87 mg was obtained in an oil bath at 70°C for 24 h with a yield of 70%. 1 H NMR (500 MHz, deuterated dichloromethane) δ 7.05 (d, J = 7.4 Hz, 0.13 H), 6.96 (s, 0.06 H), 2.30 (d, J = 2.2 Hz, 6 H). 13 C NMR(126MHz,MethyleneChloride-d 2 )δ160.49(d,J=241.9Hz).129.2-128.7(m),124.89,124.75,123.8-123.1(m),14.79,14.76.

[0226] HRMS(EI + ) Calculated value C 8 H 9 F[M(0D)] + 124.0688, measured value 124.0655.

[0227] HRMS(EI + ) Calculated value C 8 H 8 DF[M(1D)] + 125.0751 Measured value 125.0736.

[0228] HRMS(EI + ) Calculated value C 8 H 7 D 2 F[M(2D)] + 126.0814 Measured value 126.0798.

[0229] HRMS(EI + ) Calculated value C 8 H 6 D 3 F[M(3D)] + 127.0877 Measured value 127.0868.

[0230] HRMS(EI + ) Calculated value C 8 H 5 D 4 F[M(4D)] + 128.0939 Measured value 128.0913.

[0231] Mass spectrum abundance: M(0D) 3.4%, M(1D) 12.2%, M(2D) 31.9%, M(3D) 48.3%, M(4D) 4.1%. Deuteration rate: 2.38D(HRMS), 2.81D( 1 H-NMR).

[0232] Embodiment 21

[0233] Preparation of deuterated compound B21

[0234]

[0235] Using 2-chloro-1,3-dimethylbenzene as the raw material (1 mmol, 132 μL), according to the general operation procedure GP2, the target molecule B21 101 mg was obtained in an oil bath at 70°C for 24 h with a yield of 69%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.10 (d, J = 11.7 Hz, 0.2 H), 2.43 (s, 6 H). 13 C NMR (126MHz, cdcl 3)δ136.27,134.77,128.4-127.9(m),125.8-125.3(m),20.75.

[0236] HRMS(EI + ) Calculated value C 8 H 8 DCl[M(1D)] + 141.0456 Measured value 141.0443.

[0237] HRMS(EI + ) Calculated value C 8 H 7 D 2 Cl[M(2D)] + 142.0518 Measured value 142.0523.

[0238] HRMS(EI + )Calculate the value for C 8 H 6 D 3 Cl[M(3D)] + 143.0581 Measured value 143.0579.

[0239] Mass spectrum abundance: M(1D) 3.2%, M(2D) 22.6%, M(3D) 74.2%

[0240] Deuterium rate: 2.71D (calculated by HRMS), 2.79D (calculated by 1 H-NMR calculated).

[0241] Embodiment 22

[0242] Preparation of deuterated compound B22

[0243]

[0244] A14

[0245] Using 2-bromo-1,3-dimethylbenzene as the raw material (1 mmol, 138 μL), according to the general operation procedure GP2, the target molecule B22 was obtained by reacting in an oil bath at 70°C for 24 h with a yield of 78%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.11 (d, J = 11.6 Hz, 0.32 H), 2.45 (d, J = 1.8 Hz, 6 H). 13 C NMR (126MHz, cdcl 3 )δ138.31,128.3-127.7(m),126.6-126.0(m),23.94.

[0246] HRMS(EI + ) Calculated value C 8 H 8 DBr[M(1D)] + 184.9950 Measured value 184.9936.

[0247] HRMS(EI + ) Calculated value C 8 H 7 D 2 Br[M(2D)] + 186.0013 Measured value 186.0017.

[0248] HRMS(EI + ) Calculated value C 8 H 6 D 3 Br[M(3D)] + 187.0076 Measured value 186.0071.

[0249] Mass spectrum abundance: M(1D) 2.1%, M(2D) 21.0%, M(3D) 76.9%

[0250] Deuterium rate: 2.74D (calculated by HRMS), 2.68D (calculated by 1 H-NMR calculated).

[0251] Embodiment 23

[0252] Preparation of deuterated compound B23

[0253]

[0254] The compound was prepared from 2-fluoro-1,4-dimethylbenzene (1 mmol, 130 μL) and reacted in an oil bath at 70°C for 24 h to obtain 77 mg of the target molecule B23 with a yield of 60%. 1 H NMR (500 MHz, deuterated dichloromethane) δ 7.07 (d, J = 8.4 Hz, 0.26H), 6.88-6.82 (m, 0.13H), 2.31 (s, 3H), 2.23 (s, 3H). 13 C NMR(126MHz,Methylene Chloride-d 2)δ161.75(d,J=243.3Hz).138.04,137.98,137.98,131.8-131.0(m),124.9-124 .4(m),122.02-121.8(m),116.0-115.3(m).21.04,14.38,14.35,14.32,14.29.

[0255] HRMS(EI + ) Calculated value C 8 H 7 D 2 F[M(2D)] + 126.0814 Measured value 126.0807.

[0256] HRMS(EI + ) Calculated value C 8 H 6 D 3 F[M(3D)] + 127.0877 Measured value 127.0867.

[0257] HRMS(EI + ) Calculated value C 8 H 5 D 4 F[M(4D)] + 128.0939 Measured value 128.0909.

[0258] Mass spectrum abundance: M(2D) 18.1%, M(3D) 76.6%, M(4D) 5.3%

[0259] Deuterium rate: 2.87D (calculated by HRMS), 2.48D (calculated by 1 H-NMR calculated).

[0260] Embodiment 24

[0261] Preparation of deuterated compound B24

[0262]

[0263] Using 2-chloro-1,4-dimethylbenzene as the raw material (1 mmol, 130 μL), according to the general operation procedure GP2, the target molecule B24 was obtained by reacting in an oil bath at 70°C for 24 h with a yield of 80%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.20 (s, 0.06H), 7.13 (s, 0.26H), 7.00 (d, J = 4.1 Hz, 0.07H), 2.37 (s, 1H), 2.33 (s, 1H).13 C NMR (126MHz, cdcl 3 )δ136.99,136.90,136.89,134.03,132.83,132.75,130.7-130.16(m),129.6-129.1(m),127.3-126.8(m),20.65,19.62,19.55.

[0264] HRMS(EI + ) Calculated value C 8 H 7 D 2 Cl[M(2D)] + 142.0518 Measured value 142.0511.

[0265] HRMS(EI + ) Calculated value C 8 H 6 D 3 Cl[M(3D)] + 143.0581 Measured value 143.0573.

[0266] Mass spectrum abundance: M(2D) 13.0%, M(3D) 87.0%

[0267] Deuterium rate: 2.87D (calculated by HRMS), 2.68D (calculated by 1 H-NMR calculated).

[0268] Embodiment 25

[0269] Preparation of deuterated compound B25

[0270]

[0271] Using 2-bromo-1,4-dimethylbenzene as the raw material (1 mmol, 138 μL), according to the general operation procedure GP2, the target molecule B25 147 mg was obtained in an oil bath at 70°C for 12 h with a yield of 79%. 1 H NMR (500 MHz, deuterated chloroform) δ7.38 (s, 0.06H), 7.12 (s, 0.17H), 7.02 (s, 0.05H), 2.38 (s, 3H), 2.31 (s, 3H). 13 C NMR (126MHz, cdcl 3 )δ137.13,137.11,134.67,134.60,132.9-132.3(m),130.5-130.0(m),128.0-127.53,124.6,22.40,20.55.

[0272] HRMS(FI + ) Calculated value C 8 H 7 D 2 Br[M(2D)] + 186.0013 Measured value 186.0008.

[0273] HRMS(FI + ) Calculated value C 8 H 6 D 3 Br[M(3D)] + 187.0076 Measured value 187.0069.

[0274] Mass spectrum abundance: M(2D) 12.4%, M(3D) 87.6%

[0275] Deuterium rate: 2.88D (calculated by HRMS), 2.72D (calculated by 1 H-NMR calculated).

[0276] Embodiment 26

[0277] Preparation of deuterated compound B26

[0278]

[0279] Using 4-fluoro-1,2-dimethylbenzene as the raw material (1 mmol, 124 μL), according to the general operation procedure GP2, the target molecule B26 62 mg was obtained in an oil bath at 70°C for 24 h with a yield of 49%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.07 (d, J = 6.0 Hz, 0.24 H), 6.85 (d, J = 9.6 Hz, 0.07 H), 6.79 (dd, J = 8.9, 4.8 Hz, 0.07 H), 2.25 (s, 3 H), 2.22 (s, 3 H). 13 C NMR(126MHz,Chloroform-d)δ161.20(d,J=242.9Hz).160.23,138.55,138.49,13 1.95,130.6-130.1(m),116.4-115.8(m),112.3-111.6(m),19.97,19.08,19.02.

[0280] HRMS(EI + ) Calculated value C 8 H 9 F[M(0D)] +124.0688, measured value 124.0660.

[0281] HRMS(EI + ) Calculated value C 8 H 8 DF[M(1D)] + 125.0751 Measured value 125.0733.

[0282] HRMS(EI + ) Calculated value C 8 H 7 D 2 F[M(2D)] + 126.0814 Measured value 126.0799.

[0283] HRMS(EI + ) Calculated value C 8 H 6 D 3 F[M(3D)] + 127.0877 Measured value 127.0869.

[0284] HRMS(EI + ) Calculated value C 8 H 5 D 4 F[M(4D)] + 128.0939 Measured value 128.0917.

[0285] Mass spectrum abundance: M(0D)4.4%, M(1D)14.3%, M(2D)33.8%, M(3D)43.8%, M(4D)3.7%

[0286] Deuterium rate: 2.28D (calculated by HRMS), 2.62D (calculated by 1 H-NMR calculated).

[0287] Embodiment 27

[0288] Preparation of deuterated compound B27

[0289]

[0290] Using 1-chloro-2,3-dimethylbenzene as the raw material (1 mmol, 128 μL), according to the general operation procedure GP2, the target molecule B27 105 mg was obtained in an oil bath at 70°C for 24 h with a yield of 74%. 1H NMR (500 MHz, deuterated chloroform) δ 7.16 (s, 0.07H), 7.10 (d, J = 2.5 Hz, 0.07H), 7.08 (s, 0.36H), 2.27 (s, 3H), 2.26 (s, 3H). 13 C NMR (126MHz, cdcl 3 )δ138.42,138.33,134.97,134.88,131.13-130.24(m),129.5-129.0(m),125.8-125.2(m),19.65,19.22,19.16.

[0291] HRMS(EI + ) Calculated value C 8 H 8 DCl[M(1D)] + 141.0456 Measured value 141.0448.

[0292] HRMS(EI + ) Calculated value C 8 H 7 D 2 Cl[M(2D)] + 142.0518 Measured value 142.0522.

[0293] HRMS(EI + ) Calculated value C 8 H 6 D 3 Cl[M(3D)] + 143.0581 Measured value 143.0580.

[0294] Mass spectrum abundance: M(1D) 3.2%, M(2D) 21.8%, M(3D) 75.0%

[0295] Deuterium rate: 2.72D (calculated by HRMS), 2.50D (calculated by 1 H-NMR calculated).

[0296] Embodiment 28

[0297] Preparation of deuterated compound B28

[0298]

[0299] Using 4-bromo-1,2-dimethylbenzene as the raw material (1 mmol, 138 μL), according to the general operation procedure GP2, the target molecule B28 153 mg was obtained in an oil bath at 70°C for 12 h with a yield of 81%. 1H NMR (500 MHz, deuterated chloroform) δ 7.30 (s, 0.07H), 7.23 (d, J = 3.8 Hz, 0.07H), 7.01 (s, 0.2H), 2.25 (s, 3H), 2.23 (s, 3H). 13 C NMR (126MHz, cdcl 3 )δ138.77,135.51,135.43,132.4-131.8,131.1-130.61,128.7-128.2,119.04,19.62,19.28.

[0300] HRMS(EI + ) Calculated value C 8 H 7 D 2 Br[M(2D)] + 186.0013 Measured value 186.0003.

[0301] HRMS(EI + ) Calculated value C 8 H 6 D 3 Br[M(3D)] + 187.0076 Measured value 187.0068.

[0302] Mass spectrum abundance: M(2D) 12.4%, M(3D) 87.6%

[0303] Deuterium rate: 2.88D (calculated by HRMS), 2.66D (calculated by 1 H-NMR calculated).

[0304] Embodiment 29

[0305] Preparation of deuterated compound B29

[0306]

[0307] Using 1-chloro-2,3-dimethylbenzene as the raw material (1 mmol, 128 μL), according to the general operation procedure GP2, the target molecule B29 105 mg was obtained in an oil bath at 70°C for 24 h with a yield of 74%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.25-7.23 (m, 0.06H), 7.17 (s, 0.02H), 7.09-7.03 (m, 0.39H), 2.36 (s, 3H), 2.34 (s, 3H). 13 C NMR (126MHz, cdcl 3)δ138.52,134.58,134.52,128.15-127.67(m),126.9-126.6(m),126.4-125.7(m),20.89,16.29.

[0308] HRMS(EI + ) Calculated value C 8 H 8 DCl[M(1D)] + 141.0456 Measured value 141.0457.

[0309] HRMS(EI + ) Calculated value C 8 H 7 D 2 Cl[M(2D)] + 142.0518 Measured value 142.0516.

[0310] HRMS(EI + ) Calculated value C 8 H 6 D 3 Cl[M(3D)] + 143.0581 Measured value 143.0577.

[0311] Mass spectrum abundance: M(1D) 5.4%, M(2D) 26.9%, M(3D) 67.7%

[0312] Deuterium rate: 2.62D (calculated by HRMS), 2.55D (calculated by 1 H-NMR calculated).

[0313] Embodiment 30

[0314] Preparation of deuterated compound B30

[0315]

[0316] Using 1-bromo-2,3-dimethylbenzene as the raw material (1 mmol, 138 μL), according to the general operation procedure GP2, the target molecule B30 164 mg was obtained in an oil bath at 70°C for 12 h with a yield of 87%. 1 H NMR (500 MHz, deuterated chloroform) δ 7.40 (s, 0.07H), 7.08 (s, 0.07H), 6.94 (s, 0.08H), 2.37 (s, 3H), 2.33 (s, 3H). 13 C NMR (126 MHz, CDCl 3)δ138.58,136.27,130.2-129.8,128.9-128.4,126.7-126.2,125.56,21.36,19.50.

[0317] HRMS(EI + ) Calculated value C 8 H 8 DBr[M(1D)] + 184.9950 Measured value 184.9941.

[0318] HRMS(EI + ) Calculated value C 8 H 7 D 2 Br[M(2D)] + 186.0013 Measured value 186.0016.

[0319] HRMS(EI + ) Calculated value C 8 H 6 D 3 Br[M(3D)] + 187.0076 Measured value 187.0069.

[0320] Mass spectrum abundance: M(1D) 3.0%, M(2D) 22.8%, M(3D) 74.2%

[0321] Deuterium rate: 2.74D (calculated by HRMS), 2.78D (calculated by 1 H-NMR calculated).

[0322] Embodiment 31

[0323] Preparation of deuterated compound B31

[0324]

[0325] The compound was prepared from 1-chloro-2,4-dimethylbenzene (1 mmol, 124 μL) and the target molecule B31 (121 mg) was obtained according to the general operation procedure GP2 with a yield of 84% and an NMR yield of 75%.

[0326] HRMS data of X obtained from GP1:

[0327] HRMS(FI + )calculated for C 8 H 8 DCl[M(1D)] +141.0456 found 141.0462.

[0328] HRMS(FI + )calculated for C 8 H 7 D 2 Cl[M(2D)] + 142.0518 found 142.0519.

[0329] HRMS(FI + )calculated for C 8 H 6 D 3 Cl[M(3D)] + 143.0581 found 143.0581.

[0330] Deuteriumincorporation:2.73D(HRMS),xx D( 1 H-NMR).

[0331] M(2D)1.5%, M(2D)23.3%, M(3D)75.1%

[0332] Embodiment 32

[0333] Preparation of deuterated compound B32

[0334]

[0335] The compound was prepared from 1-bromo-2,4-dimethylbenzene (1 mmol, 124 μL) and the target molecule B32 (162 mg) was obtained according to the general operation procedure GP2 with a yield of 86% and an NMR yield of 76%.

[0336] HRMS data of X obtained from GP1:

[0337] HRMS(FI + )calculated for C 8 H 7 D 2 Br[M(2D)] + 186.0013 found 186.0017.

[0338] HRMS(FI + )calculated for C 8 H 6 D 3 Br[M(3D)]+ 187.0076 found 186.0074.

[0339] Deuteriumincorporation:2.75D(HRMS),2.68D( 1 H-NMR).

[0340] M(2D)22.7%,M(3D)77.3%

[0341] Embodiment 33

[0342] Preparation of deuterated compound B33

[0343]

[0344] The compound was prepared from 2-fluoro-1,3,5-trimethylbenzene (1 mmol, 141 μL). According to the general operation procedure GP2, the target molecule B33 101 mg was obtained with a yield of 72%. According to the general operation procedure GP1, the GC yield was >99% and the NMR yield was 97%. 1 H NMR (500MHz, Chloroform-d) δ6.82 (d, J = 6.9 Hz, 0.09H), 2.27 (s, 3H), 2.25 (d, J = 2.3 Hz, 6H). 13 C NMR (126MHz, Chloroform-d) δ 158.22 (d, J = 240.3Hz), 132.36 (d, J = 4.3Hz), 129.4-128.8 (m), 123.94 (d, J = 18.0Hz), 20.5, 14.59 (d, J = 4.2Hz).

[0345] HRMS(FI + )calculated for C 9 H 10 DF[M(1D)] + 139.0908 found 139.0899.

[0346] HRMS(FI + )calculated for C 9 H 9 D 2 F[M(2D)] + 140.0970 found 140.0962.

[0347] HRMS(FI + )calculated for C 9 H8 D 3 F[M(3D)] + 141.1033 found 141.1002.

[0348] Deuteriumincorporation:1.97D(HRMS),1.91D( 1 H-NMR).

[0349] M(1D)11.6%, M(2D)80.0%, M(3D)8.4%

[0350] Embodiment 34

[0351] Preparation of deuterated compound B34

[0352]

[0353] Using 2-chloro-1,3,5-trimethylbenzene as the raw material (1 mmol, 146 μL), according to the general operation procedure GP2, the target molecule B34 was obtained by reacting in an oil bath at 70°C for 1 h with a yield of 91%. 1 H NMR (500 MHz, deuterated chloroform) δ 6.90 (s, 0.2H), 2.34 (s, 6H), 2.26 (s, 3H). 13 C NMR (126 MHz, CDCl 3 )δ135.9,135.6,135.5,131.7,129.3-128.8,20.6.

[0354] HRMS(FI + ) Calculated value C 9 H 10 DCl[M(1D)] + 155.0612 Measured value 155.0609.

[0355] HRMS(FI + ) Calculated value C 9 H 9 D 2 Cl[M(2D)] + 156.0675 Measured value 156.0671.

[0356] Mass spectrum abundance: M(1D) 11.8%, M(2D) 82.2%

[0357] Deuterium rate: 1.88D (calculated by HRMS), 1.80D (calculated by 1 H-NMR calculated).

[0358] Embodiment 35

[0359] Preparation of deuterated compound B35

[0360]

[0361] Using 2-bromo-1,3,5-trimethylbenzene as the starting material (1 mmol, 153 μL), according to the general procedure GP2, the target molecule B35 was obtained in an oil bath at 70°C for 1 h with a yield of 92%. 1 H NMR (500 MHz, deuterated chloroform) δ 6.91 (s, 0.1H), 2.39 (s, 6H), 2.26 (s, 3H). 13 C NMR (126 MHz, CDCl 3 )δ137.93,136.22,129.1-128.6,124.3,23.6,20.7.

[0362] HRMS(FI + ) Calculated value C 9 H 9 D 2 Br[M(2D)] + 200.0170 Measured value 200.0162.

[0363] Mass spectrum abundance: M(2D) 100%

[0364] Deuterium rate: 2.0D (calculated by HRMS), 1.9D (calculated by 1 H-NMR calculated).

[0365] Embodiment 36

[0366] Preparation of deuterated compound B36

[0367]

[0368] Using 1-bromo-2,4,5-trimethylbenzene as the raw material (1 mmol, 199 mg), according to the general operation procedure GP2, the target molecule B36 was obtained in an oil bath at 70°C for 1 h with a yield of 91%. 1 H NMR (500 MHz, deuterated chloroform) δ7.31 (s, 0.05H), 7.01 (s, 0.05H), 2.34 (s, 3H), 2.21 (s, 3H), 2.19 (s, 3H). 13 C NMR (126 MHz, CDCl 3)δ135.86,135.66,134.75,133.0-132.5,132.1-131.6,121.45,22.21,19.18,19.02.HRMS(FI + ) Calculated value C 9 H 10 DBr[M(1D)] + 199.0107 Measured value 199.0071.

[0369] HRMS(FI + ) Calculated value C 9 H 9 D 2 Br[M(2D)] + 200.0170 Measured value 200.0166.

[0370] Mass spectrum abundance: M(1D) 11.2%, M(2D) 88.7%

[0371] Deuterium rate: 1.89D (calculated by HRMS), 1.9D (calculated by 1 H-NMR calculated).

[0372] Embodiment 37

[0373] Preparation of deuterated compound B37

[0374]

[0375] The compound was prepared using 2-bromo-1,3-diisopropylbenzene as raw material (1mmol, 205μL). According to the general operation procedure GP2, 215mg of the target molecule B37 was obtained with a yield of 88%. According to the general operation procedure GP1, the GC yield was >99% and the NMR yield was 99%. 1 H NMR (500MHz, Chloroform-d) δ7.29 (s, 0.06H), 7.18 (s, 0.11H), 3.56 (heptd, J=6.3, 5.8, 2.7Hz, 2H), 1.30 (dd, J=6.9, 1.2Hz, 12H). 13 C NMR (126MHz, cdcl 3 )δ147.85,127.2-126.6(m),124.2-123.7(m),33.7,23.20.

[0376] HRMS data of X obtained from GP1:

[0377] HRMS(EI +)calculated for C 12 H 16 DBr[M(1D)] + 241.0576 found 241.0555.

[0378] HRMS(EI + )calculated for C 12 H 15 D 2 Br[M(2D)] + 242.0639 found 242.0630.

[0379] HRMS(EI + )calculated for C 12 H 14 D 3 Br[M(3D)] + 243.0702 found 243.0693.

[0380] Deuteriumincorporation:2.73D(HRMS),2.83D( 1 H-NMR).

[0381] M(2D)1.7%, M(2D)22.9%, M(3D)75.4%

[0382] Embodiment 38

[0383] Preparation of deuterated compound B38

[0384]

[0385] The compound was prepared using 2-bromo-1,3,5-triisopropylbenzene as raw material (1 mmol, 240 μL) and according to the general operation procedure GP2, the target molecule B38 (260 mg) was obtained with a yield of 91%. 1 H NMR(500MHz,Chloroform-d)δ6.99(s,0.12H),3.59-3.42(m,2H),2.94-2.78(m,1H),1.33-1.19(m,18H). 13 C NMR (126MHz, cdcl 3 )δ147.81,147.45,123.67,122.4-121.9(m),33.66,24.16,23.24.

[0386] HRMS data of X obtained from GP1:

[0387] HRMS(EI + )calculated for C 15 H 22 DBr[M(1D)] + 199.0107 found 199.0116.

[0388] HRMS(EI + )calculated for C 13 H 21 D 2 Br[M(2D)] + 200.0170 found 200.0168.

[0389] Deuteriumincorporation:2.68D(HRMS),1.88D( 1 H-NMR).

[0390] Embodiment 39

[0391] Preparation of deuterated compound B39

[0392]

[0393] The compound was prepared from 3,3',5,5'-tetramethylbiphenyl (0.1 mmol, 21.0 mg) and the target molecule B39 (10 mg, 46%) was obtained according to the general operation procedure GP2. 1 H NMR (600MHz, Chloroform-d) δ7.20 (s, 0.29H), 6.98 (s, 0.15H), 2.38 (s, 12H). 13 C NMR (151 MHz, CDCl 3 )δ141.45,141.41,141.37,138.15,138.05,128.9-128.4(m),125.2-124.74(m),21.43.

[0394] HRMS(EI + )calculated for C 16 H 14 D 4 [M(4D)] + 214.1660 found 214.1654.

[0395] HRMS(EI+ )calculated for C 16 H 13 D 5 [M(5D)] + 215.1722 found 215.1714.

[0396] HRMS(EI + )calculated for C 16 H 12 D 6 [M(6D)] + 216.1785 found 216.1778.

[0397] HRMS(EI + )calculated for C 16 H 11 D 7 [M(7D)] + 217.1848 found 217.1819.

[0398] Deuteriumincorporation:5.8D(HRMS),5.56D( 1 H-NMR).

[0399] M(4D)4,3%,M(5D)24.0%,M(6D)60.5%,M(7D)11.2%

[0400] Embodiment 40

[0401] Preparation of deuterated compound B40

[0402]

[0403] The compound was prepared using 3,3',4,4'-tetramethylbiphenyl as raw material (0.1 mmol, 21.0 mg) and the target molecule B40 (15 mg, 69%) was obtained according to the general operation procedure GP2. 1 H NMR(600MHz,Chloroform-d)δ7.36(s,0.15H),7.32(s,0.15H),7.19(s,0.15H),2.33(s,6H),2.30(s,6H). 13 C NMR (151 MHz, CDCl 3)δ138.88,138.79,136.92,136.84,135.42,135.34,130.0-129.5(m),128.4-127.9(m),124.3-123.9(m),20.00,19.49.

[0404] HRMS(EI + )calculated for C 16 H 14 D 4 [M(4D)] + 214.1660 found 214.1658.

[0405] HRMS(EI + )calculated for C 16 H 13 D 5 [M(5D)] + 215.1722 found 215.1717.

[0406] HRMS(EI + )calculated for C 16 H 12 D 6 [M(6D)] + 216.1785 found 216.1776.

[0407] HRMS(EI + )calculated for C 16 H 11 D 7 [M(7D)] + 217.1848 found 217.1815.

[0408] Deuteriumincorporation:5.79D(HRMS),5.55D( 1 H-NMR).

[0409] M(4D)3.9%, M(5D)23.1%, M(6D)61.9%, M(7D)11.1%

[0410] Embodiment 41

[0411] Preparation of deuterated compound B41

[0412]

[0413] The compound was prepared using 2,2',5,5'-hexamethylbiphenyl as raw material (0.1 mmol, 23.8 mg) and the target molecule B41 (10 mg, 46%) was obtained according to the general operation procedure GP2. 1 H NMR(600MHz,Chloroform-d)δ7.15(s,0.15H),7.07(s,0.14H),6.93(s,0.13H),2.34(s,6H),2.03(s,6H). 13 C NMR (151 MHz, CDCl 3 )δ141.63,134.78,132.65,130.1-129.2(m),127.8-127.3(m),20.96,19.38.

[0414] HRMS(FI + )calculated for C 16 H 14 D 4 [M(4D)] + 214.1660 found 214.1659.

[0415] HRMS(FI + )calculated for C 16 H 13 D 5 [M(5D)] + 215.1722 found 215.1718.

[0416] HRMS(FI + )calculated for C 16 H 12 D 6 [M(6D)] + 216.1785 found 216.1779.

[0417] HRMS(FI + )calculated for C 16 H 11 D 7 [M(7D)] + 217.1848 found 217.1817.

[0418] Deuteriumincorporation:5.79D(HRMS),5.58D( 1 H-NMR).

[0419] M(4D)4.0%, M(5D)23.2%, M(6D)61.9%, M(7D)10.9%

[0420] Embodiment 42

[0421] Preparation of deuterated compound B42

[0422]

[0423] The compound was prepared from 2,2',4,4',6,6'-hexamethylbiphenyl (0.1 mmol, 23.8 mg) and the target molecule B42 (20 mg, 83%) was obtained according to the general operation procedure GP2. 1 H NMR (600MHz, Chloroform-d) δ6.94 (s, 0.23H), 2.33 (s, 6H), 1.86 (s, 12H). 13 C NMR (151 MHz, CDCl 3 )δ137.12,136.05,135.96,135.64,135.56,128.3-127.8(m),21.14,19.89.

[0424] HRMS(FI + )calculated for C 18 H 19 D 3 [M(3D)] + 241.1910 found 241.1901.

[0425] HRMS(FI + )calculated for C 18 H 18 D 4 [M(4D)] + 242.1973ound 242.1965.

[0426] HRMS(FI + )calculated for C 18 H 17 D 5 [M(5D)] + 243.2035found243.1997Deuteriumincorporation:3.99D(HRMS),3.77D( 1 H-NMR).

[0427] M(3D)14.9%,M(4D)70.3%,M(5D)14.8%

[0428] Embodiment 43

[0429] Preparation of deuterated compound B43

[0430]

[0431] The compound was prepared from 1,2-diphenylethane (0.1 mmol, 18.2 mg) and the target molecule was obtained according to the general operation procedure GP2 with a yield of 67%. According to the general operation procedure GP1, the GC yield was 70%.

[0432] 1 H NMR(600MHz,Methylene Chloride-d 2 )δ7.27(s,0.4H),7.19(d,J=10.4Hz,0.34H),2.92(s,4H). 13 C NMR (151 MHz, CD 2 Cl 2 )δ142.29,128.8-128.1(m),126.1-125.7(m),38.25.

[0433] HRMS(FI + )calculated for C 14 H 6 D 8 [M(8D)] + 190.1598 found 190.1596.

[0434] HRMS(FI + )calculated for C 14 H 5 D 9 [M(9D)] + 191.1660 found 191.1654.

[0435] HRMS(FI + )calculated for C 14 H 4 D 10 [M(10D)] + 192.1723 found 192.1716.

[0436] HRMS(FI + )calculated for C 14 H 3 D11 [M(11D)] + 193.1786 found 193.1768.

[0437] Deuteriumincorporation:9.7D(HRMS),9.26D( 1 H-NMR).

[0438] M(8D)7.6%, M(9D)26.3%, M(10D)56.2%, M(11D)9.9%

[0439] Embodiment 44

[0440] Preparation of deuterated compound B44

[0441]

[0442] The compound was prepared from 1,2-p-xylylethane (0.1 mmol, 21.0 mg) and the target molecule (13 mg) was obtained according to the general operation procedure GP2 with a yield of 60%. 1 H NMR(600MHz,Chloroform-d)δ7.11-7.09(m,0.68H),2.87(s,4H),2.33(s,6H). 13 C NMR (151 MHz, CDCl 3 )δ138.84,135.25,129.0-128.6(m),128.3-127.9(m),37.66,21.05.

[0443] HRMS(FI + )calculated for C 16 H 12 D 6 [M(6D)] + 216.1785 found 216.1784.

[0444] HRMS(FI + )calculated for C 16 H 11 D 7 [M(7D)] + 217.1848 found 217.1846 HRMS (FI + )calculated for C 16 H 10 D 8 [M(8D)] +218.1911 found 218.1908.

[0445] HRMS(FI + )calculated for C 16 H 9 D 9 [M(9D)] + 219.1973 found 219.1941.

[0446] Deuteriumincorporation:7.65D(HRMS),7.32D( 1 H-NMR).

[0447] M(6D)7.2%, M(7D)29.2%, M(8D)54.8%, M(9D)8.8%

[0448] Embodiment 45

[0449] Preparation of deuterated compound B45

[0450]

[0451] The compound was prepared from 2,2-diphenylpropane (0.1 mmol, 19.7 μL) and the target molecule (16 mg, 92%) was obtained according to the general operation procedure GP2. 1 H NMR (600MHz, Chloroform-d) δ7.27 (s, 0.38H), 7.24 (q, J = 1.7, 1.1Hz, 0.42H), 7.17 (s, 0.17H), 1.69 (s, 6H). 13 C NMR (151 MHz, CDCl 3 )δ151.17,128.4-127.8(m),127.2-126.7(m),125.9-125.4(m),30.96.

[0452] HRMS(FI + )calculated for C 15 H 8 D 8 [M(8D)] + 204.1754 found 204.1760.

[0453] HRMS(FI + )calculated for C 15 H 7 D 9 [M(9D)]+ 205.1817 found 205.1818.

[0454] HRMS(FI + ) calculated for SC 15 H 6 D 10 [M(10D)] + 206.1880 found 206.1876.

[0455] HRMS(FI + )calculated for C 15 H 6 D 11 [M(11D)] + 207.1942found207.1912.

[0456] Deuteriumincorporation:9.79D(HRMS),9.62D( 1 H-NMR).

[0457] M(8D)3.9%, M(9D)23.0%, M(10D)62.0%, M(11D)11.1%

[0458] Embodiment 46

[0459] Preparation of deuterated compound B46

[0460]

[0461] The compound was prepared from 2,2-bis(3,4-xylyl)hexafluoropropane (0.1 mmol, 36.3 mg) and the target molecule (22 mg, 60%) was obtained according to the general operation procedure GP2. 1 H NMR (600MHz, Chloroform-d) δ7.15 (s, 0.2H), 7.11 (d, J = 8.5Hz, 0.3H), 2.28 (s, 6H), 2.25 (s, 6H). 13 C NMR (151 MHz, CDCl 3 )δ137.49,136.34,131.3-130.8(m),129.3-128.8(m),127.7-127.3(m),124.57(d,J=285.7Hz).121.71,20.08,19.47.

[0462] HRMS(FI + )calculated for C19 H 14 D 4 F 6 [M(4D)] + 364.1564 found 364.1583

[0463] HRMS(FI + )calculated for C 19 H 13 D 5 F 6 [M(5D)] + 365.1627 found 365.1620.

[0464] HRMS(FI + )calculated for C 19 H 12 D 6 F 6 [M(6D)] + 366.1689 found 366.1679.

[0465] HRMS(FI + )calculated for C 19 H 12 D 7 F 6 [M(7D)] + 367.1752 found 367.1740.

[0466] Deuteriumincorporation:5.66D(HRMS),5.50D( 1 H-NMR).

[0467] M(4D)7.5%, M(5D)29.4%, M(6D)52.1%, M(7D)11.0%

[0468] The above is only a preferred embodiment of the present invention, and does not limit the present invention in other forms. Any technician familiar with the profession may use the above disclosed technical content to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still belongs to the protection scope of the technical solution of the present invention.

Claims

1. A catalytic system for aromatic ring hydrogen-deuterium exchange reaction, characterized in that: include: Aromatics; Deuterated trifluoroacetic acid; and Ferric perchlorate hydrate, the structural formula is Fe(ClO4)3·xH2O, where x=1-9; Among them, the trivalent iron ion coordinated by perchlorate activates the CH bond of the aromatic ring of the aromatic hydrocarbon in the weakly coordinated deuterated trifluoroacetic acid to obtain an aromatic iron intermediate, and then the C-Fe bond undergoes protolysis to obtain the deuterated aromatic hydrocarbon product.

2. The aromatic ring hydrogen-deuterium exchange reaction catalytic system according to claim 1, characterized in that: The aromatic hydrocarbon is selected from toluene, ethylbenzene, propylbenzene, isobutylbenzene, o-xylene, m-xylene, p-xylene, 1-ethyl-2-methylbenzene, 1-ethyl-4-methylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, mesitylene, 1,2,4-trimethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1,2,3,4,5-pentamethylbenzene, 1-fluoro-3,5 -Dimethylbenzene, 1-chloro-3,5-dimethylbenzene, 1-bromo-3,5-dimethylbenzene, 2-fluoro-1,3-dimethylbenzene, 2-chloro-1,3-dimethylbenzene, 2-bromo-1,3-dimethylbenzene, 2-fluoro-1,4-dimethylbenzene, 2-chloro-1,4-dimethylbenzene, 2-bromo-1,4-dimethylbenzene, 4-fluoro-1,2-dimethylbenzene, 1-chloro-2,3-dimethylbenzene, 4-bromo -1,2-dimethylbenzene, 1-chloro-2,3-dimethylbenzene, 1-bromo-2,3-dimethylbenzene, 1-chloro-2,4-dimethylbenzene, 1-bromo-2,4-dimethylbenzene, 2-fluoro-1,3,5-trimethylbenzene, 2-chloro-1,3,5-trimethylbenzene, 2-bromo-1,3,5-trimethylbenzene, 1-bromo-2,4,5-trimethylbenzene, 2-bromo-1,3-diisopropylbenzene, 2-bromo - Any one of 1,3,5-triisopropylbenzene, 3,3',5,5'-tetramethylbiphenyl, 3,3',4,4'-tetramethylbiphenyl, 2,2',5,5'-hexamethylbiphenyl, 2,2',4,4',6,6'-hexamethylbiphenyl, 1,2-diphenylethane, 1,2-p-xylylethane, 2,2-diphenylpropane and 2,2-bis(3,4-xylyl)hexafluoropropane.

3. The aromatic ring hydrogen-deuterium exchange reaction catalytic system according to claim 1, characterized in that: The amount of the ferric perchlorate hydrate used is 0.10-0.50 equivalent relative to the aromatic hydrocarbon.

4. The aromatic ring hydrogen-deuterium exchange reaction catalytic system according to claim 1, characterized in that: The amount of the ferric perchlorate hydrate used is 0.1-0.2 equivalent relative to the aromatic hydrocarbon.

5. The aromatic ring hydrogen-deuterium exchange reaction catalytic system according to claim 1, characterized in that: The molar ratio of the deuterated trifluoroacetic acid to the aromatic hydrocarbon substrate is (20:1)-(200:1).

6. The aromatic ring hydrogen-deuterium exchange reaction catalytic system according to claim 1, characterized in that: The molar ratio of the deuterated trifluoroacetic acid to the aromatic hydrocarbon substrate is (50:1)-(100:1).

7. A method for preparing deuterated aromatic hydrocarbons, characterized in that: The preparation method is based on the catalytic system as described in any one of claims 1 to 6; The preparation method comprises the following steps: adding ferric perchlorate hydrate to a mixed system of aromatic hydrocarbons and deuterated trifluoroacetic acid, reacting and separating to obtain deuterated aromatic hydrocarbons.

8. The method for preparing deuterated aromatic hydrocarbons according to claim 7, characterized in that: The reaction temperature of the reaction is 0°C-80°C, and the reaction time is 0.5h-48h.

9. The method for preparing deuterated aromatic hydrocarbons according to claim 7, characterized in that: The reaction temperature of the reaction was 70°C.

10. The method for preparing deuterated aromatic hydrocarbons according to claim 7, characterized in that: The separation step is specifically as follows: after the reaction is completed, the reaction solution is extracted with dichloromethane, the organic phase is spin-dried, silica gel column chromatography is performed, and gradient elution with n-pentane and dichloromethane is used to separate the deuterated aromatic hydrocarbons.

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