CN109694312A - A kind of method of photocatalysis cyclohexene selection synthesis cyclohexenone - Google Patents
A kind of method of photocatalysis cyclohexene selection synthesis cyclohexenone Download PDFInfo
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- CN109694312A CN109694312A CN201811599929.5A CN201811599929A CN109694312A CN 109694312 A CN109694312 A CN 109694312A CN 201811599929 A CN201811599929 A CN 201811599929A CN 109694312 A CN109694312 A CN 109694312A
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 27
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 26
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000011097 chromatography purification Methods 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 description 9
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 150000002561 ketenes Chemical class 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical group OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- -1 schiff base metal complex compound Chemical class 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- IEDJQFLYCAHDBS-UHFFFAOYSA-N 2,3-bis(1h-pyrazol-5-yl)pyridine Chemical class N1C=CC(C=2C(=NC=CC=2)C2=NNC=C2)=N1 IEDJQFLYCAHDBS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- IVUMCTKHWDRRMH-UHFFFAOYSA-N carprofen Chemical compound C1=CC(Cl)=C[C]2C3=CC=C(C(C(O)=O)C)C=C3N=C21 IVUMCTKHWDRRMH-UHFFFAOYSA-N 0.000 description 1
- 229960003184 carprofen Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B01J35/39—
Abstract
The present invention relates to photocatalysis synthesis technical field more particularly to a kind of methods of photocatalysis cyclohexene selection synthesis cyclohexenone.Reactant cyclohexene, photochemical catalyst, oxidants hydrogen peroxide and solvent are added in reactor, under magnetic stirring, ultraviolet source is opened or visible light source carries out reaction 1-6h；To which after reaction, reaction mixture is centrifuged.The features such as present invention, as reaction medium, reduces the pollution to environment without using organic solvents such as acetonitriles, and the poly- wolframic acid quaternary ammonium salt preparation process of used ten is simple, recycles convenient separation, and catalytic activity is high.
Description
Technical field
The present invention relates to photocatalysis synthesis technical field more particularly to a kind of photocatalysis cyclohexene selection synthesis cyclohexenones
Method.
Background technique
Cyclonene is also known as 2- cyclohexene -1- ketone or 2- cyclonene, and as a kind of typical six-membered cyclic α, β-is no
It is saturated carbonyls, cyclonene possesses a large amount of derivative, is widely used in the production of the fine chemistry industries such as medicine, pesticide, essence
In the synthesis of product, such as synthesizing steroid, cyclohexenone analog herbicide, anti-inflammatory analgesic Carprofen.Have very at present
Mostly about cyclonene and its derivative synthetic method report, wherein from cyclohexene be raw material Selective Oxidation
It is the hot spot of research.Early stage cyclonene synthetic method is to use chromic acid for catalyst, and solvent is glacial acetic acid, this method yield
Low, selectivity of product is poor, while environmental pollution is serious, do not meet modern chemical industry economy, green, environmental protection requirement.Therefore green
The method of efficient synthesizing cyclohexane 1 ketenes, which seems, to become more and more important.
Preparing cyclonene by cyclohexene oxide is to report more one of method at present, and common oxidant is aerobic
Gas, hydrogen peroxide (H2O2), tert-butyl hydroperoxide (TBTP) etc., but real reaction process is more complicated leads to product distribution also very
Complexity, therefore developing efficient, highly selective catalyst is the key that cyclohexene oxide prepares cyclonene.Oxygen is as oxygen
Source be considered as green oxidant, but directly using oxygen as oxidant when, oxidability is limited, and selectivity of product is poor.Mesh
The preceding catalyst research for preparing cyclonene by molecular oxygen oxidation cyclohexene focuses primarily upon the imitative of schiff base metal complex compound
Raw catalyst and containing n-donor ligand metal complex.Guo Cancheng etc. (Journal of Chemical Industry and Engineering, 2004,55 (9): 1 537-1 540) is solvent-free
Under the conditions of porphyrin cobalt complex air catalytic cyclohexene synthesizing cyclohexane 1 ketenes, cyclohexene conversion rate 21%, cyclonene selectivity
75%.Tert-butyl hydroperoxide (TBHP) is that cyclohexene oxide prepares one of efficient oxidation agent of cyclonene.Superfine (the lake of Xue
Northern college journal, 2017,39 (6): 668-672) by N- be alkylated after bis- (pyrazolyl) pyridines of 2,6- and cupric salt conjunction
Cyclohexene oxide, the substrate transformation rate 62.6%, cyclonene selectivity 97.7% are catalyzed at tridentate ligand copper complex.It removes
Outside oxygen, hydrogen peroxide (H2O2) it is also one of common Green Oxidant.Using hydrogen peroxide as oxygen source, relevant report is with multiphase
Based on catalyst.Lugue etc. (Applied Catalysis, A:General, 2008,341 (1-2): 154-159) ultrasound item
Cyclohexene oxide cyclonene yield is catalyzed up to 89% with the schiff bases cobalt that SBA-15 is supported under part.
However, these catalyst systems require to give reaction temperature appropriate, catalyst structure is complicated, higher cost, mirror
In above-mentioned all kinds of catalyst system Shortcomings, develop it is a kind of prepare it is simple, be easily isolated, the active green high-efficient catalysis of room temperature
Agent is still the emphasis of cyclohexene oxide research.The rise of photocatalysis organic synthesis opens a new synthetic route, photocatalysis
Organic synthesis is because using solar energy as energy source, with the advantages such as reaction temperature is low, low energy consumption by favor.Closely
Nian Lai, polyoxometallate (POM) has as one kind and TiO2The molecular material of identity function causes the very big emerging of people
Interest, studies have shown that POM also has preferable photocatalysis performance.Wherein ten poly- wolframic acid quaternary ammonium salts are as a kind of polyacid class photocatalysis
Agent has very strong photooxidation catalytic activity to hydrocarbon.Ten poly- wolframic acid quaternary ammonium salts have been reported for cyclohexene
Heat catalytic oxidation, under conditions of there are many hydrogen peroxide oxidation product be mainly adipic acid (chemistry and bonding: 2010,32 (3):
5-15)；Primary product is 1,2- cyclohexanediol (CN 103265405B) under inorganic acid existence condition.But up to the present do not have also
About the open report of cyclohexene photochemical catalytic oxidation synthesizing cyclohexane 1 ketenes technique.
Summary of the invention
The technical problem to be solved by the present invention is to the existing catalyst systems for preparing cyclonene by cyclohexene oxide all to need
Reaction temperature appropriate is given, catalyst structure is complicated, higher cost.
To solve the above problems, the present invention is overcome using light-catalysed method existing prepares cyclonene technique not
Foot provides a kind of method of cyclohexene photochemical catalytic oxidation synthesizing cyclohexane 1 ketenes environmental-friendly, easy to operate.
In order to achieve the above objectives, the invention discloses a kind of methods that photocatalysis cyclohexene selects synthesis cyclohexenone, will
Reactant cyclohexene, photochemical catalyst, oxidant hydrogen peroxide and solvent are added in reactor, under magnetic stirring (magnetic agitation
Reactant can be made to come into full contact with catalyst, while during stirring, it is also possible that reactant and light medium are abundant
Contact promotes the progress of reaction), it opens ultraviolet source or visible light source (providing light medium) is anti-according to following reaction formula progress
Answer 1-6h:
To which after reaction, reaction mixture is centrifuged, wherein supernatant is to contain reaction product, unreacted
Reactant and solvent liquid mixture, lower layer is catalyst, take supernatant through column chromatograph (ethyl acetate: petroleum ether volume
Than 1:100) purification obtain cyclonene.
Further, the catalyst, cyclohexene, hydrogen peroxide the mass ratio of the material be 0.002~0.01:1:0.3~
1.2。
Further, the mass concentration of the oxidant hydrogen peroxide is 20%~50%, preferred concentration 30%.
Further, the molar ratio of the hydrogen peroxide and cyclohexene is 0.5:1；The solvent adding amount and cyclohexene
Mass ratio is 5:1~20:1, preferably 10:1；Reaction temperature is 0~30 DEG C, reaction time 4h.
Further, the photochemical catalyst is ten poly- wolframic acid quaternary amines, has the following structure general formula:
Wherein, the integer that n is 0~18.
Further, described ten poly- wolframic acid quaternary ammonium salts are the poly- wolframic acid quaternary ammonium salt of cetyl trimethyl ten, the tetrabutyl ten gathers
One of wolframic acid quaternary ammonium salt, the poly- wolframic acid quaternary ammonium salt of -3 methylimidazole of heptane base ten or more than one mixture.
Further, described ten poly- wolframic acid quaternary ammonium salts the preparation method is as follows: weighing 0.01mol in 100mL round-bottomed flask
(3.3g) Na2WO4·2H210mLH is added in O2O makes it completely dissolved, and boils 5min, 6.9mL 3M HCl is added, continuous
It is added with stirring the 0.003mol Quaternary ammonium bromide for being dissolved in 4mL ethanol water (volume ratio 3:1-1:3), is maintained the temperature at
80-100 DEG C, flow back 10min, and yellow or greenish yellow solid are obtained by filtration after reaction, washes through deionized water washing, ethyl alcohol
It is dried in vacuo after washing up to target product.
Further, the dosage of described ten poly- wolframic acid quaternary ammonium salts is the 0.2%~0.4% of the amount of hexamethylene olefinic substance, preferably
It is 0.3%.
Further, the solvent is deionized water.
The invention has the benefit that
(1) present invention is using ultraviolet light or visible light as light source, and low energy consumption, without direct photocatalytic-oxidation under heating condition
Change a step and prepares cyclonene；
(2) it reduces environmental pollution without using organic solvents such as acetonitriles as reaction medium；
(3) ten poly- wolframic acid quaternary ammonium salts used in the present invention are higher to cyclohexene photocatalysis oxidation reaction activity, cyclonene
Preferably, under optimum process condition, the conversion ratio of cyclohexene is 99.9% to selectivity, and the selectivity of cyclonene is up to
91.2%.
, specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with implementation of the invention
Example, technical scheme in the embodiment of the invention is clearly and completely described.Obviously, described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1:
A kind of method of photocatalysis cyclohexene selection synthesis cyclohexenone, comprising the following steps:
(1) preparation of the poly- wolframic acid quaternary ammonium salt of cetyl trimethyl ten: 0.01mol is weighed in 100mL round-bottomed flask
(3.3g) Na2WO4·2H210mLH is added in O2O makes it completely dissolved, and boils 5min, 6.9mL 3M HCl is added, continuous
It is added with stirring 0.003mol (1.46g) the cetyl trimethylammonium bromide salt for being dissolved in 4mL ethanol water, keeps temperature
At 80-100 DEG C, flow back 10min, and greenish yellow solid is obtained by filtration after reaction, after deionized water washing, ethanol washing
It is dried in vacuo up to the poly- wolframic acid quaternary ammonium salt of cetyl trimethyl ten.
(2) cyclohexene 0.41g, photochemical catalyst 50mg, 30% hydrogen peroxide 0.35g and deionized water 5ml are added to reactor
In, under magnetic stirring, opens xenon lamp and carry out reaction 4h；Opening condensation water management reaction temperature is room temperature；To the end of reacting
Afterwards, reaction mixture is centrifuged, supernatant is taken to carry out qualitative, quantitative to product using gas chromatograph-mass spectrometer (GC-MS)
Analysis.
Embodiment 2:
A kind of method of photocatalysis cyclohexene selection synthesis cyclohexenone, wherein the preparation method of catalyst is the tetrabutyl ten
The preparation of poly- wolframic acid quaternary ammonium salt: 0.01mol (3.3g) Na is weighed in 100mL round-bottomed flask2WO4·2H210mLH is added in O2O
It makes it completely dissolved, boils 5min, 6.9mL 3M HCl is added, be added be dissolved in 4mL ethanol water under constant stirring
0.003mol (0.97g) tetrabutyl trimethylammonium bromide salt maintains the temperature at 80-100 DEG C, and flow back 10min, after reaction
Yellow solid is obtained by filtration.It is dried in vacuo after deionized water washing, ethanol washing up to the poly- wolframic acid season of tetrabutyl trimethyl ten
Ammonium salt.
Remaining is same as Example 1.
Embodiment 3:
A kind of method of photocatalysis cyclohexene selection synthesis cyclohexenone, wherein the preparation method of catalyst is 1- heptane
The preparation of the poly- wolframic acid quaternary ammonium salt of -3 methylimidazole of base ten: 0.01mol (3.3g) Na is weighed in 100mL round-bottomed flask2WO4·
2H210mLH is added in O2O makes it completely dissolved, and boils 5min, and 6.9mL 3M HCl is added, and is added is dissolved under constant stirring
- 3 methylimidazole bromide of 0.003mol (0.78g) 1- heptane base of 4mL ethyl alcohol maintains the temperature at 80-100 DEG C, and flow back 10min,
Yellow solid is obtained by filtration after reaction.It is dried in vacuo after deionized water washing, ethanol washing up to -3 first of 1- heptane base
The poly- wolframic acid quaternary ammonium salt of base imidazoles ten.
Remaining is same as Example 1.
The reaction result of embodiment 1- embodiment 3 see the table below:
Embodiment 4:
It opens xenon lamp and carries out reaction 1h, remaining is same as Example 1.
Embodiment 5:
It opens xenon lamp and carries out reaction 2h, remaining is same as Example 1.
Embodiment 6:
It opens xenon lamp and carries out reaction 3h, remaining is same as Example 1.
Embodiment 1, the reaction result of 4-7 are as follows:
Embodiment: 7:
The additive amount of hydrogen peroxide is 0, remaining is same as Example 1.
Embodiment 8:
The additive amount of hydrogen peroxide is 0.1g, remaining is same as Example 1.
Embodiment 9:
The additive amount of hydrogen peroxide is 0.3g, remaining is same as Example 1.
Embodiment 1, the reaction result of 7-9 are as follows:
As can be seen from the above embodiments, using the poly- wolframic acid quaternary ammonium salt of cetyl trimethyl ten as catalyst, water is reaction dissolvent,
Under best light-catalyzed reaction process conditions, the conversion ratio of cyclohexene can be up to 99.9%, and the selectivity of cyclonene is up to
91.2%.The present invention, as reaction medium, reduces the pollution to environment without using organic solvents such as acetonitriles.Used in the present invention
Ten poly- wolframic acid quaternary ammonium salt preparation process it is simple, recycle convenient separation, the features such as catalytic activity is high.
Claims (9)
1. a kind of method of photocatalysis cyclohexene selection synthesis cyclohexenone, it is characterised in that: by reactant cyclohexene, photocatalysis
Agent, oxidant hydrogen peroxide and solvent are added in reactor, under magnetic stirring, open ultraviolet source or visible light source according to such as
Lower reaction equation carries out reaction 1-6h:
To which after reaction, reaction mixture is centrifuged, reaction mixture is centrifuged, supernatant is taken to pass through
Column Chromatographic purification obtains cyclonene.
2. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: described to urge
Agent, cyclohexene, hydrogen peroxide the mass ratio of the material be 0.002~0.01:1:0.3~1.2.
3. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: the oxygen
The mass concentration of agent hydrogen peroxide is 20%~50%.
4. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: the mistake
The molar ratio of hydrogen oxide and cyclohexene is 1.1:1；The mass ratio of the solvent adding amount and cyclohexene is 5:1~20:1；Reaction
Temperature is 0~30 DEG C, reaction time 4h.
5. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: described
Photochemical catalyst is ten poly- wolframic acid quaternary amines, has the following structure general formula:
[cH3(cH2)nN(cH3)314w10O32
Wherein, the integer that n is 0~18.
6. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: described ten
Poly- wolframic acid quaternary ammonium salt is the poly- wolframic acid quaternary ammonium salt of cetyl trimethyl ten, the poly- wolframic acid quaternary ammonium salt of the tetrabutyl ten, -3 methyl of heptane base
One of poly- wolframic acid quaternary ammonium salt of imidazoles ten or more than one mixture.
7. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: described ten
Poly- wolframic acid quaternary ammonium salt the preparation method is as follows: weighing 0.01mol Na in 100mL round-bottomed flask2WO4·2H210mLH is added in O2O
It makes it completely dissolved, boils 5min, 6.9mL 3M HCl is added, be added be dissolved in 4mL ethanol water under constant stirring
0.003mol Quaternary ammonium bromide maintains the temperature at 80-100 DEG C, and flow back 10min, and yellow or yellowish green is obtained by filtration after reaction
Color solid is dried in vacuo after deionized water washing, ethanol washing up to target product.
8. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: described ten
The dosage of poly- wolframic acid quaternary ammonium salt is the 0.2%~0.4% of the amount of hexamethylene olefinic substance.
9. the method for photocatalysis cyclohexene selection synthesis cyclohexenone according to claim 1, it is characterised in that: described molten
Agent is deionized water.
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