CN106631649A - Method for preparing deuterated chemicals and deuterated chemicals - Google Patents
Method for preparing deuterated chemicals and deuterated chemicals Download PDFInfo
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Abstract
The invention relates to a method for preparing deuterated chemicals and deuterated chemicals. The method comprises the following step: carrying out deuteration reaction on halides and a deuterium source under the catalytic actions of a light source and a photocatalyst to obtain the deuterated chemicals, wherein the deuterium source is deuterium oxide or a deuteration solvent, and the reaction temperature is -80-150 DEG C. By using the environment-friendly cheaper deuterium oxide or deuteration reagent as the deuterium source instead of deuterium gas, the halides can be deuterated under the photocatalytic action of a photocatalyst composed of a Ru/In metal catalyst, organic dyes, inorganic and organic semiconductor nano materials and the like, thereby providing precise controllable preparation of a series of deuterated chemicals. Compared with the traditional deutration reaction, the method has the advantages of higher selectivity, milder reaction conditions, wider substrate adaptability and higher economic applicability, and is hopeful to be applied to large-scale production of deuterated chemicals.
Description
Technical field
The present invention relates to photocatalysis prepares field of chemicals, more particularly to a kind of method for preparing deuterated chemicals and deuterated
Chemicals.
Background technology
Deuterated chemicals is a class special compound, is surveyed in study on mechanism, dynamics, drug metabolism and biological structure
Surely etc. there is important application in field.The heavy isotope of hydrogen typically by multistep synthesis introduce target compound, during will relate to
And the chemical reagent of various marks.Hydrogen deuterium catalyticing exchanging reaction is then the strategy that haves a great attraction of another kind, during often
Only need a step isotope can be introduced into target molecule.The huge challenge that the method faces is the selectivity control that hydrogen deuterium is exchanged
And the universality of functional group.Most methods are related to the gold of high temperature, high pressure (deuterium is deuterium source), strong acid, highly basic or costliness
Metal catalyst.There is wider range of functional group's adaptability relative to hydrogen deuterium catalyticing exchanging reaction, plus deuterium alpha reaction (or the reaction of deuterium solution)
Higher selectivity, selects different plus deuterium (or deuterium solution) catalyst, it is possible to achieve carry out fixed point deuterium to different functional sites
Change, can be used as comparatively ideal deuterate strategy.However, due to plus deuterium alpha reaction (or deuterium solution reaction) need to use deuterium, and high temperature,
High pressure and noble metal catalyst, greatly limit the scope of application for adding deuterium alpha reaction.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of and method for preparing deuterated chemicals
And deuterated chemicals, it is intended to solve existing plus deuterium alpha reaction (or the reaction of deuterium solution) needs that deuterium, and high temperature, high pressure and your gold used
Metal catalyst, greatly limit the problem of the scope of application for adding deuterium alpha reaction.
Technical scheme is as follows：
A kind of method for preparing deuterated chemicals, wherein, including step：Halides light source, photochemical catalyst catalysis under with
Deuterium source (in terms of molal weight ratio, deuterium source:Halides>1:1) carry out plus deuterium alpha reaction, deuterated chemicals is obtained；
Wherein, the deuterium source is deuterium-oxide or deuterated solvent, and reaction temperature is between -80 DEG C～150 DEG C；
Reaction equation such as following formula (1)：
In formula (1), R is the carbon atom with substituent, and X is halogen atom, and D is D-atom.
The described method for preparing deuterated chemicals, wherein, the deuterated solvent is deuterated methanol, deuterated ethanol or deuterated
Acetone.
The described method for preparing deuterated chemicals, wherein, the photochemical catalyst is containing Ru, the catalyst of Ir, have engine dyeing
Material catalyst, inorganic semiconductor catalyst or organic semiconductor catalyst.
The described method for preparing deuterated chemicals, wherein, the inorganic semiconductor catalyst is TiO2, CdS or CdSe.
The described method for preparing deuterated chemicals, wherein, the light source is the light of any wave bands of 200～2000nm.
A kind of deuterated chemicals, wherein, it is prepared from using as above arbitrary described method for preparing deuterated chemicals.
Described deuterated chemicals, wherein, the deuterated chemicals has the structure shown in following formula (2)：
In formula (2), R1～R5Respectively hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, with substituent
Oxygen atom, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent in one kind.
Described deuterated chemicals, wherein, the deuterated chemicals has the structure shown in following formula (3)：
In formula (3), R1～R3Respectively hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, with substituent
Oxygen atom, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent in one kind.
Described deuterated chemicals, wherein, the deuterated chemicals has the structure shown in following formula (4)：
In formula (4), R is hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, the original of the oxygen with substituent
One kind in son, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent.
Described deuterated chemicals, wherein, the deuterated chemicals has in the structure shown in following formula (5)～formula (7)
One kind：
In formula (5)～formula (7), R1～R3Respectively hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, tool
In the oxygen atom of substituted base, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent
It is a kind of.
Beneficial effect：The present invention replaces deuterium using deuterium-oxide or deuterated solvent as deuterium source, realizes gentle plus deuterium (deuterium
Solution) reaction.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of obtained photochemical catalyst cadmium selenide in the embodiment of the present invention 1.
Fig. 2 is the photocatalytic water H2-producing capacity figure of obtained photochemical catalyst cadmium selenide in the embodiment of the present invention 1.
Fig. 3 is the x-ray photoelectron energy spectrum diagram of the cadmium composition of obtained photochemical catalyst cadmium selenide in the embodiment of the present invention 1.
Fig. 4 is the x-ray photoelectron power spectrum of the selenium composition of obtained photochemical catalyst cadmium selenide in the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of method and deuterated chemicals for preparing deuterated chemicals, to make the purpose of the present invention, technology
Scheme and effect are clearer, clear and definite, and below the present invention is described in more detail.It should be appreciated that described herein concrete
Embodiment only to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of method preferred embodiment for preparing deuterated chemicals, wherein, including step：Halides are in light
Source, photochemical catalyst catalysis it is lower with deuterium source (in terms of molal weight ratio, deuterium source:Halides>1:1) carry out plus deuterium alpha reaction, be obtained deuterated
Chemicals；
Wherein, the deuterium source is deuterium-oxide or deuterated solvent, and reaction temperature is (such as 20 DEG C, 60 DEG C between -80 DEG C～150 DEG C
Or 120 DEG C)；
Reaction equation such as following formula (1)：
In formula (1), R is the carbon atom with any substituent, and X is halogen atom, and D is D-atom.
Deuterium source of the present invention is deuterium-oxide or deuterated solvent, and the deuterated solvent can be but be not limited to deuterated methanol, deuterium
For ethanol or deuterated acetone etc..
Photochemical catalyst of the present invention can be but be not limited to containing Ru, the catalyst of Ir, organic dyestuff catalyst, inorganic half
Conductor catalyst or organic semiconductor catalyst are (such as g-C3N4).Preferably, the inorganic semiconductor catalyst can be but not limit
In TiO2, CdS or CdSe.
Light source of the present invention can be but be not limited to the light of 200～2000nm (such as 1000nm) arbitrarily wave bands.
The present invention replaces deuterium as deuterium source using deuterium-oxide or deuterated solvent, realizes that the gentle deuterium (deuterium solution) that adds reacts, and has
Effect solves the problems, such as that deuterium, severe reaction conditions expensive used in existing plus deuterium alpha reaction etc. do not possess practicality.
The present invention also provides a kind of deuterated chemicals, wherein, using as above arbitrary described side for preparing deuterated chemicals
Method is prepared from.
The structural formula of deuterated chemicals of the present invention is R-D；In formula, R is the carbon atom with any substituent, and D is
D-atom.
Based on the structural formula of above-mentioned deuterated chemicals, deuterated chemicals of the present invention can have shown in following formula (2)
Structure：
In formula (2), R1～R5Hydrogen atom, D-atom, halogen atom, any carbon atom with substituent, tool can be respectively
In the oxygen atom of substituted base, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent
It is a kind of.
Based on the structural formula of above-mentioned deuterated chemicals, deuterated chemicals of the present invention can have shown in following formula (3)
Structure：
In formula (3), R1～R3Hydrogen atom, D-atom, halogen atom, any carbon atom with substituent, tool can be respectively
In the oxygen atom of substituted base, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent
It is a kind of.
Based on the structural formula of above-mentioned deuterated chemicals, deuterated chemicals of the present invention can have shown in following formula (4)
Structure：
In formula (4), R can for hydrogen atom, D-atom, halogen atom, any carbon atom with substituent, with substituent
Oxygen atom, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent in one kind.
Based on the structural formula of above-mentioned deuterated chemicals, deuterated chemicals of the present invention can have following formula (5)～formula
(7) one kind in structure shown in：
In formula (5)～formula (7), R1～R3Hydrogen atom, D-atom, halogen atom, any carbon with substituent can be respectively
Atom, the oxygen atom with substituent, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus with substituent
One kind in atom.
Below by embodiment, the present invention is described in detail.
Embodiment 1
(1), catalysis material is by taking two-dimentional cadmium selenide as an example, and the method that it is prepared is as follows：
18 mMs of selenium powder dispersion liquids are added to 6.0 mMs of CdCl for being cooled to room temperature with syringe2(octylame, oil
Amine)2In complex solution, by reactant mixture be heated slowly to 100 degrees Celsius reaction 24 hours after be cooled to room temperature, stop stirring
Mix；Reactant mixture is washed with ethanol, is centrifuged three times, remove most of oleyl amine, gained solid disperses again, be centrifuged, removed
Most of unreacted selenium powder；Again by the chloroformic solution left undisturbed overnight of gained two dimension cadmium selenide, there is the unreacted selenium powder in part again
Bottom of bottle is deposited in, the solution of homodisperse two-dimentional cadmium selenide is transferred in round-bottomed bottle clean in addition with liquid-transfering gun, be used in combination
Acidic silica gel post processes this solution, and sample is washed with ethanol repeatedly, obtains two-dimentional cadmium selenide nano piece solid sample, by this sample room
Temperature vacuum drying is standby.The sign of obtained cadmium selenide nano piece is as shown in Fig. 1～Fig. 4.Wherein, Fig. 1 is cadmium selenide nano piece
Transmission electron microscope picture, Fig. 2 for cadmium selenide nano piece photocatalytic water H2-producing capacity figure, Fig. 3 for cadmium selenide cadmium composition X-ray light
Electron spectrum, Fig. 4 is the x-ray photoelectron power spectrum of the selenium composition of cadmium selenide.
(2), with water as hydrogen source, the de- hydroiodination of photocatalysis iodo aromatic hydrocarbon is as follows：
Weigh 0.1mmol iodo aromatic hydrocarbons, 5.0mg cadmium selenide nanos piece and anhydrous sodium sulfite (0.125M) respectively to be added to
In 50mL reaction bulbs, and CH is added with syringe3CN/H2O mixed solution 5.0mL, by reaction system argon gas protection shape is replaced into
State, then moves to illumination reaction 2.0 hours at light source center 10cm by reaction bulb, and reaction removes light source after terminating, will
Reactant mixture 5.0mLCH2Cl2Extraction, takes 2.0mL organic phases and with carrying out GC-MS analyses after anhydrous sodium sulfate drying, and
The calibration curve of combining target product determines the yield of the reaction.Above-mentioned net reaction is seen below shown in formula (8), the product that can be generated
And its corresponding yield is seen below shown in formula (9)～formula (12).
Embodiment 2：Prepare deuterated chemicals
Weigh 0.1mmol iodo aromatic hydrocarbons, 5.0mg cadmium selenide nanos piece and anhydrous sodium sulfite (0.125M) respectively to be added to
In 50mL reaction bulbs, and CH is separately added into syringe3CN/D2O 5.0mL, are replaced into argon gas guard mode, so by reaction system
Afterwards reaction bulb is moved into illumination reaction 2.0 hours at light source center 10cm, reaction removes light source after terminating, and reaction is mixed
Compound CH2Cl2(5.0mL × 3) extract, and merge organic phase, and with anhydrous sodium sulfate drying, vacuum desolvation agent, column chromatography for separation is obtained
Target product.The test such as products therefrom Jing GC-MS, HRMS, H-NMR, C-NMR, FT-IR determines structure.Above-mentioned reaction equation and its
The yield of correspondence product is seen below shown in formula (13)～formula (14).
Embodiment 3：Photocatalysis debrominate deuterate prepares deuterated benzene-d6
Weigh 0.02mmol iodo aromatic hydrocarbons, 20.0mg cadmium selenide nanos piece and anhydrous sodium sulfite (0.50M) respectively to add
To in 50mL reaction bulbs, and CH is added with syringe3CN/D2O(1：1, v/v) 5.0mL, by reaction system deaerate 10 minutes it is rearmounted
Argon gas guard mode is changed to, then reaction bulb illumination reaction 2.0 hours at light source center 10cm is moved into, reaction terminates
After remove light source, by reactant mixture 5.0mLCH2Cl2Extraction, takes 2.0mL organic phases and is carried out with after anhydrous sodium sulfate drying
GC-MS is analyzed, and the calibration curve of combining target product determines the yield of the reaction.The receipts of above-mentioned reaction equation and its correspondence product
Rate is seen below shown in formula (15).
In sum, a kind of method for preparing deuterated chemicals of the invention and deuterated chemicals, present invention uses warm
With and cheap deuterium-oxide or deuterated solvent replacing deuterium, realize high selectivity plus deuterium (deuterium solution) reaction, solve it is existing plus
Expensive deuterium, severe reaction conditions etc. do not possess the problem of practicality used in deuterium alpha reaction scheme.Due to reaction condition more
Gently, new method of the invention can a series of chemicals of deuterate, with the advantage such as deuterate site and number be controllable, adjustable, can drop
Low deuterated chemicals preparation cost so as to be widely used in study on mechanism, dynamics research, drug metabolism demarcation, biology
Molecular labeling etc..
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, and for those of ordinary skills, can
To be improved according to the above description or be converted, all these modifications and variations should all belong to the guarantor of claims of the present invention
Shield scope.
Claims (10)
1. a kind of method for preparing deuterated chemicals, it is characterised in that including step：Halides are catalyzed in light source, photochemical catalyst
Lower and deuterium source is carried out plus deuterium alpha reaction, and deuterated chemicals is obtained；
Wherein, the deuterium source is deuterium-oxide or deuterated solvent, and reaction temperature is between -80 DEG C～150 DEG C；
Reaction equation such as following formula (1)：
In formula (1), R is the carbon atom with substituent, and X is halogen atom, and D is D-atom.
2. the method for preparing deuterated chemicals according to claim 1, it is characterised in that the deuterated solvent is deuterated first
Alcohol, deuterated ethanol or deuterated acetone.
3. the method for preparing deuterated chemicals according to claim 1, it is characterised in that the photochemical catalyst be containing Ru,
The catalyst of Ir, organic dyestuff catalyst, inorganic semiconductor catalyst or organic semiconductor catalyst.
4. the method for preparing deuterated chemicals according to claim 3, it is characterised in that the inorganic semiconductor catalyst
For TiO2, CdS or CdSe.
5. the method for preparing deuterated chemicals according to claim 1, it is characterised in that the light source is 200～
The light of any wave bands of 2000nm.
6. a kind of deuterated chemicals, it is characterised in that using the deuterated chemicals for preparing as described in Claims 1 to 5 is arbitrary
Method is prepared from.
7. deuterated chemicals according to claim 6, it is characterised in that the deuterated chemicals has following formula (2) institute
The structure shown：
In formula (2), R1～R5Respectively hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, the oxygen with substituent
One kind in atom, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent.
8. deuterated chemicals according to claim 6, it is characterised in that the deuterated chemicals has following formula (3) institute
The structure shown：
In formula (3), R1～R3Respectively hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, the oxygen with substituent
One kind in atom, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent.
9. deuterated chemicals according to claim 6, it is characterised in that the deuterated chemicals has following formula (4) institute
The structure shown：
In formula (4), R is hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, the oxygen atom with substituent, tool
One kind in the sulphur atom of substituted base, the nitrogen-atoms with substituent, the phosphorus atoms with substituent.
10. deuterated chemicals according to claim 6, it is characterised in that the deuterated chemicals have following formula (5)～
One kind in structure shown in formula (7)：
In formula (5)～formula (7), R1～R3Respectively hydrogen atom, D-atom, halogen atom, the carbon atom with substituent, with taking
In the oxygen atom of Dai Ji, the sulphur atom with substituent, the nitrogen-atoms with substituent, the phosphorus atoms with substituent one
Kind.
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| CN201611091137.8A CN106631649B (en) | 2016-12-01 | 2016-12-01 | Method for preparing deuterated chemical and deuterated chemical |
| PCT/CN2017/111314 WO2018099271A1 (en) | 2016-12-01 | 2017-11-16 | Method for preparing deuterated chemicals, and deuterated chemicals |
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| WO2018099271A1 (en) * | 2016-12-01 | 2018-06-07 | 深圳大学 | Method for preparing deuterated chemicals, and deuterated chemicals |
| CN109174159A (en) * | 2018-10-08 | 2019-01-11 | 深圳大学 | A kind of novel fixed point adds deuterium photochemical catalyst |
| CN109265304A (en) * | 2017-07-17 | 2019-01-25 | 华中科技大学 | A kind of synthetic method of deuterated compound |
| CN109438156A (en) * | 2018-12-29 | 2019-03-08 | 中国科学院理化技术研究所 | Method for dehalogenation conversion of halogenated hydrocarbon by photocatalysis |
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| CN113149801A (en) * | 2021-01-27 | 2021-07-23 | 南京工业大学 | Deuterated polyhalogen aromatic compound, preparation method thereof and organic intermediate |
| CN114890878A (en) * | 2022-05-27 | 2022-08-12 | 安徽贵朋功能材料科技有限公司 | Method for preparing deuterated acetone by photocatalysis |
| CN115260132A (en) * | 2021-04-30 | 2022-11-01 | 复旦大学 | Sp (specific fragment) method2Deuteration method of hybridized C-H bond |
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| WO2021118827A1 (en) * | 2019-12-11 | 2021-06-17 | 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 |
| CN114075108A (en) * | 2020-08-19 | 2022-02-22 | 南开大学 | Deuteration of aldehyde and application in preparing deuteration aldehyde |
| CN113563147B (en) * | 2021-07-29 | 2023-05-09 | 西湖大学 | Method for selectively deuterating aromatic ring benzyl hydrocarbon bond |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD279376A3 (en) * | 1984-01-30 | 1990-06-06 | Adw Ddr | METHOD FOR THE PREPARATION OF DEUTERATED ORGANIC COMPOUNDS |
| CN102020521A (en) * | 2009-09-10 | 2011-04-20 | 陈松源 | Preparation mode and application of deuterium substituted Chinese herbal monomer |
| CN102901745A (en) * | 2012-11-08 | 2013-01-30 | 厦门大学 | Method for identifying olive oil |
| CN102335618B (en) * | 2011-06-23 | 2013-03-20 | 中国科学院理化技术研究所 | Semiconductor catalyst and preparation method thereof, catalytic hydrogen production system containing semiconductor catalyst and hydrogen production method thereof |
| CN103675134A (en) * | 2013-12-05 | 2014-03-26 | 上海金玺实验室有限公司 | Method for detecting benzene series pollutants in gas by using internal standard method |
| CN104181266A (en) * | 2013-05-24 | 2014-12-03 | 中国科学院大连化学物理研究所 | Dechlorination deuterium-added gas chromatography-mass spectrometry method for short-chain and medium-chain chlorinated paraffin |
| CN104692992A (en) * | 2015-03-13 | 2015-06-10 | 武汉众宇动力系统科技有限公司 | Preparation method of deuteroethylene |
| CN105198685A (en) * | 2014-06-30 | 2015-12-30 | 中国农业科学院植物保护研究所 | Synthetic method for deuterium labeled benzene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631649B (en) * | 2016-12-01 | 2020-02-18 | 深圳大学 | Method for preparing deuterated chemical and deuterated chemical |
-
2016
- 2016-12-01 CN CN201611091137.8A patent/CN106631649B/en active Active
-
2017
- 2017-11-16 WO PCT/CN2017/111314 patent/WO2018099271A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD279376A3 (en) * | 1984-01-30 | 1990-06-06 | Adw Ddr | METHOD FOR THE PREPARATION OF DEUTERATED ORGANIC COMPOUNDS |
| CN102020521A (en) * | 2009-09-10 | 2011-04-20 | 陈松源 | Preparation mode and application of deuterium substituted Chinese herbal monomer |
| CN102335618B (en) * | 2011-06-23 | 2013-03-20 | 中国科学院理化技术研究所 | Semiconductor catalyst and preparation method thereof, catalytic hydrogen production system containing semiconductor catalyst and hydrogen production method thereof |
| CN102901745A (en) * | 2012-11-08 | 2013-01-30 | 厦门大学 | Method for identifying olive oil |
| CN104181266A (en) * | 2013-05-24 | 2014-12-03 | 中国科学院大连化学物理研究所 | Dechlorination deuterium-added gas chromatography-mass spectrometry method for short-chain and medium-chain chlorinated paraffin |
| CN103675134A (en) * | 2013-12-05 | 2014-03-26 | 上海金玺实验室有限公司 | Method for detecting benzene series pollutants in gas by using internal standard method |
| CN105198685A (en) * | 2014-06-30 | 2015-12-30 | 中国农业科学院植物保护研究所 | Synthetic method for deuterium labeled benzene |
| CN104692992A (en) * | 2015-03-13 | 2015-06-10 | 武汉众宇动力系统科技有限公司 | Preparation method of deuteroethylene |
Cited By (15)
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| WO2018099271A1 (en) * | 2016-12-01 | 2018-06-07 | 深圳大学 | Method for preparing deuterated chemicals, and deuterated chemicals |
| CN109265304A (en) * | 2017-07-17 | 2019-01-25 | 华中科技大学 | A kind of synthetic method of deuterated compound |
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| CN109174159A (en) * | 2018-10-08 | 2019-01-11 | 深圳大学 | A kind of novel fixed point adds deuterium photochemical catalyst |
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| CN111116281B (en) * | 2018-10-30 | 2023-04-07 | 材料科学有限公司 | Method for preparing deuterated organic compound and deuterated organic compound prepared according to preparation method |
| CN111116281A (en) * | 2018-10-30 | 2020-05-08 | 材料科学有限公司 | Method for preparing deuterated organic compound and deuterated organic compound prepared according to preparation method |
| CN109438156A (en) * | 2018-12-29 | 2019-03-08 | 中国科学院理化技术研究所 | Method for dehalogenation conversion of halogenated hydrocarbon by photocatalysis |
| CN111718245A (en) * | 2020-07-22 | 2020-09-29 | 福州大学 | Method for preparing deuterated chemicals through photocatalytic decarboxylation conversion |
| CN113149801A (en) * | 2021-01-27 | 2021-07-23 | 南京工业大学 | Deuterated polyhalogen aromatic compound, preparation method thereof and organic intermediate |
| CN115260132A (en) * | 2021-04-30 | 2022-11-01 | 复旦大学 | Sp (specific fragment) method2Deuteration method of hybridized C-H bond |
| CN115260132B (en) * | 2021-04-30 | 2024-02-13 | 复旦大学 | Sp (sp) 2 Deuteration method for hybridized C-H bond |
| CN114890878A (en) * | 2022-05-27 | 2022-08-12 | 安徽贵朋功能材料科技有限公司 | Method for preparing deuterated acetone by photocatalysis |
| 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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