This application claims priority of the Chinese patent applications filed with China National Intellectual Property Administration (CNIPA) on Apr. 9, 2021, with application number 202110381786.6 titled “A Deuteration Method for Benzylic Carbon-Hydrogen Bonds,” filed with CNIPA on Apr. 15, 2021, with application number 202110406555.6 titled “A Deuteration Method for Methyl Sulfide Compounds,” filed with CNIPA on Apr. 30, 2021, with application number 202110479540.2 titled “A Deuteration Method for sp2 Hybridized C—H Bonds,” filed with CNIPA on Oct. 25, 2021, with application number 202111239237.1 titled “A Novel Deuteration Method for Pyridine and its Derivatives,” and filed with CNIPA on Oct. 25, 2021, with application number 202111239460.6 titled “A Novel Deuteration Method for Sulfones, Sulfoxides, Sulfonamides, and Sulfinamides Compounds,” the entirety of which are incorporated by reference herein.
This application relates to the field of organic synthesis and, more specifically, to a method for preparing deuterated chemicals through a deuteration reaction of a carbon-hydrogen bond with deuterium gas under catalysis of alkali.
Deuterated compounds, as a class of high-value-added compounds, have wide applications in organic synthesis, mechanistic studies, drug metabolism, and drug modification. In recent years, the development of new, mild, efficient, and universally applicable deuteration methods has garnered significant attention from chemists.
With the advancement of C—H bond activation reactions, transition metal-catalyzed hydrogen-deuterium exchange reactions have been widely used for the synthesis of deuterated compounds. This method typically requires expensive transition metal catalysts or complex ligands and is commonly employed for the selective deuteration reaction of C(sp2)-H bonds in aromatic and heteroaromatic compounds containing directing groups. There has been less research on the selective hydrogen-deuterium exchange reactions of C(sp2)-H and C(sp3)-H bonds in aromatic compounds without directing groups.
On the other hand, current deuteration reactions often involve heating to prepare deuterated compounds in the presence of a large quantity of deuterium water. However, due to the equilibrium of the hydrogen-deuterium exchange reaction, it is more economical to remove the resulting water and replace it with fresh deuterium water after multiple cycles of chemical equilibrium to achieve a deuterated product with a high deuteration rate. This method requires a significant amount of deuterium water as a deuterium source and involves numerous water separation operations, leading to cumbersome steps and substantial energy waste. Therefore, there is an urgent need for the development of a simple, efficient, and cost-effective method for carbon-hydrogen bond deuteration.
The purpose of this application is to provide a simple, efficient, and cost-effective method for preparing deuterated chemical compounds through a deuteration reaction of a carbon-hydrogen bond with deuterium gas under catalysis of alkali. The specific technical solution is as follows:
This application provides a method for the deuteration of carbon-hydrogen bonds, comprising the following steps:
In the presence of a catalyst, introducing deuterium gas into a compound containing carbon-hydrogen bonds for deuteration to produce deuterated compounds:
In one embodiment of this application, said alkali metal hydroxide is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide;
Said alkali metal hydride is selected from at least one of lithium hydride, sodium hydride, potassium hydride, rubidium hydride, and cesium hydride;
In this application, said alkoxyl rubidium or alkoxyl cesium can be prepared by reacting rubidium hydroxide or cesium hydroxide with methanol, ethanol, isopropanol, or tert-butanol.
In one embodiment of this application, wherein:
In this application, a mixture of alkali metal hydrocarbon compound and amine, or alkali metal salt and lithium amide, is added to the reaction system of said deuteration reaction, alkali metal amino compounds are synthesized in situ. Under the catalytic action of the in situ-synthesized alkali metal amino compounds, the deuteration reaction is carried out.
It should be noted that alkali metal amino compounds can be added directly to the reaction system of the deuteration reaction as finished catalysts for catalysis, or they can be synthesized in situ in the reaction system of the deuteration reaction for catalysis.
In this application, alkali metal amino compounds are synthesized in situ in said reaction system of the deuteration reaction by acid-base reactions between alkali metal hydrocarbon compounds and amines. Under the catalytic action of the in situ-synthesized alkali metal amino compounds, said deuterium exchange reaction is carried out.
Wherein, said alkali metal benzyl compounds are obtained by the reaction of butyl lithium, toluene and alkali metal tert-butoxide salts; said alkali metal tert-butoxide salts are selected from at least one of potassium tert-butoxide, rubidium tert-butoxide, and cesium tert-butoxide. For example, benzyl potassium is obtained by the reaction of butyl lithium, toluene and potassium tert-butoxide, and benzyl rubidium is obtained by the reaction of butyl lithium, toluene and rubidium tert-butoxide.
In this application, alkali metal amino compounds are synthesized in situ in the reaction system of said deuteration reaction by salt exchange reactions between alkali metal salts and lithium amide. Then, under the catalytic action of the in situ-synthesized alkali metal amino compounds, said deuteration reaction is carried out.
For example, a mixture of sodium tert-butoxide (NaOtBu) or potassium tert-butoxide (KOtBu) and lithium diisopropylamide (LDA) is added to the reaction system of said deuteration reaction, resulting in the in situ synthesis of sodium diisopropylamide (NaDA) or potassium diisopropylamide (KDA). Then, under the catalytic action of the in situ-synthesized NaDA or KDA, said deuteration reaction is carried out.
For example, a mixture of rubidium fluoride (RbF) and lithium bis(trimethylsilyl)amide (LiHMIDS) is added to the reaction system of said deuteration reaction, leading to the in situ synthesis of rubidium bis(trimethylsilyl)amide (RbHMDS). Then, under the catalytic action of the in situ-synthesized RbHMDS, said deuteration reaction is carried out.
A mixture of cesium salts, such as cesium chloride (CsCl), cesium carbonate (Cs2CO3), cesium trifluoroacetate (CsTFA), or cesium perchlorate (CsClO4), and lithium bis(trimethylsilyl)amide (LiHMDS) is added to the reaction system of said deuteration reaction, resulting in the in situ synthesis of cesium bis(trimethylsilyl)amide (CsHMDS). Then, under the catalytic action of the in situ-synthesized CsHMDS, said deuteration reaction is carried out.
For another example, a mixture of butyl lithium and tetramethylpiperidine is added to the reaction system of said deuteration reaction, leading to the in situ synthesis of lithium tetramethylpiperidide (TMPLi). Then, under the catalytic action of the in situ-synthesized TMPLi, said deuteration reaction is carried out.
For another example, a mixture of cesium fluoride (CsF) and lithium tetramethylpiperidide (TMPLi) is added to said reaction system of the deuteration reaction, resulting in the in situ synthesis of cesium tetramethylpiperidide (TMPCs). Then, under the catalytic action of the in situ-synthesized TMPCs, said deuteration reaction is carried out.
The above methods for in situ synthesis of catalysts are simple to operate and the above in situ-synthesized alkali metal amino compounds provide excellent catalytic effects for said deuteration reaction.
In this application, the alkali metal amino compound can also be prepared according to the method of in situ synthesis of alkali metal amino compound by the acid-base reaction between a mixture of alkali metal hydrocarbon compound and amine or the salt exchange reaction between a mixture of alkali metal salt and lithium amide. The alkali metal amino compound is then obtained through separation and purification. Subsequently, the prepared alkali metal amino compound is introduced into the reaction system of said deuteration reaction to carry out said deuteration reaction.
In one embodiment of this application, said compounds containing carbon-hydrogen bonds are selected from at least one of the following: aromatic compounds with carbon-hydrogen bonds at the benzyl position; thioether compounds with carbon-hydrogen bonds at the α position; sulfone, sulfoxide, sulfonamide, and sulfinamide compounds with carbon-hydrogen bonds at the α position; aryl ether compounds, fluorobenzene compounds; aromatic hydrocarbons, heteroaromatic hydrocarbons with aromatic carbon-hydrogen bonds, and alkene compounds with alkenyl carbon-hydrogen bonds.
In this application, said aromatic hydrocarbon compounds with carbon-hydrogen bonds at the benzyl position include but are not limited to toluene, alkylbenzenes, alkylpyridines, alkylfurans, alkylthiophenes, alkylpyrroles, benzyl ethers, benzyl thioethers, benzylamines, or benzylsilane compounds.
Said thioether compounds with carbon-hydrogen bonds at the α position include but are not limited to methyl aryl thioethers, methyl alkyl thioethers, or dialkyl thioethers.
Said sulfone, sulfoxide, sulfonamide, and sulfinamide compounds with carbon-hydrogen bonds at the α position include but are not limited to dimethyl sulfoxide, phenyl methyl sulfoxide, dialkyl sulfoxides, alkyl aryl sulfoxides, dialkyl sulfones, alkyl aryl sulfones, N,N-dimethyl sulfonamide, alkyl sulfonamides, or alkyl sulfinamides.
Said aryl ether compounds with aromatic carbon-hydrogen bonds include but are not limited to phenyl methyl ether, dimethoxybenzene, 1,3,5-trimethoxybenzene, diphenyl ether, 1,2-methylenedioxybenzene, benzodioxane, or alkoxypyridine.
Said fluorobenzene compounds include but are not limited to fluorobenzene, difluorobenzene, fluoronaphthalene or alkyl fluorobenzene.
Said aromatic hydrocarbons include but are not limited to benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, perylene, triphenylamine, or N-phenylcarbazole.
Said heteroaromatic hydrocarbons compounds include but are not limited to pyridine, phenylpyridine, bipyridine, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole, carbazole, imidazole, oxazole or thiazole.
Said alkenes with alkenyl carbon-hydrogen bonds include but are not limited to methylstyrene, allylbenzene, 2,3-dihydrofuran, or 1,4-dioxene.
In one embodiment of this application, said deuteration reaction is as shown in any one of Reaction Equations 1-5.
Reaction Equation 1 is as follows:
Reaction Equation 2 is as follows:
R1-R5 are independently selected from any one of H, C1-C10 hydrocarbon group, C6-C20 aryl group, halogens, C1-C10 hydrocarboxyl group, C3-C9 silyl group, or C1-C20 amino group. Two adjacent groups in R1-R3 can be connected into a ring. X1 is a carbon atom or a nitrogen atom, and X2 is an oxygen atom, a sulfur atom, or a nitrogen atom.
Reaction Equation 3 is as follows:
Reaction Equation 4 is as follows:
R6-R10 are independently selected from any one of H, C1-C10 hydrocarbon group, C6-C20 aryl group, halogen, C1-C10 hydrocarboxyl group, or C1-C20 amino group. Two adjacent groups in R6-R8 can be connected into a ring. X2 is an oxygen atom, a sulfur atom, or a nitrogen atom, and X3 is any one of a silicon atom, an oxygen atom, a sulfur atom, a carbon atom, or a nitrogen atom. R is a C1-C10 hydrocarbon group or a C6-C20 aryl group.
Reaction Equation 5 is as follows:
R11-R20 are independently selected from any one of H, C1-C10 hydrocarbon group, C6-C20 aryl group, halogen, C1-C10 hydrocarboxyl group, or C1-C20 amino group.
It should be noted that when the compound containing carbon-hydrogen bonds is selected from aromatic hydrocarbon compounds with carbon-hydrogen bonds at the benzyl position, i.e., the substrate of the deuteration reaction contains benzyl carbon-hydrogen bonds, said deuteration reaction includes but is not limited to the deuteration reactions shown in Reaction Equations 1 to Reaction Equation 5, and the carbon-hydrogen bonds that are deuterated are selected from the C(sp3)-H bonds at the benzyl position of the aromatic hydrocarbon compounds containing carbon-hydrogen bonds at the benzyl position.
In one embodiment of this application, said deuteration reaction is as shown in any one of Reaction Equations 6-7.
Reaction Equation 6 is as follows:
R21-R23 are independently selected from any one of H, C1-C10 hydrocarbon group, C6-C20 aryl group, C3-C9 silyl group, C1-C10 alkyloxyl group, or C1-C20 amino group. R21-R23 can be connected into an aliphatic hydrocarbon ring or an aromatic ring.
Reaction Equation 7 is as follows:
R24-R28 are independently selected from any one of H, C1-C10 hydrocarbon group, C6-C20 aryl group, halogen, C1-C10 hydrocarboxyl group, C1-C10 hydrocarbon sulfur group, or C1-C20 amino group. X4 is a carbon atom or a nitrogen atom.
It should be noted that when the compound containing carbon-hydrogen bonds is selected from thioether compounds with carbon-hydrogen bonds at the α position, said deuteration reaction includes but is not limited to the deuteration reactions shown in Reaction Equation 6-7, and the carbon-hydrogen bonds that are deuterated are selected from at least one of the C(sp3)-H bonds at the α position directly connected to sulfur atoms in the thioether compounds with carbon-hydrogen bonds at the α position.
In one embodiment of this application, the catalyst in Reaction Equation 1-7 is selected from at least one of potassium diisopropylamide, potassium bis(trimethylsilyl)amide, potassium tetramethylpiperidide, rubidium diisopropylamide, rubidium bis(trimethylsilyl)amide, rubidium tetramethylpiperidide, cesium diisopropylamide, cesium bis(trimethylsilyl)amide, and cesium tetramethylpiperidide.
In one embodiment of this application, said deuteration reaction is as shown in any one of Reaction Equations 8-12.
Reaction Equation 8 is as follows:
Reaction Equation 9 is as follows:
Reaction Equation 10 is as follows:
Reaction Equation 11 is as follows:
Reaction Equation 12 is as follows:
R29 is independently selected from any one of C1-C10 hydrocarbon group, C6-C20 aryl group, C1-C10 alkyloxyl group, or C1-C20 amino group. R30 is independently selected from any one of C1-C10 hydrocarbon group or C6-C20 aryl group, and R29 and R30 can be connected into a ring. R31-R34 are independently selected from any one of H, C1-C10 hydrocarbon group, C6-C20 aryl group, C1-C10 alkyloxyl group, or C1-C20 amino group, and two adjacent groups in R31-R34 can be connected into a ring.
It should be noted that when said compound containing carbon-hydrogen bonds is selected from said compounds with carbon-hydrogen bonds at the α position in sulfones, sulfoxides, sulfonamides, and sulfinamides, and in aromatic sulfones, sulfoxides, sulfonamides, and sulfinamides, i.e., when the reaction substrates in the deuteration reaction contains an S═O structure, said deuteration reaction includes but is not limited to the deuteration reactions as shown in any one of Reaction Equations 8-12, and the carbon-hydrogen bonds that are deuterated are selected from at least one of the C(sp3)-H bonds directly connected to sulfur atoms in the compounds containing carbon-hydrogen bonds and the C(sp2)-H bonds on the benzene ring with a group containing an S═O structure as the directing group. Wherein, the above group containing the S═O structure is selected from at least one of the sulfones, sulfoxides, sulfonamide, or sulfinamide groups in the reaction substrates mentioned above.
In one embodiment of this application, the catalyst in Reaction Equations 8-11 is selected from at least one of potassium tert-butoxide, sodium hydroxide, and potassium hydroxide.
In one embodiment of this application, said deuteration reaction is as shown in any one of Reaction Equations 13-15.
Reaction Equation 13 is as follows:
Reaction Equation 14 is as follows:
Reaction Equation 15 is as follows:
R35-R40 are independently selected from any one of H, C1-C10 hydrocarbon group, or C6-C20 aryl group, and two adjacent groups in R35-R40 can be connected into a ring.
In one embodiment of this application, said deuteration reaction is as shown in any one of Reaction Equations 16-17.
Reaction Equation 16 is as follows:
Reaction Equation 17 is as follows:
R36-R38 are independently selected from any one of H, C1-C10 hydrocarbon group, or C6-C20 aryl group, and two adjacent groups in R36-R38 can be connected into a ring. X5 is selected from any one of silicon, oxygen, sulfur, carbon, or nitrogen atoms.
It should be noted that said deuteration reaction can occur at any position on aromatic heterocycles such as pyridine, furan, and thiophene.
In one embodiment of this application, said deuteration reaction is as shown in Reaction Equation 18.
Reaction Equation 18 is as follows:
R41 and R42 are independently selected from any one of H, C1-C10, hydrocarbon group, C6-C20 aryl group, C3-C9 silyl group, C1-C10 alkoxyl group, or C1-C20 amino group, and R41 and R42 can be connected into an aliphatic hydrocarbon ring or an aromatic ring.
It should be noted that when the reaction substrate for said deuteration reaction contains a C(sp2)-H bond, said deuteration reaction includes but is not limited to the deuteration reactions as shown in Reaction Equations 12-18, and the carbon-hydrogen bonds that are deuterated are selected from at least one of the C(sp2)-H bonds contained in the above reaction substrates.
In one embodiment of this application, the catalyst in Reaction Equations 13-18 is selected from at least one of potassium diisopropylamide, potassium bis(trimethylsilyl)amide, potassium tetramethylpiperidide, rubidium diisopropylamide, rubidium bis(trimethylsilyl)amide, rubidium tetramethylpiperidide, cesium diisopropylamide, cesium bis(trimethylsilyl)amide, and cesium tetramethylpiperidide.
In this application, the chemical formula of said C3-C9 silane groups is —SiY1Y2Y3, where Y1, Y2, and Y3 are independently selected from C1-C3 alkyl groups. The chemical formula of C1-C10 alkyloxyl groups or C1-C10 hydrocarboxyl groups is —OY4, where Y4 is selected from C1-C10 alkyl groups or C6-C10 aryl groups. The chemical formula of C1-C20 amino groups is —NY5Y6, where Y5 and Y6 are independently selected from C1-C10 alkyl groups or C6-C10 aryl groups.
In one embodiment of this application, the molar amount of said catalyst is 1%-100% of the molar amount of said compound containing carbon-hydrogen bonds.
In one embodiment of this application, the pressure of deuterium gas in said deuteration reaction is 1 bar to 50 bar.
In one embodiment of this application, said deuteration reaction is carried out in an organic solvent or under solvent-free conditions, and said organic solvents are selected from at least one of aromatic hydrocarbon solvents, alkane solvents, and ether solvents. Among them, the aromatic hydrocarbon solvents are selected from at least one of deuterated benzene, benzene, and tert-butylbenzene; the alkane solvents are selected from at least one of n-hexane, cyclohexane, and decalin; the ether solvents are selected from at least one of ether, tetrahydrofuran, methyl tert-butyl ether, methyl cyclopentyl ether, and n-butyl ether.
In this application, the reaction temperature for said deuteration reaction is 40° C.-150° C., and the reaction time is 12 hours-96 hours.
In this application, after a period of the deuteration reaction, the gas in the reaction vessel can be replaced with fresh deuterium gas for further reaction, and through two or more such processes, a high deuteration rate of the reactants can be achieved.
In this application, the deuteration reaction is carried out in a sealed container, and an inert atmosphere such as nitrogen or argon can be introduced into the sealed container.
The advantageous effects of this application are as follows:
This application provides a deuteration method for carbon-hydrogen bonds, which, in the presence of a catalyst, involves the addition of deuterium gas to a compound containing a carbon-hydrogen bond to perform a deuteration reaction to generate deuterated compounds. By using deuterium gas as the deuterium source, avoiding the use of a large amount of deuterium oxide as a deuterium source, thus avoiding multiple water removal steps, cumbersome steps, and a large amount of energy waste. Additionally, using inexpensive and readily available alkali metal compounds as catalysts for deuteration reactions, instead of expensive transition metal catalysts and complex ligands, offers advantages of low cost, excellent substrate functional group compatibility, and high deuteration rate. Furthermore, the deuteration method disclosed in this application is characterized by mild reaction conditions, simple operation, and the ability to prepare deuterated products in one step. This deuteration method opens up a new, low-cost, and environmentally friendly pathway for the preparation of deuterated chemicals and pharmaceuticals, which has high practical value.
In addition, in the deuteration method of the present application, the compounds containing C—H bonds, that is, the reaction substrate of the deuteration reaction is selected from at least one of the aromatic compounds with C—H bonds at the benzyl position, thioether compounds with C—H bonds at the alphα position, sulfone, sulfoxide, sulfamide, sulfinamide compounds with C—H bonds at the α position, aryl ether compounds, fluorobenzene compounds, aromatic hydrocarbons, heteroaromatic hydrocarbons with aryl C—H bonds and alkenes with alkenyl C—H bonds. The deuterated C—H bond in the present application relates to at least one of the C(sp3)-H bond at the benzyl position in the above reaction substrate, the C(sp3)-H bond at the α position connected to the sulfur atom on the thioether group, the C(sp3)-H bond at the α position directly connected to the sulfur atom of the sulfone, sulfoxide, sulfamide or sulfinamide group, and the C(sp2)-H bonds in the benzene ring with the sulfone, sulfoxide, sulfamide or sulfinamide group as the directing group and the C(sp2)-H bonds of aryl ethers, fluorobenzenes, aromatic hydrocarbons, heteroaromatic hydrocarbons and alkenes having alkenyl hydrocarbon bonds. In addition, the deuteration method of the present application has good deuteration effect on the above-mentioned reaction substrates and the above-mentioned carbon-hydrogen bonds, and has the advantages of wide application range and high deuteration rate.
Of course, the implementation of any method of this application does not necessarily need to achieve all the advantages described above.
In order to provide a clearer understanding of the technical solutions in the embodiments of this application, a brief introduction to the drawings required for the embodiments is presented below. It is evident that the following descriptions of the drawings are only some of the embodiments of this application, and those skilled in the art can obtain additional drawings based on these.
In order to make the objectives, technical solutions, and advantages of the present application clearer and more understandable, specific embodiments are described below with reference to the attached drawings for further illustrating the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments in the present application are within the scope of protection of the present application.
Below, examples are provided to further illustrate the embodiments of the present application. The chemical structures of deuterated products in the deuteration reactions of the embodiments show the positions of deuterated carbon-hydrogen bonds and the corresponding deuteration rate.
The following abbreviations are used in the examples:
The preparation of the cesium bis(trimethylsilyl)amide (CsHMDS) catalyst used in the following examples includes:
Under an inert atmosphere, 10 mmol of lithium bis(trimethylsilyl)amide (LiHMDS), 10 mmol of cesium fluoride (CsF), and 30 mL of dry n-hexane were added to a reaction flask equipped with a magnetic stirrer. The reaction solution was heated and refluxed for 15 hours. After the reaction was completed, the solvent was evaporated. Then, 30 mL of toluene was added to dissolve cesium bis(trimethylsilyl)amide (CsHMDS), filtered, and the solvent was drained to obtain 2.20 g of white solid, with a yield of 75%.
The preparation of the benzyl potassium (BnK) catalyst used in the following examples includes:
The gas chromatography-mass spectrometry (GC-MS) analysis used in the following examples involved dissolving 1-2 mg of the reaction product obtained after the reaction in 1 mL of ethyl acetate, testing using the GCMS-Q2020 NX instrument to determine the molecular weight and abundance of the product, and then calculate deuteration rate using the IsoPat2 calculation method (the IsoPat2 calculation method of Reference J. Org. Chem. 2007, 72, 5778-5783. which is incorporated into this application by reference).
Under an inert atmosphere, in a 25 mL autoclave, 4-phenyltoluene (CAS: 644-08-6) (0.0504 g, 0.3 mmol), deuterated benzene (0.5 mL), and potassium hydride (0.0012 g, 0.03 mmol, 10 mol %) were sequentially added. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. After the reaction, the reaction solution was separated by column chromatography, and the obtained deuterated 4-phenyltoluene was subjected to nuclear magnetic resonance 1HNMR and 13C NMR testing, with 1H NMR performed at a frequency of 400 MHz using deuterated chloroform as the deuterated solvent and 13C NMR performed at a frequency of 101 MHz using deuterated chloroform as the deuterated solvent.
The deuteration rate was calculated based on 1H NMR data, and the deuteration rate of the carbon-hydrogen bond at the benzyl position of deuterated 4-phenyltoluene was determined to be 31%.
Except for the preparation parameters and deuteration rates as shown in Table 2, the rest were the same as Example 1.
In Example 6, the 1H NMR spectrum is shown in
Under an inert atmosphere, in a 25 mL autoclave, p-xylene (CAS: 106-42-3) (0.0319 g, 0.3 mmol), deuterated benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were sequentially added. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. Deuterium gas was then refilled to maintain a pressure of 4 bar for the deuterium gas inside the autoclave, and the reaction was continued for another 24 hours. After completion of the reaction, the reaction solution was directly subjected to 1H NMR and 13C NMR testing.
In Example 21, the 1H NMR spectrum is shown in
Based on the 1H NMR data, the deuteration rate was calculated, and the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated p-xylene was determined to be 94%.
Under an inert atmosphere, in a 25 mL autoclave, 4-ethylbiphenyl (CAS: 5707-44-8) (0.0547 g, 0.3 mmol), benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0264 g, 0.09 mmol, 30 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. The reaction solution was then separated by column chromatography, with a separation yield of 98%. The obtained product was subjected to 1H NMR and 13C NMR testing using deuterated chloroform (CDCl3) as the deuterated solvent.
In Example 22, the 1H NMR spectrum is shown in
Based on the 1H NMR data, the deuteration rate was calculated, and the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated 4-ethylbiphenyl was determined to be 97%.
Under an inert atmosphere, in a 25 mL autoclave, 2-methylpyridine (CAS: 109-06-8) (0.0280 g, 0.3 mmol), deuterated benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR testing.
In Example 23, the 1H NMR spectrum is shown in
Based on the 1H NMR data, the deuteration rate was calculated, and the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated 2-methylpyridine was determined to be 92%.
Under an inert atmosphere, in a 25 mL autoclave, 3-methylpyridine (CAS: 108-99-6) (0.0280 g, 0.3 mmol), deuterated benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR testing.
In Example 24, the 1H NMR spectrum is shown in
Based on the 1H NMR data, the deuteration rate was calculated, and the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated 3-methylpyridine was determined to be 82%.
Under an inert atmosphere, in a 25 mL autoclave, 1,2-dimethylindole (CAS: 875-79-6) (0.0436 g, 0.3 mmol), benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0264 g, 0.09 mmol, 30 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was separated by column chromatography, with a separation yield of 97%. The obtained product was then subjected to 1H NMR and 13C NMR testing using deuterated chloroform (CDCl3) as the deuterated solvent.
In Example 25, the 1H NMR spectrum is shown in
Based on the 1H NMR data, the deuteration rate was calculated, and the deuteration rate of the carbon-hydrogen bond at the benzyl positions on deuterated 1,2-dimethylindole was determined to be 90%.
Under an inert atmosphere, in a 25 mL autoclave, 2-methylbenzothiophene (CAS: 1195-14-8) (0.0445 g, 0.3 mmol), deuterated benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0264 g, 0.09 mmol, 30 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR testing.
In Example 26, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different deuterated positions on deuterated 2-methylbenzothiophene were obtained, as shown in the reaction Equation.
Under an inert atmosphere, in a 25 mL autoclave, diphenylmethane (CAS: 101-81-5) (0.0504 g, 0.3 mmol), benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was separated by column chromatography, with a separation yield of 94%. The resulting product was subjected to 1H NMR and 13C NMR testing using deuterated chloroform as the deuterated solvent.
In Example 27, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated diphenylmethane was found to be 97%.
Under an inert atmosphere, in a 25 mL autoclave, benzyl methyl ether (CAS: 538-86-3) (0.0366 g, 0.3 mmol), benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was separated by column chromatography, with a separation yield of 42%. The resulting product was subjected to 1H NMR and 13C NMR testing using deuterated chloroform as the deuterated solvent.
In Example 28, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated benzyl methyl ether was found to be 91%.
Under an inert atmosphere, in a 25 mL autoclave, benzyl phenyl sulfide (CAS: 831-91-4) (0.0601 g, 0.3 mmol), benzene (0.5 mL), and potassium bis(trimethylsilyl)amide (0.0060 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was separated by column chromatography, with a separation yield of 99%. The resulting product was subjected to 1H NMR and 13C NMR testing using deuterated chloroform as the deuterated solvent.
In Example 29, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated benzyl phenyl sulfide was found to be 98%.
Under an inert atmosphere, in a 25 mL autoclave, N-ethyl-N-benzyl aniline (CAS: 92-59-1) (0.0634 g, 0.3 mmol), benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was subjected to column chromatography, with a separation yield of 98%. The resulting product was subjected to 1H NMR and 13C NMR testing using deuterated chloroform as the deuterated solvent.
In Example 30, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the benzyl position on deuterated N-ethyl-N-benzyl aniline was found to be 83%.
Under an inert atmosphere, in a 25 mL autoclave, phenyl methyl sulfide (CAS: 100-68-5) (0.0372 g, 0.3 mmol), deuterated benzene (0.5 mL), and potassium bis(trimethylsilyl)amide (0.0060 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with deuterium gas to achieve the pressure of deuterium gas in the autoclave is 4 bar, heated at 60° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was subjected to 1H NMR and 13C NMR testing directly.
In Example 31, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated phenyl methyl sulfide was found to be 94%.
Under an inert atmosphere, in a 25 mL autoclave, methylthiocyclohexyl ester (CAS: 7133-37-1) (0.0391 g, 0.3 mmol), deuterated benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 48 hours to undergo the deuteration reaction. Then, deuterium gas was refilled to maintain a pressure of 4 bar for the deuterium gas inside the autoclave, and the reaction was continued for another 48 hours. Afterward, the reaction solution was subjected to 1H NMR and 13C NMR testing, and the deuteration rate is shown in the figure.
In Example 32, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated methylthiocyclohexyl ester was found to be 93%.
Under an inert atmosphere, in a 25 mL autoclave, dimethyl sulfoxide (CAS: 67-68-5) (0.0234 g, 0.3 mmol), deuterated benzene (0.5 mL), and potassium tert-butoxide (0.0034 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 48 hours to undergo the deuteration reaction. Subsequently, the reaction solution was treated with 1,3,5-Trimethoxybenzene (0.0218 g) as an internal standard, and then subjected to 1H NMR and 13C NMR testing. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rate of the the carbon-hydrogen bond at the deuterated position in deuterated dimethyl sulfoxide was found to be 91%.
Under an inert atmosphere, in a 25 mL autoclave, phenyl methyl sulfoxide (CAS: 1193-82-4) (0.0421 g, 0.3 mmol), deuterated benzene (0.5 mL), and potassium tert-butoxide (0.0034 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 48 hours to undergo the deuteration reaction. Subsequently, the reaction solution was subjected to 1H NMR and 13C NMR testing directly. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, to obtain the deuteration rates of the C—H bonds at different deuterated positions in deuterated phenyl methyl sulfoxide, as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, N,N-dimethylmethanesulfonamide (CAS: 918-05-8) (0.0370 g, 0.3 mmol), deuterated benzene (0.5 mL), and potassium tert-butoxide (0.0034 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 48 hours to undergo the deuteration reaction. Subsequently, the reaction solution was subjected to 1H NMR and 13C NMR testing directly. The 1H NMR spectrum is shown in
The deuteration rate was calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated N,N-dimethylmethanesulfonamide was found to be 72%.
Under an inert atmosphere, in a 25 mL autoclave, anisole (CAS: 100-66-3) (0.0324 g, 0.3 mmol), deuterated benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Deuterium gas was refilled to maintain a pressure of 4 bar for the deuterium gas inside the autoclave, and the reaction was continued for another 24 hours. Subsequently, the reaction solution was subjected to 1H NMR and 13C NMR analysis directly.
In Example 36, 1H NMR hydrogen spectrum is shown in
The deuteration rate was calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated anisole was found to be 97%.
Under an inert atmosphere, in a 25 mL autoclave, 1,3-benzodioxole (CAS: 274-09-9) (0.0367 g, 0.3 mmol), deuterated benzene (0.5 mL), and potassium bis(trimethylsilyl)amide (0.0180 g, 0.09 mmol, 30 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Subsequently, the reaction solution was subjected to 1H NMR and 13C NMR testing directly.
In Example 37, 1H NMR hydrogen spectrum is shown in
The deuteration rates were calculated based on 1H NMR data to obtain the deuteration rates of the C—H bonds at different deuterated positions in deuterated 1,3-benzodioxole, as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, 4-fluorobiphenyl (CAS: 324-74-3) (0.0516 g, 0.3 mmol), benzene (0.5 mL), cesium fluoride (0.0046 g, 0.03 mmol, 10 mol %), and lithium bis(trimethylsilyl)amide (0.0050 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Subsequently, deuterium gas was refilled to maintain a pressure of 4 bar for the deuterium gas inside the autoclave, and the reaction was continued for another 24 hours. Then, the reaction solution was separated by column chromatography, with a separation yield of 98%. The obtained product was analyzed by 1H NMR and 13C NMR, using deuterated chloroform as the deuterated solvent.
In Example 38, 1H NMR hydrogen spectrum is shown in
The deuteration rate was calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated 4-fluorobiphenyl was found to be 98%.
Under an inert atmosphere, in a 25 mL autoclave, 1,4-difluorobenzene (CAS: 540-36-3) (0.0342 g, 0.3 mmol), deuterated benzene (0.5 mL), and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Subsequently, deuterium gas was refilled to maintain a pressure of 4 bar for the deuterium gas inside the autoclave, and the reaction was continued for another 24 hours. Then, dibromomethane (CAS: 74-95-3) (0.0264 g) was added to the reaction solution as an internal standard. The reaction solution was directly subjected to 1H NMR and 13C NMR testing.
In Example 39, 1H NMR hydrogen spectrum is shown in
The deuteration rate was calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated 1,4-difluorobenzene was found to be 93%.
Under an inert atmosphere, in a 25 mL autoclave, benzene (CAS: 71-43-2) (0.5000 g, 6.4 mmol) and cesium bis(trimethylsilyl)amide (0.3000 g, 1.02 mmol, 16 mol %) were added sequentially. The autoclave was sealed, filled with 14 bar deuterium gas, heated at 120° C. for 60 hours to undergo the deuteration reaction. Subsequently, the reaction solution was separated and purified, added with mesitylene (2.1 mmol) as an internal standard, then subjected to 1H NMR and 13C NMR testing. 1H NMR hydrogen spectrum is shown in
The deuteration rate was calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated benzene was found to be 78%.
Under an inert atmosphere, in a 25 mL autoclave, biphenyl (CAS: 92-52-4) (0.0463 g, 0.3 mmol), benzene (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0435 g, 0.15 mmol, 50 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 120° C. for 48 hours to undergo the deuteration reaction. Deuterium gas was refilled to maintain a pressure of 4 bar for the deuterium gas inside the autoclave, and the reaction was continued for another 48 hours. The average deuteration rate was determined to be 96% through the analysis using Gas Chromatography-Mass Spectrometry (GC-MS) and IsoPat2 software.
Under an inert atmosphere, in a 25 mL autoclave, naphthalene (CAS: 91-20-3) (0.0385 g, 0.3 mmol) benzene (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0435 g, 0.15 mmol, 50 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 120° C. for 48 hours to undergo the deuteration reaction. The average deuteration rate was determined to be 81% through the analysis using Gas Chromatography-Mass Spectrometry (GC-MS) and IsoPat2 software.
Under an inert atmosphere, in a 25 mL autoclave, triphenylamine (CAS: 603-34-9) (0.0736 g, 0.3 mmol), methyl tert-butyl ether (1.0 mL) and cesium bis(trimethylsilyl)amide (0.0435 g, 0.15 mmol, 50 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 120° C. for 48 hours to undergo the deuteration reaction. Deuterium gas was refilled to maintain a pressure of 4 bar for the deuterium gas inside the autoclave, and the reaction continued for another 48 hours. The average deuteration rate was determined to be 53% through the analysis using Gas Chromatography-Mass Spectrometry (GC-MS) and IsoPat2 software.
Under an inert atmosphere, in a 25 mL autoclave, N-phenylcarbazole (CAS: 1150-62-5) (0.0730 g, 0.3 mmol), methyl tert-butyl ether (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0435 g, 0.15 mmol, 50 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 100° C. for 24 hours to undergo the deuteration reaction. The average deuteration rate was determined to be 39% through the analysis using Gas Chromatography-Mass Spectrometry (GC-MS) and IsoPat2 software.
Under an inert atmosphere, in a 25 mL autoclave, pyridine (CAS: 110-86-1) (0.0237 g, 0.3 mmol), deuterated benzene (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0435 g, 0.15 mmol, 50 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 100° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was added with mesitylene (0.0120 g, 0.1 mmol) as an internal standard, and subjected to 1H NMR and 13C NMR testing. The 1H NMR spectrum is shown in
The deuteration rate was calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated pyridine was found to be 97%.
Under an inert atmosphere, in a 25 mL autoclave, 2-phenylpyridine (CAS: 1008-89-5) (0.0467 g, 0.3 mmol), benzene (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0435 g, 0.15 mmol, 50 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 100° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was separated and purified, added with mesitylene (0.0120 g, 0.1 mmol) as an internal standard, subjected to 1H NMR and 13C NMR testing. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different positions in deuterated 2-phenylpyridine were obtained as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, 2,2′-bipyridine (CAS: 366-18-7) (0.0468 g, 0.3 mmol), ether (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0435 g, 0.15 mmol, 50 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 100° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was separated and purified, and added with mesitylene (0.0120 g, 0.1 mmol) as an internal standard, subjected to 1H NMR and 13C NMR testing. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different positions in deuterated 2,2′-bipyridine were obtained as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, N-methylindole (CAS: 603-76-9) (0.0394 g, 0.3 mmol), benzene (0.5 mL) and potassium bis(trimethylsilyl)amide (0.0060 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was separated by column chromatography with a separation yield of 95%. The obtained product was subjected to 1H NMR and 13C NMR testing, using deuterated chloroform (CDCl3) as the deuterated solvent.
In Example 47, 1H NMR hydrogen spectrum is shown in
The deuteration rate was calculated based on 1H NMR data, the deuteration rate of the carbon-hydrogen bond at the deuterated position in deuterated N-methylindole was found to be 96%.
Under an inert atmosphere, in a 25 mL autoclave, benzothiophene (CAS: 95-15-8) (0.0403 g, 0.3 mmol), deuterated benzene (0.5 mL) and potassium bis(trimethylsilyl)amide (0.0060 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR testing.
In Example 49, the 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different positions in deuterated benzothiophene were obtained as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, $-methylstyrene (CAS: 637-50-3) (0.0355 g, 0.3 mmol), deuterated benzene (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR tests. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different positions in deuterated P-methylstyrene were obtained as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, 2,3-dihydrofuran (CAS: 1191-99-7) (0.0210 g, 0.3 mmol), deuterated benzene (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 120° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR testing. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different positions in deuterated 2,3-dihydrofuran were obtained as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, 1,4-dioxene (CAS: 543-75-9) (0.0258 g, 0.3 mmol), deuterated benzene (0.5 mL) and cesium bis(trimethylsilyl)amide (0.0087 g, 0.03 mmol, 10 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 120° C. for 24 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR testing. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different positions in deuterated 1,4-dioxene were obtained as shown in the reaction equation.
Under an inert atmosphere, in a 25 mL autoclave, 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene (CAS: 141556-42-5) (0.0601 g, 0.2 mmol), deuterated benzene (0.5 mL) and potassium bis(trimethylsilyl)amide (0.0120 g, 0.06 mmol, 30 mol %) were added sequentially. The autoclave was sealed, filled with 4 bar deuterium gas, heated at 80° C. for 48 hours to undergo the deuteration reaction. Then, the reaction solution was directly subjected to 1H NMR and 13C NMR testing. The 1H NMR spectrum is shown in
The deuteration rates were calculated based on 1H NMR data, the deuteration rates of the carbon-hydrogen bonds at different positions in deuterated 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene were obtained as shown in the reaction equation.
The above description represents preferred embodiments of the present application and are not intended to limit the scope of the present application. Any modifications, equivalent replacements, improvements, and the like made within the spirit and principles of the present application should be included within the scope of protection of the present application.
Number | Date | Country | Kind |
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202110381786.6 | Apr 2021 | CN | national |
202110406555.6 | Apr 2021 | CN | national |
202110479540.2 | Apr 2021 | CN | national |
202111239237.1 | Oct 2021 | CN | national |
202111239460.6 | Oct 2021 | CN | national |
Filing Document | Filing Date | Country | Kind |
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PCT/CN2022/085660 | 4/7/2022 | WO |