Method for producing deuterated aromatic compound

Abstract

Provided is a method for producing a deuterated aromatic compound with good production efficiency. The method for producing a deuterated aromatic compound deuterates an aromatic compound raw material, the method including an irradiation step for irradiating a mixture containing the aromatic compound raw material, a deuterium source, and an acid catalyst with microwaves while heating and holding the mixture at a heating temperature of 50ºC or higher.

Description

Method for producing a deuterated aromatic compound

[0001] The present disclosure relates to a method for producing a deuterated aromatic compound.

[0002] The deuterated aromatic compound means a compound in which hydrogen in the aromatic ring of the aromatic compound raw material is replaced by deuterium. In recent years, deuterated aromatic compounds are expected as materials that can be used in various fields of industries such as pharmaceuticals, high-functional materials, organic electroluminescence (EL) devices (hereinafter also referred to as "organic EL devices").

[0003] By the way, deuterium (D) is a stable isotope of hydrogen (H), and it is known that the reaction rate of the C-D bond is 6 to 10 times slower than that of the C-H bond. By introducing deuterium into an aromatic compound as a material for optical / electronic devices, particularly for organic EL devices, it is possible to improve the light emission efficiency and durability (stability) of the device. For example, various reports have been made on the manufacturing technology related to the deuteration reaction of aromatic compounds.

[0004] In Non-Patent Document 1, coronene, heavy water, and a Pd / C catalyst are placed in an autoclave and carried out at a temperature of 260 ° C and an internal pressure in the range of 4 to 5 MPa for 30 hours, whereby coronene-d 12 (deuteration rate: 84%) is produced.

[0005] The Journal of Physical Chemistry C, 2021, 125(48), p. 26986-26998

[0006] However, in the method for producing a deuterated aromatic compound described in Non-Patent Document 1, even when a metal catalyst is used for a condensed-ring aromatic compound such as coronene during the deuteration reaction, a long reaction time of 30 hours is required.

[0007] Thus, it can be said that the manufacturing method described in Non-Patent Document 1 still has room for improvement over the prior art from the viewpoint of manufacturing efficiency.

[0008] Therefore, one of the objects of the embodiments of the present invention is to provide a method for producing a deuterated aromatic compound with good production efficiency.

[0009] The present inventors conducted diligent research to solve the above problems and found that the production efficiency of deuterated aromatic compounds can be improved by including a step of heating and maintaining a mixture containing an aromatic compound raw material, a deuterium source, and an acid catalyst at a heating temperature of 50°C or higher while irradiating the mixture with microwaves. This led to the embodiments of the present invention. The present invention is illustrated below.

[0010] [1] A method for producing a deuterated aromatic compound by deuterating an aromatic compound raw material, comprising the step of heating and holding a mixture containing the aromatic compound raw material, a deuterium source, and an acid catalyst at a heating temperature of 50°C or higher while irradiating the mixture with microwaves. [2] The method for producing a deuterated aromatic compound according to claim 1, wherein the aromatic compound raw material is a low molecular weight compound, and in the step, the mixture is heated and held for 1 minute or more and 24 hours or less. [3] The method for producing a deuterated aromatic compound according to claim 1, wherein the aromatic compound raw material is a high molecular weight compound, and in the step, the mixture is heated and held for 1 minute or more and 100 hours or less. [4] The method for producing a deuterated aromatic compound according to [1] to [3], wherein the deuterium source is a deuterium compound having an aromatic ring. [5] The method for producing a deuterated aromatic compound according to any one of [1] to [4], wherein the deuterium source comprises one or more selected from benzene-d6, chlorobenzene-d5, and toluene-d7. [6] A method for producing a deuterated aromatic compound according to any one of [1] to [5], wherein the aromatic compound raw material comprises one or more selected from polycyclic aromatic carbon compounds, condensed polycyclic aromatic compounds, polycyclic heteroaromatic compounds, condensed polycyclic heteroaromatic compounds, and polymers containing aromatic compounds. [7] The aromatic compound raw material comprises naphthalene, anthracene, fluorene, phenanthrene, pyrene, perylene, coronene, biphenyl, diphenylmethane, carbazole, benzothienobenzothiophene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, 1-methylnaphthalene, 2-methylnaphthalene, 2-aminoanthracene, 9-methylanthracene, 2-chloroanthracene, 2-methylanthracene, 1,4-diphenylbenzene A method for producing any of the deuterated aromatic compounds [1] to [6], comprising one or more selected from the group consisting of , triphenylamine, 1-naphthol, 1-methoxynaphthalene, 1-chloronaphthalene, 1,2-bis(3-bromothiophen-2-yl)ethane-1,2-dione, 2,4,6-tri(9H-carbazole-9-yl)-5-chloroisophthalonitrile, and 2,4,5,6-tetra(9H-carbazole-9-yl)isophthalonitrile.[8] The method for producing a deuterated aromatic compound according to any one of [1] to [7], wherein the pKa of the acid catalyst is 2.0 or less. [9] The method for producing a deuterated aromatic compound according to any one of [1] to [8], wherein the acid catalyst contains one or more selected from trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, and sulfuric acid.

[0011] According to an embodiment of the present invention, a method for producing a deuterated aromatic compound with good production efficiency can be provided.

[0012] For the aromatic compound raw material of Example 1 1 It is an H-NMR (400 MHz) spectrogram. For the aromatic compound raw material of Example 1 13 It is a C-NMR (100 MHz) spectrogram. For the deuterated aromatic compound of Example 1 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 1 13 It is a C-NMR (100 MHz) spectrogram. For the aromatic compound raw material of Example 2 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 2 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 3 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 4 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 5 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 6 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 7 1 It is an H-NMR (400 MHz) spectrogram. For the aromatic compound raw material of Example 8 1 It is an H-NMR (400 MHz) spectrogram. For the deuterated aromatic compound of Example 8 1 It is an H-NMR (400 MHz) spectrogram. For the aromatic compound raw material of Example 9 1This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 9. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 10. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 10. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 11. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 11. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 12. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 12. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 13. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 13. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 14. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 14. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 15. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 15. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 16. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 16. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 17. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 17. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 18. 1This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 18. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 19. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 19. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 20. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 20. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 21. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 21. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 22. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 22. 1 This is a 1H-NMR (400 MHz) spectrum gram of the aromatic compound raw material of Example 23. 1 This is a 1H-NMR (400 MHz) spectral gram of the deuterated aromatic compound of Example 23. 1 This is an H-NMR (400 MHz) spectral gram.

[0013] Preferred embodiments of the present invention will be described below, but the present invention should not be construed as being limited thereto, and various modifications and improvements can be made based on the knowledge of those skilled in the art without departing from the spirit of the invention. The multiple components disclosed in each embodiment can be combined in appropriate ways to form various inventions. For example, some components may be removed from all the components shown in each embodiment, or components from different embodiments may be combined in appropriate ways. In this specification, "mixture" is a concept that includes a mixed liquid. In this specification, when the aromatic compound raw material is an aromatic polymer, "molecular weight" means the number average molecular weight.

[0014] [Method for producing deuterated aromatic compounds] The method for producing deuterated aromatic compounds according to the present invention involves producing a deuterated aromatic compound by deuterating an aromatic compound raw material.

[0015] The present invention relates to a method for producing a deuterated aromatic compound, which includes the step of heating and maintaining a mixture containing an aromatic compound raw material, a deuterium source, and an acid catalyst at a predetermined temperature while irradiating the mixture with microwaves. According to this method, the aromatic ring of the aromatic compound raw material is activated by the acid catalyst, and the hydrogen in the aromatic ring is replaced by deuterium from the deuterium source. At this time, by heating at a predetermined temperature while irradiating with microwaves, the mixture can be heated directly, rapidly, and uniformly. As a result, the rate at which the hydrogen in the aromatic ring of the aromatic compound raw material in the mixture is replaced by deuterium from the deuterium source is accelerated. That is, in one embodiment, a deuterated aromatic compound can be obtained with a good deuteration rate and yield even if the heating and holding time is relatively short. Furthermore, in one embodiment, unlike the production method described in Non-Patent Document 1, which is the prior art, a deuterated aromatic compound can be produced from an undeuterated aromatic compound even if the mixture containing the aromatic compound raw material, the deuterium source, and the acid catalyst does not contain a metal catalyst such as a Pd / C catalyst.

[0016] There are no particular limitations on the means of irradiating with microwaves, but a commercially available microwave synthesizer can be used.

[0017] (Heating Temperature) From the viewpoint of improving the deuteration rate, the heating temperature should be 50°C or higher as the lower limit, preferably 60°C or higher, and more preferably 80°C or higher. Also, from the viewpoint of production costs, the heating temperature should be typically 200°C or lower as the upper limit. Here, the heating temperature is considered to be the temperature of the mixture.

[0018] (Heating and Holding Time) The heating and holding time can be appropriately adjusted not only by the heating temperature but also by the molecular weight of the aromatic compound raw material. Below are some examples of heating and holding times based on the molecular weight of the aromatic compound raw material. When the aromatic compound raw material is a low molecular weight compound, the heating and holding time is, for example, in the range of 1 minute to 24 hours. Here, the lower limit of the heating and holding time is, for example, 0.2 hours or more, 0.5 hours or more, or 1 hour or more. The upper limit of the heating and holding time is, for example, 12 hours or less, 6 hours or less, or 2 hours or less. In this specification, "low molecular weight compound" means a compound with a molecular weight of 500 or less. Next, when the aromatic compound raw material is a high molecular weight compound, the heating and holding time is, for example, in the range of 1 minute to 100 hours. Here, the lower limit of the heating and holding time is, for example, 0.2 hours or more, 0.5 hours or more, or 1 hour or more. In this specification, "high molecular weight compound" means a compound with a molecular weight greater than 500. The start and end times of the heating and holding time are defined as follows. In other words, when microwave irradiation is performed at a heating temperature of 50°C or higher, the start of the heating and holding time is when the heating temperature reaches 50°C or higher, and the end of the heating and holding time is when heating and microwave irradiation are stopped and the heating temperature falls below 50°C.

[0019] (Aromatic Compound Raw Materials) The aromatic compound raw materials are aromatic compounds that have not been deuterated. From the viewpoint of improving the functionality of electronic devices, etc., it is preferable that the aromatic compound raw materials include one or more selected from polycyclic aromatic carbon compounds, condensed polycyclic aromatic compounds, polycyclic heteroaromatic compounds, condensed polycyclic heteroaromatic compounds, and polymers containing aromatic compounds. Examples of compounds of polycyclic aromatic carbon compounds, condensed polycyclic aromatic compounds, polycyclic heteroaromatic compounds, condensed polycyclic heteroaromatic compounds, and polymers containing aromatics are given below.

[0020] Specific examples of polycyclic aromatic carbon compounds include biphenyl, diphenylmethane, 4-phenyl-1,1'-biphenyl, 4-{[1,1'-biphenyl]-4-yl}-1,1'-biphenyl, and 3,4-biphenyl-1,1'-biphenyl.

[0021] Specific examples of condensed polycyclic aromatic compounds include naphthalene, anthracene, tetracene, pentacene, hexacene, pyrene, perylene, coronene, fluorene, phenanthrene, 1,2-benzoanthracene, triphenylene, 1-methylnaphthalene, 2-methylnaphthalene, 1-naphthol, 1-methoxynaphthalene, and 1-chloronaphthalene.

[0022] Specific examples of polycyclic heteroaromatic compounds include 1,2-bis(3-bromothiophen-2-yl)ethane-1,2-dione.

[0023] Specific examples of condensed polycyclic heteroaromatic compounds include quinoline, isoquinoline, indole, indazole, 1,2-benzoisoxazole, 1,2-benzoisothiazole, benzimidazole, benzoxazole, benzothiazole, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, phenantholidine, pteridine, purine, carbazole, benzothienobenzothiophene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, 2,4,6-tri(9H-carbazole-9-yl)-5-chloroisophthalonitrile, and 2,4,5,6-tetrakis(9H-carbazole-9-yl)isophthalonitrile.

[0024] Specific examples of polymers containing aromatic compounds include polystyrene, polythiophene, polypyrrole, polycarbonate, and poly(4-vinylpyridine).

[0025] In one embodiment, the aromatic compound raw material preferably includes one or more compounds selected from the group consisting of naphthalene, anthracene, fluorene, phenanthrene, pyrene, perylene, coronene, biphenyl, diphenylmethane, carbazole, benzothienobenzothiophene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, 1-methylnaphthalene, 2-methylnaphthalene, 2-aminoanthracene, 9-methylanthracene, 2-chloroanthracene, 2-methylanthracene, 1,4-diphenylbenzene, triphenylamine, 1-naphthol, 1-methoxynaphthalene, 1-chloronaphthalene, 1,2-bis(3-bromothiophen-2-yl)ethane-1,2-dione, 2,4,6-tri(9H-carbazole-9-yl)-5-chloroisophthalonitrile, and 2,4,5,6-tetra(9H-carbazole-9-yl)isophthalonitrile.

[0026] (Deuterium Source) While known deuterium compounds can be used as the deuterium source, it is preferable that the deuterium source be a deuterium compound having an aromatic ring, from the viewpoint of further improving the deuteration rate. Among these, it is more preferable that the deuterium source contains one or more selected from benzene-d6, chlorobenzene-d5, and toluene-d7. It is also possible to combine two or more of the above compounds to form the deuterium source.

[0027] (Acid Catalyst) The acid catalyst can activate the aromatic ring of the aromatic compound raw material. The acid catalyst is not particularly limited as long as it is a known compound, but from the viewpoint of further activating the aromatic ring of the aromatic compound raw material, it is preferable that it be a strong acid. More specifically, the pKa of the acid catalyst is preferably 2.0 or less, more preferably 0 or less, and even more preferably -4.0 or less. Among these, it is preferable that the acid catalyst contains one or more selected from trifluoromethanesulfonic acid (pKa value: -13), perfluorobutanesulfonic acid (pKa value: -5.5), and sulfuric acid (pKa value: -3.0).

[0028] (Mixing ratio) The mixing ratio of the aromatic compound raw material, the deuterium source, and the acid catalyst can be adjusted as appropriate. As an example of such a mixing ratio, when the aromatic compound raw material is set to 1, the molar ratio of the deuterium source is 5 to 5000 and the molar ratio of the acid catalyst is 0.1 to 2.0.

[0029] (Deuteration Rate) The deuteration rate of the deuterated aromatic compound obtained by deuterating the aromatic compound raw material is, for example, 15% or more, for example, 50% or more, for example, 80% or more, for example, 90% or more. The deuteration rate is, 1 In 1H-NMR, the extent to which residual peaks originating from the aromatic compound raw material have disappeared can be calculated by comparing the integral values ​​of the peaks originating from the internal standard substance and the peaks originating from the aromatic compound raw material. Examples of such internal standards include cyclohexane, chloroform, and dimethyl sulfoxide.

[0030] After the reaction is stopped in the above step, the reaction mixture containing the deuterated aromatic compound can be purified by known chemical methods. This will yield the purified deuterated aromatic compound.

[0031] The present invention will be further described in detail by the following synthesis examples and embodiments, but these are not intended to limit the present invention and may be modified without departing from the scope of the present invention.

[0032] [Production of Deuterated Aromatic Compounds] The production of deuterated aromatic compounds will be described in Examples 1 to 23 and Comparative Examples 1 to 2. The materials and chemical analysis equipment used in these examples will also be described in detail.

[0033] The materials used in this embodiment are as follows: (Aromatic compound raw materials)・Coronene: Tokyo Chemical Industry Co., Ltd. ・Anthracene: Tokyo Chemical Industry Co., Ltd. ・Fluorene: Tokyo Chemical Industry Co., Ltd. ・9-Methylanthracene: Tokyo Chemical Industry Co., Ltd. ・2-Aminoanthracene: Tokyo Chemical Industry Co., Ltd. ・2-Chloroanthracene: Tokyo Chemical Industry Co., Ltd. ・2-Methylanthracene: Fujifilm Wako Pure Chemical Corporation ・Biphenyl: Tokyo Chemical Industry Co., Ltd. ・1,4-Diphenylbenzene: Tokyo Chemical Industry Co., Ltd. ・Carbazole: Tokyo Chemical Industry Co., Ltd. ・Dibenzofuran: Tokyo Chemical Industry Co., Ltd. ・Dibenzothiophene: Tokyo Chemical Industry Co., Ltd. ・Benzothienobenzothiophene: Tokyo Chemical Industry Co., Ltd. ・Triphenylamine: Tokyo Chemical Industry Co., Ltd. ・9-Phenylcarbazole: Tokyo Chemical Industry Co., Ltd. ・Polystyrene (PS-600, number average molecular weight Mn: 533, polydispersity PDI: 1.14): Sigma-Aldrich ・Polystyrene (PS-10000, number average molecular weight Mn: 9.19 × 10) 3Polydispersion PDI: 1.04): Sigma-Aldrich GmbH; 2,4,5,6-tetra(9H-carbazole-9-yl) isophthalonitrile (4-CzCIIPN): Fujifilm Wako Pure Chemical Corporation (Deuterium source) Deuterated benzene (benzene-d6): Kanto Chemical Co., Ltd. Deuterated toluene (toluene-d7): Sigma-Aldrich GmbH; Deuterated chlorobenzene (chlorobenzene-d5): Sigma-Aldrich GmbH (Acid catalyst) Trifluoromethanesulfonic acid: Tokyo Chemical Industry Co., Ltd. Perfluoromethanesulfonic acid: Fujifilm Wako Pure Chemical Corporation Acetic acid: Fujifilm Wako Pure Chemical Corporation Sulfuric acid: Fujifilm Wako Pure Chemical Corporation (NMR solvent) • Chloroform-d1 (containing 0.05 wt% TMS): Tokyo Chemical Industry Co., Ltd. • Dimethyl sulfoxide-d6 (containing 0.05 wt% TMS): Tokyo Chemical Industry Co., Ltd. (elution solvent for chromatography) • Hexane: Fujifilm Wako Pure Chemical Corporation • Chloroform: Tokyo Chemical Industry Co., Ltd. (washing solution) • Tripotassium phosphate: Kanto Chemical Co., Ltd. (internal standard substance) • Dimethyl sulfoxide: Tokyo Chemical Industry Co., Ltd. • Chloroform: Tokyo Chemical Industry Co., Ltd. • Cyclohexane: Fujifilm Wako Pure Chemical Corporation

[0034] The chemical analysis equipment used in this embodiment is as follows: (Nuclear Magnetic Resonance Spectrometer (NMR)) 1 H-NMR (measurement frequency 400 MHz) and 13 C-NMR (measurement frequency 100 MHz) spectra were recorded using a Bruker AVANCE III 400 (Bruker Japan Co., Ltd.), expressed in ppm relative to TMS (tetramethylsilane).

[0035] <Example 1> A magnetic stirring bar was placed in a 2 mL vial. Next, coronene (50.0 mg, 0.17 mmol, 1.0 equivalent) and benzene-d6 (1390 mg, 16.6 mmol, 100 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (25.0 mg, 0.167 mmol, 1.0 equivalent) was added to the vial. Note that the coronene did not dissolve in the trifluoromethanesulfonic acid.

[0036] Next, the vial was placed in a microwave synthesis apparatus (Biotage® Initiator+, manufactured by Biotage Japan Co., Ltd.). Then, while stirring, the mixture was heated and maintained at 180°C for 2 hours, and microwaves were irradiated onto the mixture through the vial.

[0037] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (35 mg, 0.17 mmol, 1.0 equivalent) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The organic phase after extraction was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (chloroform) to obtain a yellow purified product.

[0038] Next, NMR measurements were performed to confirm the deuterated ratio. Cyclohexane was used as the internal standard in the NMR measurement.

[0039] Coronen-d 12 The deuteration rate and yield were determined, respectively. The deuteration rate, calculated using cyclohexane as the internal standard for hydrogenated coronene, was 96%. At this time, the deuteration rate was 1 In 1H-NMR, the extent to which the residual peak derived from coronene disappeared was calculated by comparing the integral values ​​of the peak derived from cyclohexane (the internal standard) and the peak derived from coronene. The yield was 85%.

[0040] The general outline of the above reaction is shown below.

[0041]

[0042] (Koronen-d) 12 (Identification of) 1 H-NMR (chloroform-d6): δ 8.94 (br signal, residual H) 13 13C-NMR (chloroform-d6): δ 127.7, 125.1, 121.6

[0043] <Comparative Example 1> A magnetic stirring bar was placed in a 2 mL vial. Next, coronene (100 mg, 0.333 mmol, 1 equivalent) and benzene-d6 (560 mg, 6.659 mmol, 20 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (8 mg, 0.068 mmol, 0.17 equivalents) was added to the vial.

[0044] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 40°C for 1 hour, and microwaves were irradiated through the vial.

[0045] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (5 mL). Tripotassium phosphate (12 mg, 56 μmol) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The organic phase after extraction was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (chloroform) to obtain a yellow purified product.

[0046] Next, to confirm the deuteration rate, NMR measurements were performed using chloroform-d1 solvent. In this NMR measurement, cyclohexane was used as the internal standard.

[0047] Coronen-d 12 The deuteration rate and yield were determined. The deuteration rate was 4%, and the yield was 75%.

[0048] The general outline of the above reaction is shown below.

[0049]

[0050] <Comparative Example 2> A stirring bar was placed in a 2 mL vial. Next, coronene (100 mg, 0.333 mmol, 1 equivalent) and benzene-d6 (560 mg, 6.659 mmol, 20 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (8 mg, 0.057 mmol, 0.17 equivalents) was added to the vial.

[0051] Next, the vial was placed inside the heating device. Then, it was heated and maintained at 150°C for 1 hour while stirring.

[0052] Next, the heating was stopped, and after returning to room temperature, the vial was removed from the heating device. The reaction mixture in the vial was transferred to a beaker and quenched with water (5 mL). Tripotassium phosphate (14 mg, 0.068 mmol, 0.2 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (chloroform) to obtain a yellow purified product.

[0053] Next, to confirm the deuteration rate, NMR measurements were performed using chloroform-d1 solvent. In this NMR measurement, cyclohexane was used as the internal standard.

[0054] Coronen-d 12 The deuteration rate and yield were determined. The deuteration rate was 14%, and the yield was 72%.

[0055] The general outline of the above reaction is shown below.

[0056]

[0057] <Example 2> A magnetic stirring bar was placed in a 2 mL vial. Next, anthracene (40.0 mg, 0.22 mmol, 1 equivalent) and benzene-d6 (2.0 mL, 22.44 mmol, 100 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (10 μL, 0.11 mmol, 0.5 equivalents) was added to the vial.

[0058] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 150°C for 0.5 hours, and microwaves were irradiated through the vial.

[0059] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (47.6 mg, 0.22 mmol, 1.0 equivalent) was added to the resulting reaction mixture, and the mixture was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel chromatography (hexane) to obtain a yellowish-white purified product.

[0060] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0061] Anthracene-d 10 The deuteration rate and yield were determined. The deuteration rate was 95-97%, and the yield was 89%.

[0062] The general outline of the above reaction is shown below.

[0063]

[0064] (Anthracene-d) 10 (Identification of) 1 ¹H-NMR (chloroform-d1): δ 8.42 (br signal, residual H), 8.02-7.98 (br signal, residual H), 7.48-7.44 (br signal, residual H) 13 13C-NMR (chloroform-d1): δ 131.5, 127.7, 125.8, 124.9

[0065] <Example 3> The same procedure as in Example 2 was followed, except that benzene-d6 was changed to toluene-d8 (2260 mg, 224.4 mmol, 100 equivalents) as the deuterium source, and anthracene-d 10 We obtained anthracene-d.10 The deuteration rate was 97% (Da: 97%, Db: 97%, Dc: 97%).

[0066] The general outline of the above reaction is shown below.

[0067]

[0068] <Example 4> The procedure was carried out in the same manner as in Example 2, except that benzene-d6 was changed to chlorobenzene-d5 (2640 mg, 22.4 mmol, 100 equivalents) as the deuterium source, and anthracene-d 10 We obtained anthracene-d. 10 The deuteration rates were 78-80% (Da: 78%, Db: 80%, Dc: 80%).

[0069] The general outline of the above reaction is shown below.

[0070]

[0071] <Example 5> The procedure was carried out in the same manner as in Example 2, except that trifluoromethanesulfonic acid was changed to perfluorobutanesulfonic acid (28.1 mg, 0.11 mmol, 0.5 equivalents) as the acid catalyst, and anthracene-d 10 Anthracene-d was obtained. 10 The deuteration rates were 92% to 93% (Da: 92%, Db: 93%, Dc: 92%).

[0072] The general outline of the above reaction is shown below.

[0073]

[0074] <Example 6> The procedure was carried out in the same manner as in Example 2, except that trifluoromethanesulfonic acid was changed to acetic acid (6.7 mg, 0.11 mmol, 0.5 equivalents) as the acid catalyst, and anthracene-d was prepared. 10 Anthracene-d was obtained. 10 The deuteration rates were 21% to 22% (Da: 21%, Db: 21%, Dc: 22%).

[0075] The general outline of the above reaction is shown below.

[0076]

[0077] <Example 7> The procedure was carried out in the same manner as in Example 2, except that trifluoromethanesulfonic acid was changed to sulfuric acid (11.0 mg, 0.11 mmol, 0.5 equivalents) as the acid catalyst, and anthracene-d was prepared. 10 Anthracene-d was obtained. 10 The deuteration rates were 17% to 18% (Da: 17%, Db: 18%, Dc: 18%).

[0078] The general outline of the above reaction is shown below.

[0079]

[0080] <Example 8> A magnetic stirring bar was placed in a 2 mL vial. Then, fluorene (35.0 mg, 0.21 mmol, 1.0 equivalent) and benzene-d6 (1900 mg, 22.6 mmol, 107.1 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (15.8 mg, 0.11 mmol, 0.5 equivalents) was added to the vial.

[0081] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 150°C for 0.5 hours, and microwaves were irradiated through the vial.

[0082] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (22 mg, 0.11 mmol, 0.5 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash column chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a light beige purified product.

[0083] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0084] The deuteration rate and yield of fluorene-d8 were determined. The deuteration rate ranged from 84% to 97%, and the yield was 87%.

[0085] The general outline of the above reaction is shown below.

[0086]

[0087] (Identification of fluorene-d8) 1 ¹H-NMR (deuterated chloroform): δ 7.80–7.78 (br signal, residual H), 7.55–7.53 (br signal, residual H), 7.39–7.35 (br signal, residual H), 7.32–7.28 (br signal, residual H)

[0088] <Example 9> A magnetic stirring bar was placed in a 2 mL vial. Next, 9-methylanthracene (40.0 mg, 0.21 mmol, 1.0 equivalent) and benzene-d6 (1900 mg, 22.6 mmol, 108.7 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (15.6 mg, 0.10 mmol, 0.5 equivalents) was added to the vial.

[0089] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 150°C for 0.5 hours, and microwaves were irradiated through the vial.

[0090] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (22 mg, 0.11 mmol, 0.5 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash column chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a white purified product.

[0091] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0092] The deuteration rate and yield of 9-methylanthracene-d9 were determined. The deuteration rate ranged from 88% to 97%, and the yield was 82%.

[0093] The general outline of the above reaction is shown below.

[0094]

[0095] (Identification of 9-methylanthracene-d9) 1 H-NMR (chloroform-d1): δ8.35 (br signal, residual residual H), 8.29 (br signal, residual residual H), 8.01 (br signal, residual H), 7.51 (br signal, residual H), 7.46 (br signal, residual H)

[0096] <Example 10> A magnetic stirring bar was placed in a 2 mL vial. Next, 2-aminoanthracene (40.0 mg, 0.21 mmol, 1.0 equivalent) and benzene-d6 (1900 mg, 22.6 mmol, 109.2 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (62.1 mg, 0.41 mmol, 2.0 equivalents) was added to the vial.

[0097] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 150°C for 0.5 hours, and microwaves were irradiated through the vial.

[0098] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (132 mg, 0.62 mmol, 3.0 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash column chromatography (chloroform) to obtain a white purified product.

[0099] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0100] The deuteration rate and yield of 2-aminoanthracene-d9 were determined. The deuteration rate ranged from 14% to 60%, and the yield was 32%.

[0101] The general outline of the above reaction is shown below.

[0102]

[0103] (Identification of 2-aminoanthracene-d9) 1 H-NMR (chloroform-d1): δ8.28 (br signal, residual residual H), 8.03 (br signal, residual residual H), 7.92-7.86 (br signal, residual H), 7.83-7.81 (br signal, residual H), 7.39-7.35 (br signal, residual H), 7.31-7.27 (br signal, residual H), 7.06-7.03 (br signal, residual H), 6.90 (br signal, residual H)

[0104] <Example 11> A magnetic stirring bar was placed in a 2 mL vial. Next, 2-chloroanthracene (50.0 mg, 0.24 mmol, 1.0 equivalent) and benzene-d6 (1978 mg, 23.5 mmol, 100.0 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (17.6 mg, 0.12 mmol, 0.5 equivalents) was added to the vial.

[0105] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 150°C for 0.5 hours, and microwaves were irradiated through the vial.

[0106] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (100 mg, 0.47 mmol, 2.0 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash column chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a pale yellow purified product.

[0107] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0108] The deuteration rate and yield of 2-chloroanthracene-d9 were determined. The deuteration rate ranged from 28% to 68%, and the yield was 92%.

[0109] The general outline of the above reaction is shown below.

[0110]

[0111] (Identification of 2-chloroanthracene-d9) 1H-NMR (chloroform-d1): δ8.41 (br signal, residual residual H), 8.33 (br signal, residual residual H), 8.01-7.94 (br signal, residual H), 7.49 (br signal, residual H), 7.39-7.37 (br signal, residual H)

[0112] <Example 12> A magnetic stirring bar was placed in a 2 mL vial. Next, 2-methylanthracene (45.0 mg, 0.23 mmol, 1.0 equivalent) and benzene-d6 (1969 mg, 23.4 mmol, 100.0 equivalent) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (35.1 mg, 0.23 mmol, 1.0 equivalent) was added to the vial.

[0113] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 150°C for 0.5 hours, and microwaves were irradiated through the vial.

[0114] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (99 mg, 0.47 mmol, 2.0 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash column chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a brown purified product.

[0115] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0116] The deuteration rate and yield of 2-methylanthracene-d9 were determined. The deuteration rate ranged from 93% to 99%, and the yield was 47%.

[0117] The general outline of the above reaction is shown below.

[0118]

[0119] (Identification of 2-methylanthracene-d9) 1 H-NMR (chloroform-d1): δ8.38 (br signal, residual residual H), 8.32 (br signal, residual residual H), 7.98 (br signal, residual H), 7.91 (br signal, residual H), 7.76 (br signal, residual H), 7.43-7.42 (br signal, residual H), 7.30 (br signal, residual H)

[0120] <Example 13> A magnetic stirring bar was placed in a 2 mL vial. Then, biphenyl (35.0 mg, 0.227 mmol, 1.0 equivalent) and benzene-d6 (1910 mg, 22.7 mmol, 100.0 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (170.3 mg, 1.14 mmol, 5.0 equivalents) was added to the vial.

[0121] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 180°C for 2 hours, and microwaves were irradiated through the vial.

[0122] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (361 mg, 1.70 mmol, 7.5 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a colorless purified product.

[0123] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0124] biphenyl-d 10 The deuteration rate and yield were determined. The deuteration rate was 97% to 98%, and the yield was 68%.

[0125] The general outline of the above reaction is shown below.

[0126]

[0127] (Biphenyl-d 10 (Identification of) 1 ¹H-NMR (chloroform-d1): δ 7.61–7.58 (br signal, residual H), 7.46–7.42 (br signal, residual H), 7.37–7.32 (br signal, residual H)

[0128] <Example 14> A magnetic stirring bar was placed in a 2 mL vial. Then, 1,4-diphenylbenzene (50.0 mg, 0.217 mmol, 1.0 equivalent) and benzene-d6 (1826 mg, 21.7 mmol, 100.0 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (162.9 mg, 1.09 mmol, 5.0 equivalents) was added to the vial.

[0129] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 150°C for 0.5 hours, and microwaves were irradiated through the vial.

[0130] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (5 mL). Tripotassium phosphate (346 mg, 1.63 mmol, 7.5 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a colorless purified product.

[0131] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0132] 1,4-diphenylbenzene-d 14 The deuteration rate and yield were determined. The deuteration rate was 97-98%, and the yield was 95%.

[0133] The general outline of the above reaction is shown below.

[0134]

[0135] (1,4-diphenylbenzene-d 14 (Identification of) 1 H-NMR (chloroform-d1): δ7.68 (br signal, residual H), 7.65 (br signal, residual H), 7.46 (br signal, residual H), 7.36 (br signal, residual H)

[0136] <Example 15> A magnetic stirring bar was placed in a 2 mL vial. Next, carbazole (50.0 mg, 0.30 mmol, 1.0 equivalent) and benzene-d6 (1900 mg, 22.4 mmol, 75.0 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (224.42 mg, 1.50 mmol, 5 equivalents) was added to the vial.

[0137] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 180°C for 2 hours, and microwaves were irradiated through the vial.

[0138] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (444 mg, 2.09 mmol, 7.0 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel chromatography (hexane / chloroform = 1:1 (volume ratio)) to obtain a pale gray purified product.

[0139] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0140] The deuteration rate and yield of carbazole-d8 were determined. The deuteration rate ranged from 94% to 97%, and the yield was 97%.

[0141] The general outline of the above reaction is shown below.

[0142]

[0143] (Identification of carbazole-d8) 1 H-NMR (dimethyl sulfoxide-d6): δ8.12-8.10 (br signal, residual H), 7.50-7.48 (br signal, residual H), 7.41-7.37 (br signal, residual H), 7.17-7.14 (br signal, residual H)

[0144] <Example 16> A magnetic stirring bar was placed in a 2 mL vial. Then, dibenzofuran (35.0 mg, 0.21 mmol, 1 equivalent) and benzene-d6 (1925 mg, 22.88 mmol, 110 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (156.1 mg, 1.04 mmol, 5.0 equivalents) was added to the vial.

[0145] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 180°C for 2 hours, and microwaves were irradiated through the vial.

[0146] Next, the microwave irradiation was stopped, and after returning to room temperature, the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (309 mg, 1.46 mmol, 7.0 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extract was dried over magnesium sulfate and filtered. The resulting filtrate was heated under reduced pressure and dried to obtain the residue. Next, the residue was purified by silica gel flash chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a white purified product.

[0147] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0148] The deuteration rate and yield of dibenzofuran-d8 were determined. The deuteration rate was 97-98%, and the yield was 99%.

[0149]

[0150] (Identification of dibenzofuran-d8) 1 ¹H-NMR (deuterated chloroform): δ 8.12–8.10 (br signal, residual H), 7.50–7.48 (br signal, residual H), 7.41–7.37 (br signal, residual H), 7.17–7.14 (br signal, residual H)

[0151] <Example 17> A magnetic stirring bar was placed in a 2 mL vial. Then, dibenzothiophene (40.0 mg, 0.22 mmol, 1 equivalent) and benzene-d6 (1826 mg, 22.8 mmol, 105 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (32.6 mg, 0.22 mmol, 1.0 equivalent) was added to the vial.

[0152] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 180°C for 2 hours, and microwaves were irradiated through the vial.

[0153] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (55 mg, 0.26 mmol, 1.2 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extract was dried over magnesium sulfate and filtered. The resulting filtrate was heated under reduced pressure and dried to obtain the residue. Next, the residue was purified by silica gel flash chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a colorless purified product.

[0154] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0155] The deuteration rate and yield of dibenzothiophene-d8 were determined. The deuteration rate was 98%, and the yield was 92%.

[0156]

[0157] (Identification of dibenzothiophene-d8) 1 ¹H-NMR (chloroform-d1): δ 8.16 (br signal, residual H), 7.86 (br signal, residual H), 7.46 (br signal, residual H)

[0158] <Example 18> A magnetic stirring bar was placed in a 2 mL vial. Next, benzothienobenzothiophene (50.0 mg, 0.21 mmol, 1.0 equivalent) and benzene-d6 (1750 mg, 20.8 mmol, 100 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (31.2 mg, 0.21 mmol, 1.0 equivalent) was added to the vial.

[0159] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 180°C for 2 hours, and microwaves were irradiated through the vial.

[0160] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (44 mg, 0.21 mmol, 1.0 equivalent) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a colorless purified product.

[0161] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0162] The deuteration rate and yield of benzothienobenzothiophene-d8 were determined. The deuteration rate was 98%, and the yield was 89%.

[0163] The general outline of the above reaction is shown below.

[0164]

[0165] (Identification of benzothienobenzothiophene-d8) 1H-NMR (chloroform-d1): δ7.93 (br signal, residual H), 7.89 (br signal, residual H), 7.46 (br signal, residual H), 7.41 (br signal, residual H)

[0166] <Example 19> A magnetic stirring bar was placed in a 2 mL vial. Then, triphenylamine (50.0 mg, 0.20 mmol, 1.0 equivalent) and benzene-d6 (1717 mg, 20.4 mmol, 100 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (153.1 mg, 1.02 mmol, 5.0 equivalents) was added to the vial.

[0167] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 200°C for 2 hours, and microwaves were irradiated through the vial.

[0168] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (325 mg, 1.53 mmol, 7.5 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (hexane / chloroform = 10:1 (volume ratio)) to obtain a colorless purified product.

[0169] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0170] Triphenylamine-d 15 The deuteration rate and yield were determined. The deuteration rate was 95-96%, and the yield was 68%.

[0171] The general outline of the above reaction is shown below.

[0172]

[0173] (Triphenylamine-d 15 (Identification of) 1 H-NMR (chloroform-d1): δ7.93 (br signal, residual H), 7.89 (br signal, residual H), 7.46 (br signal, residual H), 7.41 (br signal, residual H)

[0174] <Example 20> A magnetic stirring bar was placed in a 2 mL vial. Next, 9-phenylcarbazole (50.0 mg, 0.21 mmol, 1.0 equivalent) and benzene-d6 (1733 mg, 20.6 mmol, 100 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (308.7 mg, 2.06 mmol, 10.0 equivalents) was added to the vial.

[0175] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 210°C for 2 hours, and microwaves were irradiated through the vial.

[0176] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (655 mg, 3.09 mmol, 15.0 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel chromatography (hexane) to obtain a colorless purified product.

[0177] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0178] 9-Phenylcarbazole-d 13 The deuteration rate and yield were determined. The deuteration rate ranged from 80% to 98%, and the yield was 49%.

[0179] The outline of the above reaction is shown below.

[0180]

[0181] (Identification of 9-phenylcarbazole-d 13 ) 1 H-NMR (dimethyl sulfoxide-d6): δ 7.69 (br signal, residual H), 7.64 (br signal, residual H), 7.55 (br signal, residual H), 7.45 - 7.43 (br signal, residual H), 7.39 (br signal, residual H), 7.30 (br signal, residual H)

[0182] <Example 21> A magnetic stir bar was placed in a 2 mL vial. Next, PS-600, which is polystyrene (50.0 mg, 0.08 mmol, 1 equivalent) and benzene-d6 (1380 mg, 16.4 mmol, 200 equivalents) were added into the vial. Then, trifluoromethanesulfonic acid (24.72 mg, 0.17 mmol, 2.0 equivalents) was added into the vial under an argon atmosphere.

[0183] Next, the vial was placed in a microwave synthesizer. Then, while stirring, the mixture was irradiated with microwaves through the vial while heating and holding at 180 °C for 8 hours.

[0184] Next, the irradiation of microwaves was stopped, and after returning to room temperature, the vial was taken out from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (87 mg, 0.41 mmol, 5.0 mol%) was added to the obtained reaction mixture, and it was washed and extracted with chloroform. The organic phase after extraction was dried with magnesium sulfate and filtered. The obtained filtrate was removed under reduced pressure to obtain a residue. Next, the residue was purified by silica gel chromatography (hexane / chloroform = 1:1 (volume ratio)) to obtain a colorless purified product.

[0185] Next, NMR measurement was performed to confirm the deuteration rate. At this time, dimethyl sulfoxide was used as an internal standard substance in the NMR measurement.

[0186] The deuteration rate and yield of deuterated polystyrene were determined. The deuteration rate was 100%, and the yield was 69%.

[0187] The general outline of the above reaction is shown below.

[0188]

[0189] (Identification of deuterated polystyrene) 1 H-NMR (chloroform-d1): δ 7.23-6.73 (br signal, residual H)

[0190] <Example 22> A magnetic stirring bar was placed in a 2 mL vial. Next, PS-10000 (30.0 mg, 0.005 mmol, 1.0 equivalent), which is polystyrene, and toluene-d7 (1890 mg, 22.5 mmol, 4500 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (30.0 mg, 0.20 mmol, 40.0 equivalents) was added to the vial.

[0191] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 180°C for 8 hours, and microwaves were irradiated through the vial.

[0192] Next, the microwave irradiation was stopped, and after returning to room temperature, the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (64 mg, 0.20 mmol, 60 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The solvent was removed under reduced pressure to obtain a pale gray residue.

[0193] Next, NMR measurements were performed to confirm the deuterated ratio. Dimethyl sulfoxide was used as the internal standard in the NMR measurement.

[0194] The deuteration rate and yield of deuterated polystyrene were determined. The deuteration rate was 98%, and the yield was 91%.

[0195] The general outline of the above reaction is shown below.

[0196]

[0197] (Identification of deuterated polystyrene) 1 1H-NMR (dimethyl sulfoxide-d6): δ 7.18-6.98 (br signal, residual H)

[0198] <Example 23> A magnetic stirring bar was placed in a 2 mL vial. Next, 2,4,5,6-tetra(9H-carbazole-9-yl) isophthalonitrile (40.0 mg, 0.05 mmol, 1.0 equivalent) and benzene-d6 (1900 mg, 22.6 mmol, 444 equivalents) were added to the vial. Then, under an argon atmosphere, trifluoromethanesulfonic acid (38.0 mg, 0.25 mmol, 5.0 equivalents) was added to the vial.

[0199] Next, the vial was placed inside the microwave synthesis apparatus. Then, while stirring, the mixture was heated and maintained at 190°C for 6 hours, and microwaves were irradiated through the vial.

[0200] Next, the microwave irradiation was stopped and the mixture returned to room temperature, after which the vial was removed from the microwave synthesizer. The reaction mixture in the vial was transferred to a beaker and quenched with water (10 mL). Tripotassium phosphate (100 mg, 0.47 mmol, 9.2 equivalents) was added to the resulting reaction mixture, and it was washed with chloroform and extracted. The extracted organic phase was dried over magnesium sulfate and filtered. The resulting filtrate was removed under reduced pressure to obtain the residue. Next, the residue was purified by silica gel flash chromatography (hexane / chloroform = 1:2 (volume ratio)) to obtain a yellow purified product.

[0201] Next, NMR measurements were performed to confirm the deuterated ratio. Chloroform was used as the internal standard in the NMR measurement.

[0202] 2,4,5,6-Tetra(9H-carbazole-9-yl)isophthalonitrile-d 32 The deuteration rate and yield were determined. The deuteration rate was 98% to 100%, and the yield was 76%.

[0203] The general outline of the above reaction is shown below.

[0204]

[0205] (2,4,5,6-tetra(9H-carbazole-9-yl)isophthalonitrile-d 32 (Identification of) 1 H-NMR (dimethyl sulfoxide-d6): δ8.22 (br signal, residual H), 7.71-7.68 (br signal, residual H), 7.52 (br signal, residual H), 7.33 (br signal, residual H), 7.22 (br signal, residual H), 7.09-6.99 (br signal, residual H), 6.83-6.82 (br signal, residual H), 6.62 (br signal, residual H)

[0206] (Discussion based on examples) In Example 1, a mixture containing an aromatic compound raw material, a deuterium source, and an acid catalyst was heated and maintained at a heating temperature of 50°C or higher while being irradiated with microwaves, resulting in a deuteration rate of 96% for coronene-d8. In Example 1, it was confirmed that a deuterated aromatic compound could be obtained in a short reaction time. On the other hand, in Comparative Example 1, compared to Example 1, the deuteration rate of coronene-d8 was low at 4% because the temperature was heated and maintained at 40°C during the deuteration reaction. In Comparative Example 2, compared to Example 1, the deuteration rate of coronene-d8 was low at 14% because microwave irradiation was not performed. Therefore, in Examples 1 to 23, it can be said that the production efficiency of deuterated aromatic compounds can be improved by heating and maintaining a mixture containing an aromatic compound raw material, a deuterium source, and an acid catalyst at a heating temperature of 50°C or higher while being irradiated with microwaves during the deuteration reaction. Furthermore, it is presumed that using the deuterated aromatic compounds obtained in this way can extend the lifespan of electronic devices such as liquid crystal displays compared to using non-deuterated aromatic compounds.

Claims

1. A method for producing a deuterated aromatic compound by deuterating an aromatic compound raw material, comprising the step of heating and maintaining a mixture containing the aromatic compound raw material, a deuterium source, and an acid catalyst at a heating temperature of 50°C or higher, while irradiating the mixture with microwaves.

2. The method for producing a deuterated aromatic compound according to claim 1, wherein the aromatic compound raw material is a low molecular weight compound, and in the step, heating and holding for 1 minute or more and 24 hours or less.

3. The method for producing a deuterated aromatic compound according to claim 1, wherein the aromatic compound raw material is a polymer compound, and in the step, the heating and holding is performed for 1 minute or more and 100 hours or less.

4. The method for producing a deuterated aromatic compound according to any one of claims 1 to 3, wherein the deuterium source is a deuterium compound having an aromatic ring.

5. The method for producing a deuterated aromatic compound according to any one of claims 1 to 4, wherein the deuterium source comprises one or more selected from benzene-d6, chlorobenzene-d5, and toluene-d7.

6. The method for producing a deuterated aromatic compound according to any one of claims 1 to 5, wherein the aromatic compound raw material comprises one or more selected from polymers containing polycyclic aromatic carbon compounds, condensed polycyclic aromatic compounds, polycyclic heteroaromatic compounds, condensed polycyclic heteroaromatic compounds, and aromatic compounds.

7. The aromatic compound raw materials include naphthalene, anthracene, fluorene, phenanthrene, pyrene, perylene, coronene, biphenyl, diphenylmethane, carbazole, benzothienobenzothiophene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, 1-methylnaphthalene, 2-methylnaphthalene, 2-aminoanthracene, 9-methylanthracene, 2-chloroanthracene, 2-methylanthracene, 1,4-diphenylbenzene, A method for producing a deuterated aromatic compound according to any one of claims 1 to 6, comprising one or more selected from the group consisting of triphenylamine, 1-naphthol, 1-methoxynaphthalene, 1-chloronaphthalene, 1,2-bis(3-bromothiophen-2-yl)ethane-1,2-dione, 2,4,6-tri(9H-carbazole-9-yl)-5-chloroisophthalonitrile, and 2,4,5,6-tetra(9H-carbazole-9-yl)isophthalonitrile.

8. The method for producing a deuterated aromatic compound according to any one of claims 1 to 7, wherein the pKa of the acid catalyst is 2.0 or less.

9. The method for producing a deuterated aromatic compound according to any one of claims 1 to 8, wherein the acid catalyst comprises one or more selected from trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, and sulfuric acid.

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