CN105777466A - Method for converting halogenated aromatic hydrocarbon into aromatic hydrocarbon through visible light catalysis - Google Patents
Method for converting halogenated aromatic hydrocarbon into aromatic hydrocarbon through visible light catalysis Download PDFInfo
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- CN105777466A CN105777466A CN201610205806.3A CN201610205806A CN105777466A CN 105777466 A CN105777466 A CN 105777466A CN 201610205806 A CN201610205806 A CN 201610205806A CN 105777466 A CN105777466 A CN 105777466A
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- visible light
- halogenated aryl
- aromatic hydrocarbon
- catalyst
- aryl hydrocarbon
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 27
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 25
- -1 halogenated aryl hydrocarbon Chemical class 0.000 claims description 19
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 claims description 5
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 claims description 3
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 claims 1
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 claims 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 claims 1
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 claims 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 claims 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims 1
- 125000006575 electron-withdrawing group Chemical group 0.000 claims 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 230000002035 prolonged effect Effects 0.000 claims 1
- 208000011580 syndromic disease Diseases 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 13
- 238000005286 illumination Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/63—Platinum group metals with rare earths or actinides
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for converting halogenated aromatic hydrocarbon into aromatic hydrocarbon by visible light catalysis. The method comprises the steps of taking halogenated aromatic hydrocarbon derivatives as raw materials, adding alkali and alcohol, taking a supported semiconductor material as a catalyst, vacuumizing or introducing nitrogen under the condition of magnetic stirring, removing air in a system, irradiating by using a visible light source, wherein the light intensity is 0.2-0.8W/cm2And reacting for 6-24 h at 20-60 ℃. The method has the advantages of simple and convenient operation, easily obtained raw materials, mild reaction conditions, high conversion rate, good selectivity and capability of recycling the catalyst.
Description
Technical field
The invention belongs to virtue hydrocarbons and their derivates preparing technical field, be specifically related to a kind of method that visible light catalytic halogenated aryl hydrocarbon changes into aromatic hydrocarbons.
Background technology
Along with the high speed development of human society, it is more and more comfortable that the life of people becomes, and everything all has inseparable contacting with the development of chemical industry.But, they, while bringing our more chemical products, also result in a series of problem, creates substantial amounts of organic and inorganic pollutant, and the health of human body is all had a significant impact by these.Organohalogen compounds are main ingredients in these pollutant.Early stage people be all by with burying, burn, the mode such as biodegradation carry out processing organohalogen compounds, but these methods all can produce carbon dioxide isothermal chamber gas.Therefore, seeking new transformation technology and halogenated aryl hydrocarbon changes into the utilizable chemicals of people, this thinking turned waste into wealth becomes the study hotspot of people.
The method that disclosed a lot of halogenated aryl hydrocarbon changes into aromatic hydrocarbons in recent years.Report has use catalyst at present, the method for synthesis when high temperature, atmosphere of hydrogen.Or use certain solvent to provide hydrogen source when high temperature, halogenated aryl hydrocarbon is reduced.As adopting the heterogeneous catalysis of the reusable edible prepared of noble-metal-supported semi-conducting material in this article, reacting when visible ray, and have that green, safety, conversion ratio be high and yield advantages of higher.
Summary of the invention
It is an object of the invention to provide a kind of operating condition simple, catalyst can Reusability, reaction condition is gentle, and selectivity is high, and the halogenated aryl hydrocarbon that yield is high changes into the method for aromatic hydrocarbons.Compared with method described in prior art, the maximum feature of this system be use heterogeneous catalysis, be easily isolated, and easy and simple to handle, raw material is easy to get, it is little to pollute, productivity is high, safety is cheap and environmental protection.
The present invention is with quasiconductor carried noble metal material for catalyst, and halogenated aryl hydrocarbon is reaction substrate, and reaction temperature is 20 DEG C～60 DEG C, and the response time is 6～24 hours, and in isopropyl alcohol phase, efficient catalytic prepares corresponding aromatic hydrocarbons.Wherein, halogenated aryl hydrocarbon used is parachlorotoluene, and described halogen can be chlorine, bromine, iodine etc.；Described substituent group is hydrogen, electrophilic, donor residues.The position relationship of halogen and substituent group can be ortho position, a position, para-position.
The following chemical equation of the concrete reaction equation (1) of the present invention:
Wherein X represents halogen, it is possible to being chlorine, bromine, iodine etc., R represents hydrogen, electrophilic, donor residues.The position relationship of R and X can be ortho position, a position, para-position.
The preferred reaction step of the present invention is as follows:
Beaker weighs 2.00gCeO2Nanometer powder does carrier, and the lysine solution that concentration is 0.53mol/L adding 20.0mL makees stabilizer, quickly stirs, and adds the PdCl that concentration is 0.01mol/L of 56.8mL2Solution does carried metal source, is stirred vigorously 30min, the NaBH being 0.035mol/L with the concentration of the speed of 1/s dropping 7mL4Solution reduces.Standing 24h after stirring 30min, described mixed solution cloth funnel filters, and 60 DEG C of dry 12h of vacuum drying oven put into by filter cake.Grinding obtains quasiconductor loaded palladium catalyst, obtains Pd/CeO2Catalyst.
Reaction vessel adds the halogenated aryl hydrocarbon of 10mmol, then add 5～20mL solvent to being completely dissolved, add 0.10gPd/CeO2Catalyst and 1～2mmol alkali, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, range of light intensity 0.2～0.8W/cm2, react under 20～60 DEG C of conditions of temperature.Terminate after reaction a period of time, separate purification and obtain product.
Solvent used in this reaction has ethanol, isopropanol, and wherein isopropanol effect is best.
The invention have the advantages that and use heterogeneous catalysis in the reaction, it is easy to separate and can recycle.Synthetic reaction is easy and simple to handle, and raw material is easy to get, and reaction selectivity is high, and conversion ratio is high, and yield is high, pollutes little, and productivity is high, and safety is cheap, environmental protection and low energy consumption.
Detailed description of the invention
Lifting specific embodiment below again the present invention is further described, single present disclosure is not limited thereto.
Embodiment 1: use Pd/CeO2Catalysis parachlorotoluene is changed into toluene
Reaction vessel adds the parachlorotoluene of the 10mmol of 1.26g, then adds 5mL isopropanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.60g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 99%, and productivity is 97%.
Embodiment 2: use Pd/CeO2Catalysis parachlorotoluene is changed into toluene
Reaction vessel adds the parachlorotoluene of the 10mmol of 1.26g, then adds 5mL isopropanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.60g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.30W/cm2, react under 25 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 82%, and productivity is 81%.
Embodiment 3: use Pd/CeO2Catalysis parachlorotoluene is changed into toluene
Reaction vessel adds the parachlorotoluene of the 10mmol of 1.26g, then adds 10mL ethanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.80g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, react when temperature 50 C.Terminate after reacting 6 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 89%, and productivity is 87%.
Embodiment 4: use Pd/CeO2Catalysis ortho-chlorotolu'ene is changed into toluene
Reaction vessel adds the ortho-chlorotolu'ene of the 10mmol of 1.26g, then adds 5mL isopropanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.60g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.60W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 99%, and productivity is 98%.
Embodiment 5: use Pd/CeO2Catalysis m-chlorotoluene is changed into toluene
Reaction vessel adds the m-chlorotoluene of the 10mmol of 1.26g, then adds 10mL isopropanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.60g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.60W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 96%, and productivity is 94%.
Embodiment 6: use Pd/CeO2Catalysis chloroanisole will be changed into methyl phenyl ethers anisole
Reaction vessel adds 1.42g 10mmol to chloroanisole, then add 5mL isopropanol, add 0.10gPd/CeO2The potassium hydroxide of catalyst and 0.70g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 18 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 96%, and productivity is 94%.
Embodiment 7: use Pd/CeO2Catalysis bromobenzene is changed into benzene
Reaction vessel adds the bromobenzene of the 10mmol of 1.57g, then adds 5mL isopropanol, add 0.10gPd/CeO2The sodium carbonate of catalyst and 0.12g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 98%, and productivity is 73%.
Embodiment 8: use Pd/CeO2Catalysis parabromotoluene is changed into toluene
Reaction vessel adds the parabromotoluene of the 10mmol of 1.71g, then adds 5mL isopropanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.60g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 90%, and productivity is 88%.
Embodiment 9: use Pd/CeO2Catalysis iodotoluene will be changed into toluene
Reaction vessel adds 2.18g 10mmol to iodotoluene, then add 10mL ethanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.60g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 12 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 98%, and productivity is 97%.
Embodiment 10: use Pd/CeO2Catalysis chlorobenzene is changed into benzene
Reaction vessel adds the chlorobenzene of the 10mmol of 1.12g, then adds 5mL isopropanol, add 0.10gPd/CeO2The sodium hydroxide of catalyst and 0.60g, and bottom liquid level, it is continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, react under 40 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 86%, and productivity is 82%.
Embodiment 11: use Pd/CeO2Catalysis Nitrobromobenzene will be changed into Nitrobenzol
Reaction vessel adds 2.02g 10mmol to Nitrobromobenzene, then add 20mL isopropanol, add the sodium hydroxide of 0.10gPd/CeO2 catalyst and 0.60g, and bottom liquid level, be continually fed into nitrogen 5 minutes, rapid sealed reactor.Under visible light illumination, light intensity 0.50W/cm2, reacts under 40 DEG C of conditions of temperature.Terminate after reacting 24 hours, separate purification and obtain product.Being detected by high performance liquid chromatography, can obtain conversion ratio is 83%, and productivity is 80%.
Claims (7)
1. the method that halogenated aryl hydrocarbon is changed into aromatic hydrocarbons by visible light catalytic, adds solvent in reaction vessel, adds substrate halogenated aryl hydrocarbon, alkali and Pd/CeO2Catalyst, passes into nitrogen when magnetic agitation, uses visible light source prolonged exposure, and reaction certain time obtains product；Following chemical equation (1) X therein represents chlorine, bromine, iodine；R represents hydrogen, donor residues, electron-withdrawing group；The position relationship of R and X can be ortho position, a position, para-position.
。
2. the substrate halogenated aryl hydrocarbon described in claim 1 makes consumption be 1 with the amount of substance of alkali: (1～2), the quality of reacting middle catalyst and halogenated aryl hydrocarbon mass ratio 1: (0.02～0.10), the amount adding solvent is that the substance withdrawl syndrome ensureing halogenated aryl hydrocarbon is maintained at 0.5～2.0mol/L.
3. the solvent described in claim 1 is ethanol, isopropanol.
4. the alkali described in claim 1 is sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, in order to neutralize the hydrogen halides produced in reaction.
5. visible light source used in claim 1, its range of light intensity 0.2～0.8W/cm2。
6. in claim 1, reaction temperature is 20～60 DEG C, and the response time is 6-24h.
7. claim 1 substrate be chlorobenzene, bromobenzene, iodobenzene, parachlorotoluene, parabromotoluene, to iodotoluene, ortho-chlorotolu'ene, m-chlorotoluene, o-bromotoluene, m-bromotoluene, adjacent iodotoluene, an iodotoluene, to halogenated aryl hydrocarbons such as chloroanisole, para-bromoanisole, paraiodoanisole, p-Nitrobromobenzene, o-chloro-anisole, o-bromo-anisole, parachloronitrobenzene, m-chloro-nitrobenzene, o-chloronitrobenzenes.
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| CN110152649A (en) * | 2019-06-14 | 2019-08-23 | 昆明理工大学 | A kind of preparation method and application of pros' phase bismuth oxide active carbon photochemical catalyst |
| CN110294661A (en) * | 2018-03-23 | 2019-10-01 | 中国科学院化学研究所 | A method of more complete debrominates of bromo aromatic compound are realized using photo-reduction |
| CN111715262A (en) * | 2020-07-03 | 2020-09-29 | 重庆工商大学 | Preparation of palladium-gold loaded nitrogen-rich carbon nitride photocatalyst and C-C bonding |
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| CN110294661A (en) * | 2018-03-23 | 2019-10-01 | 中国科学院化学研究所 | A method of more complete debrominates of bromo aromatic compound are realized using photo-reduction |
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| CN110152649A (en) * | 2019-06-14 | 2019-08-23 | 昆明理工大学 | A kind of preparation method and application of pros' phase bismuth oxide active carbon photochemical catalyst |
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