Method for preparing deuterated compound through Birch type reduction reaction under transition metal-free condition and deuterated compound obtained by method

Abstract

The invention discloses a method for preparing a deuterated compound through a Birch type reduction reaction under a transition metal-free condition and the deuterated compound obtained by the method. The method comprises the following steps: under inert atmosphere protection, normal temperature and normal pressure conditions and in the presence of a deuterated reagent, performing dearomatization deuteration on (hetero) aromatic hydrocarbon by adopting an electro-optical catalysis method to obtain the deuterated compound. According to the method, an organic photocatalyst independent of transition metal is directly reduced into a corresponding anion free radical by virtue of an electro-optical catalytic synthesis technology, and the anion free radical has strong reduction capability after being excited by light, so that Birch type reduction deuterization of inert (hetero) aromatic hydrocarbon is realized. The method is milder in reaction, few in side reaction and high in target product yield.

Description

Technical Field

[0001] The present invention relates to the technical field of functionalization of aromatic compounds, and more specifically, to a method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions and a deuterated compound obtained by the method. Background Art

[0002] Due to the unique properties of deuterium atoms, deuterated chemicals play an important role in the fields of kinetic isotope effect research, drug discovery, material modification, and biochemical technology, and their synthesis has also attracted much attention. As an important fossil resource extracted from coal and crude oil, aromatic hydrocarbon molecules are the basic chemical building blocks of molecular science, and their reduction deuteration reactions are therefore regarded as a very attractive method for obtaining various deuterated chemicals. However, the synthetic options for reducing deuterated aromatic compounds are very limited, and the few existing methods generally rely on transition metal catalysis (Nature 2020, 581, 288-293; Chem. Commun. 1985, 373-374; ACS. Catal. 2018, 8, 5276-5285; J. Am. Chem. Soc. 1988, 110, 7906-7907; J. Am. Chem. Soc. 1992, 114, 10358-10368.). The hazardous and expensive deuterium sources (e.g., D2, NaBD4), harsh reaction conditions, and residual transition metals in these transition metal-catalyzed methods clearly limit their applications in pharmaceuticals and industry. Given the high utility of aromatic structures and the growing demand for constructing deuterium-labeled compounds, it is imperative to develop a mild strategy for the selective reduction of deuterated planar (hetero)arenes without transition metal catalysts and with high deuterium insertion rates.

[0003] Due to the inherent aromatic stabilization energy of aromatic compounds, transition metal-free catalytic schemes face the following major challenges: (1) the reduction potential of (hetero)arenes is high; (2) side reactions such as over-reduction are prone to occur; and (3) site selectivity is difficult to control. Summary of the invention

[0004] Based on the above problems, the purpose of the present invention is to provide a method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions and a deuterated compound obtained by the method, so as to solve the problems in the existing (hetero)aromatic hydrocarbon deuteration reaction that the expensive and dangerous deuterium source, harsh reaction conditions and precious metal catalysts greatly limit the scope of application of the reaction.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides a method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions, the method comprising the following steps:

[0007] Under the conditions of inert atmosphere protection, normal temperature and pressure, and in the presence of a deuterated reagent, an electro-photocatalytic method is used to dearomatize (hetero) aromatic hydrocarbons to obtain the deuterated compound.

[0008] In the technical solution of the present invention, "normal temperature and pressure" means that the temperature is 25°C and the pressure is 101.325KPa.

[0009] Furthermore, the inert atmosphere is argon.

[0010] Furthermore, in the preparation method, the materials used do not contain transition metal catalysts.

[0011] Furthermore, the raw materials for dearomatization deuteration of (hetero)aromatic hydrocarbons also include an electrolyte, a solvent and an optional photocatalyst.

[0012] It is understood that the deuterated reagent and (hetero)aromatic hydrocarbon are also part of the raw material. In the technical solution of the present invention, the components in the raw material are combined together to form a mixed solution.

[0013] Furthermore, the deuterated reagent is selected from one or more of deuterated water, deuterated methanol, deuterated ethanol and deuterated isopropanol. The deuterated reagent is environmentally friendly, cheap, and more suitable for industrial production.

[0014] Furthermore, the electro-photocatalytic reaction is to electrolyze the raw material under visible light irradiation.

[0015] Furthermore, the electrolysis of the raw material is carried out in an electrolytic cell equipped with a cathode and an anode.

[0016] Furthermore, the electrolysis method is constant current electrolysis.

[0017] Furthermore, the materials of the cathode and anode include but are not limited to a mixture of one or more of mesh glassy carbon, carbon rods, carbon cloth, nickel foam, platinum sheets, zinc sheets, magnesium sheets, etc.

[0018] Furthermore, the electrolytic cell is one of a single-tank, double-tank or MEA electrolytic cell.

[0019] Furthermore, the current of the constant current electrolysis is 0.1 mA-20 mA, and the electrolysis time is 1 h-200 h.

[0020] Preferably, the current of the constant current electrolysis includes but is not limited to 0.1 mA-10 mA, 0.1 mA-5 mA, 0.5 mA-10 mA, 0.5 mA-5 mA, 0.1 mA-1 mA, 0.5 mA-1 mA, 1 mA, etc. In this case, the reaction yield is higher.

[0021] Furthermore, the electrolyte is selected from LiOTf, 1-ethyl-3-methylimidazoline bis(trifluoromethylsulfonyl)imide, n One or more of Bu4NBF4, LiClO4 and LiBr.

[0022] The solvent in the present invention is only to provide a solution environment for the reactants. Those skilled in the art are capable of selecting a suitable solvent, and the present invention does not limit this. Further, the solvent is selected from one or more of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane.

[0023] Preferably, when the solvent is THF, the molar ratio of the deuterated reagent to the (hetero) aromatic hydrocarbon is 1 to 100. In some examples, the molar ratio of the deuterated reagent to the (hetero) aromatic hydrocarbon includes but is not limited to 45 to 100, 45 to 70, 45 to 60, 55 to 100, 55 to 70, 65 to 100, 49.8, 55.3, 66.4, 99.6, etc.

[0024] In the technical solution of the present invention, the photocatalyst is optional. Wherein "optionally present" means that the photocatalyst may be present or not. When the photocatalyst is present in the raw material system, it is directly reduced to anion radicals at the cathode, and the latter is excited by visible light to generate excited anion radicals with strong reducing properties, thereby reducing the (hetero)aromatic hydrocarbons to anion radicals and returning the photocatalyst to the ground state. When the photocatalyst is not present in the raw material system, the (hetero)aromatic hydrocarbons are directly reduced at the cathode. Then, the (hetero)aromatic hydrocarbon anion radicals react with the deuterated reagent to generate a deuterated radical intermediate, which is further reduced by the (excited) photocatalyst anion radical and then deuterated by the deuterated reagent, and finally converted into a dearylated deuterated product.

[0025] The photocatalyst in the present invention can catalyze the cyclic reaction process as long as the reduction potential is appropriate. Therefore, when using the photocatalyst, those skilled in the art are capable of selecting an appropriate photocatalyst, and the present invention does not impose any limitation on this.

[0026] Furthermore, the photocatalyst is selected from N,N'-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic acid diimide (PDI), 9-mesityl-10-methylacridine perchlorate (Mes-Acr + -ClO4 - ) and 9,10-dicyanoanthracene (DCA) or more thereof.

[0027] In the technical solution of the present invention, the (hetero) aromatic hydrocarbons include heteroaromatic hydrocarbons and aromatic hydrocarbons. Further, the (hetero) aromatic hydrocarbons have a structure shown in any one of the following formulae:

[0028]

[0029] in:

[0030] In formula I-1, R1 and R2 are each independently selected from H, Me, Et, Ph or CON(Et)2.

[0031] In formula I-2, R3, R4 and R5 are each independently selected from H, Me or F.

[0032] In formula I-3, R6, R7, R8, R9 and R 10 Each is independently selected from H, Me, OMe, Ph or F.

[0033] In Formula I-4, R 11 , R 12 , R 13 and R 14 Each is independently selected from H, Me, OMe, Ph, F or pyridyl.

[0034] In Formula I-5, R 15 Independently selected from H or Me.

[0035] Furthermore, in Formula I-1, the reaction sites of dearomatization deuteration are C9 and C10.

[0036] Furthermore, in Formula I-2, the reaction sites of dearomatization deuteration are C2 and C3 of indene.

[0037] Furthermore, in Formula I-3, the reaction sites for dearomatization deuteration are C2 and C3 of indene.

[0038] Furthermore, in formula I-4, the reaction sites of dearomatization deuteration are C2 and C3.

[0039] Furthermore, in formula I-5, the reaction sites of dearomatization deuteration are C2 and C3.

[0040] Further, In the reaction site of dearomatization, C5 and C8 are the sites.

[0041] Further, In the case of dearomatization, the reaction sites are C1 and C2.

[0042] Further, In the reaction site of dearomatization, C9 is the reaction site.

[0043] Further, In the reaction, the dearomatization deuteration reaction sites are C2 and C3 of benzofuran.

[0044] Further, In the reaction, the dearomatization deuteration reaction sites are C2 and C3 of benzothiophene.

[0045] In the technical solution of the present invention, the molar concentration of the photocatalyst in the raw material is between zero and the saturated molar concentration, including zero; the molar concentration of the deuterated reagent in the raw material is between zero and the saturated molar concentration, including zero; the molar concentration of the (hetero)aromatic hydrocarbon in the raw material is between zero and the saturated molar concentration, including zero; the molar concentration of the electrolyte in the raw material is between zero and the saturated molar concentration, including zero.

[0046] Furthermore, in the raw materials, the concentration of (hetero)aromatic hydrocarbons is 0.001M-10M, the concentration of deuterated reagents is 0.001M-10M, the concentration of electrolytes is 0.001M-10M, and the concentration of photocatalysts is 5×10 -3 M-5×10 -5 M.

[0047] Preferably, in the raw material, the concentration of (hetero)aromatic hydrocarbons includes but is not limited to 0.01M-10M, 0.01M-5M, 0.01M-1M, 0.01M-0.5M, 0.01M-0.1M, 0.01M-0.05M, 0.02M-10M, 0.02M-5M, 0.02M-1M, 0.02M-0.5M, 0.02M-0.1M, 0.02M-0.05M, 0.02M-0.03M, etc. In this case, the reaction yield is higher.

[0048] Preferably, in the raw material, the concentration of the electrolyte includes but is not limited to 0.1M-10M, 0.1M-5M, 0.1M-1M, 0.1M-0.5M, 0.1M-0.2M, etc.

[0049] Preferably, the concentration of the photocatalyst in the raw material includes but is not limited to 1×10 -4 M-8×10 -4 M, 1×10 - 4 M-6×10 -4 M, 1×10 -4 M-5×10 -4 M, 2×10 -4 M-8×10 -4 M, 2×10 -4 M-6×10 -4 M, 2×10 -4 M-5×10 - 4 M, 4×10 -4 M-8×10 -4 M, 4×10-4 M-6×10 -4 M, 4×10 -4 M-5×10 -4 M, 4×10 -4 M-4.5×10 -4 M et al.

[0050] Furthermore, the light source for the electro-photocatalysis is selected from LED lamps, simulated sunlight or xenon lamps.

[0051] Furthermore, the wavelength λ of the simulated sunlight is greater than 400 nm.

[0052] The present invention uses an economical, green and safe deuterated reagent, does not require a transition metal catalyst, and uses electro-photocatalytic technology to achieve a selective reduction and deuteration reaction of (hetero) aromatic hydrocarbons at room temperature and pressure to synthesize high value-added deuterated chemicals. The method has mild reaction conditions, inputs a relatively low constant current at room temperature, and can deuterate a variety of (hetero) aromatic hydrocarbon chemicals by irradiation with visible light or sunlight, and no excessive reduction and deuteration side reactions occur. The method has the characteristics of a simple, efficient, green and economical reaction process, solves the problems of using dangerous and expensive deuterium sources, harsh reaction conditions, and low selectivity in existing deuteration reactions, and reflects the potential application of the method in the production of deuterated chemicals, especially in the field of medicine.

[0053] In another aspect, the present invention provides a deuterated compound prepared by the preparation method described above.

[0054] The beneficial effects of the present invention are as follows:

[0055] In the method of the present invention, an organic photocatalyst that does not rely on transition metals is directly reduced to a corresponding anion free radical by means of electro-photocatalytic synthesis technology, and the latter can have a strong reducing ability when excited by light, thereby realizing the Birch-type reductive deuteration of inert (hetero) aromatic hydrocarbons. The method has a milder reaction, fewer side reactions, and a high yield of the target product. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] The specific implementation modes of the present invention will be further described in detail below in conjunction with the accompanying drawings.

[0057] Figure 1 The 9,10-dideutero-9,10-dihydroanthracene in Example 1 is shown 1 H NMR spectra.

[0058] Figure 2 The 9,10-dideutero-9,10-dihydroanthracene in Example 1 is shown 13 C NMR spectrum.

[0059] Figure 3 The 9-deuteryl-9,10-dihydroacridine in Example 6 is shown1 H NMR spectra.

[0060] Figure 4 The 9-deuteryl-9,10-dihydroacridine in Example 6 is shown 13 C NMR spectrum.

[0061] Figure 5 The 1,2-dideutero-1,2-dihydrocyclopenta[3,2,1-ij]naphthalene of Example 7 is shown in FIG. 1 H NMR spectra.

[0062] Figure 6 The 1,2-dideutero-1,2-dihydrocyclopenta[3,2,1-ij]naphthalene of Example 7 is shown in FIG. 13 C NMR spectrum.

[0063] Figure 7 The 1,2-dideutero-2-phenyl-2,3-dihydro-1H-indene in Example 9 is shown 1 H NMR spectra.

[0064] Figure 8 The 1,2-dideutero-2-phenyl-2,3-dihydro-1H-indene in Example 9 is shown 13 C NMR spectrum.

[0065] Fig. 9 The example of 14 1,2-dideutero-1-phenyl-2,3-dihydro-1H-indene is shown. 1 H NMR spectra.

[0066] Fig.10 The example of 14 1,2-dideutero-1-phenyl-2,3-dihydro-1H-indene is shown. 13 C NMR spectrum.

[0067] Fig.11 The example shows 18 2,3-dideutero-3-methyl-2,3-dihydrobenzo[b]thiophene 1 H NMR spectra.

[0068] Fig.12 Example 18 shows 2,3-dideutero-3-methyl-2,3-dihydrobenzo[b]thiophene 13 C NMR spectrum.

[0069] Fig.13 The 2,3-dideutero-2-phenyl-2,3-dihydro-1-benzofuran in Example 25 is shown 1 H NMR spectra.

[0070] Fig.14The 2,3-dideutero-2-phenyl-2,3-dihydro-1-benzofuran in Example 25 is shown 13 C NMR spectrum.

[0071] Fig.15 The 8-({4-[4-(2,3-dideuteroyl-2,3-dihydrobenzo[b]thien-4-yl)piperazin-1-yl]butyl}oxy)-1,2-dihydroquinolin-2-one in Example 29 is shown. 1 H NMR spectra.

[0072] Fig.16 8-({4-[4-(2,3-dideuteuro-2,3-dihydrobenzo[b]thien-4-yl)piperazin-1-yl]butyl}oxy)-1,2-dihydroquinolin-2-one in Example 29 13 C NMR spectrum. DETAILED DESCRIPTION

[0073] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0074] Example 1

[0075] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0076] Weigh 0.002mmol PDI photocatalyst, 0.1mmol anthracene, 90μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL of ultra-dry THF / DME (6:1) mixed solvent and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 7 hours at room temperature and atmospheric pressure. After the reaction is completed, separate by chromatographic column. H NMR spectrum, C spectrum (such as Figure 1 and Figure 2 The product was identified as 9,10-dideutero-9,10-dihydroanthracene by mass spectrometry with a yield of 83% (80% D). No over-reduced deuterated byproducts were generated in the reaction.

[0077] Example 2

[0078] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0079] 0.002mmol PDI photocatalyst, 0.1mmol 9-methylanthracene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously for 8 hours at room temperature and atmospheric pressure using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 9,10-dideuteryl-9-methyl-9,10-dihydroanthracene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 90% (85% D1, 78% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0080] Example 3

[0081] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0082] 0.002mmol PDI photocatalyst, 0.1mmol 2-ethylanthracene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the solution was separated by a chromatographic column. The product was identified as 9,10-dideuteryl-2-ethyl-9,10-dihydroanthracene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 57% (82% D). No over-reduction deuterated byproducts were generated in the reaction.

[0083] Example 4

[0084] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0085] 0.002mmol PDI photocatalyst, 0.1mmol 9-phenylanthracene, 120μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 10 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 9,10-dideuteryl-9-phenyl-9,10-dihydroanthracene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 83% (85% D1, 90% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0086] Example 5

[0087] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0088] 0.002mmol PDI photocatalyst, 0.1mmol N,N-diethylanthracene-9-carboxamide, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrometry as 9,10-dideuteryl-N,N-diethyl-9,10-dihydroanthracene-9-carboxamide with a yield of 78% (74% D1, 94% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0089] Example 6

[0090] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0091] Weigh 0.002mmol PDI photocatalyst, 0.1mmol acridine, 90μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL of ultra-dry THF and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 9 hours at room temperature and atmospheric pressure. After the reaction is completed, separate by chromatographic column. Nuclear magnetic hydrogen spectrum, carbon spectrum (such as Figure 3 and Figure 4 The product was identified as 9-deuteryl-9,10-dihydroacridine by mass spectrometry with a yield of 38% (84% D). No over-reduced deuterated by-products were generated in the reaction.

[0092] Example 7

[0093] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0094] Weigh 0.002mmol PDI photocatalyst, 0.1mmol erene, 120μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL of ultra-dry THF and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 10 hours at room temperature and atmospheric pressure. After the reaction is completed, separate the chromatographic column. H NMR spectrum, C spectrum (such as Figure 5 and Figure 6 The product was identified by mass spectrometry as 1,2-dideutero-1,2-dihydrocyclopenta[3,2,1-ij]naphthalene with a yield of 48% (82% D). No over-reduced deuterated byproducts were generated in the reaction.

[0095] Example 8

[0096] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0097] 0.002mmol PDI photocatalyst, 0.1mmol 1,4-dimethoxynaphthalene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 1,4-dideuteryl-5,8-dimethoxy-1,4-dihydronaphthalene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 63% (80% D). No over-reduction deuterated byproducts were generated in the reaction.

[0098] Example 9

[0099] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0100] Weigh 0.002mmol PDI photocatalyst, 0.1mmol 2-phenylindene, 180μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL of ultra-dry THF and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 12 hours at room temperature and atmospheric pressure. After the reaction is completed, separate the solution with a chromatographic column. H NMR spectrum, C NMR spectrum (such as Figure 7 and Figure 8 The product was identified as 1,2-dideutero-2-phenyl-2,3-dihydro-1H-indene by mass spectrometry with a yield of 85% (93% D1, 84% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0101] Example 10

[0102] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0103] 0.002mmol PDI photocatalyst, 0.1mmol 2-(2-methylphenyl)-1H-indene, 180μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed for 12 hours at room temperature and atmospheric pressure using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified by H NMR, C NMR and mass spectrometry as 1,2-dideuteryl-2-(2-methylphenyl)-2,3-dihydro-1H-indene with a yield of 72% (95% D1, 82% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0104] Embodiment 11

[0105] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0106] 0.002mmol PDI photocatalyst, 0.1mmol 2-(3-methylphenyl)-1H-indene, 180μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 20 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the product was separated by a chromatographic column. The product was identified as 1,2-dideuteryl-2-(3-methylphenyl)-2,3-dihydro-1H-indene by H NMR, C NMR and MS, with a yield of 85% (91% D1, 86% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0107] Example 12

[0108] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0109] 0.002mmol PDI photocatalyst, 0.1mmol 2-(4-methylphenyl)-1H-indene, 180μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 16 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the product was separated by a chromatographic column. The product was identified as 1,2-dideuteryl-2-(4-methylphenyl)-2,3-dihydro-1H-indene by H NMR, C NMR, and MS, with a yield of 60% (92% D1, 96% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0110] Embodiment 13

[0111] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0112] 0.002mmol PDI photocatalyst, 0.1mmol 2-(4-fluorophenyl)-1H-indene, 180μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 10 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the solution was separated by a chromatographic column. The product was identified as 1,2-dideuteryl-2-(4-fluorophenyl)-2,3-dihydro-1H-indene by H NMR, C NMR, F NMR and MS, with a yield of 75% (93% D1, 95% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0113] Embodiment 14

[0114] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0115] Weigh 0.002mmol PDI photocatalyst, 0.1mmol 3-phenyl-1H-indene, 100μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL ultra-dry THF and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 9 hours at room temperature and atmospheric pressure. After the reaction is completed, separate the solution with a chromatographic column. H NMR spectrum, C NMR spectrum (such as Fig. 9 and Fig.10 The product was identified by mass spectrometry as 1,2-dideutero-1-phenyl-2,3-dihydro-1H-indene with a yield of 70% (86% D). No over-reduced deuterated byproducts were generated in the reaction.

[0116] Embodiment 15

[0117] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0118] 0.002mmol PDI photocatalyst, 0.1mmol 6-methoxy-3-phenyl-1H-indene, 180μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm). 4.50mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 12 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the product was separated by a chromatographic column. The product was identified as 1,2-dideuteryl-5-methoxy-1-phenyl-2,3-dihydro-1H-indene by H NMR, C NMR and MS, with a yield of 63% (92% D1, 88% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0119] Example 16

[0120] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0121] 0.002mmol PDI photocatalyst, 0.1mmol 5,6-dimethoxy-3-phenyl-1H-indene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 20 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 1,2-dideuteryl-5,6-dimethoxy-1-phenyl-2,3-dihydro-1H-indene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 42% (93% D1, 86% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0122] Embodiment 17

[0123] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0124] 0.002mmol PDI photocatalyst, 0.1mmol 5-fluoro-3-phenyl-1H-indene, 180μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 10 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 1,2-dideuteryl-6-fluoro-1-phenyl-2,3-dihydro-1H-indene by nuclear magnetic hydrogen spectrum, carbon spectrum, fluorine spectrum and mass spectrum, with a yield of 93% (90% D). No over-reduction deuterated byproducts were generated in the reaction.

[0125] Embodiment 18

[0126] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0127] Weigh 0.002mmol PDI photocatalyst, 0.1mmol 3-methyl-benzothiophene, 90μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL of ultra-dry THF and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 9 hours at room temperature and atmospheric pressure. After the reaction is completed, separate by chromatographic column. Nuclear magnetic hydrogen spectrum, carbon spectrum (such as Fig.11 and Fig.12 The product was identified by mass spectrometry as 2,3-dideutero-3-methyl-2,3-dihydrobenzo[b]thiophene with a yield of 45% (85% D1, 88% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0128] Embodiment 19

[0129] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0130] 0.002mmol PDI photocatalyst, 0.1mmol 5-methyl-benzothiophene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 2,3-dideuteryl-5-methyl-2,3-dihydrobenzo[b]thiophene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 43% (83% D1, 84% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0131] Embodiment 20

[0132] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0133] 0.002mmol PDI photocatalyst, 0.1mmol 5-methoxy-benzothiophene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 2,3-dideuteryl-5-methoxy-2,3-dihydrobenzo[b]thiophene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 49% (93% D1, 82% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0134] Embodiment 21

[0135] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0136] 0.002mmol PDI photocatalyst, 0.1mmol 5-fluoro-benzothiophene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the solution was separated by a chromatographic column. The product was identified as 2,3-dideuteryl-5-fluoro-2,3-dihydrobenzo[b]thiophene by nuclear magnetic hydrogen spectrum, carbon spectrum, fluorine spectrum and mass spectrum, with a yield of 58% (84% D1, 90% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0137] Embodiment 22

[0138] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0139] 0.002mmol PDI photocatalyst, 0.1mmol 4-fluoro-benzothiophene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 2,3-dideuteryl-4-fluoro-2,3-dihydrobenzo[b]thiophene by nuclear magnetic hydrogen spectrum, carbon spectrum, fluorine spectrum and mass spectrum, with a yield of 57% (88% D1, 91% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0140] Embodiment 23

[0141] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0142] 0.002mmol PDI photocatalyst, 0.1mmol 2-phenyl-benzothiophene, 120μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed for 10 hours at room temperature and atmospheric pressure using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 2,3-dideuteryl-2-phenyl-2,3-dihydrobenzo[b]thiophene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 80% (88% D1, 95% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0143] Embodiment 24

[0144] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0145] 0.002mmol PDI photocatalyst, 0.1mmol 2-pyridyl-benzothiophene, 120μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 10 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified by H NMR, C NMR and MS as 2-(2,3-dideuteryl-2,3-dihydrobenzo[b]thiophene-2-yl)pyridine with a yield of 51% (93% D1, 81% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0146] Embodiment 25

[0147] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0148] Weigh 0.002mmol PDI photocatalyst, 0.1mmol 2-phenyl-benzofuran, 120μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL ultra-dry THF and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 10 hours at room temperature and atmospheric pressure. After the reaction is completed, separate by chromatographic column. H NMR spectrum, C NMR spectrum (such as Fig.13 and Fig.14 The product was identified by mass spectrometry as 2,3-dideutero-2-phenyl-2,3-dihydro-1-benzofuran with a yield of 68% (95% D1, 82% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0149] Embodiment 26

[0150] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0151] 0.002mmol PDI photocatalyst, 0.1mmol 2-phenyl-indole, 180μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 10 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 2,3-dideuteryl-2-phenyl-2,3-dihydro-1H-indole by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrometry, with a yield of 65% (95% D1, 93% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0152] Embodiment 27

[0153] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0154] 0.002mmol PDI photocatalyst, 0.1mmol N-methyl-2-phenyl-indole, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 9 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 2,3-dideuteryl-2-phenyl-2,3-dihydro-1H-indole by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrometry, with a yield of 41% (88% D1, 85% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0155] Embodiment 28

[0156] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0157] 0.002mmol PDI photocatalyst, 0.1mmol 4,7-dimethylindene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 12 hours using a 1mA current under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified by H NMR, C NMR and mass spectrometry as 1,2-dideuteryl-4,7-dimethyl-2,3-dihydro-1H-indene with a yield of 28% (72% D1, 70% D2). No over-reduction deuterated byproducts were generated in the reaction.

[0158] Embodiment 29

[0159] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0160] Weigh 0.002mmol PDI photocatalyst, 0.1mmol epiprazole, 100μL deuterated water, 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL of ultra-dry THF and degas with argon for 20 minutes. Then, under 440nm LED irradiation, use 1mA current to continuously electrolyze the solution for 12 hours at room temperature and atmospheric pressure. After the reaction is completed, separate by chromatographic column. H NMR spectrum, C NMR spectrum (such as Fig.15 and Fig.16 The product was identified by mass spectrometry as 8-({4-[4-(2,3-dideutero-2,3-dihydrobenzo[b]thien-4-yl)piperazin-1-yl]butyl}oxy)-1,2-dihydroquinolin-2-one with a yield of 80% (99% D1, 40% D2). No over-reduced deuterated byproducts were generated in the reaction.

[0161] Embodiment 30

[0162] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0163] Weigh 0.002mmol Mes-Acr + -ClO4 - Photocatalyst, 0.1mmol anthracene, 90μL deuterated water, 0.675mmol LiClO4 were placed in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm). 4.50mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed for 7 hours at room temperature and atmospheric pressure using a 1mA current under 440nm LED irradiation. After the reaction, 1,3,5-trimethoxybenzene was used as an internal standard. 1 The yield of 9,10-dideutero-9,10-dihydroanthracene was 8.5% as determined by H NMR. No over-reduced deuterated byproducts were generated in the reaction.

[0164] Embodiment 31

[0165] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0166] Weigh 0.1mmol anthracene, 90μL deuterated water, and 0.675mmol LiClO4 in a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), add 4.50mL of ultra-dry THF / DME (6:1) mixed solvent and degas with argon for 20 minutes. Then, under 440nm LED irradiation, the solution was electrolyzed at room temperature and atmospheric pressure for 7 hours using a current of 1mA. After the reaction, 1,3,5-trimethoxybenzene was used as an internal standard. 1 The yield of 9,10-dideutero-9,10-dihydroanthracene was 16% as determined by H NMR. No over-reduced deuterated byproducts were generated in the reaction.

[0167] Example 32 (Simulated Sunlight Experiment)

[0168] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0169] 0.002mmol PDI photocatalyst, 0.1mmol anthracene, 90μL deuterated water, 0.675mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (1.0cm×1.0cm×0.5cm) and a magnesium sheet anode (1.0cm×1.0cm×0.2cm), and 4.50mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 20 minutes. Subsequently, the solution was electrolyzed continuously at room temperature and atmospheric pressure for 10 hours under simulated sunlight (λ>400nm). After the reaction was completed, the chromatographic column was separated. The product was identified as 9,10-dideuteryl-9,10-dihydroanthracene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrometry, with a yield of 70% (80% D). No over-reduction deuterated byproducts were generated in the reaction.

[0170] Example 33 (Gram-scale scale-up experiment of Example 1)

[0171] A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions comprises the following steps:

[0172] 0.16mmol PDI photocatalyst, 8.0mmol anthracene, 7.2mL deuterated water, 42.8mmol LiClO4 were weighed into a single-tank electrolytic cell equipped with a mesh glassy carbon cathode (5.0cm×1.0cm×0.6cm) and a magnesium sheet anode (5.0cm×5.0cm×0.2cm), and 322.0mL of ultra-dry THF / DME (6:1) mixed solvent was added and degassed with argon for 60 minutes. Subsequently, the solution was electrolyzed continuously for 165 hours at room temperature and atmospheric pressure using a current of 2.5mA under 440nm LED irradiation. After the reaction was completed, the chromatographic column was separated. The product was identified as 9,10-dideuteryl-9,10-dihydroanthracene by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, with a yield of 69% (79% D). No over-reduction deuterated byproducts were generated in the reaction.

[0173] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A method for preparing a deuterated compound by a Birch-type reduction reaction under transition metal-free conditions, characterized in that: The steps include: Under the conditions of inert atmosphere protection, normal temperature and pressure, and in the presence of a deuterated reagent, an electro-photocatalytic method is used to dearomatize (hetero) aromatic hydrocarbons to obtain the deuterated compound.

2. The preparation method according to claim 1, characterized in that: In the preparation method, the materials used do not contain transition metal catalysts.

3. The method according to claim 1 or 2, characterized in that: The raw materials for the dearomatization deuteration reaction also include an electrolyte, a solvent and an optional photocatalyst.

4. The method according to claim 3, characterized in that: The electro-photocatalysis is to electrolyze the raw material under visible light irradiation.

5. The method according to claim 4, characterized in that The electrolysis method is constant current electrolysis, and the current of the constant current electrolysis is 0.1mA-20mA.

6. The method according to claim 3, characterized in that The deuterated reagent is selected from one or more of deuterated water, deuterated methanol, deuterated ethanol and deuterated isopropanol; and / or The electrolyte is selected from LiOTf, 1-ethyl-3-methylimidazoline bis(trifluoromethylsulfonyl)imide, n One or more of Bu4NBF4, LiClO4 and LiBr; and / or The solvent is selected from one or more of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; and / or The photocatalyst is selected from one or more of N,N'-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic acid diimide, 9-mesityl-10-methylacridine perchlorate and 9,10-dicyanoanthracene.

7. The method according to claim 3, characterized in that In the raw materials, the concentration of (hetero)aromatic hydrocarbon is 0.001M-10M, the concentration of deuterated reagent is 0.001M-10M, the concentration of electrolyte is 0.001M-10M, the concentration of photocatalyst is 5×10 -3 M-5×10 -5 M.

8. The method according to claim 1, characterized in that The (hetero)aromatic hydrocarbon has a structure as shown in any one of the following formulae: in: In formula I-1, R1 and R2 are each independently selected from H, Me, Et, Ph or CON(Et)2; In formula I-2, R3, R4 and R5 are each independently selected from H, Me or F; In formula I-3, R6, R7, R8, R9 and R 10 Each independently selected from H, Me, OMe, Ph or F; In Formula I-4, R 11 , R 12 , R 13 and R 14 are each independently selected from H, Me, OMe, Ph, F or pyridyl; In Formula I-5, R 15 Independently selected from H or Me.

9. The method according to claim 1 or 4, characterized in that: The light source for electro-photocatalysis is selected from LED lamps, simulated sunlight or xenon lamps.

10. The deuterated compound prepared by the method according to any one of claims 1 to 9.

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