CN106631649B - Method for preparing deuterated chemical and deuterated chemical - Google Patents
Method for preparing deuterated chemical and deuterated chemical Download PDFInfo
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Abstract
The invention relates to a method for preparing a deuterated chemical and the deuterated chemical, which comprises the following steps: carrying out deuterium addition reaction on the halide and a deuterium source under the catalysis of a light source and a photocatalyst to prepare a deuterated chemical; wherein the deuterium source is deuterium water or a deuterated solvent, and the reaction temperature is between-80 ℃ and 150 ℃. The invention uses more environment-friendly and cheap deuterium water or deuterium reagent as a deuterium source to replace deuterium gas, and uses Ru, In metal catalyst, organic dye, inorganic and organic semiconductor nano material and the like as a photocatalyst to realize deuterolysis of halogenated matters under the action of photocatalysis, thereby providing accurate and controllable preparation of a series of deuterium chemicals. Compared with the traditional deuteration reaction, the method has higher selectivity, milder reaction conditions, wider substrate adaptability and more economic applicability, and is expected to be applied to large-scale production of deuterated chemicals.
Description
Technical Field
The invention relates to the field of photocatalytic preparation of chemicals, in particular to a method for preparing a deuterated chemical and the deuterated chemical.
Background
The deuterated chemicals are special compounds and have important application in the fields of reaction mechanism research, kinetics, drug metabolism, biological structure determination and the like. Heavy isotopes of hydrogen are typically introduced into target compounds by multi-step synthesis, in which a variety of labeled chemical reagents will be involved. Deuterium-catalyzed exchange reactions are another attractive strategy, and often only one step is required to introduce the isotope into the target molecule. The great challenge facing this approach is the selective control of deuterium exchange and the versatility of the functional groups. Most processes involve high temperature, high pressure (deuterium is the source of deuterium), strong acids, strong bases or expensive metal catalysts. Compared with a hydrogen-deuterium catalytic exchange reaction, the deuterium addition reaction (or deuterium decomposition reaction) has wider functional group adaptability and higher selectivity, and different deuterium addition (or deuterium decomposition) catalysts are selected, so that site-directed deuteration on different functional sites can be realized, and the deuterium-adding catalyst can be used as an ideal deuteration strategy. However, the application range of the deuterium addition reaction is greatly limited due to the deuterium gas required for the deuterium addition reaction (or deuterolysis reaction), and the high temperature, high pressure and noble metal catalyst.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention provides a method for preparing a deuterated chemical and a deuterated chemical, which aims to solve the problem that the prior deuterium addition reaction (or deuterolysis reaction) requires deuterium gas, and high temperature, high pressure and noble metal catalyst, which greatly limits the application range of the deuterium addition reaction.
The technical scheme of the invention is as follows:
a method of preparing a deuterated chemical, comprising the steps of: carrying out deuterium addition reaction on the halide and a deuterium source (the molar mass ratio of the deuterium source to the halide is more than 1:1) under the catalysis of a light source and a photocatalyst to prepare a deuterated chemical;
wherein the deuterium source is deuterium water or a deuterated solvent, and the reaction temperature is between-80 ℃ and 150 ℃;
the reaction formula is shown as the following formula (1):
in the formula (1), R is a carbon atom having a substituent, X is a halogen atom, and D is a deuterium atom.
The method for preparing the deuterated chemical comprises the step of preparing a deuterated chemical, wherein the deuterated solvent is deuterated methanol, deuterated ethanol or deuterated acetone.
The method for preparing the deuterated chemical comprises the step of preparing a photocatalyst, wherein the photocatalyst is a catalyst containing Ru and Ir, an organic dye catalyst, an inorganic semiconductor catalyst or an organic semiconductor catalyst.
The method for preparing the deuterated chemical, wherein the inorganic semiconductor catalyst is TiO2CdS or CdSe.
The method for preparing the deuterated chemicals comprises the step of irradiating the deuterium chemical with light of any wave band of 200-2000 nm.
A deuterated chemical, wherein the deuterated chemical is prepared by the method for preparing the deuterated chemical.
The deuterated chemical is characterized by having a structure represented by the following formula (2):
in the formula (2), R1～R5Each is one of a hydrogen atom, a deuterium atom, a halogen atom, a substituted carbon atom, a substituted oxygen atom, a substituted sulfur atom, a substituted nitrogen atom, and a substituted phosphorus atom.
The deuterated chemical is characterized by having a structure represented by the following formula (3):
in the formula (3), R1～R3Are respectively hydrogen atom, deuterium atom, halogen atomA carbon atom having a substituent, an oxygen atom having a substituent, a sulfur atom having a substituent, a nitrogen atom having a substituent, a phosphorus atom having a substituent.
The deuterated chemical is characterized by having a structure represented by the following formula (4):
in the formula (4), R is one of a hydrogen atom, a deuterium atom, a halogen atom, a substituted carbon atom, a substituted oxygen atom, a substituted sulfur atom, a substituted nitrogen atom, and a substituted phosphorus atom.
The deuterated chemical is one of structures represented by the following formulas (5) to (7):
in the formulae (5) to (7), R1～R3Each is one of a hydrogen atom, a deuterium atom, a halogen atom, a substituted carbon atom, a substituted oxygen atom, a substituted sulfur atom, a substituted nitrogen atom, and a substituted phosphorus atom.
Has the advantages that: the invention uses deuterium water or deuterated solvent to replace deuterium gas as a deuterium source, and realizes mild deuterium addition (deuterolysis) reaction.
Drawings
Fig. 1 is a transmission electron microscope image of the photocatalyst cadmium selenide prepared in the embodiment 1 of the present invention.
Fig. 2 is a graph of the performance of photolyzing water to produce hydrogen of the photocatalyst cadmium selenide prepared in example 1 of the present invention.
Fig. 3 is an X-ray photoelectron spectrum of the cadmium component of the photocatalyst cadmium selenide prepared in example 1 of the present invention.
FIG. 4 is an X-ray photoelectron spectrum of the selenium component of the photocatalyst cadmium selenide prepared in example 1 of the present invention.
Detailed Description
The present invention provides a method for preparing a deuterated chemical and a deuterated chemical, and the following further detailed description is provided to make the purpose, technical scheme and effect of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preferred embodiment of a method for preparing a deuterated chemical, which comprises the following steps: carrying out deuterium addition reaction on the halide and a deuterium source (the molar mass ratio of the deuterium source to the halide is more than 1:1) under the catalysis of a light source and a photocatalyst to prepare a deuterated chemical;
wherein the deuterium source is deuterium water or a deuterated solvent, and the reaction temperature is between-80 ℃ and 150 ℃ (such as 20 ℃, 60 ℃ or 120 ℃);
the reaction formula is shown as the following formula (1):
in the formula (1), R is a carbon atom having an optional substituent, X is a halogen atom, and D is a deuterium atom.
The deuterium source in the invention is deuterium water or a deuterated solvent, and the deuterated solvent can be, but not limited to, deuterated methanol, deuterated ethanol, deuterated acetone or the like.
The photocatalyst of the present invention may be, but is not limited to, a Ru, Ir containing catalyst, an organic dye catalyst, an inorganic semiconductor catalyst, or an organic semiconductor catalyst (e.g., g-C)3N4). Preferably, the inorganic semiconductor catalyst may be, but is not limited to, TiO2CdS or CdSe.
The light source of the invention can be, but is not limited to, light with any wave band of 200-2000 nm (such as 1000 nm).
The invention uses deuterium water or a deuterated solvent to replace deuterium gas as a deuterium source, realizes mild deuterium addition (deuterolysis) reaction, and effectively solves the problems that expensive deuterium gas is used in the existing deuterium addition reaction, the reaction conditions are harsh, and the like, and the problems of no practicability are solved.
The invention also provides a deuterated chemical, wherein the deuterated chemical is prepared by adopting the method for preparing the deuterated chemical.
The structural formula of the deuterated chemical is R-D; wherein R is a carbon atom having an optional substituent, and D is a deuterium atom.
Based on the structural formula of the deuterated chemical, the deuterated chemical can have a structure shown in the following formula (2):
in the formula (2), R1～R5May be one of a hydrogen atom, a deuterium atom, a halogen atom, any carbon atom having a substituent, an oxygen atom having a substituent, a sulfur atom having a substituent, a nitrogen atom having a substituent, a phosphorus atom having a substituent, respectively.
Based on the structural formula of the deuterated chemical, the deuterated chemical can have a structure shown in the following formula (3):
in the formula (3), R1～R3May be one of a hydrogen atom, a deuterium atom, a halogen atom, any carbon atom having a substituent, an oxygen atom having a substituent, a sulfur atom having a substituent, a nitrogen atom having a substituent, a phosphorus atom having a substituent, respectively.
Based on the structural formula of the deuterated chemical, the deuterated chemical can have a structure shown in the following formula (4):
in formula (4), R may be one of a hydrogen atom, a deuterium atom, a halogen atom, any carbon atom having a substituent, an oxygen atom having a substituent, a sulfur atom having a substituent, a nitrogen atom having a substituent, a phosphorus atom having a substituent.
Based on the structural formula of the deuterated chemical, the deuterated chemical can have one of the structures shown in the following formulas (5) to (7):
in the formulae (5) to (7), R1～R3May be one of a hydrogen atom, a deuterium atom, a halogen atom, any carbon atom having a substituent, an oxygen atom having a substituent, a sulfur atom having a substituent, a nitrogen atom having a substituent, a phosphorus atom having a substituent, respectively.
The present invention will be described in detail below with reference to examples.
Example 1
(1) The photocatalytic material takes two-dimensional cadmium selenide as an example, and the preparation method comprises the following steps:
18 mmole of selenium powder dispersion was added by syringe to 6.0 mmole of CdCl cooled to room temperature2(octylamine, oleylamine)2In the compound solution, slowly heating the reaction mixture to 100 ℃, reacting for 24 hours, cooling to room temperature, and stopping stirring; washing the reaction mixture with ethanol, centrifuging for three times to remove most of oleylamine, re-dispersing the obtained solid, centrifuging to remove most of unreacted selenium powder; standing the obtained chloroform solution of the two-dimensional cadmium selenide overnight, precipitating part of unreacted selenium powder at the bottom of the bottle, transferring the uniformly dispersed solution of the two-dimensional cadmium selenide into another clean round-bottom bottle by using a liquid transfer gun, treating the solution by using an acidic silica gel column, repeatedly washing the sample by using ethanol to obtain a solid sample of the two-dimensional cadmium selenide nanosheet, and drying the sample at room temperature in vacuum for later use. The characteristics of the prepared cadmium selenide nanosheets are shown in fig. 1-4. Wherein, fig. 1 is a transmission electron microscope image of cadmium selenide nanosheets, fig. 2 is a photolysis water-splitting hydrogen production performance image of the cadmium selenide nanosheets, fig. 3 is an X-ray photoelectron energy spectrum of cadmium components of cadmium selenide, and fig. 4 is an X-ray photoelectron energy spectrum of selenium components of cadmium selenide.
(2) Taking deuterium water as a deuterium source, and carrying out the de-iodination and deuteration reaction of the photo-catalytic iodoaromatic hydrocarbon as follows:
0.1mmol of iodoarene, 5.0mg of cadmium selenide nanosheet and anhydrous sodium sulfite (0.125M) are respectively weighed and added into a 50mL reaction bottle, and CH is added by a syringe3CN/D25.0mL of O mixed solution, replacing the reaction system with the protection state of argon, moving the reaction bottle to a position 10cm away from the center of the light source for illumination reaction for 2.0 hours, removing the light source after the reaction is finished, and using 5.0mLCH for the reaction mixture2Cl2Extraction, 2.0mL of organic phase taken and dried over anhydrous sodium sulfate followed by GC-MS analysis and determination of the yield of the reaction combined with a standard curve of the desired product. The above-mentioned total reaction formula is shown in the following formula (8), and the products which can be produced and the corresponding yields are shown in the following formulae (9) to (12).
Example 2: preparation of deuterated chemicals
0.1mmol of iodoarene, 5.0mg of cadmium selenide nanosheet and anhydrous sodium sulfite (0.125M) are respectively weighed and added into a 50mL reaction bottle, and CH is respectively added by a syringe3CN/D2O5.0 mL, replacing the reaction system with argon protection, moving the reaction bottle to a position 10cm away from the center of the light source for illumination reaction for 2.0 hours, removing the light source after the reaction is finished, and using CH to react the reaction mixture2Cl2(5.0mL multiplied by 3), the organic phases are combined, dried by anhydrous sodium sulfate, desolventized in vacuum, and separated by column chromatography to obtain the target product. The structure of the obtained product is determined by GC-MS, HRMS, H-NMR, C-NMR, FT-IR and other tests. The yields of the above reaction formulae and the corresponding products are shown in the following formulae (13) to (14).
Example 3: preparation of deuterated benzene-d 6 by photocatalytic debromination and deuteration
0.02mmol of iodoarene, 20.0mg of cadmium selenide nanosheet and anhydrous sodium sulfite (0.50M) are respectively weighed and added into a 50mL reaction bottle, and are added by a syringeCH3CN/D2O (1: 1, v/v)5.0mL, degassing the reaction system for 10 minutes, replacing the degassed reaction system with an argon protection state, moving the reaction bottle to a position 10cm away from the center of a light source for illumination reaction for 2.0 hours, removing the light source after the reaction is finished, and using 5.0mLCH for the reaction mixture2Cl2Extraction, 2.0mL of organic phase taken and dried over anhydrous sodium sulfate followed by GC-MS analysis and determination of the yield of the reaction combined with a standard curve of the desired product. The yield of the reaction formula and the corresponding product is shown in the following formula (15).
In summary, the present invention uses mild and cheap deuterium water or solvent instead of deuterium gas to realize highly selective deuterium addition (deuterolysis) reaction, and solves the problems of expensive deuterium gas, harsh reaction conditions, and the like in the existing deuterium addition reaction scheme that the method for preparing deuterium chemicals and the deuterium chemicals have no practicability. Because the reaction condition is milder, the new method can deuterate a series of chemicals, has the advantages of controllable and adjustable deuteration sites and number and the like, can reduce the preparation cost of the deuterated chemicals, and can be widely applied to reaction mechanism research, dynamics research, drug metabolism calibration, biomolecule marking and the like.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (3)
1. A method of preparing a deuterated chemical comprising the steps of: carrying out deuterium addition reaction on the halide and a deuterium source under the catalysis of a light source and a photocatalyst to prepare a deuterated chemical;
wherein the deuterium source is deuterium water or a mixed solution of deuterium water and a deuterated solvent, and the reaction temperature is between-80 and 150 ℃;
the reaction formula is shown as the following formula (1):
in the formula (1), R is a carbon atom with a substituent, X is a halogen atom, and D is a deuterium atom;
the photocatalyst is a CdSe nanosheet.
2. The method of preparing a deuterated chemical as recited in claim 1, wherein the deuterated solvent is deuterated methanol, deuterated ethanol or deuterated acetone.
3. The method for preparing a deuterated chemical according to claim 1, wherein the light source is light with any wavelength range from 200 nm to 2000 nm.
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| CN106631649B (en) * | 2016-12-01 | 2020-02-18 | 深圳大学 | Method for preparing deuterated chemical and deuterated chemical |
| CN109265304B (en) * | 2017-07-17 | 2020-09-08 | 华中科技大学 | Synthesis method of deuterated compound |
| CN110294661B (en) * | 2018-03-23 | 2020-11-24 | 中国科学院化学研究所 | Method for realizing complete debromination of polybrominated aromatic compound by photoreduction |
| CN109174159B (en) * | 2018-10-08 | 2021-01-26 | 深圳大学 | Fixed-point deuterium adding photocatalyst |
| KR101978651B1 (en) * | 2018-10-30 | 2019-05-15 | 머티어리얼사이언스 주식회사 | Method for preparing deuterated orgarnic compounds and deuterated orgarnic compounds produced by the same |
| CN109438156A (en) * | 2018-12-29 | 2019-03-08 | 中国科学院理化技术研究所 | A kind of method of photocatalysis halogenated hydrocarbons dehalogenation conversion |
| US20230016922A1 (en) * | 2019-12-11 | 2023-01-19 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Visible-light mediated organophotoredox catalytic deuteration of aromatic and aliphatic aldehydes |
| WO2021158781A1 (en) * | 2020-02-06 | 2021-08-12 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Methods for practical synthesis of deuterated amino acids |
| CN111718245B (en) * | 2020-07-22 | 2021-06-25 | 福州大学 | Method for preparing deuterated chemicals through photocatalytic decarboxylation conversion |
| CN114075108A (en) * | 2020-08-19 | 2022-02-22 | 南开大学 | Deuteration of aldehyde and application in preparing deuteration aldehyde |
| CN113149801A (en) * | 2021-01-27 | 2021-07-23 | 南京工业大学 | Deuterated polyhalogen aromatic compound, preparation method thereof and organic intermediate |
| CN115260132B (en) * | 2021-04-30 | 2024-02-13 | 复旦大学 | Sp (sp) 2 Deuteration method for hybridized C-H bond |
| CN113563147B (en) * | 2021-07-29 | 2023-05-09 | 西湖大学 | Method for selectively deuterating aromatic ring benzyl hydrocarbon bond |
| CN114890878B (en) * | 2022-05-27 | 2023-01-13 | 诺泰生物科技(合肥)有限公司 | Method for preparing deuterated acetone by photocatalysis |
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