CN115007177B - CdSeS phantom number nanocluster and application thereof as photocatalyst - Google Patents
CdSeS phantom number nanocluster and application thereof as photocatalyst Download PDFInfo
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- CN115007177B CN115007177B CN202210688800.1A CN202210688800A CN115007177B CN 115007177 B CN115007177 B CN 115007177B CN 202210688800 A CN202210688800 A CN 202210688800A CN 115007177 B CN115007177 B CN 115007177B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 24
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003862 amino acid derivatives Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- KADXVMUKRHQBGS-UHFFFAOYSA-L cadmium(2+);tetradecanoate Chemical compound [Cd+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O KADXVMUKRHQBGS-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000011669 selenium Substances 0.000 claims abstract description 12
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000006698 induction Effects 0.000 claims abstract description 8
- ZTSAVNXIUHXYOY-CVBJKYQLSA-L cadmium(2+);(z)-octadec-9-enoate Chemical compound [Cd+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O ZTSAVNXIUHXYOY-CVBJKYQLSA-L 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical group CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006552 photochemical reaction Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 150000002466 imines Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- HORUORWMBOHPIB-UHFFFAOYSA-N 4,4-diethyl-2,6-dimethyl-1H-pyridine-3,5-dicarboxylic acid Chemical compound C(C)C1(C(=C(NC(=C1C(=O)O)C)C)C(=O)O)CC HORUORWMBOHPIB-UHFFFAOYSA-N 0.000 claims description 3
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- CWMOGYSHLXSGDW-UHFFFAOYSA-N 3,4-dichlorothiolane 1-oxide Chemical compound ClC1C(CS(=O)C1)Cl CWMOGYSHLXSGDW-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000003513 alkali Substances 0.000 claims 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 16
- 239000002243 precursor Substances 0.000 description 13
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 12
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- -1 amino acid ester Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 229910052950 sphalerite Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003275 alpha amino acid group Chemical group 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002463 imidates Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
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- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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Abstract
The invention belongs to the technical field of semiconductor phantom number nanocluster catalytic materials, and particularly relates to a CdSeS phantom number nanocluster and application thereof as a photocatalyst. The CdSeS phantom number nanocluster is prepared by the following method: the feed is prepared from a cadmium source, a selenium-containing raw material and a sulfur-containing raw material, wherein the molar ratio of Cd, se and S in the raw material is 20: (5-10): (1-5); the cadmium source is one or a mixture of two of cadmium myristate and cadmium oleate; the selenium-containing raw material is selected from one or a mixture of more than two of selenium powder, a CdSe induction period sample and CdSe phantom nano clusters; the sulfur-containing raw material is selected from one or a mixture of two of sulfur powder and CdS induction period samples. The invention provides a low-cost choice for synthesizing the amino acid derivative, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of semiconductor phantom number nanocluster catalytic materials, and particularly relates to a CdSeS phantom number nanocluster and application thereof as a photocatalyst.
Background
Phantom nanoclusters are a class of substances that are intermediate between molecules and conventional crystals, the specific structure of which is unknown. The magic number nanocluster such as CdS, cdSe and the like is a semiconductor luminescent material. In addition, there is also much research on complex hallucinations nanoclusters of CdS and CdSe, such as: the Chinese patent application CN113046083A provides a luminescent phantom nano-cluster, a preparation method and application thereof, and a CdSeS phantom nano-cluster capable of emitting blue light. The semiconductor luminescent material is a material which emits light by energy released by the recombination of electrons and holes, and has great application prospect in the fields of luminescent devices, photocatalysis and the like.
In the preparation process of amino acid, the reduction of the imidic acid ester is one of the most common and widely applied methods, and the method can be used for efficiently preparing the amino acid ester and then obtaining the amino acid through simple deprotection. The reduction method of the iminoester mainly comprises two methods of direct hydrogenation and transfer hydrogenation. The method for transferring and hydrogenating and reducing the iminoester mainly adopts the traditional hydrogen source to carry out hydrogenation in a catalysis mode by noble metal, and has the defects of higher cost and harsh reaction conditions.
The Chinese patent application CN114436871A discloses a preparation method of amino acid ester or deuterated amino acid ester compound: the iminoester can undergo a photocatalytic reaction under blue light irradiation, thereby preparing the amino acid ester. However, the existing photosensitizer material is usually noble metal salt compound, and the problem of high cost still exists.
Therefore, developing new, green, simple to synthesize, inexpensive photocatalysts to replace noble metal catalysis would be a significant challenge and opportunity. The semiconductor phantom nano-cluster catalytic material can promote separation and recombination of electrons and holes through illumination, so that the semiconductor phantom nano-cluster catalytic material has great application potential in the field of photocatalysis. However, the catalytic mechanism of such catalysts is currently not fully known. It is found that even the semiconductor phantom nano-cluster materials with similar structural composition and close luminescence wavelength have great difference on the catalytic performance of the reaction.
Thus, for the reduction of iminoesters, the use of semiconductor phantom nanoclusters as photocatalysts has not been reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a CdSeS phantom number nanocluster and application thereof as a photocatalyst. Aims to provide a semiconductor phantom nano-cluster catalytic material for realizing the purpose of preparing amino acid derivatives by photocatalytic reduction of iminoesters. The amino acid derivative can be further used as an intermediate for preparing amino acid compounds, and provides a low-cost method for introducing amino acid fragments into medicine design synthesis, practical chemicals and natural products.
The CdSeS phantom number nanocluster is prepared by the following method: mixing cadmium source, selenium-containing raw material and sulfur-containing raw material to react and obtain the product;
the cadmium source is one or a mixture of two of cadmium myristate and cadmium oleate, the selenium-containing raw material is one or a mixture of two or more of selenium powder, a CdSe induction period sample and CdSe phantom nano clusters, and the sulfur-containing raw material is one or a mixture of two of sulfur powder and a CdS induction period sample;
the feeding ratio of the cadmium source, the selenium-containing raw material and the sulfur-containing raw material meets the molar ratio of Cd, se and S of 20: (5-10): (1-5), preferably 20:5:2.5.
preferably, the selenium-containing raw material is selenium powder, and the sulfur-containing raw material is sulfur powder.
Preferably, the reaction conditions for preparing the CdSeS phantom nanoclusters are: the temperature is 230-250 ℃ and the time is 30-180 minutes, and the solvent is 1-octadecene.
Preferably, the reaction conditions for preparing the CdSeS phantom nanoclusters are: the temperature was 230℃for 60 minutes.
Preferably, the feeding ratio of the cadmium source, the selenium-containing raw material and the sulfur-containing raw material satisfies the mole ratio of Cd, se and S as follows: 5:2.5.
the invention also provides application of the CdSeS phantom number nanocluster as a photocatalyst.
The invention also provides a preparation method of the amino acid derivative, which comprises the steps of carrying out photochemical reaction on an imine compound A and an alkyl active ester B under the action of blue light and a photocatalyst to generate the amino acid derivative, wherein the reaction formula is as follows:
wherein R is 1 、R 2 Are respectively and independently selected from C 1 -C 10 Alkyl of (a);
the photocatalyst is the CdSeS phantom number nanocluster.
Preferably, the reaction formula is:
preferably, in the photochemical reaction, the ratio of the photocatalyst, the imine compound A and the alkyl active ester B is (5-200 mg): 0.5mmol: (0.5-3 mmol), or the photochemical reaction takes 4-8h.
Preferably, in the photochemical reaction, the ratio of the photocatalyst to the imine compound A to the alkyl active ester B is 100mg:0.5mmol:0.75mmol, or the photochemical reaction time is 4h.
Preferably, the photochemical reaction is carried out under the action of a base selected from one or more of potassium carbonate, potassium phosphate, potassium dihydrogen phosphate, cesium carbonate or pyridine, preferably potassium carbonate;
and/or the photochemical reaction is carried out under the action of a reducing agent, wherein the reducing agent is selected from one or more than two of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridine dicarboxylic acid, N-diisopropylethylamine, triethylamine or 1, 8-diazabicyclo undec-7-ene, preferably diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridine dicarboxylic acid;
and/or the photochemical reaction is carried out in a solvent, wherein the solvent is selected from one or a mixture of two or more of dichloromethane, 1, 2-dichloroethylene, dimethyl sulfoxide, N-dimethylformamide or acetonitrile, and is preferably dichloromethane.
The Induction Phase Samples (IPS) according to the invention are an intermediate proposed by the teaching topic Yu Kui (chem. Mater.2017,29,5727-5735; nat. Commun.2017,8,15467; j. Phys. Chem. Lett.2018,9,2818-2824; adv. Sci.2018,5, 1800632.) in which the active ingredient is a precursor compound which does not show characteristic uv absorption at the end of the synthesis but which can be converted into the corresponding pseudodigital nanoclusters (MSCs) by a hatching time or by the addition of additives, and which in turn shows uv characteristic absorption. The induction period sample used in the invention can be synthesized by referring to the prior art (J.Phys.chem. Lett.2018,9,6356-6363. Or Chinese invention patent application CN 113046083A).
The CdSeS phantom number nanocluster is obtained by adding CdS monomers into the CdSe phantom number nanocluster. The semiconductor material has a semiconductor energy band structure, and has the photo-induced charge-hole separation and recombination capability, so that the photocatalysis performance is improved. Meanwhile, the phantom number nanocluster is formed by adding the CdS monomer into the CdSe phantom number nanocluster, and the process does not lead to the increase of the particle size of the nanocluster, so that the emission peak does not red shift, and the purity of the blue light material is ensured. The luminescent properties of the specifically synthesized phantom-nanocluster CdSeS dMSC-455 in the examples are: the absorption peak is located at 450-460nm, the emission wavelength is located at 455-465nm, and the half-peak width is less than 12nm.
The invention discovers that CdSeS phantom number nanoclusters can be used as a photocatalyst to catalyze the reduction of iminoester to obtain the amino acid derivative for the first time. In addition, the CdSeS phantom nanocluster provided by the invention has higher yield compared with the CdSeS quantum dot, the CdSeS phantom nanocluster and the CdSeS phantom nanocluster with core-shell structures. The invention provides a low-cost choice for synthesizing the amino acid derivative, the amino acid derivative obtained by the invention can be further used as an intermediate for preparing the amino acid compound, and a low-cost method is provided for the design and synthesis of medicines, practical chemicals and natural products, and amino acid fragments need to be introduced. Therefore, the invention has good application prospect.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is an XRD characterization of CdSeS dMSC-455 prepared in example 1;
FIG. 2 is an absorption spectrum and an emission spectrum of CdSeS dMSC-455 prepared in example 1;
FIG. 3 is a graph showing nuclear magnetic data of hydrogen spectrum and carbon spectrum of amino acid derivatives obtained by catalytic imine reduction addition of CdSeS dMSC-455 as a photocatalyst in example 1;
FIG. 4 is high resolution mass spectrum data of the amino acid derivatives obtained by catalytic imine reductive addition with CdSeS dMSC-455 as a photocatalyst in example 1.
Detailed Description
The reagents and materials used in the following examples and experimental examples are commercially available, unless otherwise specified.
EXAMPLE 1 preparation of amino acid derivatives
1. Preparation of CdSeS dMSC-455
(1) Preparation of cadmium myristate (Cd (MA)) by cadmium oxide (CdO) and tetradecanoic acid (MA) 2 ) A precursor; the method comprises the following specific steps:
cadmium oxide (1.284 g,10 mmol) and tetradecanoic acid (5.255 g,23 mmol) and 1-octadecene (43.692 g) were placed in a 250mL three-necked flask;
vacuum was applied at room temperature, vacuum/nitrogen pumping was performed three times (completed in 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes, wherein the obtained product is the precursor of the cadmium tetradecanoate.
(2) Cadmium myristate precursor (3 g,0.6 mmol) and selenium powder (0.0118 g,0.15 mmol), sulfur powder (0.0024 g,0.075 mmol) and 1-octadecene (4.5 g) are placed in a 50mL three-neck flask;
(3) Vacuum is applied for 30 minutes at room temperature, and the vacuum/nitrogen displacement operation is performed three times (completed in 30 minutes); and vacuum was applied at 110℃for 30 minutes.
(4) Adding glacial acetic acid under the protection of nitrogen, and stirring at 110 ℃ for reaction for 30 minutes;
(5) Under the protection of nitrogen, the temperature is raised to 230 ℃ and the reaction is carried out for 60 minutes, thus synthesizing the target product CdSeS dMSC-455MSC.
2. Characterization of CdSeS dMSC-455
XRD characterization results of CdSeS dMSC-455 prepared according to the above method are shown in FIG. 1.
The second curve (in the middle) of the XRD data pattern is the XRD test results of the sample. The results match to some extent, but are different, from the standard crystal sizes of the CdSe sphalerite crystal forms (top) and CdSe sphalerite crystal forms (bottom). The characterization result of XRD can be used for supposing that the sample structure is based on sphalerite CdSe, and part of Se atoms are replaced by S atoms. Meanwhile, the proportion of the doped S element is extremely low, because the XRD does not show diffraction peaks which are quite matched with the CdS sphalerite standard card.
The absorption spectrum (UV) and the emission spectrum (PL) of CdSeS dMSC-455 of this example are shown in FIG. 2. From the emission spectrum it can be seen that the emission peak is at 462nm, which is blue shifted with respect to the other cdse@cds composites already present (j.am. Chem. Soc.2012,134, 19685-19693). In addition, the half-width of the emission peak is about 12nm, the emission is in a defect-free state, and the relative quantum yield is 85%. The CdSeS dMSC-455 provided by the present invention is therefore capable of emitting blue light with a narrow emission bandwidth and without defects.
3. CdSeS dMSC-455 phantom nano-cluster as photocatalytic material to participate in catalytic property of synthesizing amino acid derivative
CdSeS dMSC-455 phantom-number nanoclusters are used as photocatalysts for synthesizing amino acid derivatives, and specifically comprise the following steps:
(1) Imine SM1 (90 mg,0.5 mmol), alkyl active ester SM2 (174 mg,0.75 mmol), catalyst CdSeS dMSC-455 (60 mg), potassium carbonate (138 mg,1 mmol), diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate (HE, 190mg,0.75 mmol) and dichloromethane (9 mL) were placed in a 50mL three-neck flask, and nitrogen was protected under a 45W blue light;
the structural formula HE is as follows:
(2) At room temperature, nitrogen protection reaction is carried out for 4 hours;
(3) Concentrating to dryness by a direct rotary evaporator after the reaction is finished;
(4) Column chromatography, petroleum ether/ethyl acetate as eluent gave the product (TM-1 a) 49mg, 43% yield.
The reaction equation is as follows:
the hydrogen and carbon spectra of TM-1a are shown in FIG. 3 and the mass spectrum in FIG. 4, where the mass spectrum peak positions are consistent with literature (J. Org. Chem.2019,84, 8177-8184.) demonstrating that this example did successfully synthesize TM-1a.
Comparative example 1 conventional core-shell alloy quantum dots
(1) Preparation of cadmium myristate (Cd (MA)) by cadmium oxide (CdO) and tetradecanoic acid (MA) 2 ) A precursor; the method comprises the following specific steps:
cadmium oxide (1.284 g,10 mmol) and tetradecanoic acid (5.255 g,23 mmol) and 1-octadecene (43.692 g) were placed in a 250mL three-necked flask;
vacuum was applied at room temperature, vacuum/nitrogen pumping was performed three times (completed in 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes, wherein the obtained product is the precursor of the cadmium tetradecanoate.
(2) Cadmium myristate precursor (3 g,0.6 mmol) and selenium powder (0.0118 g,0.15 mmol), sulfur powder (0.0024 g,0.075 mmol) and 1-octadecene (4.5 g) are placed in a 50mL three-neck flask;
(3) Vacuum is applied for 30 minutes at room temperature, and the vacuum/nitrogen displacement operation is performed three times (completed in 30 minutes); and vacuum was applied at 110℃for 30 minutes.
(4) Stirring and reacting for 30 minutes at the constant temperature of 110 ℃ under the protection of nitrogen;
(5) Under the protection of nitrogen, heating to 230 ℃, and reacting for 60 minutes to synthesize the conventional core-shell alloy quantum dot
The absorption wavelength of the conventional core-shell alloy quantum dot is 533nm and 465nm, and the emission wavelength is 624 nm.
Comparative example 2CdSe phantom nanoclusters
(1) Preparation of cadmium myristate (Cd (MA)) by cadmium oxide (CdO) and tetradecanoic acid (MA) 2 ) A precursor; the method comprises the following specific steps:
cadmium oxide (1.284 g,10 mmol) and tetradecanoic acid (5.255 g,23 mmol) and 1-octadecene (43.692 g) were placed in a 250mL three-necked flask;
vacuum was applied at room temperature, vacuum/nitrogen pumping was performed three times (completed in 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes, wherein the obtained product is the precursor of the cadmium tetradecanoate.
(2) Cadmium myristate precursor (3 g,0.6 mmol) and selenium powder (0.0118 g,0.15 mmol), 1-octadecene (4.5 g) were placed in a 50mL three-necked flask;
(3) Vacuum is applied for 30 minutes at room temperature, and the vacuum/nitrogen displacement operation is performed three times (completed in 30 minutes); and vacuum was applied at 110℃for 30 minutes.
(4) Adding glacial acetic acid under the protection of nitrogen, and stirring at 110 ℃ for reaction for 30 minutes;
(5) Under the protection of nitrogen, heating to 230 ℃, and reacting for 30 minutes to synthesize the CdSe phantom nano-cluster.
The CdSe phantom nanoclusters absorb at 462nm and 434nm and emit at 466 nm.
Comparative example 3CdS phantom nanoclusters
(1) Preparation of deca by cadmium oxide (CdO) and tetradecanoic acid (MA)Cadmium tetraate (Cd (MA) 2 ) A precursor; the method comprises the following specific steps:
cadmium oxide (1.284 g,10 mmol) and tetradecanoic acid (5.255 g,23 mmol) and 1-octadecene (43.692 g) were placed in a 250mL three-necked flask;
vacuum was applied at room temperature, vacuum/nitrogen pumping was performed three times (completed in 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes, wherein the obtained product is the precursor of the cadmium tetradecanoate.
(2) Cadmium myristate precursor (3 g,0.6 mmol) and sulfur powder (0.0024 g,0.075 mmol), 1-octadecene (4.5 g) were placed in a 50mL three-necked flask;
(3) Vacuum is applied for 30 minutes at room temperature, and the vacuum/nitrogen displacement operation is performed three times (completed in 30 minutes); and vacuum was applied at 110℃for 30 minutes.
(4) Adding glacial acetic acid under the protection of nitrogen, and stirring at 110 ℃ for reaction for 30 minutes;
(5) Under the protection of nitrogen, heating to 230 ℃, and reacting for 15 minutes to synthesize the CdS phantom number nanocluster.
The CdS phantom nanocluster absorption wavelength was at 374nm and the emission wavelength was at 387 nm.
The beneficial effects of the invention are further illustrated by experiments below.
Experimental example 1 comparison of the photocatalytic performance of the photocatalyst
The experimental example is preferred for the type of photocatalyst.
The experimental set was set as follows:
(1) The catalyst in number 1 is the phantom-number nanocluster cdsedsmsc-455 prepared in example 1;
(2) The catalyst in the number 2 is the core-shell alloy quantum dot prepared in the comparative example 1;
(3) The catalyst in number 3 is the CdSe phantom nanocluster prepared in comparative example 2;
(4) The catalyst in number 4 is the CdS phantom nanocluster prepared in comparative example 3;
(5) No catalyst in No. 5 was involved in the imine reduction reaction.
The amount of the photocatalyst used was 20mg, and the other undescribed synthesis conditions were the same as in part 3 of example 1.
The product yields for each experimental group are shown in the following table:
| numbering device | Photocatalyst | Wavelength of light emission | Yield is good |
| 1 | CdSeSdMSC-455 | 462nm | 52％ |
| 2 | CdSeS core-shell alloy quantum dot | 624nm | 28％ |
| 3 | CdSe phantom nanoclusters | 466nm | 44％ |
| 4 | CdS phantom number nanocluster | 387nm | 12％ |
| 5 | Without any means for | - | 5％ |
The experiment shows that in a series of photocatalysts with similar structure and light emission performance, the CdSeS phantom number nanocluster provided by the invention can obviously improve the yield of the synthesis reaction and has optimal catalytic performance.
Experimental example 2 preference for reaction conditions
In this experimental example, the reaction conditions for synthesizing the amino acid derivative are preferable, and the reaction steps and conditions not specifically described are the same as in example 1.
The results of the comparative experiments on the reaction conditions are shown in the following table:
the experimental result shows that the yield of the reaction is improved along with the increase of the dosage of the photocatalyst CdSeS dMSC-455 phantom number nanocluster and the increase of the reaction time, and the yield reaches the maximum value of 65 percent along with the continuous increase of the dosage of the catalyst and the extension of the time.
It can be seen from the above examples and experimental examples that the present invention prepares a CdSeS phantom nanocluster having a good photocatalytic effect on photochemical reactions for the preparation of amino acid derivatives by reduction of imidoesters. The invention provides a low-cost choice for synthesizing the amino acid derivative, and has good application prospect.
Claims (8)
1. A method for preparing an amino acid derivative, characterized by comprising the steps of: the imine compound A and the alkyl active ester B are subjected to photochemical reaction under the action of blue light and a photocatalyst to generate amino acid derivatives, and the reaction formula is as follows:
wherein R is 1 、R 2 Are respectively and independently selected from C 1 -C 10 Alkyl of (a);
the photocatalyst is a CdSeS phantom number nanocluster;
the CdSeS phantom number nanocluster is prepared from a cadmium source, a selenium-containing raw material and a sulfur-containing raw material, wherein the molar ratio of Cd, se and S in the raw material is 20: (5-10): (1-5);
the cadmium source is one or a mixture of two of cadmium myristate and cadmium oleate; the selenium-containing raw material is selected from one or a mixture of more than two of selenium powder, a CdSe induction period sample and CdSe phantom nano clusters; the sulfur-containing raw material is selected from one or a mixture of two of sulfur powder and CdS induction period samples.
2. The method of manufacturing according to claim 1, wherein: the selenium-containing raw material is selenium powder, and the sulfur-containing raw material is sulfur powder.
3. The method of manufacturing according to claim 2, wherein: the reaction conditions for preparing the CdSeS phantom number nanocluster are as follows: the temperature is 230-250 ℃ and the time is 30-180 minutes, and the solvent is 1-octadecene.
4. A method of preparation according to claim 3, characterized in that: the reaction conditions for preparing the CdSeS phantom number nanocluster are as follows: the temperature was 230℃for 60 minutes.
5. The method of manufacturing according to claim 1, wherein: the feeding ratio of the cadmium source, the selenium-containing raw material and the sulfur-containing raw material meets the molar ratio of Cd, se and S of 20:5:2.5.
6. the method of manufacturing according to claim 1, wherein: the reaction formula is as follows:
7. the method of manufacturing according to claim 1, wherein: in the photochemical reaction, the dosage ratio of the photocatalyst to the imine compound A to the alkyl active ester B is (5-200 mg): 0.5mmol: (0.5-3 mmol), or the photochemical reaction takes 4-8h.
8. The method of manufacturing according to claim 1, wherein: the photochemical reaction is carried out under the action of alkali, and the alkali is selected from one or a mixture of two or more of potassium carbonate, potassium phosphate, monopotassium phosphate, cesium carbonate or pyridine;
and/or the photochemical reaction is carried out under the action of a reducing agent, wherein the reducing agent is selected from one or a mixture of two or more of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridine dicarboxylic acid, N-diisopropylethylamine, triethylamine or 1, 8-diazabicyclo undec-7-ene;
and/or the photochemical reaction is carried out in a solvent, wherein the solvent is selected from one or a mixture of two or more of dichloromethane, 1, 2-dichloroethylene, dimethyl sulfoxide, N-dimethylformamide or acetonitrile.
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