Applications of amorphous carbon materials and methods for synthesizing polydeuterated aromatic compounds

Abstract

This invention discloses an application of amorphous carbon materials and a method for synthesizing polydeuterated aromatic compounds, belonging to the field of organic chemistry. Under a specific temperature, a reaction solution consisting of aromatic compounds, deuterium water, and a solvent flows through an amorphous carbon material in a carrier gas atmosphere, reacting to form polydeuterated aromatic compounds. This process, based on amorphous carbon materials to catalyze polydeuteration reactions, has advantages such as low cost, stable and efficient reaction, good functional group compatibility, and environmental friendliness, and has promising application prospects.

Description

Technical Field

[0001] This invention relates to the field of organic chemistry, and in particular to the application of amorphous carbon materials and methods for synthesizing polydeuterated aromatic compounds. Background Technology

[0002] Due to their unique properties, polydeuterated aromatic compounds are widely used in optoelectronic materials, bioimaging and other fields, and there is a huge demand for them.

[0003] For the preparation of polydeuterated aromatic compounds, the commonly used method currently is to utilize heterogeneous noble metal catalysts (such as supported noble metal carbon-based catalysts like Pd / C, Pt / C, and Ru / C) to perform polydeuteration on aromatic compounds (Tetrahedron 2006, 62, 10954; Angew. Chem., Int. Ed. 2020, 59, 21114). The principle of this synthetic method is to use noble metals to form MH (metallic hydrogen) species with hydrogen gas, then perform hydrogen-deuterium exchange with a deuterium source (such as deuterated water) in the reaction system, and subsequently perform hydrogen-deuterium exchange with the aromatic ring, thus achieving polydeuteration of the aromatic compound.

[0004] However, these methods generally suffer from high costs, poor stability, and poor compatibility. The expensive noble metal catalysts used in these methods result in low economic viability. Furthermore, due to thermodynamic reasons, heterogeneous metal nanocatalysts tend to agglomerate into larger particles. These large particles reduce the exposed metal surface area, thus significantly lowering catalytic efficiency compared to dispersed forms. Since noble metal catalyst systems require hydrogen to form MH species, the synthesis is conducted in a reducing system, making it difficult to simultaneously contain easily reduced functional groups. In a reducing system, the reduction of electron-depleted aromatic rings often yields products of aromatic ring reduction, increasing raw material loss and separation costs and difficulties. Finally, noble metal catalysts pose a risk of metal detachment during the reaction, as well as the risk of product contamination by metal and environmental impact.

[0005] Therefore, in order to address the problems of high cost, easy catalyst deactivation, low functional group compatibility, and environmental unfriendliness in existing multi-deuterated reaction systems, a new synthetic method is proposed to solve the above defects, which is of positive significance for expanding the application of multi-deuterated aromatic compounds. Summary of the Invention

[0006] In view of the above-mentioned deficiencies of the prior art, in a first aspect of the present invention, an application of amorphous carbon material in deuteration reaction is provided, which is used as a catalyst to catalyze the substitution of hydrogen atoms with deuterium in the deuteration reaction of aromatic compounds.

[0007] The amorphous carbon materials used in this application can be obtained from various sources, including existing commercially available products and those prepared in-house. As demonstrated in one or more embodiments of this invention, amorphous carbon materials prepared using biomass and additives offer advantages such as low production costs, wide availability of raw materials, and ease of operation, making them a particularly suitable method for preparing amorphous carbon materials for this application. Furthermore, modifying the carbon catalyst with additives can adjust the catalytic activity of oxygen-containing functional groups. The D species on the catalyst can undergo a hydrogen-deuterium exchange reaction with the CH groups on the substrate benzene ring, thereby improving the deuteration efficiency.

[0008] Preferably, the method for preparing the amorphous carbon material includes the following steps:

[0009] (1) Biomass, additives and solvents are mixed at a certain temperature;

[0010] (2) Separate the solvent to obtain a mixture;

[0011] (3) The mixture is calcined to obtain amorphous carbon material.

[0012] More preferably, in step (1), the biomass includes at least one of starch, lignin, cellulose, sodium alginate, and chitosan.

[0013] More preferably, in step (1), the additive includes at least one of melamine, 2-phenylpyridine, 1,3,5-trimethoxybenzene, and 1,2,4-triazole.

[0014] In the preparation of amorphous carbon materials, those skilled in the art can select a suitable solvent according to the type of raw material used, such as at least one of ethanol, propanol, ethyl acetate, and dichloromethane, all of which are suitable types.

[0015] More preferably, in step (1), the mass ratio of the solvent, biomass, and additive is (10-1000):(1-10):(0.1-3).

[0016] More preferably, in step (1), the mixing temperature is 40-80°C and the time is 2-16 hours.

[0017] When the solvent is one of the organic solvent types recommended above, it is suitable to separate the organic solvent by rotary evaporation and then dry the mixture in an oven. The suitable separation temperature for rotary evaporation is 30–60°C, and the time is 2–16 h; the suitable drying temperature for oven drying is 60–120°C, and the time is 1–7 days, to completely remove the organic solvent.

[0018] More preferably, in step (3), the carrier gas for calcination is one of nitrogen, argon, or a mixture of hydrogen and argon.

[0019] For preparation requirements and safety considerations, the hydrogen content in the hydrogen-argon mixture is 10% by volume.

[0020] More preferably, in step (3), the calcination temperature is 600-1200℃ and the time is 1-5h.

[0021] In a second aspect of the invention, a method for synthesizing polydeuterated aromatic compounds is provided, which is low-cost, stable and efficient, has good energy group compatibility, and is environmentally friendly, comprising the following steps:

[0022] At a certain temperature, a reaction liquid consisting of aromatic compounds, deuterium water, and solvent flows through an amorphous carbon material under a carrier gas atmosphere, and reacts to form polydeuterated aromatic compounds.

[0023] Aromatic compounds are aromatic molecules whose structural formulas contain an n-membered ring-shaped large conjugated system, where n is 5 or 6.

[0024] Preferably, the n-membered cyclic macroconjugated system of the aromatic compound includes an n-membered carbocyclic macroconjugated system or an n-membered heterocyclic macroconjugated system substituted by at least one atom selected from N, S, and O; the aromatic compound may contain one or more functional groups, including at least one of C1-C4 alkyl, amino, dimethylamino, hydroxyl, C1-C3 alkoxy, aldehyde, C1-C2 ester, fluorine, chlorine, bromine, iodine, sulfonyl, and nitro groups.

[0025] Preferably, the aromatic compound includes at least one selected from naphthalene, quinoline, N,N-dimethylaniline, anthracene, benzothiophene, benzofuran, 2-bromonaphthalene, nitrobenzene, 2-(2,4-difluorophenyl)pyridine, 5-methoxyindole, methyl 5-indolecarboxylate, ethyl 5-indolecarboxylate, 5-indolecarboxaldehyde, 6-methylquinoline, and 4,4'-di-tert-butyl-2,2'-dipyridine.

[0026] Preferably, the mass ratio of the aromatic compound to the solvent and deuterium water is (0.01-1):(10-100):(0.01-1).

[0027] The solvent plays a role in dissolving the reactants and mixing the deuterium water, creating a suitable solution environment for the reaction. In this art, the solvent is chemically inert relative to the substrate and does not participate in the reaction between the substrates. Therefore, those skilled in the art can select a suitable solvent based on the specific type of aromatic compound used. Organic solvents, such as at least one of diethyl ether, methyl ethyl ether, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile, are particularly suitable for the preparation of this invention.

[0028] Preferably, the mass ratio of the amorphous carbon material to the aromatic compound is (0.01–10):1.

[0029] The carrier gas provides the reaction atmosphere, while the hydrogen-argon mixture and the oxygen-nitrogen mixture provide reducing and oxidizing atmospheres, respectively, to ensure that easily oxidized or easily reduced substrates are consumed by the active species generated during the reaction. Slightly reducing, oxidizing, or redox-neutral systems can broaden the substrate applicability of deuterated aromatic compounds and improve the stability of the reaction system.

[0030] Preferably, the carrier gas is at least one of an inert gas, a hydrogen-argon mixture, and an oxygen-nitrogen mixture; the inert gas includes at least one of nitrogen and argon.

[0031] Preferably, the flow rate of the reaction liquid through the amorphous carbon material is 10–100 mL / min.

[0032] Preferably, the reaction temperature is 100–650°C.

[0033] As presented in one or more embodiments of the present invention, the polydeuterated process of the present invention can be implemented with only simple equipment, and no pressure vessel or other specialized equipment is required during the reaction, which is beneficial for widespread application. The synthesis process of polydeuterated aromatic compounds is shown below:

[0034] (1) When aromatic compounds contain substituted functional groups:

[0035]

[0036] Where m is 0 or 1, m is 0 when it represents a five-membered ring; X and Y are each independently selected from one of C, O, S, N, and the types of atoms in X and Y can be the same or different; the dashed line represents one or two six-membered fused rings, or rings without fused rings; R represents one or more functional groups of an aromatic compound.

[0037] (2) When aromatic compounds do not contain substituted functional groups:

[0038]

[0039] Where m is 0 or 1; X and Y are each independently selected from one of C, O, S, and N, and the types of atoms in X and Y can be the same or different; the dashed line represents one or two six-membered rings or no rings.

[0040] Under laboratory conditions, the following steps are performed: first, quartz wool, quartz sand, catalyst, and quartz wool are filled into a quartz tube in that order, and the quartz tube is placed in a reaction apparatus. The temperature of the reaction apparatus is set to the reaction temperature. Then, the reaction solution is pumped into the quartz tube to carry out the reaction. During this process, the reaction system is purged with a carrier gas, which pushes the reaction solution out. The product is collected at the end of the apparatus, and collection is complete once all the reaction solution has passed through. Extraction, separation, and concentration are then performed to obtain the polydeuterated product. This method is also applicable to industrial-scale production conditions. The product collection time can be determined according to the specific production scale, for example, within a time range of 0.5 to 100 hours, a suitable time can be selected based on requirements. The type of solvent used for extraction and the method of concentration can be methods commonly used in the art. For example, extraction can use at least one of dichloromethane, ethyl acetate, and chloroform; concentration can be completed by rotary evaporation at 40–70°C.

[0041] Based on the above technical solutions, the design concept and principle of this invention lies in using amorphous carbon materials to catalyze the process of deuterium replacing hydrogen atoms in deuteration reactions, and providing a method for synthesizing polydeuterated aromatic compounds. Simultaneously, the carbon material catalyst is modified using additives containing N and O elements to adjust the catalytic activity of oxygen-containing functional groups, thereby improving the deuteration efficiency. The D species on the catalyst can undergo a hydrogen-deuterium exchange reaction with the CH on the substrate benzene ring, synthesizing polydeuterated aromatic compounds as the reaction liquid flows through the catalyst. Based on this, this invention uses biomass as a catalyst precursor and prepares a carbon-based catalyst by adding additives to adjust the catalytic activity of oxygen-containing functional groups. Since the catalyst precursor is inexpensive biomass, the cost is significantly lower than that of precious metals, and its type is a non-metallic catalyst, fundamentally avoiding the problems of metal agglomeration and deactivation, as well as the risk of metal shedding. This catalyst can directly obtain active deuterium species from a deuterium source (such as deuterated water) without passing through metallic hydrogen species, thus exhibiting weaker reducing power and achieving better functional group compatibility. The deuteration reaction dominated by amorphous carbon materials is clean and has low separation cost; its precursor is biomass and its main component is amorphous carbon, which can directly participate in the carbon cycle of the environment after disposal, making it highly environmentally friendly and in line with the theme of green chemistry.

[0042] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0043] This invention provides an application of amorphous carbon materials in deuteration reactions. By adjusting the catalytic activity of oxygen-containing functional groups, the efficiency of deuteration is improved, showing promising application prospects.

[0044] This invention provides a method for synthesizing polydeuterated aromatic compounds, which uses amorphous carbon materials to catalyze the polydeuteration reaction. This method has the advantages of low cost, stable and efficient reaction, good energy group compatibility, and environmental friendliness. Attached Figure Description

[0045] Figure 1 X-ray photoelectron spectroscopy (XPS) for CAI10325(a) and CAI10326(b);

[0046] Figure 2 X-ray diffraction (XRD) patterns of CAI10325 before and after use;

[0047] Figure 3 The thermogravimetric analysis (TGA) curves for CAI10325. Detailed Implementation

[0048] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0049] Example 1

[0050] This embodiment prepared a series of amorphous carbon materials for the synthesis of deuterated aromatic compounds.

[0051] The preparation method of amorphous carbon material (CAI10056) is as follows:

[0052] (1) Add 100g ethyl acetate, 6g starch, 6g lignin and 0.2g melamine to a flask, and place the flask in a 60℃ oil bath and heat and mix for 12h.

[0053] (2) Ethyl acetate was separated by rotary evaporation (60℃, 8h) and dried in an oven for 2d to obtain a dried mixture sample;

[0054] (3) The mixture sample was placed in a tube furnace and calcined (600℃, 5h) using nitrogen as the carrier gas to obtain amorphous carbon material, which was denoted as CAI10056.

[0055] The preparation method of amorphous carbon material (CAI10072) is as follows:

[0056] (1) Add 50g ethanol, 50g ethyl acetate, 5g cellulose, 5g lignin and 1g 2-phenylpyridine to a flask, and heat the flask in an oil bath at 60℃ for 16h.

[0057] (2) Ethanol and ethyl acetate were separated by rotary evaporation (60℃, 8h) and dried in an oven for 2d to obtain a dried mixture sample;

[0058] (3) The mixture sample was placed in a tube furnace and calcined (1100℃, 5h) using nitrogen as the carrier gas to obtain amorphous carbon material, which was denoted as CAI10072.

[0059] The preparation method of amorphous carbon material (CAI10325) is as follows:

[0060] (1) Add 25g ethanol, 25g propanol, 50g ethyl acetate, 2g cellulose, 8g lignin, and 3g 1,3,5-trimethoxybenzene to a flask, and place the flask in an oil bath at 60℃ and heat and mix for 16h.

[0061] (2) Ethanol, propanol and ethyl acetate were separated by rotary evaporation (60℃, 8h) and dried in an oven for 2d to obtain a dried mixture sample;

[0062] (3) The mixture sample was placed in a tube furnace and calcined (800℃, 1h) using nitrogen as the carrier gas to obtain amorphous carbon material, denoted as CAI10325.

[0063] The preparation method of amorphous carbon material (CAI10326) is as follows:

[0064] (1) Add 25g ethanol, 25g propanol, 50g ethyl acetate, 2g cellulose, 8g lignin, and 3g 1,3,5-trimethoxybenzene to a flask, and place the flask in an oil bath at 60℃ and heat and mix for 12h.

[0065] (2) Ethanol, propanol and ethyl acetate were separated by rotary evaporation (60℃, 8h) and dried in an oven for 2d to obtain a dried mixture sample;

[0066] (3) The mixture sample was placed in a tube furnace and calcined (800℃, 1h) using a hydrogen-argon mixture (1:9, v / v) as the carrier gas to obtain an amorphous carbon material, denoted as CAI10326.

[0067] In the CAI series, CAI10325 is the standard catalyst. CAI10326 improves its performance on some substrates by increasing the concentration of hydroxyl groups in the catalyst through a reducing gas atmosphere provided by a hydrogen-argon mixture during calcination. CAI10056 and CAI10072 are nitrogen-doped catalysts. Nitrogen-doped catalysts are used when the substrate contains almost no heteroatoms (e.g., naphthalene, anthracene, etc.). The specific type of catalyst is determined through experimental results. A possible reason is that nitrogen doping can increase the adsorption efficiency of the substrate.

[0068] CAI10325 and CAI10326 were characterized by X-ray photoelectron spectroscopy, and the results are as follows: Figure 1 As shown. Figure 1 This indicates that amorphous carbon materials contain a wide range of O-containing functional groups, mainly C=O, CO, and a small amount of OC=O.

[0069] The properties of CAI10325 before and after 100 hours of reaction were studied by X-ray diffraction. The test results are shown below. Figure 2 The red line represents the area before the reaction, and the black line represents the area after the reaction. Figure 2 This indicates that the catalyst mainly exists in the form of amorphous carbon, and the catalyst structure has good stability, with its basic morphological characteristics remaining unchanged after catalysis.

[0070] CAI10325 was characterized by thermogravimetric analysis, and the results are as follows: Figure 3 As shown. Figure 3 This indicates that the catalyst maintains good stability at 600℃. The mass loss below 100℃ is mainly due to air adsorption.

[0071] Example 2

[0072] The aromatic compound used in this embodiment is naphthalene, and its structural formula is as follows:

[0073]

[0074] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0075] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10072 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 500℃.

[0076] 0.1 g naphthalene, 10 g tetrahydrofuran, and 1 g deuterium water were pumped into the reaction tube using a liquid phase pump; during this process, the reaction system was purged with nitrogen gas, and the products were collected in a reaction flask after the apparatus.

[0077] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 0.097 g of product, with a yield of 97% and a total deuteration rate of 98%.

[0078] 1 HNMR(399MHz,Chloroform-d)δ7.67(d,0.12H),7.32(d,0.12H).HRMS(ESI)136.1128.

[0079] Example 3

[0080] The aromatic compound used in this embodiment is quinoline, and its structural formula is as follows:

[0081]

[0082] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0083] 0.1g of quartz wool, 0.1g of quartz sand, and 0.2g of CAI10326 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 450℃.

[0084] 0.1 g quinoline, 5 g acetonitrile, 5 g acetone, and 1 g deuterium water were pumped into the reaction tube using a liquid phase pump. During the process, the reaction system was purged with nitrogen gas, and the product was collected in a reaction flask after the apparatus.

[0085] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 0.092 g of product, with a yield of 92% and a total deuteration rate of 98%.

[0086] 1 HNMR(399MHz,Chloroform-d)δ8.81(d,0.02H),8.05(d,0.02H),8.00(d,0.03H),7.6 8(dd,0.01H)7.61(dd,0.01H),7.43(m,0.03H)7.26(m,0.02H).HRMS(ESI)136.1017.

[0087] Example 4

[0088] The aromatic compound used in this embodiment is N,N-dimethylaniline, whose structural formula is as follows:

[0089]

[0090] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0091] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 350℃.

[0092] 0.3 g N,N-dimethylaniline, 10 g tetrahydrofuran, and 1 g deuterium water were pumped into the reaction tube using a liquid-phase pump. During the reaction, the reaction system was purged with nitrogen, and the products were collected in a reaction flask after the apparatus was installed.

[0093] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 0.285 g of product, with a yield of 95% and a total deuteration rate of 95%.

[0094] 1 HNMR(399MHz,Chloroform-d)δ7.19(dd,0.05H),6.77(m,0.10H),4.52(s,0.03H).HRMS(ESI)100.1021.

[0095] Example 5

[0096] The aromatic compound used in this embodiment is anthracene, and its structural formula is as follows:

[0097]

[0098] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0099] 0.1g of quartz wool, 0.1g of quartz sand, and 0.2g of CAI10056 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 450℃.

[0100] 0.5 g anthracene, 10 g dimethyl sulfoxide, and 1 g deuterium water were pumped into the reaction tube using a liquid phase pump. During the process, the reaction system was purged with nitrogen, and the products were collected in a reaction flask after the apparatus.

[0101] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 0.495 g of product, with a yield of 99% and a total deuteration rate of 98%.

[0102] 1 HNMR(399MHz,Chloroform-d)δ8.93(dd,0.05H),8.21(m,0.04H),7.84(s,0.03H),7.71(d,0.10H).HRMS(ESI)188.1409.

[0103] Example 6

[0104] The aromatic compound used in this embodiment is benzothiophene, whose structural formula is as follows:

[0105]

[0106] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0107] 0.1g of quartz wool, 0.1g of quartz sand, and 6g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 450℃.

[0108] 100g of benzothiophene, 1000g of dimethyl sulfoxide, and 100g of deuterium water were pumped into the reaction tube using a liquid phase pump; during the process, the reaction system was purged with nitrogen gas, and the products were collected in a reaction flask after the apparatus.

[0109] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 82g of product, with a yield of 82% and a total deuteration rate of 96%.

[0110] 1HNMR(399MHz,Chloroform-d)δ7.86(d,0.05H),7.78(m,0.04H),7.39(s,0.03H),7.29(d,0.10H).HRMS(ESI)140.0567.

[0111] Example 7

[0112] The aromatic compound used in this embodiment is benzofuran, and its structural formula is as follows:

[0113]

[0114] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0115] 0.1g of quartz wool, 0.1g of quartz sand, and 3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 500℃.

[0116] 20g of benzofuran, 200g of dimethyl sulfoxide, and 20g of deuterium water were pumped into the reaction tube using a liquid phase pump. During the process, the reaction system was purged with nitrogen gas, and the products were collected in a reaction flask after the apparatus was installed.

[0117] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 17g of product, with a yield of 86% and a total deuteration rate of 94%.

[0118] 1 HNMR(399MHz,Chloroform-d)δ7.52(d,0.05H),7.49(m,0.10H),7.32(s,0.03H),7.29(d,0.08H).HRMS(ESI)124.0795

[0119] Example 8

[0120] The aromatic compound used in this embodiment is 2-bromonaphthalene, and its structural formula is as follows:

[0121]

[0122] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0123] 0.1g of quartz wool, 0.1g of quartz sand, and 2g of CAI10072 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 350℃.

[0124] 10 g of 2-bromonaphthalene, 100 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid phase pump. During the process, the reaction system was purged with nitrogen gas, and the products were collected in a reaction flask after the apparatus was installed.

[0125] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 9.1 g of product, with a yield of 91% and a total deuteration rate of 87%.

[0126] 1 HNMR(399MHz,Chloroform-d)δ8.67(s,0.15H),8.01(m,0.21H),7.81(m,0.10H),7.43(m,0.12H).HRMS(ESI)213.0171.

[0127] Example 9

[0128] The aromatic compound used in this embodiment is nitrobenzene, and its structural formula is as follows:

[0129]

[0130] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0131] 0.1g of quartz wool, 0.1g of quartz sand, and 5g of CAI10056 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 350℃.

[0132] 50g of nitrobenzene, 500g of dimethyl sulfoxide, and 50g of deuterium water were pumped into the reaction tube using a liquid phase pump. During this process, the reaction system was purged with an oxygen-nitrogen mixture (5% oxygen content), and the products were collected in a reaction flask after the apparatus.

[0133] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 48g of product, with a yield of 95% and a total deuteration rate of 99%.

[0134] 1 HNMR(399MHz,Chloroform-d)δ8.19(d,0.01H),7.53(m,0.02H).HRMS(ESI)128.0634.

[0135] Example 10

[0136] The aromatic compound used in this embodiment is 2-(2,4-difluorophenyl)pyridine, whose structural formula is as follows:

[0137]

[0138] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0139] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 400℃.

[0140] 0.5 g of 2-(2,4-difluorophenyl)pyridine, 20 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid-phase pump. During the reaction, the reaction system was purged with nitrogen gas, and the products were collected in a reaction flask after the apparatus was installed.

[0141] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 0.48 g of product, with a yield of 96% and a total deuteration rate of 99%.

[0142] 1 HNMR(399MHz,Chloroform-d)δ8.37(s,0.01H),8.12(m,0.02H),7.38(m,0.02H),7.02(m,0.02H),6.50(s,0.01H).HRMS(ESI)198.0991.

[0143] Example 11

[0144] The aromatic compound used in this embodiment is 5-methoxyindole, whose structural formula is as follows:

[0145]

[0146] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0147] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 400℃.

[0148] 0.5 g of 5-methoxyindole, 20 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid-phase pump. During the reaction, the reaction system was purged with nitrogen, and the products were collected in a reaction flask after the apparatus was installed.

[0149] After collection, the product was extracted and separated using dichloromethane, and concentrated by rotary evaporation to obtain 0.49 g of product, with a yield of 99% and a total deuteration rate (in the aromatic ring) of 99%. Among them, NH (peak at δ 11.21) is an active H, which undergoes hydrogen-deuterium exchange with water during extraction, and therefore is mainly H rather than its isotope D.

[0150] 1HNMR(399MHz,Chloroform-d)δ11.21(s,0.86H),7.61(m,0.01H),7.11(m,0.02H),6.54(m,0.02H),3.72(s,1.02H).HRMS(ESI)152.0996.

[0151] Example 12

[0152] The aromatic compound used in this embodiment is methyl 5-indolecarboxylate, whose structural formula is as follows:

[0153]

[0154] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0155] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 400℃.

[0156] 0.5 g of methyl 5-indolecarboxylate, 20 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid-phase pump. During the reaction, the reaction system was purged with an oxygen-nitrogen mixture. The products were collected in a reaction flask after the apparatus was installed.

[0157] After collection, the product was extracted and separated using dichloromethane, and concentrated by rotary evaporation to obtain 0.49 g of product, with a yield of 99% and a total deuteration rate (in the aromatic ring) of 99%. Among them, NH (peak at δ 11.05) is an active H, which undergoes hydrogen-deuterium exchange with water during extraction, so it is mainly H rather than its isotope D.

[0158] 1 HNMR(399MHz,Chloroform-d)δ11.05(s,0.87H),9.05(s,0.01H),8.21(m,0.01H),7.24(m,0.02H),6.41(m,0.02H),4.12(s,1.52H).HRMS(ESI)180.0942.

[0159] Example 13

[0160] The aromatic compound used in this embodiment is ethyl 5-indolecarboxylate, whose structural formula is as follows:

[0161]

[0162] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0163] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 400℃.

[0164] 0.5 g of ethyl 5-indolecarboxylate, 20 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid-phase pump. During the reaction, the reaction system was purged with an oxygen-nitrogen mixture. The products were collected in a reaction flask after the apparatus was installed.

[0165] After collection, the product was extracted and separated using dichloromethane, and concentrated by rotary evaporation to obtain 0.48 g of product, with a yield of 97% and a total deuteration rate (in the aromatic ring) of 98%. Among them, NH (peak at δ 11.03) is an active H, which undergoes hydrogen-deuterium exchange with water during extraction, so it is mainly H rather than its isotope D.

[0166] 1 HNMR(399MHz,Chloroform-d)δ11.03(s,0.86H),9.01(s,0.01H),8.22(d,0.04H),7. 68(m,0.02H),6.71(s,0.02H),4.12(s,1.22H),1.30(s,1.49H).HRMS(ESI)194.1111.

[0167] Example 14

[0168] The aromatic compound used in this embodiment is 5-indolecarboxaldehyde, whose structural formula is as follows:

[0169]

[0170] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0171] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 400℃.

[0172] 0.5 g of 5-indolecarboxaldehyde, 20 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid-phase pump. During the process, the reaction system was purged with an oxygen-nitrogen mixture, and the products were collected in a reaction flask after the apparatus was installed.

[0173] After collection, the product was extracted and separated using dichloromethane, and concentrated by rotary evaporation to obtain 0.48 g of product, with a yield of 96% and a total deuteration rate (in the aromatic ring) of 98%. Among them, NH (peak at δ 11.05) is an active H, which undergoes hydrogen-deuterium exchange with water during extraction, so it is mainly H rather than its isotope D.

[0174] 1HNMR(399MHz,Chloroform-d)δ11.05(s,0.86H),10.01(s,0.21H),8.67(s,0.01H),8. 03(d,0.02H),7.67(m,0.01H),7.05(d,0.01H),6.73(m,0.01H).HRMS(ESI)150.0839.

[0175] Example 15

[0176] The aromatic compound used in this embodiment is 6-methylquinoline, whose structural formula is as follows:

[0177]

[0178] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0179] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 400℃.

[0180] 0.5 g of 6-methylquinoline, 20 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid-phase pump. During the process, the reaction system was purged with an oxygen-nitrogen mixture, and the products were collected in a reaction flask after the apparatus.

[0181] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 0.48 g of product, with a yield of 96% and a total deuteration rate (in the aromatic ring) of 98%.

[0182] 1 HNMR(399MHz,Chloroform-d)δ8.76(d,0.01H),7.84(m,0.03H),7.55(m,0.02H),7.30(m,0.02H),2.43(s,1.21H).HRMS(ESI)149.1101.

[0183] Example 16

[0184] The aromatic compound used in this embodiment is 4,4'-di-tert-butyl-2,2'-dipyridine, whose structural formula is as follows:

[0185]

[0186] The method for synthesizing polydeuterated aromatic compounds comprises the following steps:

[0187] 0.1g of quartz wool, 0.1g of quartz sand, and 0.3g of CAI10325 were packed into the reaction tube in sequence, and the reaction tube was placed in a multiphase reaction apparatus at a reaction temperature of 400℃.

[0188] 0.5 g of 4,4'-di-tert-butyl-2,2'-dipyridine, 20 g of tetrahydrofuran, and 10 g of deuterium water were pumped into the reaction tube using a liquid phase pump. During the reaction, the reaction system was purged with an oxygen-nitrogen mixture. The products were collected in a reaction flask after the apparatus.

[0189] After collection, the product was extracted and separated using dichloromethane and concentrated by rotary evaporation to obtain 0.48 g of product, with a yield of 96% and a total deuteration rate (in the aromatic ring) of 97%.

[0190] 1 HNMR(399MHz,Chloroform-d)δ8.85(s,0.03H),8.43(m,0.02H),7.23(m,0.02H),1.43(s,8.24H).HRMS(ESI)274.2315.

[0191] The above embodiments illustrate the process of using amorphous carbon materials to catalyze polydeuteration reactions and synthesize polydeuterated aromatic compounds according to the present invention. The catalyst uses biomass as a catalyst precursor, and the catalytic activity of oxygen-containing functional groups is adjusted by adding additives to prepare a carbon-based catalyst. The deuterium species on the catalyst undergoes a hydrogen-deuterium exchange reaction with the CH group on the substrate benzene ring. Combined with modification of the carbon catalyst, the catalytic activity of the oxygen-containing functional groups is adjusted, thereby improving the deuteration efficiency. Since the catalyst precursor is inexpensive biomass, the cost is significantly lower than that of precious metals. Furthermore, as a non-metallic catalyst, it fundamentally avoids the problems of metal agglomeration and deactivation, as well as the risk of metal shedding. This catalyst can directly obtain active deuterium species from a deuterium source (such as deuterated water) without passing through metallic hydrogen species, thus exhibiting weaker reducing power and achieving better functional group compatibility. The deuteration reaction dominated by amorphous carbon materials is clean and has low separation cost. Its precursor is biomass and its main component is amorphous carbon. After disposal, it can directly participate in the carbon cycle of the environment, which is highly environmentally friendly and matches the theme of green chemistry, showing good application prospects.

[0192] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. An application of an amorphous carbon material, characterized in that, It can be used as a catalyst to catalyze the substitution of hydrogen atoms with deuterium in the deuteration reaction of aromatic compounds; The method for preparing the amorphous carbon material includes the following steps: (1) Biomass, additives and solvents are mixed at a certain temperature; (2) Separate the solvent to obtain a mixture; (3) The mixture is calcined to obtain amorphous carbon material; In step (1), the biomass includes at least one of starch, lignin, cellulose, sodium alginate, and chitosan; the additive includes at least one of melamine, 2-phenylpyridine, 1,3,5-trimethoxybenzene, and 1,2,4-triazole. The method of application includes the following steps: at a temperature of 350~500 °C, a reaction liquid consisting of aromatic compounds, deuterium water and solvent flows through an amorphous carbon material under a reaction carrier gas atmosphere, and reacts to form polydeuterated aromatic compounds.

2. The application according to claim 1, characterized in that: In step (1), the mass ratio of the solvent, biomass, and additive is (10~1000):(1~10):(0.1~3); the mixing temperature is 40~80 ℃, and the time is 2~16 h.

3. The application according to claim 1, characterized in that: In step (3), the carrier gas for calcination is one of nitrogen, argon, or a mixture of hydrogen and argon; the calcination temperature is 600~1200 ℃ and the time is 1~5 h.

4. The application according to claim 1, characterized in that: The aromatic compound is an aromatic molecule whose structural formula contains an n-membered cyclic large conjugated system, where n is 5 or 6.

5. The application according to claim 1, characterized in that: The n-membered cyclic macroconjugated system of the aromatic compound includes an n-membered carbon ring macroconjugated system or an n-membered heterocyclic macroconjugated system in which at least one atom of N, S, or O is substituted. Aromatic compounds contain one or more functional groups, including at least one of the following: C1-C4 alkyl, amino, dimethylamino, hydroxyl, C1-C3 alkoxy, aldehyde, C1-C2 ester, fluorine, chlorine, bromine, iodine, sulfonyl, and nitro.

6. The application according to claim 1, characterized in that: The aromatic compounds include at least one of naphthalene, quinoline, N,N-dimethylaniline, anthracene, benzothiophene, benzofuran, 2-bromonaphthalene, nitrobenzene, 2-(2,4-difluorophenyl)pyridine, 5-methoxyindole, methyl 5-indolecarboxylate, ethyl 5-indolecarboxylate, 5-indolecarboxaldehyde, 6-methylquinoline, and 4,4'-di-tert-butyl-2,2'-dipyridine.

7. The application according to claim 1, characterized in that: The mass ratio of the aromatic compound to the solvent and deuterium water is (0.01~1):(10~100):(0.01~1); the mass ratio of the amorphous carbon material to the aromatic compound is (0.01~10):

1.

8. The application according to claim 1, characterized in that: The carrier gas is at least one of an inert gas, a hydrogen-argon mixture, and an oxygen-nitrogen mixture; the inert gas includes at least one of nitrogen and argon.

9. The application according to claim 1, characterized in that: The flow rate of the reaction liquid through the amorphous carbon material is 10~100 mL / min.

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