Electrochemical method for preparing deuterated silane

Abstract

The invention discloses an electrochemical method of deuterated silane. The method comprises the following steps: in a protective atmosphere, mixing substituted silane, an electrolyte, a nickel catalyst, a ligand and deuterium water in a solvent, carrying out an electrochemical deuterization reaction under a constant current condition, and carrying out post-treatment to prepare the deuterated silane compound. The method takes deuterium water as a deuterium source, and is green, economical, cheap and easy to obtain; a catalytic amount of nickel and silane form a silicon-nickel intermediate, so that the polarity of silicon is reversed, and the generation of a silane self-coupling product and a silanol byproduct is effectively avoided; the electrochemical synthesis method has the characteristics of mild reaction conditions, cleanness, greenness and simplicity in reaction operation. The electrochemical synthesis method provided by the invention realizes successful preparation of the natural product post-modified deuterated silane, and has important significance in the aspects of drug development and deuterated compound research; the electrochemical synthesis method disclosed by the invention can resist high current to prepare the ten-gram-grade deuterated silane, and has a wide industrial application prospect. In addition, the deuterated silane synthetic product can be used as a silicon deuteration reagent, the practicability of the deuterated silane synthetic product in unsaturated bond reduction reaction is proved, and the deuterated silane synthetic product has a wide development prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electrochemical synthesis, further relates to an electrochemical method for preparing deuterated silane, and more particularly relates to a constant current catalysis method for preparing deuterated silane by using deuterium water as a deuterium source and application thereof. BACKGROUND

[0002] The organic electrochemical synthesis technology has the advantages of adjustable electrode potential, no need of external chemical oxidant / reducing agent, and feasibility of industrial production, thereby promoting the extensive research on the organic electrochemical deuteriation reaction.

[0003] However, the current electrochemical deuteriation research using oxidized deuterium (D2O) as an economic deuterium source mainly focuses on the construction of carbon-deuterium (C-D) bond, which is in sharp contrast to the research on the construction of silicon-deuterium (Si-D) bond, which is still in the unknown and extremely challenging stage: under the condition of electro-reduction, the silicon free radical / silicon anion is prone to self-coupling reaction; under the condition of electro-oxidation, the silicon cation has strong oxygen affinity and is easy to be attacked by nucleophilic attack to generate silanol byproduct. Meanwhile, in view of the fact that deuterated silane is widely used in organic synthesis reaction, catalytic mechanism research, etc., it is still an urgent goal to be achieved to develop a general and greener electrochemical method for preparing various deuterated silanes by using economic and environment-friendly deuterium source (D2O). SUMMARY

[0004] To solve the problems in the prior art, the present application provides a method for preparing deuterated silane by direct current catalysis using deuterium water as a deuterium source and application thereof. The present application successfully realizes the deuteriation of various alkyl-substituted, aryl-substituted silane and natural product post-modification substituted silane by direct current catalysis, and obtains the corresponding deuterated silane product. The method of the present application realizes the polarity inversion of silicon by adding a catalytic amount of metal nickel reagent to form a silicon-nickel intermediate, thereby effectively avoiding the self-coupling product formed by silicon species under electrochemical conditions and the silanol byproduct formed by the high oxygen affinity of silicon species. Moreover, the electrochemical synthesis method has the characteristics of mild reaction conditions, clean and green, and simple reaction operation.

[0005] One of the purposes of the present application is to provide an electrochemical method for preparing deuterated silane, which comprises the following steps:

[0006] In a protective atmosphere, the silane compound shown in formula 1, a deuterium source, a nickel catalyst, a ligand and an electrolyte are mixed in a solvent, and then a silane deuteriation reaction occurs under constant current conditions, followed by post-treatment to obtain the deuterated silane compound;

[0007] The silane compound shown in formula 1 has the following structural formula:

[0008]

[0009] In Formula 1, R1 is phenyl or substituted phenyl, C1-C10 alkyl, biphenyl, or naphthyl;

[0010] R2 is a C1-C10 alkyl, phenyl, naphthyl, C1-C5 alkylnaphthyl, heteroaryl, or other alkyl-naphthyl groups.

[0011] In this context, R3 is a C1-C10 alkyl group; R4 is hydrogen, a C1-C5 alkyl group, a phenyl group, a C1-C5 alkoxy group, a C2-C5 ester group, a halogen, or a phenyl group;

[0012] In this context, R5 represents a C1-C5 alkyl group, a C1-C5 alkoxy group, a C2-C25 ester group, a benzyloxy group, a halogen, an N,N-dialkyl group, a C1-C5 haloalkyl group, or a phenyl group. base, base;

[0013] In this context, R6 represents a C1-C5 alkyl group, a halogen, or a C1-C5 alkoxy group;

[0014] In this context, R7 is a C1-C5 alkyl group;

[0015] The deuterated silane compound has the structural formula shown in Formula 2:

[0016] R1 and R2 in Equation 2 correspond to the same R1 and R2 described in Equation 1.

[0017] The protective gas of this invention refers to commonly used gases, such as nitrogen and inert gases.

[0018] As a preferred implementation method,

[0019] In Formula 1, R1 is phenyl, C1-C5 alkyl-substituted phenyl, halogen-substituted phenyl, C1-C5 alkoxy-substituted phenyl, biphenyl, C1-C8 alkyl, naphthyl; and / or,

[0020] R2 is a C1-C10 alkyl, phenyl, naphthyl, C1-C5 alkylnaphthyl, heteroaryl, or other alkyl-naphthyl groups.

[0021] In this context, R3 is a C1-C6 alkyl group; R4 is hydrogen, a C1-C3 alkyl group, a phenyl group, a C1-C3 alkoxy group, a C2-C4 ester group, a halogen, or a phenyl group;

[0022] In this context, R5 represents a C1-C3 alkyl group, a C1-C3 alkoxy group, a C2-C20 ester group, a benzyloxy group, a halogen, an N,N-dialkyl group, a C1-C3 haloalkyl group, a phenyl group, or a group of other alkyl groups. base, base;

[0023] In this context, R6 represents a C1-C3 alkyl group, a halogen, or a C1-C3 alkoxy group;

[0024] In this context, R7 is a C1-C3 alkyl group;

[0025] heteroaryl is And / or,

[0026] The halogen or haloalkyl group in the halogen is F, chlorine, or bromine.

[0027] C1-C5 alkyl groups include: methyl (-CH3), ethyl (-CH2CH3), propyl (-CH2CH2CH3), isopropyl (-CH(CH3)2), butyl (-CH2CH2CH2CH3), tert-butyl (-C(CH3)3), etc.

[0028] C1-C5 alkoxy groups include: methoxy (-OCH3), ethoxy (-OCH2CH3), propoxy (-OCH2CH2CH3), isopropoxy (-OCH(CH3)2), etc.

[0029] The C2-C25 ester group usually refers to the -C(O)OR form, where R is an alkyl group and the number of carbon atoms includes carbonyl carbons and carbons of the R group (total carbon number from 2 to 25).

[0030] Benzyloxy group (-OCH2C6H5)

[0031] Halogens include: fluorine (-F), chlorine (-Cl), bromine (-Br), and iodine (-I).

[0032] N,N-dialkyl, for example, N,N-dimethylamino(-N(CH3)2)

[0033] C1-C5 haloalkyl refers to an alkyl group in which one or more halogen atoms are substituted, such as: C1 haloalkyl: fluoromethyl (-CH2F), trifluoromethyl (-CF3), etc.

[0034] As a preferred implementation method,

[0035] The silanes represented by Formula 1 are selected from at least one of the following compounds:

[0036]

[0037]

[0038] In a preferred embodiment, the silane substance represented by Formula 1 is selected from at least one of the following compounds:

[0039] Where, n hexyl - Correct one's own foundation.

[0040] As a preferred implementation method,

[0041] The electrolyte is selected from at least one alkyl salt; preferably, the alkyl salt is selected from at least one tetraalkylammonium salt; more preferably, the tetraalkylammonium salt is selected from at least one tetrabutylammonium hexafluorophosphate, tetrabutylammonium bromide, tetrabutylammonium perchlorate, and tetrabutylammonium tetrafluoroborate; and / or,

[0042] Based on 100% of the silane-based substance shown in Formula 1, the amount of electrolyte added is 50 mol% to 200 mol%; that is, the molar ratio of the electrolyte to the substituted silane is (0.5 to 2):1); and / or,

[0043] The nickel catalyst is selected from at least one of bis(1,5-cyclooctadiene) nickel, nickel bromide with ethylene glycol dimethyl ether, nickel chloride with ethylene glycol dimethyl ether, nickel chloride, nickel bromide, or nickel iodide; and / or,

[0044] The amount of nickel catalyst added is 10 mol% to 15 mol%, based on 100% of the silanes shown in Formula 1; and / or,

[0045] The ligand is selected from at least one of 4,4'-di-tert-butyl-2,2'-dipyridine, 4,4'-dimethyl-2,2'-dipyridine, 4,4'-dimethoxy-2,2'-dipyridine, 4,4'-diamino-2,2'-dipyridine, α,α,α-terpyridine, or 2,2'-biquinoline; and / or

[0046] The amount of the ligand added is 15 mol% to 20 mol%, based on 100% of the silane-based substance shown in Formula 1.

[0047] As a preferred implementation method,

[0048] The deuterium source is selected from at least one of deuterated water, deuterated acetic acid, deuterated methanol, or deuterated benzene; and / or,

[0049] The molar ratio of the deuterium source to the substituted silane is (50–100):1; and / or,

[0050] The solvent is selected from at least one of amide solvents, nitrile solvents, ester solvents, ether solvents, and sulfoxide solvents; preferably, the solvent is selected from at least one of N,N-dimethylformamide, acetonitrile, ethyl acetate, ethylene glycol dimethyl ether, and dimethyl sulfoxide; and / or,

[0051] The concentration of the silane-based substance shown in Formula 1 in the solvent is 0.06–0.10 mol / L.

[0052] As a preferred implementation method,

[0053] The constant current is 5–15 mA; and / or,

[0054] The time for the silane deuteration reaction is 13–36 h; and / or,

[0055] The temperature for the silane deuteration reaction is 10–30 °C; and / or,

[0056] Preferably, the constant current is 5–15 mA; and / or,

[0057] The time for the silane deuteration reaction is 13–36 h; and / or,

[0058] The temperature for the silane deuteration reaction is room temperature; and / or,

[0059] In the silane deuteration reaction, the cathode material used in the electrodes is selected from graphite felt, carbon felt, or lead sheet; the anode material is selected from aluminum sheet, iron sheet, or magnesium sheet; and / or,

[0060] The post-processing includes vacuum filtration and column chromatography.

[0061] A second objective of this invention is to prepare a deuterated silane by the method described in one of the objectives of this invention, wherein the deuterated silane has the general structural formula shown in Formula 2:

[0062]

[0063] In Formula 2, R1 and R2 correspond to the same R1 and R2 described in one of the objectives of this invention;

[0064] Preferably, the deuterated silane compound is selected from the following compounds:

[0065]

[0066]

[0067] A third objective of this invention is to provide an application of a deuterated silane prepared by the method described in one objective of this invention, or a deuterated silane as described in another objective of this invention, as a reducing agent in the hydrosilylation addition reaction of reducing unsaturated bonds.

[0068] The fourth objective of this invention is to provide a method for silylation of unsaturated bonds using deuterated silanes as reducing agents, comprising the following steps:

[0069] In a protective atmosphere, a compound containing unsaturated bonds, a catalyst, and a solvent are added and mixed evenly. Then, the deuterated silane described in the second objective of this invention is added dropwise as a reducing agent to carry out a silanization reaction. After post-treatment, the silanized deuterated product is obtained.

[0070] The deuterated silicides are as shown in Formulas 3, 4, and 5:

[0071]

[0072] R1 and R2 in Equations 3, 4, and 5 correspond to the same R1 and R2 described in Equation 1.

[0073] As a preferred implementation method,

[0074] The deuterated silane is selected from at least one of the following compounds:

[0075] And / or,

[0076] The compound containing unsaturated bonds is selected from 4-methylstyrene, 4-methylbenzaldehyde, or 4-nitroacetophenone; and / or,

[0077] The catalyst is tris(pentafluorophenyl)borane; and / or,

[0078] The catalyst is added at a rate of 3 mol% to 5 mol%, based on 100% of compounds containing unsaturated bonds; and / or,

[0079] The amount of deuterated silane added is 100 mol% to 120 mol%, based on 100% of compounds containing unsaturated bonds; and / or,

[0080] The solvent is selected from at least one of benzene solvents, ether solvents, and halogenated hydrocarbon solvents; preferably, the solvent is selected from at least one of toluene, dichloromethane, or tetrahydrofuran; and / or,

[0081] The concentration of compounds containing unsaturated bonds in the solvent is 0.4–0.5 mol / L; and / or,

[0082] The time for the silylation reaction is 12–20 h; and / or,

[0083] The temperature for the silylation reaction is 18–30 °C; and / or,

[0084] The post-processing includes rotary evaporation and column chromatography.

[0085] The reaction mechanism of this invention is as follows:

[0086] [Ni] 0 First, it undergoes oxidative addition with a substituted silane to form [Ni]. II -Si intermediate Int-1, which then undergoes a reduction reaction at the cathode to form [Ni]. I -Si intermediate Int-2; subsequently, nucleophilic attack with deuterium water yields substituted silane products; simultaneously [Ni] I It gains electrons again at the cathode and is reduced to [Ni]. 0 This completes the entire catalytic cycle.

[0087]

[0088] The present invention has the following advantages:

[0089] This invention utilizes constant current catalysis. By adding a catalytic amount of nickel catalyst to the reaction system, a silane-nickel intermediate is formed, achieving a polarity reversal of silicon. This effectively avoids the generation of silicon free radicals and self-coupling products under electrochemical conditions, and also avoids the generation of silanol byproducts caused by the oxygen affinity of silicon itself.

[0090] This invention uses deuterium water as a deuterium source, which is greener, more economical, cheaper, and more readily available than traditional deuterium sources.

[0091] This invention enables efficient electrochemical deuteration of reaction substrates by adjusting the parameters of the constant current. It is applicable to substituted silanes containing different substituents and is compatible with sensitive functional groups such as halogen atoms, ester groups, and alkoxy groups. Furthermore, it can achieve good yields and high deuteration rates for disilane compounds, substituted germananes, and post-modified silane compounds from natural products.

[0092] This invention enables the preparation of 10-gram quantities of deuterated silanes under high current conditions, demonstrating its promising prospects for industrial applications.

[0093] The deuterated silane synthesis products of the present invention can be used as silyuterization reagents, demonstrating their practicality in unsaturated bond reduction reactions and showing broad development prospects.

[0094] In summary, this invention a) achieves the electrochemical synthesis of deuterated silanes using green and economical deuterium water as the deuterium source through direct current electrocatalysis; b) the formation of the silicon-nickel intermediate achieves the polarity reversal of silicon, avoiding the generation of self-coupling products and silanol byproducts; c) it has a broad substrate range, covering substituted silane substrates with various substituents as well as naturally modified molecules, and exhibits good tolerance to sensitive functional groups; d) it can prepare deuterated products in the tens of grams range under high current, and can carry out hydrosilylation reduction reactions of unsaturated bonds, showing broad application prospects. Detailed Implementation

[0095] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0096] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

[0097] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0098] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0099] Example 1

[0100] The preferred embodiment of this invention provides a method for synthesizing deuterated silanes using deuterated water as a deuterium source via direct current electrocatalysis, the specific steps of which are as follows:

[0101] In a glove box filled with argon, Ni(COD)2 (10 mol% of the substituted silane), dtbbpy ligand (20 mol% of the substituted silane), and tetrabutylammonium perchlorate (TBAClO4) electrolyte (100 mol% of the substituted silane) were added sequentially to a dry 10 mL sample vial. The reaction tube was then removed from the glove box. Then, using a microsyringe, 0.4 mmol of substituted silane was added, followed by 4.0 mL of ultradry ethyl acetate and 50 equiv. of deuterium water (i.e., 50 times the volume of the substituted silane). The sample vial was sealed with rubber stoppers using pre-loaded graphite felt electrodes (cathode, 20 mm × 10 mm × 5 mm) and aluminum electrodes (anode, 20 mm × 10 mm × 0.3 mm). The two electrodes were connected by electrodisplacement and energized at a constant current (10 mA) for 13 h. After the reaction was complete, the sample was filtered using EtOAc or DCM (3 × 15 mL). The filtrates were combined and concentrated under vacuum. The desired product was obtained by rapid column chromatography purification. The deuteration rate of the product was determined by... 1 HNMR analysis confirmed this.

[0102] The substituted silane substrates in Example 1 (i.e., silanes represented by Formula 1) are as follows:

[0103]

[0104] The ligand dtbbpy in Example 1 is as follows:

[0105] The results for the deuterated silane in Example 1 are as follows:

[0106]

[0107] This method is applicable to diaryl-substituted silanes (1-4, 7, 9-18), dialkyl-substituted substrates (21), trialkyl-substituted substrates (23-25), and triaryl-substituted substrates (29-33, 35-37, 39-44, 46). Compatible functional groups include alkoxy (4, 15, 29, 30, 41, 46), alkyl (2, 3, 9, 13, 14), aminomethyl (31), and phenyl (7, 18, 35). Notably, substrates containing halogen substituents also exhibit good tolerance (17, 33, 39) to the corresponding deuterated products with high deuteration rates and yields. Heterocyclic substituted substrates can also be successfully converted, including naphthalene (42), nitroxide heterocycles (36), benzofurans (41), and dibenzofurans (43), to the corresponding deuterated silanes with high deuteration rates and yields.

[0108] Example 2

[0109] The preferred embodiment of this invention provides a method for synthesizing deuterated silanes using deuterated water as a deuterium source via direct current electrocatalysis, the specific steps of which are as follows:

[0110] In an argon-filled glove box, NiBr2 dme (10 mol% of the substituted silane), dtbbpy ligand (20 mol% of the substituted silane), and tetrabutylammonium perchlorate (TBAClO4) electrolyte (100 mol% of the substituted silane) were added sequentially to a dry 10 mL sample vial. The reaction tube was then removed from the glove box. Next, 0.4 mmol of the substituted silane was added, followed by 4.0 mL of ultradry ethyl acetate using a syringe, and 50 equiv. of deuterium water using a microsyringe. The sample vial was sealed with a rubber stopper fitted with a pre-attached graphite felt electrode (cathode, 20 mm × 10 mm × 5 mm) and an aluminum electrode (anode, 20 mm × 10 mm × 0.3 mm). The two electrodes were connected by an electrodisplacement electrode and energized at a constant current (10 mA) for 13 h. After the reaction was complete, the sample was filtered using EtOAc or DCM (3 × 15 mL). The filtrates were combined and concentrated under vacuum. The desired product can be obtained by rapid column chromatography purification. The deuteration rate of the product is determined by... 1 HNMR analysis confirmed this.

[0111] The substituted silane substrates in Example 2 are as follows:

[0112]

[0113] The ligand dtbbpy in Example 2 is as follows:

[0114]

[0115] The results for the deuterated silane in Example 2 are as follows:

[0116]

[0117] This method is applicable to diaryl-substituted silanes (5-19), triaryl-substituted silanes (38, 45), and trialkyl-substituted silanes (20, 22). It is worth noting that some sensitive groups such as ester groups (16), halogen fluorine (5), and chlorine (6) can also be used to obtain the corresponding deuterated silane products with high deuteration rates and yields.

[0118] Example 3

[0119] The preferred embodiment of this invention provides a method for synthesizing deuterated silanes using deuterated water as a deuterium source via direct current electrocatalysis, the specific steps of which are as follows:

[0120] In an argon-filled glove box, NiBr2 dme (10 mol% of the substituted silane), dtbbpy ligand (20 mol% of the substituted silane), and tetrabutylammonium perchlorate (TBAClO4) electrolyte (100 mol% of the substituted silane) were added sequentially to a dry 10 mL sample vial. The reaction tube was then removed from the glove box. Next, 0.4 mmol of the substituted silane was added, followed by 4.0 mL of ultradry ethyl acetate using a syringe, and 50 equiv. of deuterium water using a microsyringe. The sample vial was sealed with a rubber stopper fitted with a pre-attached graphite felt electrode (cathode, 20 mm × 10 mm × 5 mm) and an aluminum electrode (anode, 20 mm × 10 mm × 0.3 mm). The two electrodes were connected by an electrodisplacement electrode and energized at a constant current (7 mA) for 13 h. After the reaction was complete, the sample was filtered using EtOAc or DCM (3 × 15 mL). The filtrates were combined and concentrated under vacuum. The desired product can be obtained by rapid column chromatography purification. The deuteration rate of the product is determined by... 1 Determined by H NMR analysis.

[0121] The substituted silane substrates in Example 3 are as follows:

[0122]

[0123] The results for the deuterated silane in Example 3 are as follows:

[0124]

[0125] This method is applicable to triaryl-substituted silanes containing sensitive groups such as ester groups and trifluoromethyl groups (33, 34); post-modified silane compounds of natural products (such as benzoyl alcohol, menthol, borneol, D-glucose, etc.) (49-52); post-modified silane compounds of drug molecules (such as ibuprofen, fenofofen, gemfibrozil) (55, 59, 60); post-modified silane compounds of pharmaceutical intermediates (54, 56); and post-modified silane compounds used as the main molecules of herbicides and insecticides (57, 58), and yields the corresponding deuterated silane products with high deuteration rates and yields.

[0126] Example 4

[0127] The preferred embodiment of this invention provides a method for synthesizing deuterated silanes using deuterated water as a deuterium source via direct current electrocatalysis, the specific steps of which are as follows:

[0128] In an argon-filled glove box, Ni(COD)₂ (10 mol% of the substituted silane), dtbbpy ligand (20 mol% of the substituted silane), and tetrabutylammonium perchlorate (TBAClO₄) electrolyte (100 mol% of the substituted silane) were added sequentially to a dry 10 mL sample vial. The reaction tube was then removed from the glove box. Next, substituted silane (0.4 mmol) or (natural product-modified silane compound, 0.3 mmol) was added, followed by ultra-dry ethyl acetate (4.0 mL) using a syringe, and deuterium water (100 equiv.) using a microsyringe. The sample vial was sealed with a rubber stopper fitted with a pre-mounted graphite felt electrode (cathode, 20 mm × 10 mm × 5 mm) and an aluminum electrode (anode, 20 mm × 10 mm × 0.3 mm). The two electrodes were connected by electrodisplacement, and a constant current (10 mA) was applied for 13 h. After the reaction was complete, the sample was filtered using EtOAc or DCM (3 × 15 mL). The filtrates were combined and concentrated under vacuum. The desired product was obtained by rapid column chromatography purification. The deuteration rate of the product was determined by... 1 Determined by H NMR analysis.

[0129] The substituted silane substrates in Example 4 are as follows:

[0130]

[0131] The results for the deuterated silane in Example 4 are as follows:

[0132]

[0133] This method is applicable to the post-modification of silane compounds (flurbiprofen) (53) containing β-hydrogen and carbonyl α-hydrogen, and yields the corresponding deuterated silane products with high deuteration rates and yields. The electrochemical synthesis method of this invention enables the successful preparation of post-modified deuterated silanes from natural products, which is of great significance in drug development and the research of deuterated compounds.

[0134] Examples 5-17

[0135] The reaction conditions were changed, and the yield and deuteration rate were compared.

[0136] Reaction conditions: In an argon-filled glove box, Ni(COD)₂ (10 mol% of the substituted silane), dtbbpy ligand (20 mol% of the substituted silane), and tetrabutylammonium perchlorate (TBAClO₄) electrolyte (100 mol% of the substituted silane) were added sequentially to a dry 10 mL sample vial. The reaction tube was then removed from the glove box. Next, 0.4 mmol of the substituted silane, 4.0 mL of ultradry ethyl acetate, and 100 equiv. of deuterium water were added using a microsyringe. The sample vial was sealed with a rubber stopper fitted with a pre-attached graphite felt electrode (cathode, 20 mm × 10 mm × 5 mm) and an aluminum electrode (anode, 20 mm × 10 mm × 0.3 mm). The two electrodes were connected by an electrodisplacement electrode and energized at a constant current (10 mA) for 13 h. After the reaction was complete, the sample was filtered using EtOAc or DCM (3 × 15 mL). The filtrates were combined and concentrated under vacuum. The desired product was obtained by rapid column chromatography purification. The deuteration rate of the product was determined by... 1 Determined by H NMR analysis.

[0137]

[0138] The changes in reaction conditions and their yields are shown in the table below:

[0139] Table 1

[0140]

[0141]

[0142] The yields in Table 1 above are the separation yields, and the deuteration rate of the products is determined by... 1 HNMR analysis confirmed this.

[0143] As shown in Table 1 above, under the reaction conditions of this invention, the yield of deuterated silane is as high as 93%, and the deuteration rate is as high as 95%. A series of controlled experiments showed that increasing or decreasing the 10mA current would lead to a decrease in yield or deuteration rate. Using NiBr2.(PPh3)2 or other cobalt or iron catalysts instead of Ni(COD)2 would significantly reduce the yield. Increasing or decreasing the amount of nickel catalyst Ni(COD)2 or ligand dtbbpy would also lead to a decrease in product yield or deuteration rate. Increasing or decreasing the amount of deuterated water would also lead to a decrease in deuteration rate. Extending or shortening the reaction time would also reduce the product yield or deuteration rate to varying degrees.

[0144] The electrochemical synthesis method of this invention can also withstand high current to prepare 10-gram-level deuterated silanes, and has broad prospects for industrial application.

[0145] The parameters of some of the products synthesized in this invention are as follows:

[0146] Product 1, Appearance: Colorless liquid (74.1 mg, 93%, 95% D). 1 H NMR (400MHz, Chloroform-d) δ7.70–7.54(m,4H),7.52–7.30(m,6H),4.98(q,J=3.9Hz,0.05H),0.65(s,3H). 13 C NMR(100MHz,Chloroform-d)δ135.5,135.0,129.7,128.1,-4.9.

[0147] Product 2, Appearance: Colorless liquid (78.2 mg, 86%, 94% D). 1 H NMR (400MHz, Chloroform-d) δ7.44(d,J=7.7Hz,4H),7.17(d,J=7.5Hz,4H),4.90(q,J=3.9Hz,0.06H),2.34(s,6H),0.57(s,3H). 13 C NMR(100MHz,Chloroform-d)δ139.5,135.0,132.0,128.9,21.6,-4.6.HR-MS(EI)m / z calc.for C 15 H 17 DSi[M] + :227.1235,found:227.1236.

[0148] Product 3, Appearance: White solid. Melting point: 80–81℃. (113.5 mg, 91% % D) 1 HNMR(400MHz,Chloroform-d)δ7.54(d,J=7.7Hz,4H),7.42(d,J=7.8Hz,4H),4.94(q,J=3.6Hz,0.06H),1.34(s,18H),0.62(s,3H). 13 C NMR(100MHz,Chloroform-d)δ152.6,134.9,132.1,125.1,34.8,31.4,-4.8.HR-MS(EI)m / z calc.for C 21 H 29 DSi[M] + :311.2174,found:311.2174.

[0149] Product 4, Properties: Colorless liquid (94.4 mg, 91% %, 92% D). 1 H NMR (400MHz, Chloroform-d) δ7.50 (d, J = 8.1Hz, 4H), 6.94 (d, J = 8.1Hz, 4H), δ 4.93 (q, J = 3.8Hz, 0.08H), 3.83 (s, 6H), 0.59 (s, 3H). 13 C NMR(100MHz,Chloroform-d)δ160.9,136.4,126.6,113.9,55.2,-4.5.HR-MS(EI)m / z calc.for C 15 H 17 DO2Si[M] + :259.1133,found:259.1130.

[0150] Product 5, Properties: Colorless liquid (65.9 mg, 70%, 93% D). 1 H NMR (400MHz, Chloroform-d) δ7.51 (dd, J=8.4, 6.1Hz, 4H), 7.20–6.98 (m, 4H), 4.94 (q, J=3.8Hz, 0.07H), 0.61 (s, 3H). 13 C NMR (100MHz, Chloroform-d) δ164.2 (d, J = 249.1Hz), 136.9 (d, J = 7.7Hz), 130.7 (d, J = 3.8Hz), 115.4 (d, J = 19.8Hz), -4.68.19 F NMR(375MHz,Chloroform-d)δ-110.89.HR-MS(EI)m / z calc.for C 13 H 11 DF2Si[M] + :235.0734,found:275.0731.

[0151] Product 6, Appearance: Colorless liquid (83.6 mg, 78%, 95% D). 1 H NMR (400MHz, Chloroform-d) δ7.46 (d, J = 8.3 Hz, 4H), 7.36 (d, J = 8.2 Hz, 4H), 4.92 (q, J = 3.8 Hz, 0.05H), 0.62 (s, 3H). 13 C NMR(100MHz,Chloroform-d)δ136.2,134.9,133.2,128.5,-5.0.HR-MS(EI)m / zcalc.for C 13 H 11 DCl2Si[M] + :267.0143,found:267.0144.

[0152] Product 7, Appearance: White solid. Melting point: 97–98℃. (86 mg, 82% D, 93% D) 1 H NMR(400MHz,Chloroform-d)δ7.72(d,J=8.1Hz,4H),7.66(dd,J=7.6,4.1Hz,8H),7 .49(t,J=7.5Hz,4H),7.40(t,J=7.3Hz,2H),5.08(q,J=3.8Hz,0.07H),0.73(s,3H). 13 CNMR(100MHz,Chloroform-d)δ142.5,141.1,135.5,134.1,128.9,127.6,127.3,126.9,-4.8.HR-MS(ESI)m / zcalc.for C 25 H 21 DSi[M] + :351.1548,found:351.1547.

[0153] Product 8, Appearance: White solid. Melting point: 81–82℃. (58.0 mg, 65% , 93% D) 1H NMR(400MHz,Chloroform-d)δ8.15(s,2H),7.90–7.77(m,6H),7.67(d,J=9.0Hz,2H),7.52(dt,J=6.2,2.9Hz,4H),5.23(q,J=4.0Hz,0.07H)0.81(s,3H). 13 C NMR(100MHz,Chloroform-d)δ136.0,134.1,133.1,132.8,130.9,128.3,127.9,127.4,126.8,126.2,-4.8.HR-MS(EI)m / z calc.for C 21 H 17 DSi[M] + :299.1235,found:299.1232.

[0154] Product 9, Appearance: Colorless liquid (73.6 mg, 81%, 93% D). 1 H NMR (400MHz, Chloroform-d) δ7.42–7.30(m,4H),7.25(t,J=7.3Hz,2H),7.22–7.17(m,2H),4.90(q,J=3.9Hz,0.07H),2.33(s,6H),0.59(s,3H). 13 C NMR(100MHz,Chloroform-d)δ137.5,135.6,135.4,132.0,130.4,128.0,21.6,-4.9.HR-MS(EI)m / z calc.for C 15 H 17 DSi[M] + :227.1235,found:227.1235.

[0155] Product 10, Appearance: Colorless liquid (55.1 mg, 65% , 91% D). 1 H NMR (400MHz, Chloroform-d) δ7.67–7.48(m,4H),7.40(p,J=6.4Hz,6H),4.87(t,J=3.5Hz,0.09H),1.22–1.08(m,5H). 13 C NMR(100MHz,Chloroform-d)δ135.3,134.5,129.6,128.1,8.3,4.2.HR-MS(EI)m / z calc.for C 14H 15 DSi[M] + :213.1079,found:213.1080.

[0156] Product 11, Appearance: White solid (95.0 mg, 98%, 85% D). 1 H NMR (400MHz, Chloroform-d) δ7.78–7.61(m,4H),7.50–7.32(m,6H),4.67(s,0.15H),1.10(s,9H). 13 C NMR (100MHz, Chloroform-d) δ135.9,134.1,129.6,128.0,27.7,17.9.

[0157] Product 12, Appearance: Colorless liquid (101.6 mg, 88%, 92% D). 1 H NMR(400MHz,Chloroform-d)δ7.57(dd,J=7.6,1.8Hz,4H),7.44–7.29(m,6H),7.28–7.20( m,2H),7.19–7.09(m,3H),4.89(t,J=3.7Hz,0.08H),2.83–2.65(m,2H),1.56–1.44(m,2H). 13 CNMR(100MHz,Chloroform-d)δ144.5,135.3,134.2,129.8,128.5,128.2,128.0,125.9,30.6,14.3.

[0158] Product 13, Appearance: Colorless liquid (92.2 mg, 76%, 90% D). 1 H NMR(400MHz,Chloroform-d)δ7.62(dd,J=7.6,1.8Hz,4H),7.47–7.38(m,6H),7.12( s,4H),4.95(t,J=3.7Hz,0.10H),2.83–2.72(m,2H),2.36(s,3H),1.58–1.51(m,2H). 13 C NMR (100MHz, Chloroform-d) δ141.5,135.3,135.2,134.3,129.8,129.2,128.2,127.9,30.1,21.1,14.5.

[0159] Product 14, Appearance: Colorless oily liquid (84.1 mg, 81%, 93% D). 1 H NMR(400MHz,Chloroform-d)δ7.66–7.57(m,4H),7.48–7.37(m,6H),7.33(d,J=8.4Hz,2H),7.17 (d,J=8.4Hz,2H),2.85–2.75(m,2H),4.96(t,J=3.7Hz,0.07H),1.62–1.51(m,2H),1.35(s,9H). 13 C NMR (100MHz, Chloroform-d) δ148.7,141.4,135.3,134.3,129.8,128.2,127.6,125.4,34.5,31.6,30.0,14.2.

[0160] Product 15, Appearance: Colorless liquid (114.7 mg, 90%, 92% D). 1 H NMR(400MHz,Chloroform-d)δ7.64–7.53(m,4H),7.42–7.37(m,6H),7.11(d,J=8.5Hz,2H),6.82 (d,J=8.6Hz,2H),4.90(t,J=3.7Hz,0.08H),3.80(s,3H),2.78–2.67(m,2H),1.54–1.45(m,2H). 13 CNMR(100MHz,Chloroform-d)δ157.9,136.6,135.3,134.3,129.8,128.9,128.2,113.9,55.4,29.7,14.6.

[0161] Product 16, Appearance: Colorless liquid (86.1 mg, 83% % D, 91% D) 1 H NMR(400MHz,Chloroform-d)δ7.92(d,J=8.3Hz,2H),7.63–7.51(m,4H),7.47–7.31(m,6H),7.22 (d,J=8.1Hz,2H),4.89(t,J=3.7Hz,0.09H),3.88(s,3H),2.88–2.74(m,2H),1.56–1.45(m,2H). 13C NMR(100MHz,Chloroform-d)δ167.3,149.9,135.3,133.9,129.9,129.8,128.2,128.0,127.9,52.1,30.7,14.0.HR-MS(ESI)m / z calc.for C 22 H 22 DO2Si[M+H] + :348.1525,found:348.1530.

[0162] Product 17, Properties: Colorless oily liquid (82.6 mg, 90%, 94% D). 1 H NMR(400MHz,Chloroform-d).δ7.60(dt,J=6.3,1.7Hz,4H),7.44–7.38(m,6H),7.19–7.08( m,2H),7.04–6.91(m,2H),4.91(t,J=3.6Hz,0.06H),2.86–2.71(m,2H),1.57–1.46(m,2H). 13 CNMR (100MHz, Chloroform-d) δ161.3 (d, J = 243.4Hz), 140.0 (d, J = 3.1Hz), 135.3, 134.1, 129.8, 129.3 (d, J = 7.7Hz), 128.2, 115.1 (d, J = 21.1Hz), 29.8, 14.5. 19 F NMR(375MHz,Chloroform-d)δ-117.96.HR-MS(EI)m / z calc.for C 20 H 18 DFSi[M] + :307.1297,found:307.1298.

[0163] Product 18, Properties: Colorless oily liquid (80.0 mg, 73%, 94% D). 1 H NMR(400MHz,Chloroform-d)δ7.66–7.53(m,6H),7.49(d,J=8.3Hz,2H),7.46–7.34(m,8H),7.31(t,J =7.3Hz,1H),7.24(d,J=8.2Hz,2H),4.92(t,J=3.6Hz,0.06H),2.90–2.73(m,2H),1.60–1.49(m,2H). 13C NMR(100MHz,Chloroform-d)δ143.6,141.3,138.9,135.3,134.2,129.8,128.8,128.4,128.2,127.2,127.1,30.2,14.3.HR-MS(EI)m / z calc.forC 26 H 23 DSi[M] + :365.1705,found:365.1704.

[0164] Product 19, Appearance: Colorless liquid (96.1 mg, 94%, 90% D). 1 H NMR(400MHz,Chloroform-d)δ7.80(dd,J=17.1,7.6Hz,3H),7.71–7.58(m,5H),7. 47–7.39(m,9H),4.97(t,J=3.7Hz,0.10H),3.05–2.91(m,2H),1.69–1.58(m,2H). 13 C NMR(100MHz,Chloroform-d)δ142.0,135.3,134.2,133.8,132.1,129.8,128. 2,128.0,127.7,127.6,127.1,126.0,125.8,125.2,30.8,14.2.HR-MS(EI)m / z calc.for C 24 H 21 DSi[M] + :339.1548,found:339.1547.

[0165] Product 20, Appearance: Colorless liquid (48.1 mg, 80%, 95% D). 1 H NMR(400MHz,Chloroform-d)δ7.16(t,J=7.7Hz,2H),7.05–6.87(m,3H),3.89(p,J=3.5Hz,0.05H).2.09(s,2H),0.00(s,6H). 13 C NMR(100MHz,Chloroform-d)δ140.2,128.4,128.3,124.3,24.3,-4.7.

[0166] Product 21, Appearance: Colorless liquid (43.9 mg, 80% , 90% D). 1H NMR (400MHz, Chloroform-d) δ7.61–7.50 (m, 2H), 7.37 (dd, J=5.0, 2.0Hz, 3H), 4.44 (p, J=3.8Hz, 0.10H), 0.35 (s, 6H). 13 CNMR(100MHz,Chloroform-d)δ137.6,134.2,129.3,128.0,-3.7.

[0167] Product 22, Appearance: Colorless liquid (50.4 mg, 79%, 94% D). 1 H NMR (400MHz, Chloroform-d) δ3.70 (p, J=3.2Hz, 0.06H), 1.49–1.32 (m, 6H), 0.97 (t, J=7.3Hz, 9H), 0.68–0.53 (m, 6H). 13 CNMR(100MHz,Chloroform-d)δ18.3,18.1,14.1.

[0168] Product 23, Appearance: Colorless liquid (52.9 mg, 83% D). 1 H NMR (400MHz, Chloroform-d)δ

[0169] 3.31 (s, 0.17H), 1.06 (s, 21H). 13 C NMR(100MHz,Chloroform-d)δ19.5,10.3.

[0170] Product 24, Appearance: Colorless liquid (65.3 mg, 81%, 92% D). 1 H NMR (400MHz, Chloroform-d)δ

[0171] 3.67(p,J=3.2Hz,0.08H),1.32(td,J=7.6,3.0Hz,12H),0.96–0.78(m,9H),0.58(t,J=8.0Hz,6H). 13 C NMR(100MHz,Chloroform-d)δ27.1,26.5,14.00,11.2.

[0172] Product 25, Appearance: Colorless liquid (109.2 mg, 96%, 85% D). 1H NMR (400MHz, Chloroform-d) 3.67 (dt, J=6.2, 3.2Hz, 0.15H), δ1.43–1.14 (m, 24H), 0.89 (t, J=6.9Hz, 9H), 0.58 (t, J=7.5Hz, 6H). 13 C NMR(100MHz,Chloroform-d)δ33.2,31.8,24.8,22.8,14.3,11.4.

[0173] Product 26, Appearance: White solid (81.5 mg, 78% % D, 94% D) 1 H NMR (400MHz, Chloroform-d) δ7.75–7.54(m,6H),7.54–7.31(m,9H),5.53(s,0.06H). 13 C NMR(100MHz,Chloroform-d)δ136.0,133.5,130.0,128.2.

[0174] Product 27, Properties: Colorless oily liquid (70.5 mg, 64%, 93% D). 1 H NMR (400MHz, Chloroform-d) δ7.57(d,J=7.1Hz,4H),7.52–7.45(m,2H),7.44–7.25(m,6H),7.24–7.15(m,2H),5.46(s,0.07H),2.36(s,3H). 13 C NMR(100MHz,Chloroform-d)δ140.0,136.0,135.9,133.8,129.9,129.7,129.1,128.2,21.7.HR-MS(EI)m / z calc.for C 19 H 17 DSi[M] + :275.1235,found:275.1239.

[0175] Product 28, Properties: Colorless oily liquid (103.5 mg, 81%, 93% D). 1 H NMR (400MHz, Chloroform-d) δ7.64 (dd, J=7.8, 1.6Hz, 4H), 7.60–7.55 (m, 2H), 7.51–7.36 (m, 8H), 5.52 (s, 0.07H), 1.37 (s, 9H). 13C NMR(100MHz,Chloroform-d)δ153.0,136.0,135.9,133.8,129.9,129.8,128.2,125.2,34.9,31.4.HR-MS(EI)m / z calc.for C 22 H 23 DSi[M] + :317.1705,found:317.1707.

[0176] Product 29, Appearance: Colorless oily liquid (100.8 mg, 86%, 94% D). 1 H NMR (400MHz, Chloroform-d) δ7.61(dd,J=7.8,1.6Hz,4H),7.57–7.51(m,2H),7.47–7.37(m,6H),7.00–6.94(m,2H),5.50(s,0.06H),3.84(s,3H). 13 C NMR(100MHz,Chloroform-d)δ161.2,137.5,135.9,133.9,129.9,128.2,124.1,114.0,55.2.HR-MS(EI)m / z calc.forC 19 H 17 DOSi[M] + :291.1184,found:291.1186.

[0177] Product 30, Appearance: White solid. Melting point: 78–79℃. (75.0 mg, 68% % D) 1 H NMR (400MHz, Chloroform-d) δ7.65–7.56(m,4H),7.55–7.49(m,2H),7.49–7.30(m,11H),7.06–6.99(m,2H),5.48(s,0.07H),5.10(s,2H). 13 C NMR(100MHz,Chloroform-d)δ160.5,137.5,137.0,135.9,133.9,129.9,128.8,128.2,127.6,124.4,114.9,69.9.HR-MS(EI)m / z calc.for C 25 H 21 DOSi[M] + :367.1497,found:367.1496.

[0178] Product 31, Properties: Colorless oily liquid (113.1 mg, 93%, 90% D). 1 HNMR (400MHz, Chloroform-d) δ7.69–7.56 (m, 4H), 7.53–7.32 (m, 8H), 6.77 (d, J = 8.2Hz, 2H), 5.48 (s, 0.10H), 3.00 (s, 6H). 13 C NMR(100MHz,Chloroform-d)δ151.4,136.9,135.7,134.4,129.5,127.9,117.5,111.9,40.1.HR-MS(ESI)m / z calc.for C 20 H 21 DNSi[M+H] + :305.1579,found:305.1582.

[0179] Product 32, Properties: Colorless oily liquid (99.0 mg, 74%, 94%-D) 1 H NMR(400MHz,Chloroform-d)δ8.07–7.98(m,2H),7.71–7.62(m,2H),7.61–7.50(m,4 H),7.48–7.32(m,6H),5.50(s,0.06H),4.38(q,J=7.1Hz,2H),1.38(t,J=7.1Hz,3H). 13 C NMR(100MHz,Chloroform-d)δ166.7,139.6,135.9,135.9,132.6,131.8,130.2,128.9,128.3,61.2,14.5.HR-MS(ESI)m / z calc.for C 21 H 20 DO2Si[M+H] + :334.1368,found:334.1374.

[0180] Product 33, Properties: Colorless oily liquid (69.8 mg, 63% , 94% D). 1 H NMR (400MHz, Chloroform-d) δ7.67–7.50 (m, 6H), 7.42 (dt, J=14.1, 7.0Hz, 6H), 7.16–6.99 (m, 2H), 5.49 (s, 0.06H).13 C NMR (100MHz, Chloroform-d) δ164.4 (d, J = 249.4Hz), 138.0 (d, J = 8.0Hz), 135.9, 133.2, 130.1, 129.0, 128.3, 115.5 (d, J = 19.9Hz) 19 F NMR(375MHz,Chloroform-d)δ-110.56.HR-MS(EI)m / z calc.for C 18 H 14 DFSi[M] + :279.0984,found:279.0989.

[0181] Product 34, Appearance: Colorless oily liquid (100.9 mg, 77% , 93% D). 1 H NMR (400MHz, Chloroform-d) δ7.72 (d, J = 7.8Hz, 2H), 7.67–7.55 (m, 6H), 7.50–7.37 (m, 6H), 5.53 (s, 0.07H). 13 C NMR (100MHz, Chloroform-d) δ138.7, 136.2, 135.9, 132.4, 131.9 (q J = 32Hz), 130.3, 128.4, 127.0 (q, J = 270Hz), 124.7 (q, J = 3.7Hz). 19 F NMR(375MHz,Chloroform-d)δ-62.97.HR-MS(EI)m / z calc.for C 19 H 14 DF3Si[M] + :329.0952,found:329.0949.

[0182] Product 35, properties: colorless oily liquid (79.1 mg, 78%, 94% D). 1 H NMR(400MHz,Chloroform-d)δ7.75–7.60(m,10H),7.58–7.33(m,9H),5.56(s,0.06H). 13C NMR(100MHz,Chloroform-d)δ142.7,141.0,136.4,136.0,133.4,132.2,130.0,129.0,128.2,127.7,127.3,126.9.HR-MS(EI)m / z calc.for C 24 H 19 DSi[M] + :337.1392,found:337.1392.

[0183] Product 36, Properties: Colorless oily liquid (103.8 mg, 75%, 92% D). 1 HNMR(400MHz,Chloroform-d)δ7.72–7.59(m,4H),7.53(d,J=8.1Hz,2H),7.47–7.39(m ,6H),6.96(d,J=8.2Hz,2H),5.51(s,0.08H),3.89(t,J=4.8Hz,4H),3.33–3.13(m,4H). 13 C NMR(100MHz,Chloroform-d)δ152.3,137.1,135.9,134.0,129.8,128.1,122.3,114.8,66.9,48.5.HR-MS(ESI)m / z calc.for C 22 H 23 DNOSi[M+H] + :347.1684,found:347.1689.

[0184] Product 37, Properties: Colorless oily liquid (93.6 mg, 85%, 90% D). 1 H NMR (400MHz, Chloroform-d) δ7.66–7.51 (m, 4H), 7.50–7.32 (m, 8H), 7.25 (dt, J = 14.9, 8.5Hz, 2H), 5.45 (s, 0.10H), 2.32 (s, 3H). 13 C NMR(100MHz,Chloroform-d)δ137.6,136.5,136.0,133.6,133.2,133.0,130.8,129.9,128.2,128.1,21.6.HR-MS(EI)m / z calc.for C 19 H 17 DSi[M] +:275.1235,found:275.1239.

[0185] Product 38, Properties: Colorless oily liquid (99.2 mg, 85%, 95%-D). 1 H NMR(400MHz,Chloroform-d)δ7.62(dd,J=8.0,1.7Hz,4H),7.51–7.29(m,7H),7.18(dd,J=14.5,4.9Hz,2H),7.04–6.95(m,1H),5.50(s,0.05H)3.80(s,3H). 13 C NMR(100MHz,Chloroform-d)δ159.2,135.9,134.9,133.3,129.9,129.4,128.2,128.1,127.9,121.1,115.4.HR-MS(EI)m / z calc.for C 19 H 17 DOSi[M] + :291.1184,found:291.1187.

[0186] Product 39, Properties: Colorless oily liquid (90.5 mg, 81%, 94% D). 1 H NMR (400MHz, Chloroform-d) δ7.63–7.49(m,4H),7.48–7.28(m,8H),7.28–7.20(m,1H),7.11–7.06(m,1H),5.46(s,0.06H). 13 C NMR(100MHz,Chloroform-d)δ162.8(d,J=248.8Hz),135.9,132.7,131.5(d,J= 3.1Hz).,130.0(d,J=7.0Hz),129.9,128.3,122.2,122.1,117.0(d,J=21.0Hz) 19 F NMR(375MHz,CDCl3)δ-113.08.HR-MS(EI)m / z calc.forC 18 H 14 DFSi[M] + :279.0984,found:279.0990.

[0187] Product 40, properties: colorless oily liquid (101.1 mg, 87%, 93% D). 1H NMR (400MHz, Chloroform-d) δ7.53–7.41 (m, 4H), 7.33–7.20 (m, 6H), 7.08 (d, J = 1.0Hz, 2H), 6.93 (s, 1H), 5.31 (s, 0.07H) 2.17 (s, 6H). 13 C NMR(100MHz,Chloroform-d)δ137.5,136.0,133.8,133.6,133.1,131.8,129.8,128.2,21.5.HR-MS(EI)m / z calc.for C 20 H 19 DSi[M] + :289.1392,found:289.1392.

[0188] Product 41, Properties: Colorless oily liquid (99.0 mg, 81%, 91%-D). 1 H NMR(400MHz,Chloroform-d)δ7.71–7.52(m,4H),7.45–7.38(m,6H),7.10(d,J =7.7Hz,1H),7.03(s,1H),6.89(d,J=7.6Hz,1H),5.96(s,2H),5.46(s,0.09H). 13 C NMR(100MHz,Chloroform-d)δ149.3,147.8,135.9,133.6,130.5,130.0,128.2,126.2,115.0,109.0,100.8.HR-MS(ESI)m / z calc.for C 19 H 16 DO2Si[M+H] + :306.1055,found:306.1053.

[0189] Product 42, Appearance: White solid. Melting point: 85–86℃. (119.9 mg, 96% % D) 1 HNMR(400MHz,Chloroform-d)δ8.17–8.04(m,1H),8.01–7.85(m,2H),7.71–7.56(m,5H),7.54–7.30(m,9H),5.94(s,0.09H). 13C NMR(100MHz,Chloroform-d)δ137.5,137.0,136.1,133.4,133.4,131.6,131.0,130.0,129.0,128.4,128.2,126.3,125.9,125.4.HR-MS(EI)m / z calc.for C 22 H 17 DSi[M] + :311.1235,found:311.1235.

[0190] Product 43, Appearance: White solid. Melting point: 114–115℃ (88.6 mg, 84% D, 94% D). 1 H NMR (400MHz, Chloroform-d) δ8.03(dd,J=7.7,1.4Hz,1H),7.94(d,J=7.6Hz,1H),7.73–7.63(m,4H),7.57–7.48(m,2H),7.44–7.29(m,9H),5.80(s,0.06H). 13 C NMR(100MHz,Chloroform-d)δ161.1,156.1,135.9,135.3,135.0,132.7,129.9,128.1,127.6,127.1,124.1,123.1, 122.8,122.7,122.7 (1C),120.7,116.4,111.9.HR-MS(EI)m / z calc.forC 24 H 17 DOSi[M] + :351.1184,found:351.1183.

[0191] Product 44, Properties: Colorless oily liquid (75.2 mg, 82%, 90% D). 1 H NMR (400MHz, Chloroform-d) δ7.50–7.32 (m, 6H), 7.25 (dt, J = 14.5, 7.6Hz, 6H), 5.40 (s, 0.10H), 2.33 (s, 9H). 13 C NMR(100MHz,Chloroform-d)δ137.5,136.5,133.6,133.0,130.7,128.1,21.6.HR-MS(EI)m / z calc.for C 21 H 21 DSi[M] +:303.1548,found:303.1550.

[0192] Product 45, Appearance: White solid. Melting point: 75–76℃. (81.7 mg, 90%, 92% D) 1 H NMR (400MHz, Chloroform-d) δ7.50 (d, J = 7.4Hz, 6H), 7.22 (d, J = 7.5Hz, 6H), 5.45 (s, 0.08H), 2.39 (s, 9H). 13 C NMR(100MHz,Chloroform-d)δ139.8,136.0,130.3,129.0,21.7.HR-MS(EI)m / zcalc.for C 21 H 21 DSi[M] + :303.1548,found:303.1556.

[0193] Product 46, Appearance: White solid. Melting point: 70–71℃. (94.6 mg, 90%, 92% D) 1 HNMR(400MHz,Chloroform-d)7.57–7.43(m,6H),6.95–6.91(m,6H),5.43(s,0.08H),3.83(s,9H). 13 C NMR(100MHz,Chloroform-d)δ161.1137.3,125.0,113.9,55.2.HR-MS(ESI)m / zcalc.for C 21 H 21 DO3SiNa[M+Na] + :374.1293,found:374.1300.

[0194] Product 47, Appearance: Colorless liquid (52.2 mg, 66% % D, 88% D) 1 H NMR (400MHz, Chloroform-d) δ7.67–7.48 (m, 4H), 4.45 (dq, J = 7.3, 3.8Hz, 0.24H), 0.36 (s, 12H). 13 C NMR(100MHz,Chloroform-d)δ138.6,133.5,-3.8.

[0195] Product 48, Properties: Colorless oily liquid (59.7 mg, 65%, 90% D). 1 H NMR (400MHz, Chloroform-d) δ7.56 (dd, J=7.1, 2.1Hz, 6H), 7.48–7.37 (m, 9H), 5.74 (s, 0.10H). 13 C NMR(100MHz,Chloroform-d)δ135.6,135.3,129.3,128.5.

[0196] Product 49, Properties: Colorless oily liquid (95.4 mg, 72%, 91% D). 1 HNMR(400MHz,Chloroform-d)δ8.06(d,J=7.9Hz,2H),7.69(d,J=8.0Hz,2H),7.58(d,J=7.9Hz,4H),7.36–7.47(m,6H),5.51(s,0.09H), 4.63(s,1H),1.95–1.88(m,1H),1.81–1.74(m,2H),1.69(s,1H),1.55–1.48(m,1H),1.27(s,2H),1.19(s,3H),1.11(s,3H),0.85(s,3H). 13 C NMR(100MHz,Chloroform-d)δ167.0,139.7,135.9,135.9,132.6,131.9,130.2,128.9,12 8.3,86.9,48.7,48.5,41.6,40.0,29.9,27.0,26.0,20.4,19.6.HR-MS(ESI)m / zcalc.for C 29 H 31 DO₂SiNa[M+Na] + :464.2127,found:464.2131.

[0197] Product 50, properties: colorless oily liquid (93.1 mg, 70%, 88%-D). 1HNMR(400MHz,Chloroform-d)δ8.04(d,J=8.2Hz,2H),7.67(d,J=8.0Hz,2H),7 .57(d,J=7.5Hz,4H),7.47–7.35(m,6H),5.51(s,0.12H),4.94(td,J=10.9,4. 3Hz,1H),2.13(d,J=12.0Hz,1H),2.03–1.90(m,1H),1.77–1.69(m,2H),1.60– 1.52(m,2H),1.17–1.05(m,2H),0.92(t,J=7.2Hz,7H),0.79(d,J=7.0Hz,3H). 13 C NMR(100MHz,Chloroform-d)δ166.2,139.6,135.9,135.8,132.6,132.1,130.2,128. 9,128.3,75.1,47.4,41.1,34.4,31.6,26.6,23.8,22.2,20.9,16.6.HR-MS(ESI)m / z calc.for C 29 H 33 DO₂SiNa[M+Na] + :466.2283,found:466.2282.

[0198] Product 51, Properties: Colorless oily liquid (87.9 mg, 66%, 93% D). 1 H NMR(400MHz,Chloroform-d)δ8.07(d,J=7.9Hz,2H),7.69(d,J=7.7Hz,2H),7.58( d,J=6.4Hz,4H),7.51–7.33(m,6H),5.52(s,0.07H),5.19–5.06(m,1H),2.53–2.4 5(m,1H),2.16–2.09(m,1H),1.88–1.70(m,2H),1.47–1.36(m,1H),1.31(dd,J=13 .0,3.8Hz,1H),1.12(dd,J=13.8,3.5Hz,1H),0.98(s,3H),0.92(d,J=2.5Hz,6H). 13C NMR(100MHz,Chloroform-d)δ166.9,139.6,135.9,132.6,132.2,130.2,128.9,1 28.3,80.8,49.3,48.0,45.2,37.1,28.2,27.5,19.9,19.1,13.7.HR-MS(ESI)m / z calc.for C 29 H 31 DO₂SiNa[M+Na] + :464.2127,found:464.2128.

[0199] Product 52, properties: colorless oily liquid (126.9 mg, 77% , 93% D). 1 H NMR(400MHz,Chloroform-d)δ8.04(d,J=7.5Hz,2H),7.66(d,J=7.7Hz,2H),7.57 (d,J=7.7Hz,4H),7.47–7.37(m,6H),5.57(d,J=5.0Hz,1H),4.65(d,J=11.2Hz,1 H),5.50(s,0.07H),4.53(dd,J=11.4,5.0Hz,1H),4.48–4.42(m,1H),4.34(t,J= 9.0Hz, 2H), 4.19 (t, J = 6.3Hz, 1H), 1.50 (d, J = 12.8Hz, 6H), 1.35 (d, J = 9.7Hz, 6H). 13 C NMR(100MHz,Chloroform-d)δ166.6,139.9,135.9,132.6,131.3,130.2,129.0,128.3,1 09.8,108.9,96.5,71.3,70.9,70.6,66.2,64.1,26.2,26.1,25.1,24.6.HR-MS(ESI)m / z calc.forC 31 H 33 DO7SiNa[M+Na] + :570.2029,found:570.2026. Product 53, properties: colorless oily liquid (101.1 mg, 67% %, 89% D). 1H NMR(400MHz,Chloroform-d)δ7.47(dd,J=7.2,5.2Hz,8H),7.40–7.23(m,10H),7.18–7.11(m, 2H),6.98(d,J=7.9Hz,2H),5.38(s,0.11H),3.91(q,J=7.1Hz,0.51H).1.57(d,J=6.7Hz,3H). 13 CNMR(100MHz,Chloroform-d)δ172.4,158.7,152.4,141.3,137.2,135.9,135.5,133.1,131.2,131.1 ,130.1, δ129.1(d,J=3.1Hz).,128.6,128.2,127.9,123.7,121.2, δ115.5(d,J=24.3Hz),45.3,18.5. 19 F NMR(375MHz,Chloroform-d)δ-117.25.HR-MS(ESI)m / z calc.for C 33 H 26 DFO2SiNa[M+Na] + :526.1719,found:526.1716.

[0200] Product 54, Properties: Colorless oily liquid (103.2 mg, 68%, 94% D). 1 HNMR(400MHz,Chloroform-d)δ8.03(d,J=10.1Hz,2H),7.66(d,J=7.9Hz,2H),7.56(d,J=7.8Hz,4H),7.47–7.36(m,6H) ,5.50(s,0.06H),4.36(t,J=5.9Hz,2H),3.91(s,3H),3.77(s,1H),3.56(s,1H),2.98(s,1H),2.82(s,1H),1.47(s,9H). 13 C NMR(100MHz,Chloroform-d)δ166.4,154.8,140.2,135.9,135.9,132.5,131.0,130.2,129.0,128.3,80.4,73.4,66.6,65.0,28.5.HR-MS(ESI)m / z calc.for C 29 H 32 DNO5SiNa[M+Na] +:527.2083,found:527.2082.

[0201] Product 55, properties: colorless oily liquid (119.4 mg, 83%, 91% D). 1 HNMR(400MHz,Chloroform-d)δ7.58–7.47(m,6H),7.43–7.34(m,6H),7.20(dd,J=8.0,5.7Hz,4H),7.07(d,J=8.1Hz,2H),5.45(s,0 .09H),5.11(s,2H),3.75(q,J=7.1Hz,1H),2.42(d,J=7.2Hz,2H),1.85–1.78(m,1H),1.50(d,J=7.2Hz,3H),0.87(d,J=6.7Hz,6H). 13 C NMR(100MHz,Chloroform-d)δ174.6,140.7,137.9,137.7,136.1,135.9,133.2,130.0, 129.5,128.2,128.2,127.4,127.3,66.2,45.3,45.2,30.3,22.5,18.5.HR-MS(ESI)m / z calc.for C 32 H 33 DO₂SiNa[M+Na] + :502.2283,found:502.2280.

[0202] Product 56, Properties: Colorless oily liquid (117.2 mg, 77% , 93% D). 1 HNMR(400MHz,Chloroform-d)δ8.00(d,J=8.0Hz,2H),7.60(d,J=7.8Hz,2H),4.43(p,J=3.9Hz,0.07H),4.40–4.31(m,2H) ,3.91(d,J=14.5Hz,3H),3.79–3.70(m,1H),3.55(t,J=11.6Hz,1H),2.97(s,1H),2.81(s,1H),1.46(s,9H),0.34(s,6H). 13 C NMR(100MHz,Chloroform-d)δ166.4,154.8,144.2,134.1,130.4,128.8,80.3,73.4,66.6,65.0,28.5,-4.0.HR-MS(ESI)m / z calc.for C19 H 28 DNO5SiNa[M+Na] + :403.1770,found:403.1773.

[0203] Product 57, Properties: Colorless oily liquid (91.4 mg, 59%, 93% D). 1 H NMR(400MHz,Chloroform-d)δ8.03(d,J=7.8Hz,2H),7.66(d,J=7.7Hz,2H),7.61–7.52(m, 4H),7.47–7.36(m,6H),5.50(s,0.07H),4.74(p,J=6.2Hz,1H),4.53(s,1H),4.35–4.31(m 2H),4.08(s,1H),2.86(t,J=13.5Hz,1H),2.27–2.16(m,1H),1.93–1.83(m,1H), 1.69–1.59(m,5H),1.55–1.38(m,3H),1.16(d,J=6.2Hz,3H),0.89–0.84(m,3H). 13 C NMR(100MHz,Chloroform-d)δ166.7,155.7,155.6,135.9,135.4,132.6,131.6,130.2,128 .9,128.3,128.1,73.1,62.8,48.1,29.2,29.0,28.7,25.6,19.9,19.2,9.9.HR-MS(ESI)m / z calc.forC 31 H 37 DNO4Si[M+H] + :517.2627,found:517.2628.

[0204] Product 58, Appearance: Colorless oily liquid (100.9 mg, 75%, 90% D). 1 H NMR(400MHz,Chloroform-d)δ7.57(d,J=8.4Hz,2H),7.19–7.07(m,4H),6.75( d,J=8.7Hz,1H),4.87(s,2H),4.46–4.42(m,0.10H),2.30(s,3H),0.35(s,6H). 13C NMR(100MHz,Chloroform-d)δ167.4,154.8,151.1,135.8,135.5,131.1,129.6,126.7,126.5,120.8,112.6,66.0,16.3,-3.7.HR-MS(EI)m / z calc.for C 17 H 18 DClO3Si[M] + :335.0849,found:335.0849.

[0205] Product 59, Properties: Colorless oily liquid (111.8 mg, 74%, 90% D). 1 HNMR(400MHz,Chloroform-d)δ7.53(d,J=8.6Hz,2H),7.39–7.32(m,3H),7.18–7.10(m,3H),7.03(dd,J=16.4,8.0Hz ,4H),6.95(dd,J=7.6,2.0Hz,1H),4.46–4.42(m,0.10H),3.96(q,J=7.1Hz,1H),1.62(d,J=7.1Hz,3H),0.34(s,6H). 13 C NMR(100MHz,Chloroform-d)δ172.7,157.7,157.2,151.9,142.1,135.3,135.0,130. 2,129.9,123.5,122.5,121.0,119.1,118.2,117.8,45.6,18.6,-3.7.HR-MS(EI)m / z calc.for C 23 H 23 DO3Si[M] + :377.1552,found:377.1550.

[0206] Product 60, properties: colorless oily liquid (118.3 mg, 77% , 92% D). 1H NMR(400MHz,Chloroform-d)δ7.68–7.53(m,6H),7.49–7.40(m,6H),7.11(d,J=8.4Hz,2H),7.04(d,J=7.4Hz,1H),6 .75–6.62(m,2H),5.53(s,0.08H),4.05–4.00(m,2H),2.34(s,3H),2.22(s,3H),1.93(t,J=3.8Hz,4H),1.42(s,6H). 13 C NMR(100MHz,Chloroform-d)δ176.3,157.0,152.7,137.2,136.6,135.9,133.2,130.7,130.5,13 0.0,128.2,123.7,121.4,120.9,112.1,67.9,42.6,37.3,25.4,25.3,21.5,15.9.HR-MS(ESI)m / z calc.for C 33 H 35 DO3SiNa[M+Na] + :532.2389,found:532.2390.

[0207] Example 18

[0208] The deuterated silane 1 prepared by this invention can be used as a reducing agent to perform a silylation addition reaction on unsaturated bonds. Specifically, the prepared deuterated silane 1, as a reducing agent, undergoes a silylation addition reaction with compounds with unsaturated bonds, such as aryl alkenes, aldehydes, and ketones. The equation for the reaction is as follows:

[0209]

[0210] The specific steps are as follows:

[0211] A compound containing unsaturated bonds (0.5 mmol) and tris(pentafluorophenyl)borane (0.04 equiv.) were added to a 5 mL reaction flask equipped with a magnetic stirrer. The sealed flask was then evacuated and purged with argon gas, repeated three times. Anhydrous toluene or dichloromethane (1.0 mL) was added to the flask, and the mixture was stirred for 5 minutes. Deuterated methyldiphenylsilane 1 (1.2 equiv.) was then added to the mixture, and the reaction was carried out at room temperature for 15 hours. After the reaction was complete, the reaction solvent (anhydrous toluene or dichloromethane) was removed from the system by rotary evaporation, and the product was purified by column chromatography. The deuteration rate of the product was determined by... 1 HNMR analysis confirmed this.

[0212] Compounds containing unsaturated bonds, such as 4-methylstyrene, 4-methylbenzaldehyde, or 4-nitroacetophenone;

[0213] The structural formula of deuterated silane 1 is as follows:

[0214] The deuterated silicide obtained in Example 18 is as follows:

[0215] Product 61, Properties: Colorless oily liquid (111.8 mg, 70%, 97% D). 1 H NMR(400MHz,Chloroform-d)δ7.61(dd,J=7.8,1.7Hz,4H),7.42–7.34(m,6H),7.20 (d,J=7.2Hz,2H),7.12(d,J=8.1Hz,2H),4.73(s,1.03H),2.33(s,3H),0.64(s,3H). 13 C NMR(100MHz,Chloroform-d)δ137.7,136.9,136.1,134.6,130.0,129.1,128.0,126.8, 65.2, 65.0,64.8 (1C),21.3,-2.7.HR-MS(EI)m / z calc.for C 21 H 21 DOSi[M] + :319.1497,found:319.1494.

[0216] Product 62, properties: colorless oily liquid (101.5 mg, 64%, 96% D). 1 HNMR(400MHz,Chloroform-d)δ7.63–7.49(m,4H),7.39(d,J=5.6Hz,6H),7.10(s, 4H),2.66(t,J=8.8Hz,1.04H),2.33(s,3H),1.44(d,J=10.9Hz,2H),0.59(s,3H). 13 C NMR(100MHz,Chloroform-d)δ141.9,137.2,135.2,134.6,129.3,129.1,128.0,127.8, 29.4,29.2,29.0 (1C),21.1,16.5,-4.3.HR-MS(EI)m / z calc.for C 22 H 23 DSi[M] + :317.1705,found:317.1713.

[0217] Product 63, properties: colorless oily liquid (136.7 mg, 75%, 92% D). 1 H NMR(400MHz,Chloroform-d)δ8.15(d,J=8.8Hz,2H),7.60–7.51(m,4H),7.47(d,J= 8.9Hz,2H),7.45–7.32(m,6H),5.01(q,J=6.4Hz,0.08H),1.45(s,3H),0.59(s,3H). 13 C NMR(100MHz,Chloroform-d)δ153.6,147.2, 135.8,135.7 (1C), 134.5,134.4 (1C), 130.2,130.1 (1C),128.1,126.3,123.7,70.7,26.7,-2.3.HR-MS(EI)m / z calc.for C 21 H 20 DNO3Si[M] + :364.1348,found:364.1346.

[0218] The results above demonstrate that the deuterated diphenylmethylsilane 1 of this invention successfully silylated unsaturated bonds in alkenes, aldehydes, ketones, etc., achieving a deuteration rate as high as 97% and a high yield. The deuterated silane products synthesized in this invention can be used as silylated reagents, proving their practicality in unsaturated bond reduction reactions and demonstrating broad development prospects.

[0219] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. An electrochemical method for preparing deuterated silanes, characterized in that, Includes the following steps: In a protective atmosphere, the silane substance shown in Formula 1, a deuterium source, a nickel catalyst, a ligand, and an electrolyte are mixed in a solvent and then subjected to a silane deuteration reaction under constant current conditions. After post-treatment, the deuterated silane compound is obtained. The silane-based substances shown in Formula 1 have the following structural formulas: In Formula 1, R1 is phenyl or substituted phenyl, C1-C10 alkyl, biphenyl, or naphthyl; R2 is a C1-C10 alkyl, phenyl, naphthyl, C1-C5 alkylnaphthyl, heteroaryl, or other alkyl-naphthyl groups. In this context, R3 is a C1-C10 alkyl group; R4 is hydrogen, a C1-C5 alkyl group, a phenyl group, a C1-C5 alkoxy group, a C2-C5 ester group, a halogen, or a phenyl group; In this context, R5 represents a C1-C5 alkyl group, a C1-C5 alkoxy group, a C2-C25 ester group, a benzyloxy group, a halogen, an N,N-dialkyl group, a C1-C5 haloalkyl group, or a phenyl group. base, base; In this context, R6 represents a C1-C5 alkyl group, a halogen, or a C1-C5 alkoxy group; In this context, R7 is a C1-C5 alkyl group; The deuterated silane compound has the structural formula shown in Formula 2: R1 and R2 in Equation 2 correspond to the same R1 and R2 described in Equation 1.

2. The method according to claim 1, characterized in that: In Formula 1, R1 is phenyl, C1-C5 alkyl-substituted phenyl, halogen-substituted phenyl, C1-C5 alkoxy-substituted phenyl, biphenyl, C1-C8 alkyl, naphthyl; and / or, R2 is a C1-C10 alkyl, phenyl, naphthyl, C1-C5 alkylnaphthyl, heteroaryl, or other alkyl-naphthyl groups. In this context, R3 is a C1-C6 alkyl group; R4 is hydrogen, a C1-C3 alkyl group, a phenyl group, a C1-C3 alkoxy group, a C2-C4 ester group, a halogen, or a phenyl group; In this context, R5 represents a C1-C3 alkyl group, a C1-C3 alkoxy group, a C2-C20 ester group, a benzyloxy group, a halogen, an N,N-dialkyl group, a C1-C3 haloalkyl group, a phenyl group, or a group of other alkyl groups. base, base; In this context, R6 represents a C1-C3 alkyl group, a halogen, or a C1-C3 alkoxy group; In this context, R7 is a C1-C3 alkyl group; heteroaryl is And / or, The halogen or haloalkyl group in the halogen is F, chlorine, or bromine.

3. The method according to claim 1 or 2, characterized in that: The silanes represented by Formula 1 are selected from at least one of the following compounds:

4. The method according to claim 1 or 2, characterized in that: The silanes represented by Formula 1 are selected from at least one of the following compounds:

5. The method according to claim 1, characterized in that: The electrolyte is selected from at least one alkyl salt; preferably, the alkyl salt is selected from at least one tetraalkylammonium salt; more preferably, the tetraalkylammonium salt is selected from at least one tetrabutylammonium hexafluorophosphate, tetrabutylammonium bromide, tetrabutylammonium perchlorate, and tetrabutylammonium tetrafluoroborate; and / or, The amount of electrolyte added is 50 mol% to 200 mol%, based on 100% of the silane-based substance shown in Formula 1; and / or, The nickel catalyst is selected from at least one of bis(1,5-cyclooctadiene) nickel, nickel bromide with ethylene glycol dimethyl ether, nickel chloride with ethylene glycol dimethyl ether, nickel chloride, nickel bromide, or nickel iodide; and / or, The amount of nickel catalyst added is 10 mol% to 15 mol%, based on 100% of the silanes shown in Formula 1; and / or, The ligand is selected from at least one of 4,4'-di-tert-butyl-2,2'-dipyridine, 4,4'-dimethyl-2,2'-dipyridine, 4,4'-dimethoxy-2,2'-dipyridine, 4,4'-diamino-2,2'-dipyridine, α,α,α-terpyridine, or 2,2'-biquinoline; and / or The amount of the ligand added is 15 mol% to 20 mol%, based on 100% of the silane-based substance shown in Formula 1.

6. The method according to claim 1, characterized in that: The deuterium source is selected from at least one of deuterated water, deuterated acetic acid, deuterated methanol, or deuterated benzene; and / or, The molar ratio of the deuterium source to the substituted silane is (50–100):1; and / or, The solvent is selected from at least one of amide solvents, nitrile solvents, ester solvents, ether solvents, and sulfoxide solvents; preferably, the solvent is selected from at least one of N,N-dimethylformamide, acetonitrile, ethyl acetate, ethylene glycol dimethyl ether, and dimethyl sulfoxide; and / or, The concentration of the silane-based substance shown in Formula 1 in the solvent is 0.06–0.10 mol / L.

7. The method according to claim 1, characterized in that: The constant current is 5–15 mA; and / or, The time for the silane deuteration reaction is 13–36 h; and / or, The temperature for the silane deuteration reaction is 10–30 °C; and / or, Preferably, the constant current is 5–15 mA; and / or, The time for the silane deuteration reaction is 13–36 h; and / or, The temperature for the silane deuteration reaction is room temperature; and / or, In the silane deuteration reaction, the cathode material used in the electrodes is selected from graphite felt, carbon felt, or lead sheet; the anode material is selected from aluminum sheet, iron sheet, or magnesium sheet; and / or, The post-processing includes vacuum filtration and column chromatography.

8. The deuterated silane prepared by the method according to any one of claims 1-7, characterized in that: The deuterated silane has the general structural formula shown in Formula 2: In Formula 2, R1 and R2 correspond to the same R1 and R2 as in any one of claims 1-7; preferably, the deuterated silane compound is selected from the following compounds:

9. A method for silylation of unsaturated bonds using deuterated silanes as reducing agents, characterized in that, Includes the following steps: In a protective atmosphere, a compound containing unsaturated bonds, a catalyst, and a solvent are added and mixed evenly. Then, the deuterated silane described in claim 8 is added dropwise as a reducing agent to carry out a silanization reaction. After post-treatment, the silanized deuterated product is obtained. The deuterated silicides are as shown in Formulas 3, 4, and 5: R1 and R2 in Equations 3, 4, and 5 correspond to the same R1 and R2 described in Equation 1.

10. The method for silylation reaction according to claim 9, characterized in that: The deuterated silane is selected from at least one of the following compounds: And / or, The compound containing unsaturated bonds is selected from 4-methylstyrene, 4-methylbenzaldehyde, or 4-nitroacetophenone; and / or, The catalyst is tris(pentafluorophenyl)borane; and / or, The catalyst is added at a rate of 3 mol% to 5 mol%, based on 100% of compounds containing unsaturated bonds; and / or, The amount of deuterated silane added is 100 mol% to 120 mol%, based on 100% of compounds containing unsaturated bonds; and / or, The solvent is selected from at least one of benzene solvents, ether solvents, and halogenated hydrocarbon solvents; preferably, the solvent is selected from at least one of toluene, dichloromethane, or tetrahydrofuran; and / or, The concentration of compounds containing unsaturated bonds in the solvent is 0.4–0.5 mol / L; and / or, The time for the silylation reaction is 12–20 h; and / or, The temperature for the silylation reaction is 18–30 °C; and / or, The post-processing includes rotary evaporation and column chromatography.

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