CN115433112A - Tri (methylthio) benzene tricarbonal derivative and preparation method and application thereof - Google Patents
Tri (methylthio) benzene tricarbonal derivative and preparation method and application thereof Download PDFInfo
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- CN115433112A CN115433112A CN202210234632.9A CN202210234632A CN115433112A CN 115433112 A CN115433112 A CN 115433112A CN 202210234632 A CN202210234632 A CN 202210234632A CN 115433112 A CN115433112 A CN 115433112A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- RSRDUZOSVGCSGX-UHFFFAOYSA-N 1,2,3-tris(methylsulfanyl)benzene Chemical compound CSC1=CC=CC(SC)=C1SC RSRDUZOSVGCSGX-UHFFFAOYSA-N 0.000 title description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000007983 Tris buffer Substances 0.000 claims abstract description 18
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 12
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000010931 gold Substances 0.000 claims abstract 2
- 229910052737 gold Inorganic materials 0.000 claims abstract 2
- 239000002105 nanoparticle Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000004440 column chromatography Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- ZXAWPXINCIZGEV-UHFFFAOYSA-N 1,3,5-tribromo-2,4,6-tris(bromomethyl)benzene Chemical compound BrCC1=C(Br)C(CBr)=C(Br)C(CBr)=C1Br ZXAWPXINCIZGEV-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 9
- LTSSSVHTLGQZAQ-UHFFFAOYSA-N 1,3,5-tribromo-2,4,6-trimethylbenzene Chemical compound CC1=C(Br)C(C)=C(Br)C(C)=C1Br LTSSSVHTLGQZAQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- -1 biology Substances 0.000 abstract description 14
- 239000003814 drug Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004873 anchoring Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 abstract 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 abstract 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 abstract 1
- 239000002262 Schiff base Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000013310 covalent-organic framework Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- XHXXWWGGXFUMAJ-UHFFFAOYSA-N methanethiol;sodium Chemical compound [Na].SC XHXXWWGGXFUMAJ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RINWGRJHXCCLOV-UHFFFAOYSA-N BPO Chemical compound BPO RINWGRJHXCCLOV-UHFFFAOYSA-N 0.000 description 1
- ZJUPBXGYFLOSGJ-UHFFFAOYSA-N CN1C(C=C(C=C2)N)=C2OC2=CC(N)=CC=C12 Chemical compound CN1C(C=C(C=C2)N)=C2OC2=CC(N)=CC=C12 ZJUPBXGYFLOSGJ-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- DNTYGIFJYSSHRM-UHFFFAOYSA-N [2,4,6-tribromo-3,5-bis(hydroxymethyl)phenyl]methanol Chemical compound OCC1=C(Br)C(CO)=C(Br)C(CO)=C1Br DNTYGIFJYSSHRM-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method and application of a 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative. The 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative has a structure represented by the following formula:
the preparation method based on the 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative provided by the invention is simple to operate, easily available in raw materials, low in price, extremely high in purity and high in reaction yield. The sulfydryl of the 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative can be used as an anchoring site for in-situ growth of gold nanoparticles for catalytic reduction reaction; 2,4, 6-tris (formazan) prepared by the inventionThe sulfenyl) benzene-1, 3, 5-trimethyl aldehyde derivative has wide application prospect in the fields of medicine, biology, materials and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative and a preparation method thereof, in particular to 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene, 2,4, 6-tribromobenzene-1, 3, 5-trimethyl alcohol and 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde, and a preparation method and application thereof.
Background
The 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative is a kind of aromatic heterocyclic structure containing sulfur atom, and the S element has special property to serve as the anchoring growth site of metal nano particle, so that the S element has wide application in medicine, biology, material and other fields. The aldehyde group can be synthesized with amine through Schiff base condensation reaction to realize the synthesis of specific functional compounds, so that the compound has wide application in the fields of medicine, catalysis, luminescence, material science and the like.
With the continuous development of novel materials, the functionality of the materials is very important, and the size of functional groups and monomers carried by the materials greatly influences the application field of the materials. The sulfur atom carried in the 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative improves the functionality and the design of the material, so that the material can be used as an anchoring growth site of the metal nano particle; and the larger conjugated system and the good rigid conjugated plane provide guarantee for the stability of the material, and further expand the application field of the material.
Disclosure of Invention
The invention discloses a preparation method and application of a 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative. The 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative has a structure represented by the following formula:
the embodiment of the invention also provides a preparation method of 2,4, 6-tri (methylthio) benzene-1, 3, 5-triformol, which comprises the following steps:
(1) 1,3, 5-tribromo-2, 4, 6-trimethylbenzene, N-bromosuccinimide, benzoyl peroxide and tetrachloromethane are mixed, heated and refluxed for 20 to 24 hours, and then cooled. Filtering, concentrating, and performing column chromatography to obtain 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene;
(2) Adding 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene, potassium acetate and DMF into a flask, heating to 80-100 ℃, and stirring for 15-20 h. Cooling the reaction mixture to room temperature, adding water, extracting with DCM, concentrating the organic phase, adding potassium hydroxide and water into the solid, heating to 80-90 ℃, stirring for 24-48 h, cooling the reaction mixture to room temperature after the completion, washing with water, and drying to obtain 2,4, 6-tribromobenzene-1, 3, 5-tricarbonol;
(3) 2,4, 6-tribromobenzene-1, 3, 5-tricarbol, PCC, diatomaceous earth and DCM were added to the flask and stirred at room temperature for 2-3 days. After the reaction is finished, adding silica gel into the reaction mixture, concentrating, and carrying out column chromatography to obtain 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde;
(4) 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde and DMF were mixed at 0 ℃ under nitrogen atmosphere, after which sodium methanethiol was added to the mixture, returned to room temperature and the reaction mixture was stirred for 20-25 hours. Diluting with ethyl acetate, washing with saturated saline water, concentrating the organic phase, and purifying the crude product by column chromatography to obtain 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde;
the embodiment of the invention also provides the application of the 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative in the fields of medicine, biology, materials and the like.
Compared with the prior art, the invention has the beneficial effects that: the preparation method provided by the invention synthesizes a target product by four steps, and adds 1,3, 5-tribromo-2, 4, 6-trimethylbenzene, NBS and BPO into CCl 4 Stirring and refluxing, performing column chromatography after the reaction is finished, then obtaining 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde through substitution reaction and oxidation reaction, and finally adding sodium methyl mercaptide for substitution to obtain a target product.
The 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative prepared by the invention can be used for realizing the synthesis of specific functional compounds (such as covalent organic framework materials) by Schiff base condensation reaction with amines with different topological structures. The 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative provides an important synthesis precursor for the material, and the obtained corresponding covalent organic framework material has wide application in the fields of medicine, biology, catalysis and the like, so that the preparation of the 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative has important significance.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1,3, 5-tribromo-2, 4, 6-tris (bromomethyl) benzene produced in step (1) of example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 2,4, 6-tribromobenzene-1, 3, 5-tricarbol prepared in step (2) of example 1 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde prepared in step (3) of example 1 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde prepared in step (4) of example 1 of the present invention;
FIG. 5 is a graph showing the infrared spectrum (FT-IR) of the Schiff base compound TMLTD-DAPO-COF based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde obtained in example 2 of the present invention;
FIG. 6 is a Scanning Electron Microscope (SEM) picture of the Schiff base compound TMLTD-DAPO-COF based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde obtained in example 2 of the present invention;
FIG. 7 is a solid powder diffraction (PXRD) pattern of the Schiff base compound TMLTD-DAPO-COF based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde obtained in example 2 of the present invention;
FIG. 8 is a graph showing the nitrogen isothermal adsorption of the Schiff base compound TMLTD-DAPO-COF based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde obtained in example 2 of the present invention;
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and practiced in great numbers to provide the technical solution of the present invention, which will be clearly and completely described below. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The invention mainly aims to provide a 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde derivative, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative, which has a structure shown in a formula (I):
in another aspect of the embodiments of the present invention, there is also provided a method for preparing a 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative, which includes:
(1) 1,3, 5-tribromo-2, 4, 6-trimethylbenzene, N-bromosuccinimide, benzoyl peroxide and tetrachloromethane are mixed, heated and refluxed for 20 to 24 hours, and then cooled. Filtering, concentrating, and performing column chromatography to obtain 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene;
(2) Adding 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene, potassium acetate and DMF into a flask, heating to 80-100 ℃, and stirring for 15-20 h. Cooling the reaction mixture to room temperature, adding water, extracting with DCM, concentrating the organic phase, adding potassium hydroxide and water into the solid, heating to 80-90 ℃, stirring for 24-48 h, cooling the reaction mixture to room temperature after the completion, washing with water, and drying to obtain 2,4, 6-tribromobenzene-1, 3, 5-tricarbonol;
(3) 2,4, 6-tribromobenzene-1, 3, 5-tricarbol, PCC, diatomaceous earth and DCM were added to the flask and stirred at room temperature for 2-3 days. Adding the reaction mixture into silica gel, concentrating, and performing column chromatography to obtain 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde;
(4) 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde and DMF were mixed at 0 ℃ under nitrogen atmosphere, after which sodium methanethiol was added to the mixture, returned to room temperature and the reaction mixture was stirred for 20-25 hours. After the reaction is finished, adding ethyl acetate for dilution, washing the mixture by using water and saturated saline solution, concentrating an organic phase, and carrying out column chromatography purification on a crude product to obtain 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde;
in some more specific embodiments, the molar ratio of 1,3, 5-tribromo-2, 4, 6-trimethylbenzene, N-bromosuccinimide and benzoyl peroxide in step (1) is 1: 3-6: 0.05-0.1;
further, the first solvent includes a chloromethane solvent, and is not limited thereto.
Further, the alcohol solvent includes carbon tetrachloride, and is not limited thereto.
In some more specific embodiments, the preparation method further comprises: and after the reaction of the first mixed reaction system is finished, filtering, washing, drying and purifying the obtained mixture.
Further, the purification treatment includes column chromatography separation purification treatment.
In some more specific embodiments, the molar ratio of 1,3, 5-tribromo-2, 4, 6-tris (bromomethyl) benzene, potassium acetate, and potassium hydroxide in step (2) is 1: 6-9: 10;
further, the first solvent includes DMF, and is not limited thereto.
In some more specific embodiments, the preparation method further comprises: and after the first mixed reaction system finishes the reaction, filtering, washing and drying the obtained mixture.
In some more specific embodiments, the molar ratio of the 2,4, 6-tribromobenzene-1, 3, 5-trimethanol, PCC, diatomite in step (3) is 1: 6-9: 10;
in some more specific embodiments, the preparation method further comprises: and after the first mixed reaction system finishes the reaction, filtering, washing, drying and purifying the obtained mixture.
Further, the purification treatment includes column chromatography separation purification treatment.
In some more specific embodiments, the molar ratio of the 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde to the sodium methyl mercaptide in step (4) is 1: 3-6;
in some more specific embodiments, the preparation method further comprises: and after the reaction of the first mixed reaction system is finished, washing, drying and purifying the obtained mixture.
Further, the purification treatment includes a column chromatography separation purification treatment.
In the invention, 1,3, 5-tribromo-2, 4, 6-trimethylbenzene is used as a raw material to synthesize the 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative, and the reaction route is shown as follows:
the technical solutions of the present invention will be further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were commercially available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Synthesis of 1,3, 5-tribromo-2, 4, 6-tris (bromomethyl) benzene:
under nitrogen atmosphere, 1,3, 5-tribromo-2, 4, 6-trimethylbenzene (1.76g, 5 mmol), N-bromosuccinimide(2.93g, 16.5 mmol) and benzoyl peroxide (60mg, 0.25mmol) were charged in a Schlenk bottle, to which 50mL of carbon tetrachloride was added. After the raw materials were dissolved, the mixture was warmed to 90 ℃ in an oil bath and heated under reflux for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, washed by DCM, collected and concentrated, and the obtained crude product is purified by column chromatography to obtain the product 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene with the yield of 95%, and the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 1. 1 H NMR(400MHz，DMSO-d 6 )δ3.28(s，6H)。
(2) Synthesis of 2,4, 6-tribromobenzene-1, 3, 5-tricarboxyiie:
1,3, 5-tribromo-2, 4, 6-tris (bromomethyl) benzene (593 mg, 1mmol) and potassium acetate (588 mg, 6 mmol) were added to the flask, after which 2.4mL of DMF was added to the flask. Then the temperature is increased to 80 ℃ and the mixture is heated and stirred for 20 hours. After the reaction is finished, the reaction mixture is cooled to room temperature, water is added into the mixture, DCM is used for extraction, 1M HCl, water and saturated saline are used for washing, KOH (605mg, 10mmol) and 10mL of water are added into a flask to be heated to 90 ℃ continuously for reaction for 24 hours, after the reaction is finished, the reaction mixture is cooled to room temperature, and the product 2,4, 6-tribromobenzene-1, 3, 5-tricarboxynol is obtained after filtration and drying, wherein the yield is 97%, and the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 2. 1 H NMR(400MHz，DMSO-d 6 )δ5.22(t，J ＝5.2Hz，3H)，4.85(d，J＝5.2Hz，6H)。
(3) Synthesis of 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde:
after 2,4, 6-tribromobenzene-1, 3, 5-trimethyl alcohol (202mg, 0.5 mmol), PCC (193mg, 8.9 mmol) and diatomaceous earth (0.7g, 12mmol) were added to a flask, 50mL of LPCM was added to the flask, the mixture was stirred at room temperature for 3 days, and after the reaction was completed,adding silica gel into the mixture, concentrating, and purifying by column chromatography to obtain the product with nuclear magnetic resonance hydrogen spectrum shown in FIG. 3. 1 H NMR(400MHz，DMSO-d 6 )δ10.07(s，3H)。
(4) Synthesis of 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde:
adding 2,4, 6-tribromobenzene-1, 3, 5-trimethyl aldehyde (80mg, 0.2mmol) into a Schlenk tube under the nitrogen atmosphere, then adding 2ml DMF into the Schlenk tube, reducing the temperature of a reaction system to 0 ℃, then adding sodium methyl mercaptide (44mg, 0.62mmol), stirring for 24 hours after the temperature is recovered to room temperature, adding ethyl acetate for dilution after the reaction is finished, then washing with water and saturated salt water, concentrating an organic phase, and purifying by column chromatography to obtain a product, wherein the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 4. 1 H NMR(400MHz， Chloroform-d)δ10.52(s，1H)，2.41(s，3H)。
Example 2
Preparation of Schiff base compounds based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde
18mg of 2,4, 6-tris (methylthio) benzene-1, 3, 5-triformal (TMLTD), 20.4mg of 10-methylphenoxazine-2, 7-Diamine (DAPO) were charged into a 10mL Schlenk's tube, followed by addition of 1.5mL of n-butanol and 1.5mL of o-dichlorobenzene, ultrasonic dissolution and addition of 0.2mL of a 3mol/L acetic acid solution. The reaction system was then subjected to three degassing cycles of freeze-vacuum-thaw in liquid nitrogen. And sealing the reaction mixture in a constant-temperature oven, heating to 120 ℃ and keeping the temperature for 3 days, cooling to room temperature after the reaction is finished, centrifuging the obtained mixture, collecting a solid, then centrifugally washing the solid by using DMF and THF, and drying in vacuum at 80 ℃ for 24 hours to obtain the red powder based on the Schiff base compound TMLTD-DAPO-COF of 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde, wherein the yield is 70%.
The Schiff base compound TMLTD-DAPO-COF based on 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde obtained in the example 2 of the invention is subjected to infrared spectrum test, X-ray powder diffraction, scanning electron microscope scanning and nitrogen adsorption and desorption test, the molecular structure, the crystalline state and the specific surface area are respectively characterized, and the characterization results are shown in figures 5-8; scanning electron microscope
As shown in FIG. 5, the obtained Schiff base compound based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde has an infrared spectrum. The result shows that the amino and aldehyde group in the raw material obviously disappear, and imine bond is generated, thus successfully preparing the target product;
as shown in FIG. 6, the scanning electron microscope image of the obtained Schiff base compound based on 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethylaldehyde shows that the material forms small spherical particles with uniform shapes, and the material structure is proved to be more uniform and regular.
As shown in fig. 7, the obtained powder X-ray diffraction pattern of the schiff base compound based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-triformal is consistent with the theoretical simulation results;
and FIG. 8 shows the nitrogen adsorption-desorption isotherms of the obtained Schiff base compounds based on 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde;
in addition, the inventors of the present invention have also made experiments with reference to the above examples and by using other raw materials, process operations, and process conditions described in the present specification, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered illustrative in all respects and not restrictive, the scope of the invention being defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the invention.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, as long as the teachings of the present invention remain operable. Further, two or more steps or actions may be performed simultaneously.
Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (8)
1. A2, 4, 6-tris (methylthio) benzene-1, 3, 5-triformylaldehyde derivative having the structure shown in formula (I):
2. the process for producing 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde derivatives according to claim 1, which comprises:
(1) 1,3, 5-tribromo-2, 4, 6-trimethylbenzene, N-bromosuccinimide, benzoyl peroxide and tetrachloromethane are mixed, heated and refluxed for 20 to 24 hours, and then cooled to room temperature. Filtering, removing solvent under reduced pressure, and performing column chromatography to obtain 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene;
(2) Adding 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene, potassium acetate and DMF into a flask, heating to 80-100 ℃, and stirring for 15-20 h. After the reaction is finished, cooling the reaction mixture, adding water, extracting with DCM, concentrating an organic phase, adding potassium hydroxide and water into the solid, heating to 80-90 ℃, stirring for 24-48 h, cooling to room temperature, washing with water, and drying to obtain 2,4, 6-tribromobenzene-1, 3, 5-tricarboxynol;
(3) 2,4, 6-tribromobenzene-1, 3, 5-tricarboxyiie, PCC, diatomaceous earth and DCM were added to the flask and stirred at room temperature for 2-3 days. After the reaction is finished, adding silica gel into the reaction mixture, concentrating, and carrying out column chromatography to obtain 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde;
(4) Under nitrogen atmosphere, 2,4, 6-tribromobenzene-1, 3, 5-trimethylaldehyde and DMF are mixed at 0 ℃, sodium methyl mercaptide is added into the mixture, the temperature is returned to room temperature, and the reaction mixture is stirred for 20-25 hours. Then ethyl acetate is added for dilution, the mixture is washed by saturated saline solution, the solvent is evaporated, and the crude product is purified by column chromatography to obtain 2,4, 6-tri (methylthio) benzene-1, 3, 5-trimethyl aldehyde.
3. The production method according to claim 2, characterized in that: the mol ratio of the 1,3, 5-tribromo-2, 4, 6-trimethylbenzene, the N-bromosuccinimide and the benzoyl peroxide in the step (1) is 1 to (3-6) to (0.05-0.1);
and/or, the first solvent comprises carbon tetrachloride;
the preparation method further comprises the following steps: and after the second uniform mixing reaction system finishes the reaction, filtering, washing the obtained mixture by using normal hexane, drying and purifying.
4. The method of claim 2, wherein: the molar ratio of the 1,3, 5-tribromo-2, 4, 6-tri (bromomethyl) benzene, the potassium acetate and the potassium hydroxide in the step (2) is 1: 6-9: 10;
and/or, the first solvent comprises DMF;
the preparation method further comprises the following steps: and after the third uniformly mixed reaction system finishes the reaction, washing and drying the obtained mixture.
5. The method of claim 2, wherein: in the step (3), the molar ratio of the 2,4, 6-tribromobenzene-1, 3, 5-tricarboxyane, the PCC and the diatomite is 1: 6-9: 10;
the preparation method further comprises the following steps: and after the third uniformly mixed reaction system finishes the reaction, filtering and purifying the obtained mixture.
6. The method of claim 2, wherein: in the step (4), the molar ratio of the 2,4, 6-tribromobenzene-1, 3, 5-trimethyl aldehyde to the sodium methyl mercaptide is 1: 3-6;
and/or, the protective atmosphere comprises a nitrogen atmosphere;
the preparation method further comprises the following steps: after the reaction of the third uniformly mixed reaction system is completed, the obtained mixture is neutralized, washed with saturated brine, dried and purified.
7. 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde derivative prepared by the process according to any one of claims 2 to 6.
8. A catalyst for catalytic reduction reaction of supported gold nanoparticles is characterized in that: comprising the 2,4, 6-tris (methylthio) benzene-1, 3, 5-trimethylaldehyde-based derivative according to any one of claims 1 and 7.
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| Title |
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| BASTIAN FELDSCHER 等: "A streamlined synthesis of extended thiophloroglucinol ligands and their trinuclear NiII 3 complexes", 《DALTON TRANS》, pages 4102 - 4114 * |
| QING-PU ZHANG 等: "Highly dispersed gold nanoparticles anchoring on post-modified covalent organic framework for catalytic application", 《CHEMICAL ENGINEERING JOURNAL》, 13 November 2019 (2019-11-13), pages 123471 * |
| RYAN MCCAFFREY 等: "本申请所述的2，4，6-三(甲硫基)苯-1，3，5-三甲醛基衍生物可用于制备负载金纳米粒子催化还原反应的催化剂", 《J. AM. CHEM. SOC.》, 16 January 2014 (2014-01-16), pages 1782 - 1785 * |
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