CN113372947A - Method for hydrogenating aromatic hydrocarbon by aqueous phase photocatalysis - Google Patents
Method for hydrogenating aromatic hydrocarbon by aqueous phase photocatalysis Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 title claims description 7
- 239000008346 aqueous phase Substances 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005286 illumination Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000004065 semiconductor Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- -1 alkane compound Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- PXACLMDMQJIEEB-UHFFFAOYSA-N 5,6-dihydroisoquinoline Chemical compound C1=NC=C2C=CCCC2=C1 PXACLMDMQJIEEB-UHFFFAOYSA-N 0.000 description 1
- MWPLVEDNUUSJAV-QDRJLNDYSA-N 9,10-dideuterioanthracene Chemical compound C1=CC=C2C([2H])=C(C=CC=C3)C3=C([2H])C2=C1 MWPLVEDNUUSJAV-QDRJLNDYSA-N 0.000 description 1
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 description 1
- XXPBFNVKTVJZKF-UHFFFAOYSA-N 9,10-dihydrophenanthrene Chemical compound C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 description 1
- 238000006027 Birch reduction reaction Methods 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for water-phase photocatalytic aromatic hydrocarbon hydrogenation, which takes semiconductor material boron, nitrogen and carbon as a photocatalyst and takes water as a hydrogen source to realize aromatic hydrocarbon hydrogenation under the conditions of room temperature and visible light illumination. According to the invention, the boron-nitrogen-carbon material is used for photocatalytic hydrogenation reaction for the first time, the reaction process is simple to operate, the used solvent is water, the catalytic effect is good, the reaction can be carried out under visible light, the conditions are mild, the cost is low, the requirements of actual production are met, and the application potential is great.
Description
Technical Field
The invention belongs to the technical field of photocatalytic organic synthesis, and particularly relates to a method for hydrogenation of aromatic hydrocarbon by aqueous phase photocatalysis.
Background
The hydrogenation of aromatic hydrocarbons is an important organic transformation in the form of the addition dearomatization of conjugated aromatic rings by hydrogen atoms to form olefinic or paraffinic compounds. The technology has important application in the industrial, agricultural and medical fields, for example, 1, 4-cyclohexadiene-containing compounds obtained by hydrogenation of benzene rings can be used as raw materials of bioactive molecules, natural products, spices and polymer materials.
Birch reduction is the best known method for hydrogenation of aromatics, however, this reaction requires the use of liquid ammonia as a solvent and the addition of pyrophoric alkali metal lithium or sodium to generate solvated electrons at low temperatures (j.am. chem. soc.2020,142, 13573-13581). The traditional industrial high-temperature high-pressure hydrogen reduction method usually needs to use noble metal or transition metal (Ru, Rh, Pd, Ni, Co, etc.) to catalyze the reaction, and has the problems of low atom economy and high synthesis cost (coord. chem. Rev.2016,314, 134-181; J.Am. chem. Soc.2018,140, 8624-8628.). Therefore, the search and development of green methods for aromatic hydrogenation are always the research hotspots of researchers.
The aromatic hydrogenation realized by the photocatalysis technology is more in line with green synthetic chemistry.
Subject groups have reported a conversion route to photocatalytic aromatics hydrogenation using the more expensive Ir [ dF (CF)3)ppy]2(dtbpy)PF6As a photosensitizer, DMF is used as a reaction solvent, so that efficient conversion is realized, but the method cannot recycle the catalyst and has higher reaction cost (Angew. chem. int. Ed.2019,58, 14289-14294.). Therefore, an innovative method with simple and easily available catalyst, simple and convenient reaction operation, mild reaction conditions, environmental protection and low cost needs to be developed.
Disclosure of Invention
The invention aims to provide a method for hydrogenating aromatic hydrocarbon by aqueous phase photocatalysis, which has higher selectivity, milder reaction condition and economic applicability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for hydrogenating aromatic hydrocarbon by water phase photocatalysis takes semiconductor material boron, nitrogen and carbon as photocatalyst and water as solvent, and aromatic hydrocarbon is hydrogenated under the conditions of room temperature and visible light illumination; the reaction equation is as follows:
wherein, the aromatic hydrocarbon is a compound containing benzene ring and conjugated heterocyclic ring.
The preparation method of the boron-nitrogen-carbon material with the graphite-like structure comprises the following steps:
(1) mixing urea, boric acid and citric acid in a mass ratio (1-10): (1-5): (1-10) grinding and uniformly mixing;
(2) calcining the mixed powder obtained in the step (1) at the temperature of 1000-1200 ℃ for 1-6h in an ammonia atmosphere to obtain the boron-nitrogen-carbon photocatalyst, and obtaining the BCN material with the specific surface area of 600-900m by using the isothermal adsorption-desorption curve shown in figure 1 and according to the BET (Brunauer-Emmet-Teller) formula2(ii)/g; from the ultraviolet-visible diffuse reflectance spectrum of fig. 2, it can be seen that the BCN material is a material with visible light response, and the absorption band edge is 400-600 nm.
Adding a photocatalyst, a surfactant and aromatic hydrocarbon into a solvent, and stirring and reacting for 7-24 hours at room temperature under the illumination condition of visible light; after the reaction is finished, dichloromethane or ethyl acetate is used for extracting reaction liquid, the photocatalyst is filtered out, organic phases are combined, dried, filtered, the solvent is distilled under reduced pressure, a crude product is obtained, and then column chromatography purification is carried out, so that the olefin or alkane compound subjected to hydrogenation and dearomatization is obtained.
Wherein the mass ratio of the photocatalyst to the aromatic hydrocarbon is 0.3: 1.
The surfactant is cetyl trimethyl ammonium bromide, sodium dodecyl sulfate or sodium lauryl sulfate.
The solvent is water.
The column chromatography purification adopts pure petroleum ether or a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5: 1-200: 1 as an eluent.
Boron nitrogen carbon (BCN) is a visible light response ternary semiconductor photocatalyst without metal elements, and has the advantages of low price, easy obtaining, good chemical stability, high specific surface area, no toxicity, no harm, proper forbidden bandwidth and energy band position and the like. The method takes aromatic hydrocarbon as a raw material, and obtains a product by hydrogenation of the aromatic hydrocarbon under the combined action of a photocatalyst and solvent water under the illumination of visible light.
The invention has the beneficial effects that:
(1) the method avoids the use of organic solvent and metal-containing catalyst, and is simple and easy to implement, mild in condition, green and safe;
(2) the method disclosed by the invention has the advantages that heating is not needed, higher yield can be obtained at room temperature under visible light, and the method is energy-saving and environment-friendly;
(3) the method has high economy, mild reaction conditions and good application prospects in the industrial, agricultural and medical fields;
(4) the catalyst used in the invention is simple and easy to obtain, and can be repeatedly used.
Drawings
FIG. 1 is a nitrogen adsorption and desorption graph of a boron-nitrogen-carbon material according to the present invention;
FIG. 2 is a diagram showing the UV-VIS absorption spectrum of the boron-nitrogen-carbon material of the present invention.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Adding 50mg of anthracene, 15mg of boron nitrogen carbon photocatalyst, 30mg of surfactant and 3ml of water into a reactor, stirring and reacting for 7 hours under room temperature illumination, extracting by using ethyl acetate after the reaction is finished, combining organic phases, drying, filtering, evaporating the solvent under reduced pressure to obtain a crude product, and purifying by using pure petroleum ether as an eluent through column chromatography to obtain 46.0mg of 9, 10-dihydroanthracene
Was obtained in 91% yield.
1H NMR(600MHz，CDCl3)：δ7.31(dd,J＝5.5,3.4Hz,4H),7.21(dd,J＝5.6,3.3Hz，4H),3.96(s,4H)。13C NMR(151MHz，CDCl3)：δ136.82,127.52,126.22,36.30。MS(m/z，EI)：180。
Example 2
Adding 50mg of phenanthrene and 15mg of boron nitrogen carbon light into a reactorCatalyst, 30mg of surfactant and 3ml of water are stirred and reacted for 7 hours under the illumination of room temperature, ethyl acetate is used for extraction after the reaction is finished, organic phases are combined, dried and filtered, the solvent is evaporated under reduced pressure to obtain a crude product, and then column chromatography purification is carried out by using pure petroleum ether as eluent to obtain 43.0mg of 9, 10-dihydrophenanthrene
Was obtained in 85% yield.
1H NMR(600MHz，CDCl3)：δ7.76(d,J＝7.7Hz，2H),7.33–7.29(m，2H),7.25–7.21(m，4H),2.88(s，4H)。13C NMR(151MHz，CDCl3)：δ137.53,134.61,128.26,127.51,127.08,123.83,29.18。MS(m/z，EI)：180。
Example 3
Adding 50mg of isoquinoline, 15mg of boron nitrogen carbon photocatalyst, 30mg of surfactant and 3ml of water into a reactor, stirring and reacting for 24 hours under room temperature illumination, extracting by using ethyl acetate after the reaction is finished, combining organic phases, drying, filtering, evaporating the solvent under reduced pressure to obtain a crude product, and purifying by column chromatography by using a petroleum ether-ethyl acetate mixed solvent with the volume ratio of 5:1 as an eluent to obtain 40.1mg of 5, 6-dihydroisoquinoline
Was obtained in 79% yield as a pale yellow oily liquid.
1H NMR(600MHz，CDCl3)：δ8.35(s,1H),8.32(d,J＝3.4Hz,1H),7.02(d,J＝4.5Hz,1H),5.95(d,J＝10.1Hz,1H),5.88(d,J＝10.3Hz,1H),3.36(s,4H)。13CNMR(151MHz，CDCl3)：δ149.88,146.89,143.39,130.36,124.72,123.78,123.27,29.09,26.70。MS(m/z，EI)：131。
Example 4
In a reactor, 50mg of 2-phenyl-6-fluoroimidazo [1,2-a ] was added]Pyridine, 15mg boron nitrogen carbon photocatalyst, 30mg surfactant and 3ml water are stirred and reacted for 24 hours under the illumination of room temperature, ethyl acetate is used for extraction after the reaction is finished, organic phases are combined, drying and filtering are carried out, the solvent is evaporated under reduced pressure to obtain a crude product, and the crude product is further processed into a solidPerforming column chromatography purification by using petroleum ether-ethyl acetate mixed solvent with volume ratio of 2:1 as eluent to obtain 42.4mg of 2-phenyl-6-fluoro-7, 8-dihydroimidazo [1,2-a ]]Pyridine compound
White solid (g), yield 84%.
1H NMR(600MHz，CDCl3)：δ7.80–7.71(m，2H),7.37(t,J＝7.8Hz，2H),7.26–7.22(m，1H),7.13(s,1H),5.63(dt,J＝16.0,3.9Hz，1H),4.64(t,J＝4.8Hz，2H),3.61(p,J＝4.9Hz，2H)。13C NMR(151MHz，CDCl3)：δ152.44,150.79,142.56,141.73(d,J＝2.4Hz),133.99,128.72,127.06,124.92,113.16(d,J＝2.8Hz),99.55(d,J＝16.3Hz),43.80(d,J＝41.6Hz),22.80(d,J＝8.2Hz)。19F NMR(565MHz，CDCl3)：δ-116.83(dt,J＝15.9,4.8Hz).MS(m/z，EI)：214。
Example 5
Adding 50mg of anthracene, 15mg of boron nitrogen carbon photocatalyst, 30mg of surfactant and 3ml of deuterium water into a reactor, stirring and reacting for 7 hours under room temperature illumination, extracting by using ethyl acetate after the reaction is finished, combining organic phases, drying, filtering, evaporating the solvent under reduced pressure to obtain a crude product, and purifying by using pure petroleum ether as an eluent through column chromatography to obtain 46.5mg of 9, 10-dideuteroanthracene
Was obtained in 91% yield.
1H NMR(600MHz，CDCl3)：δ7.31(dd,J＝5.2,3.5Hz,4H),7.21(dd,J＝5.4,3.3Hz,4H),3.94(s,2H)。13C NMR(151MHz，CDCl3)：δ136.80,127.51,126.23,36.19。MS(m/z，EI)：182。
The above description is only a preferred embodiment of the present invention, and all the changes of the precursor ratio for preparing the catalyst and the amounts of the catalyst and the reaction substrate according to the claims of the present invention should be covered by the present invention.
Claims (8)
1. A method for hydrogenating aromatic hydrocarbon by aqueous phase photocatalysis is characterized in that: the hydrogenation reaction of aromatic hydrocarbon in a water phase is realized by taking semiconductor material boron, nitrogen and carbon as a photocatalyst under the conditions of room temperature and visible light illumination; the aromatic hydrocarbon is a compound containing a benzene ring or a conjugated heterocyclic ring.
2. The method of claim 1, wherein: the boron, nitrogen and carbon is of a graphite-like structure, and the specific surface area is 600-900m2The absorption band edge is 400-600 nm.
3. The method of claim 1, wherein: the preparation of the boron nitrogen carbon comprises the following steps:
(1) urea, boric acid and citric acid are mixed according to the mass ratio of 1-10: 1-5: 1-10, and grinding uniformly;
(2) and (2) calcining the mixed powder in the step (1) for 1-6h at 1000-1200 ℃ in an ammonia atmosphere to obtain the boron nitrogen carbon.
4. The method of claim 1, wherein: the method comprises the following specific steps: directly adding a photocatalyst, a surfactant and an aromatic hydrocarbon raw material into a solvent, and stirring and reacting for 7-24 hours at room temperature under the illumination condition of visible light; after the reaction is finished, dichloromethane or ethyl acetate is used for extracting reaction liquid, the photocatalyst is filtered out, the organic phase is dried, filtered and distilled under reduced pressure to obtain a crude product, and then column chromatography purification is carried out to obtain the olefin or alkane compound subjected to hydrogenation and dearomatization.
5. The method of claim 4, wherein: the mass ratio of the photocatalyst to the aromatic hydrocarbon is 0.3: 1.
6. The method of claim 4, wherein: the solvent is water.
7. The method of claim 4, wherein: the surfactant is cetyl trimethyl ammonium bromide, sodium dodecyl sulfate or sodium lauryl sulfate.
8. The method of claim 4, wherein: the column chromatography purification adopts pure petroleum ether or a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5-200: 1 as an eluent.
Priority Applications (1)
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161006A (en) * | 2011-03-10 | 2011-08-24 | 济南大学 | Nano amorphous photocatalyst capable of utilizing sunlight and preparation method |
| CN108440236A (en) * | 2018-05-09 | 2018-08-24 | 福州大学 | A method of utilizing conductor photocatalysis hydrogenating reduction organohalogen compounds |
| CN109336756A (en) * | 2018-11-20 | 2019-02-15 | 河南大学 | A kind of hydrogenation-dehalogenation method of halogenated aromatic |
| CN111115649A (en) * | 2018-11-01 | 2020-05-08 | 国家纳米科学中心 | Preparation method of BCN nanosheet, BCN nanosheet prepared by preparation method and application of BCN nanosheet |
| CN111644131A (en) * | 2020-06-12 | 2020-09-11 | 中国科学院生态环境研究中心 | Method for degrading hexabromocyclododecane by using graphite-phase carbon nitride |
| US20200399196A1 (en) * | 2017-04-03 | 2020-12-24 | The Board Of Regents For Oklahoma State University | Hydrogen Bond Directed Photocatalytic Hydrodefluorination and Methods of Use Thereof |
-
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- 2021-06-10 CN CN202110650828.1A patent/CN113372947A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161006A (en) * | 2011-03-10 | 2011-08-24 | 济南大学 | Nano amorphous photocatalyst capable of utilizing sunlight and preparation method |
| US20200399196A1 (en) * | 2017-04-03 | 2020-12-24 | The Board Of Regents For Oklahoma State University | Hydrogen Bond Directed Photocatalytic Hydrodefluorination and Methods of Use Thereof |
| CN108440236A (en) * | 2018-05-09 | 2018-08-24 | 福州大学 | A method of utilizing conductor photocatalysis hydrogenating reduction organohalogen compounds |
| CN111115649A (en) * | 2018-11-01 | 2020-05-08 | 国家纳米科学中心 | Preparation method of BCN nanosheet, BCN nanosheet prepared by preparation method and application of BCN nanosheet |
| CN109336756A (en) * | 2018-11-20 | 2019-02-15 | 河南大学 | A kind of hydrogenation-dehalogenation method of halogenated aromatic |
| CN111644131A (en) * | 2020-06-12 | 2020-09-11 | 中国科学院生态环境研究中心 | Method for degrading hexabromocyclododecane by using graphite-phase carbon nitride |
Non-Patent Citations (1)
| Title |
|---|
| 曹声春等编著: "《催化原理及其工业应用技术》", 31 October 2001, 湖南大学出版社 * |
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