CN106518634A - Preparing method of photocatalytic alpha-diketone compound - Google Patents
Preparing method of photocatalytic alpha-diketone compound Download PDFInfo
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- CN106518634A CN106518634A CN201610917645.0A CN201610917645A CN106518634A CN 106518634 A CN106518634 A CN 106518634A CN 201610917645 A CN201610917645 A CN 201610917645A CN 106518634 A CN106518634 A CN 106518634A
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- preparation
- alpha
- derivatires
- diketone compound
- benzils
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- -1 methoxyl group Chemical group 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 9
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical group SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- PWOBDMNCYMQTCE-UHFFFAOYSA-N 2-chlorobenzenethiol Chemical compound SC1=CC=CC=C1Cl PWOBDMNCYMQTCE-UHFFFAOYSA-N 0.000 claims description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- WJTZZPVVTSDNJJ-UHFFFAOYSA-N 2-fluorobenzenethiol Chemical compound FC1=CC=CC=C1S WJTZZPVVTSDNJJ-UHFFFAOYSA-N 0.000 claims description 3
- 241001025261 Neoraja caerulea Species 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DSCJETUEDFKYGN-UHFFFAOYSA-N 2-Methoxybenzenethiol Chemical compound COC1=CC=CC=C1S DSCJETUEDFKYGN-UHFFFAOYSA-N 0.000 claims description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- JKIFPWHZEZQCQA-UHFFFAOYSA-N 2-nitrobenzenethiol Chemical compound [O-][N+](=O)C1=CC=CC=C1S JKIFPWHZEZQCQA-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 claims 1
- QSKWJTXWJJOJFP-UHFFFAOYSA-N chloroform;ethoxyethane Chemical compound ClC(Cl)Cl.CCOCC QSKWJTXWJJOJFP-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 125000005594 diketone group Chemical group 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- KXFSUVJPEQYUGN-UHFFFAOYSA-N trimethyl(phenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1 KXFSUVJPEQYUGN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910002915 BiVO4 Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- UZXDEYWUHSZPLQ-UHFFFAOYSA-N ClC1=CC=CC=C1.[S] Chemical group ClC1=CC=CC=C1.[S] UZXDEYWUHSZPLQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GJRLIZQTXAMQBS-UHFFFAOYSA-N [O-][N+](C1=CC=CC=C1)=O.SC1=CC=CC=C1 Chemical compound [O-][N+](C1=CC=CC=C1)=O.SC1=CC=CC=C1 GJRLIZQTXAMQBS-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000005784 autoimmunity Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004985 diamines Chemical group 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 description 1
- FGFUBBNNYLNVLJ-UHFFFAOYSA-N indolone Natural products C1=CC=C2C(=O)C=NC2=C1 FGFUBBNNYLNVLJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of medical and chemical intermediates and related chemicals, and provides a preparing method of photocatalytic alpha-diketone compound. Phenylacetylene and the derivative thereof are used as raw materials, and under the lighting condition, under the combined action of a semiconductor photocatalyst and an additive, alpha-diketone compound is generated through air oxygen in organic solvent. The preparing method has the advantages of being easy to operate, mild in condition and environmentally friendly, has probability of industrialization and obtains the alpha-diketone compound at the high yield, and the catalyst is recyclable. The alpha-diketone compound synthesized through the method can be further functionalized to obtain various compounds applied to development and research of natural products, function materials and fine chemicals.
Description
Technical field
The invention belongs to pharmaceutical-chemical intermediate and related chemistry technical field, are related to a kind of photocatalysis α-diketone chemical combination
The preparation method of thing.
Background technology
α-cyclohexadione compounds are the important fine chemicals such as synthesis imidazoles, quinoxaline and indolone oxynitride
Important intermediate, while itself is just prevalent in many natural products and bioactive molecule.[Maurya R.,
Singh R.,Deepak M.,et al.Phytochemistry 2004,65,915–920].Therefore, develop efficiently, synthesis α-
The method of cyclohexadione compounds, is of great significance and value.At present, the method for synthesizing α-cyclohexadione compounds is main
Have：Three kinds of methods such as nucleophilic addition-method of elimination, coupling method and oxidizing process.Wherein, nucleophilic addition-method of elimination development is relatively early, main
If there is nucleophilic addition elimination reaction using Grignard reagent, organolithium, organotin reagent etc. and carboxylic acid derivates.But,
Grignard reagent and organolithium reagent are very active, and reaction typically will be carried out at low temperature and the substrate functional group suitability is poor；Separately
Outward, organotin reagent toxicity is larger, therefore, limit application [Sibi M.P., the Marvin M., Sharma of the method
R.J.Org.Chem.,1995,56,5016–5023].Coupling method is single carbonyl of two molecules in the presence of metal or slaine
Based compound autoimmunity syndrome generates α-dione compounds.The reaction has the disadvantage the method one typically through free radical reaction course
As can only prepare symmetrical α-dione compounds [Collin, J., Namy, J.L., Dallemer, F., et
al.J.Org.Chem.,1991,56,3118–3122].Oxidizing process synthesis α-diketone is studied at present and using most one kind
Method, alkynes or alkene, ketone, alpha-alcohol ketone, vicinal diamines etc. can aoxidize generation α-dione compounds.But, report at present
The synthetic method in road, has that metal onidiges are expensive, reaction temperature is higher, and transition-metal catalyst cannot be recycled
Shortcoming.
The content of the invention
The invention provides a kind of novel fabrication method of photocatalysis α-dione compounds, the method environmental friendliness, condition
Gently, easy to operate, catalyst is recyclable and yield is higher.
Technical scheme：
A kind of preparation method of photocatalysis α-dione compounds, with 1,2- diphenyl acetylene derivatires for raw material, inorganic half
In the presence of conductor catalyst and additive, under illumination condition, react 12～18 hours in organic solvent, obtain α-diketone
Compound, synthetic route are as follows：
Wherein, R1, R2Selected from hydrogen (H), alkyl (alkyl), halogen (halogens), trifluoromethyl (CF3), formoxyl
(COMe), methoxyl group (OMe) and trimethyl silicon substrate (SiMe3), R1And R2It is identical or different；
Described 1,2- diphenyl acetylene derivatires are 1 with the mol ratio of inorganic semiconductor catalyst:0.1～1:0.5；
Described 1,2- diphenyl acetylene derivatires are 1 with the mol ratio of additive:0.5～1:2；
The molar concentration of described 1,2- diphenyl acetylene derivatires is 0.01mmol/mL～2mmol/mL.
Organic solvent includes tetrahydrofuran, ethanol, dichloromethane, acetone, acetonitrile, 1,4- dioxane, N, N- dimethyl
Methanamide etc., preferably acetonitrile.
Inorganic semiconductor catalyst includes titanium dioxide (TiO2), cadmium sulfide (CdS), Zinc Oxide (ZnO), nitrogen carbide
(C3N4), bismuth tungstate (Bi2WO6), pucherite (BiVO4)。
Additive includes phenylmercaptan., methylbenzene phenyl-sulfhydrate, chloro phenylmercaptan., fluorothiophenol, methoxybenzenethiol, Nitrobenzol
Thiophenol and correspondence thio-ether type compounds.
Light source includes the blue-ray LED of 5W-12W, the domestic white electricity-saving lamp and the xenon lamp of 50W-500W of 5W-25W.
Separation method includes recrystallization, column chromatography etc..Recrystallization method using solvent include benzene, ethanol, petroleum ether, second
Nitrile, tetrahydrofuran, chloroform, normal hexane, acetone, ethyl acetate, dichloromethane；When carrying out product separation with column chromatography method, can
So that using silica gel or aluminium oxide, used as fixing phase, developing solvent is generally polarity and nonpolar mixed solvent, such as ethyl acetate-
Petroleum ether, ethyl acetate-hexane, dichloromethane-petroleum ether, methanol-petroleum ether.
The invention has the beneficial effects as follows easy to operate, mild condition, environmental friendliness, industrialized probability is realized, and
And α-dione compounds are obtained with higher yields；Further functionalization can be obtained using the α-dione compounds synthesized by the method
To classes of compounds, the exploitation and research of natural product, functional material and fine chemicals is applied to.
Description of the drawings
Fig. 1 is 1- (4- methoxyphenyls) -2- benzils in embodiment 11H nuclear magnetic spectrograms.
Fig. 2 is 1- (4- methoxyphenyls) -2- benzils in embodiment 113C nuclear magnetic spectrograms.
Fig. 3 is 1- (3- bromophenyls) -2- benzils in embodiment 21H nuclear magnetic spectrograms.
Fig. 4 is 1- (3- bromophenyls) -2- benzils in embodiment 213C nuclear magnetic spectrograms.
Fig. 5 is 1- (3- aminomethyl phenyls) -2- benzils in embodiment 31H nuclear magnetic spectrograms.
Fig. 6 is 1- (3- aminomethyl phenyls) -2- benzils in embodiment 313C nuclear magnetic spectrograms.
Fig. 7 is 1- (4- chlorphenyls) -2- benzils in embodiment 41H nuclear magnetic spectrograms.
Fig. 8 is 1- (4- chlorphenyls) -2- benzils in embodiment 413C nuclear magnetic spectrograms.
Fig. 9 is 1- (4- acetyl phenyl) -2- benzils in embodiment 51H nuclear magnetic spectrograms.
Figure 10 is 1- (4- acetyl phenyl) -2- benzils in embodiment 513C nuclear magnetic spectrograms.
Figure 11 is 1- (4- halogen trimethylsilylbenzene bases) -2- benzils in embodiment 61H nuclear magnetic spectrograms.
Figure 12 is 1- (4- halogen trimethylsilylbenzene bases) -2- benzils in embodiment 613C nuclear magnetic spectrograms.
Figure 13 is 1,2- bis- (3- chlorphenyls) second diketone in embodiment 71H nuclear magnetic spectrograms.
Figure 14 is 1,2- bis- (3- chlorphenyls) second diketone in embodiment 713C nuclear magnetic spectrograms.
Figure 15 is 1- (1- naphthyls) -2- benzils in embodiment 81H nuclear magnetic spectrograms.
Figure 16 is 1- (1- naphthyls) -2- benzils in embodiment 813C nuclear magnetic spectrograms.
Specific embodiment
The preparation method of α-dione compounds of the present invention, with low in raw material price, reactions steps are few, react bar
Part is gentle, environmental friendliness, the advantages of be easy to high operation, reaction yield and catalyst recoverable.
With reference to specific embodiment, the present invention is expanded on further.These embodiments be merely to illustrate the present invention and without
In restriction the scope of the present invention.The simple replacement or improvement done to the present invention by technical staff in the art belongs to this
Within bright protected technical scheme.
Embodiment 1：The synthesis of 1- (4- methoxyphenyls) -2- benzils
In 25mL reactors, 1- methoxyl group -4- (phenylene-ethynylene) benzene (0.052g, 0.025mmol) is added, to methyl
Phenylmercaptan. (0.031g, 0.25mmol), TiO2(0.010g, 0.125mmol), ethanol 2mL are stirred under 12W Blue-LED lamps
After 16h, column chromatography for separation (silica gel, 200-300 mesh；Petroleum ether：Ethyl acetate=50:1) obtain 1- (4- methoxyphenyls) -2-
Benzil 0.041g, yield 68%.
1- (4- methoxyphenyls) -2- benzils
Yellow liquid,1H NMR(CDCl3, 400MHz) and δ 7.98 7.93 (m, 4H), 7.65 7.61 (m, 1H), 7.51
(7.47 m, 2H), 7.98 7.93 (m, 2H), 6.98 6.96 (m, 2H), 3.87 (s, 3H)；13C NMR(CDCl3,100MHz):δ
194.9,193.2,165.0 134.7,133.2,132.4,129.9,129.0,126.1,114.4,55.7.
Embodiment 2：The synthesis of 1- (3- bromophenyls) -2- benzils
Operation obtains 1- (3- bromophenyls) -2- phenyl second two with embodiment 1 by the reaction of 1- bromo- 3- (phenylene-ethynylene) benzene
Ketone 0.056g, yield 78%.
1- (3- bromophenyls) -2- benzils
Yellow solid；1H NMR(CDCl3, 400MHz) and δ 8.13 (s, 1H), 7.97 (d, J=7.2,2H), 7.884 (d, J=
7.6,1H), 7.78 (d, J=8.0,1H), 7.69 7.66 (m, 1H), 7.55 7.51 (m, 2H), 7.32-7.43 (m, 1H)；13C
NMR(100MHz,CDCl3)δ193.6,192.9,137.7,135.2,134.7,132.7,130.6,130.0,129.1,
128.6,123.3.
Embodiment 3：The synthesis of 1- (3- aminomethyl phenyls) -2- benzils
In 25mL reactors, 1- methyl -3- (phenylene-ethynylene) benzene (0.048g, 0.025mmol), adjacent chlorobenzene sulfur is added
Phenol (0.036g, 0.25mmol), BiVO4(0.040g, 0.125mmol), ethanol 2mL stir 16h under 12W Blue-LED lamps
Afterwards, column chromatography for separation (silica gel, 200-300 mesh；Petroleum ether：Ethyl acetate=50:1) obtain 1- (3- aminomethyl phenyls) -2- phenyl
Second diketone 0.040g, yield 65%.
1- (3- aminomethyl phenyls) -2- benzils
Yellow solid；1H NMR(CDCl3, 400MHz) and δ 7.97 (d, J=7.6Hz, 2H), 7.78 7.76 (m, 2H),
7.67–7.64(m,1H),7.53–7.38(m,4H),2.41(s,3H)；13C NMR(100MHz,CDCl3)δ194.8,139.0,
135.8,134.8,133.1,130.0,129.0,128.9,127.2.
Embodiment 4：The synthesis of 1- (4- chlorphenyls) -2- benzils
In 25mL reactors, 1- chloro- 4- (phenylene-ethynylene) benzene (0.052g, 0.025mmol) is added, to chlorothio-phenol
(0.036g, 0.25mmol), CdS (0.018g, 0.125mmol), tetrahydrofuran 2mL, stirs 10h under 12W Blue-LED lamps
Afterwards, column chromatography for separation (silica gel, 200-300 mesh；Petroleum ether：Ethyl acetate=50:1) obtain 1- (4- chlorphenyls) -2- phenyl second
Diketone 0.046g, yield 75%.
1- (4- chlorphenyls) -2- benzils
Yellow solid；1H NMR(CDCl3,400MHz)δ7.98–7.92(m,4H),7.67–7.65(m,1H),7.54–
7.48(m,4H)；13C NMR(100MHz,CDCl3)δ193.9,193.0,141.6,135.1,132.8,131.4,131.2,
130.0,129.4,129.1.
Embodiment 5：The synthesis of 1- (4- acetyl phenyl) -2- benzils
In 25mL reactors, 4- (phenylene-ethynylene) 1-Phenylethanone. (0.055g, 0.025mmol) is added, to chlorothio-phenol
(0.036g, 0.25mmol), ZnO (0.010g, 0.125mmol), tetrahydrofuran 2mL, stirs 10h under 12W Blue-LED lamps
Afterwards, column chromatography for separation (silica gel, 200-300 mesh；Petroleum ether：Ethyl acetate=50:1) obtain 1- (4- acetyl phenyl) -2- phenyl
Second diketone 0.041g, yield 65%.
1- (4- acetyl phenyl) -2- benzils
Yellow solid；1H NMR(CDCl3, 400MHz) and δ 8.07 (s, 4H), 7.98 (d, J=7.6Hz, 2H), 7.71 7.67
(m,1H),7.55–7.52(m,2H),2.65(s,3H)；13C NMR(100MHz,CDCl3)δ197.2,193.8,193.6,
141.3,136.0,135.2,132.7,130.1,130.0,129.1,128.7,26.9.
Embodiment 6：The synthesis of 1- (4- halogen trimethylsilylbenzene bases) -2- benzils
In 25mL reactors, 4- (trimethylsilyl) tolan (0.062g, 0.025mmol) is added, to chlorothio-phenol
(0.036g, 0.25mmol), ZnO (0.010g, 0.125mmol) are stirred under dichloromethane 2mL, 20W domestic white energy-conservation light irradiation
After mixing 18h, column chromatography for separation (silica gel, 200-300 mesh；Petroleum ether：Ethyl acetate=100:1) obtain 1- (4- trimethylsilyl benzene
Base) -2- benzil 0.051g, yield 72%.
1- (4- trimethylsilyl phenyl) -2- benzils
Yellow solid；1H NMR(CDCl3,400MHz)δ7.98–7.91(m,4H),7.68–7.63(m,3H),7.52–
7.48(m,2H),0.29(s,9H)；13C NMR(100MHz,CDCl3)δ194.9,194.7,150.0,134.9,133.9,
133.1,133.0,129.9,128.7,-1.42.
Embodiment 7：The synthesis of 1,2- bis- (3- chlorphenyls) second diketone
Operation obtains 1,2- bis- (3- chlorphenyls) second diketone with embodiment 6 by 1,2- bis- (3- chlorphenyls) acetylene reaction
0.055g, yield 78%.
1,2- bis- (3- chlorphenyls) second diketone
Yellow solid；1H NMR(CDCl3, 400MHz) and δ 7.96 (s, 2H), 7.83 (d, J=8.0Hz, 2H), 7.65 1.63
(m,1H)；13C NMR(100MHz,CDCl3)δ192.0,135.5,135.0,134.1,130.4,129.6,128.2.
Embodiment 8：The synthesis of 1- (1- naphthyls) -2- benzils
In 25mL reactors, 1- (1- naphthyls) -2- phenylacetylenes (0.057g, 0.025mmol) are added, to fluoro thiophenol
(0.032g, 0.25mmol), BiVO4(0.040g, 0.125mmol), dichloromethane 2mL, the lower stirring 18h of 100W xenon lamps irradiation
Afterwards, column chromatography for separation (silica gel, 200-300 mesh；Petroleum ether：Ethyl acetate=20:1) obtain 1- (1- naphthyls) -2- phenyl second two
Ketone 0.020g, yield 31%.
1- (1- naphthyls) -2- benzils
Yellow solid；1H NMR(CDCl3, 400MHz) and δ 9.30 (d, J=8.8Hz, 1H), 8.12 (d, J=8.4Hz, 1H),
8.04–8.02(m,2H),7.95-7.90(m,2H),7.77–7.73(m,1H),7.68–7.61(m,2H),7.54–7.47(m,
3H)；13C NMR(100MHz,CDCl3)δ197.2,194.6,136.0,135.1, 134.8,134.1,133.4,129.5,
128.6,126.0,124.4。
Claims (8)
1. a kind of preparation method of photocatalysis α-dione compounds, it is characterised in that with 1,2- diphenyl acetylene derivatires for raw material,
In the presence of inorganic semiconductor catalyst and additive, under illumination condition, react 12～18 hours in organic solvent, obtain
To α-dione compounds, synthetic route is as follows：
Wherein, R1, R2Selected from hydrogen, alkyl, halogen, trifluoromethyl, formoxyl, methoxyl group and trimethyl silicon substrate, R1And R2It is identical or
It is different；
Described 1,2- diphenyl acetylene derivatires are 1 with the mol ratio of inorganic semiconductor catalyst:0.1～1:0.5；
Described 1,2- diphenyl acetylene derivatires are 1 with the mol ratio of additive:0.5～1:2；
The molar concentration of described 1,2- diphenyl acetylene derivatires is 0.01mmol/mL～2mmol/mL.
2. preparation method according to claim 1, it is characterised in that described organic solvent is dichloromethane, ethylene glycol
Dimethyl ether, chloroform ether, tetrahydrofuran, dimethyl sulfoxide, carbon tetrachloride, N,N-dimethylformamide, acetone, toluene,
1,4- dioxane, normal hexane.
3. preparation method according to claim 1 and 2, it is characterised in that described additive is phenylmercaptan., methylbenzene sulfur
One kind or two in phenol, chloro phenylmercaptan., fluorothiophenol, methoxybenzenethiol, nitro thiophenol, correspondence thio-ether type compounds
Plant mixed above.
4. preparation method according to claim 1 and 2, it is characterised in that described inorganic semiconductor catalyst is dioxy
Change one or more mixing in titanium, cadmium sulfide, Zinc Oxide, nitrogen carbide, bismuth tungstate, pucherite.
5. preparation method according to claim 3, it is characterised in that described inorganic semiconductor catalyst is titanium dioxide
One or more mixing in titanium, cadmium sulfide, Zinc Oxide, nitrogen carbide, bismuth tungstate, pucherite.
6. the preparation method according to claim 1,2 or 5, it is characterised in that blue light of the described light source for 5W-12W
The white electricity-saving lamp or the xenon lamp of 50-500W of LED, 5-25W.
7. preparation method according to claim 3, it is characterised in that blue-ray LED, 5- of the described light source for 5W-12W
The white electricity-saving lamp or the xenon lamp of 50-500W of 25W.
8. preparation method according to claim 4, it is characterised in that blue-ray LED, 5- of the described light source for 5W-12W
The white electricity-saving lamp or the xenon lamp of 50-500W of 25W.
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| CN110467524B (en) * | 2018-05-09 | 2022-08-30 | 中国科学院理化技术研究所 | Method for preparing 1, 2-dicarbonyl compound through photocatalytic oxidation reaction |
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