CN100494149C - A kind of green synthetic method of α, β-unsaturated ketone or aryl ketone - Google Patents
A kind of green synthetic method of α, β-unsaturated ketone or aryl ketone Download PDFInfo
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- CN100494149C CN100494149C CNB2006100536353A CN200610053635A CN100494149C CN 100494149 C CN100494149 C CN 100494149C CN B2006100536353 A CNB2006100536353 A CN B2006100536353A CN 200610053635 A CN200610053635 A CN 200610053635A CN 100494149 C CN100494149 C CN 100494149C
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- beta
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- arone
- unsaturated
- ketone
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- 150000002576 ketones Chemical class 0.000 title claims abstract description 30
- -1 aryl ketone Chemical class 0.000 title description 3
- 238000010189 synthetic method Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 150000003949 imides Chemical class 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000011790 ferrous sulphate Substances 0.000 claims description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 11
- 238000001308 synthesis method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 230000005587 bubbling Effects 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- YEJCDKJIEMIWRQ-UHFFFAOYSA-N Linopirdine Chemical compound O=C1N(C=2C=CC=CC=2)C2=CC=CC=C2C1(CC=1C=CN=CC=1)CC1=CC=NC=C1 YEJCDKJIEMIWRQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- 229940117955 isoamyl acetate Drugs 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000006884 silylation reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract 4
- 150000008365 aromatic ketones Chemical class 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229940117975 chromium trioxide Drugs 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BUXKULRFRATXSI-UHFFFAOYSA-N 1-hydroxypyrrole-2,5-dione Chemical compound ON1C(=O)C=CC1=O BUXKULRFRATXSI-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000007788 liquid 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a green synthesizing method of alpha, beta-unsaturated ketone or aromatic ketone, which is characterized by the following: adopting relative unsaturated hydrocarbons or aromatic hydrocarbons as raw material; setting imide as catalyst; making azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as initiator; oxidizing in the organic solvent; dehydrating through dehydrant; separating and purifying to obtain the alpha, beta-unsaturated ketone; improving reacting receiving rate; reducing manufacturing cost; possessing mild reacting condition; using little catalyst; avoiding pollution.
Description
(1) technical field
The present invention relates to the green synthesis method of a kind of alpha, beta-unsaturated ketone or arone, especially a kind of green chemical synthesis method for preparing alpha, beta-unsaturated ketone or arone with air or oxygen-rich air or oxygen as cleaning oxidizer.These series product are widely used in the synthetic of medicine, agricultural chemicals and dyestuff, have very high practical value and economic benefit.
(2) background technology
Before the present invention made, the synthetic of prior art alpha, beta-unsaturated ketone or arone was to prepare with traditional oxygenants such as high price chromic salts, chromium trioxide, periodides.As J.Org.Chem.1969,3587, propose with 25 normal CrO
3/ pyridine obtains target product as oxygenant, yield about 70%; Syn.Commun.1987,1227, propose to finish oxidizing reaction to allylic, yield about 80% as oxygenant with 25 normal PCC (Pyridinium chlorochromate on silica gel).
Traditional oxygenants such as high price chromic salts, chromium trioxide, periodide can improve reaction efficiency under the condition of gentleness, existing application widely in organic synthesis, yet the shortcoming of this production technique is that consumptions such as oxygenant high price chromic salts, chromium trioxide, periodide are big, because traditional mostly oxygenant need excessively greatly just can be finished reaction, what have then costs an arm and a leg, and is not suitable for large-scale industrial production.Most importantly there is serious pollution hidden trouble in above-mentioned oxygenant, and industrial chromium-containing waste water is the arch-criminal of environmental pollution, and aftertreatment is very difficult.Therefore, though traditional oxygenant has been widely used in multiple reaction, they also exist such as above problem needs to solve.So seeking a kind of method of effectively holding concurrently environmental protection is the task of top priority.
(3) summary of the invention
For solving α in the prior art, the deficiency that the preparation catalyst levels of alpha, beta-unsaturated ketone or arone is big, cost is high, aftertreatment is difficult and easily pollute, the invention provides that a kind of technology is reasonable, reaction yield is high, catalyst levels can make things convenient for again less that recovery set is low with, production cost, the alpha, beta-unsaturated ketone of clean environment firendly or the green chemical synthesis method of arone.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of α, the green synthesis method of alpha, beta-unsaturated ketone or arone, described method is to be raw material with corresponding unsaturated hydrocarbons or aromatic hydrocarbons, with the imide is catalyzer, with azo-bis-isobutyl cyanide (AIBN) or benzoyl peroxide (BPO) is initiator, carries out oxidizing reaction with oxygen in organic solvent, dewaters through dewatering agent, separation and purification obtains described alpha, beta-unsaturated ketone; Described corresponding unsaturated hydrocarbons or aromatic hydrocarbons are meant the precursor of described alpha, beta-unsaturated ketone or arone, and the Sauerstoffatom that is about on the ketone group of described alpha, beta-unsaturated ketone or arone is reduced to 2 resulting unsaturated hydrocarbons of hydrogen atom or aromatic hydrocarbons;
Described oxygen comes from air or oxygen-rich air or pure oxygen;
Described imide is one of following: 1. N-hydroxyl fourth dicarboximide
2. N-hydroxyl maleic dicarboximide
3. N-hydroxyphthalimide
4. N-hydroxyl-2, the 3-naphthalimide
Described organic solvent is one of following or the mixture of two or more arbitrary proportion wherein: 1. contain the halohydrocarbon of 1～4 carbon atom, 2. contain the ester of 1～7 carbon atom, 3. contain the ketone of 3～10 carbon atoms, 4. contain the ether of 2～6 carbon atoms, 5. carbonatoms is 5～6 stable hydrocarbon;
Described dewatering agent is the mixture of ferrous sulfate and pyridine or triethylamine.
All alpha, beta-unsaturated ketones or arone all can prepare as stated above, and described alpha, beta-unsaturated ketone is chain or the ring structure that contains the C=C-C=O key; Described arone is aryl ketones or the heterocyclic ketone that contains the C=C-C=O key, and described heterocycle is for containing O or N or S five-membered ring.
Described unsaturated hydrocarbons or aromatic hydrocarbons structural formula are one of following formula:
Above-mentioned unsaturated hydrocarbons or aromatic hydrocarbons correspondence obtain alpha, beta-unsaturated ketone or the arone structural formula is as follows:
R in the formula
1For hydrogen or contain the alkyl of 1～6 carbon atom or contain the acyl group of 2～4 carbon atoms or contain the benzoyl or the benzenesulfonyl of 6～8 carbon atoms or contain the silylation of 1～6 carbon atom;
R
2For hydrogen or contain the alkyl or alkenyl of 1～10 carbon atom;
R
3Be the alkyl of the straight or branched that contains 1～10 carbon atom, described alkyl head and the tail link to each other with C=C-C=O key two ends respectively to constitute and encircle;
R
4, R
5Be respectively hydrogen or contain the alkyl of 1～6 carbon atom;
R
6, R
7Independent separately is hydrogen or alkyl or the phenyl that contains 1～6 carbon atom;
Y is S or O or NH or NCH
3
Described organic solvent is one of following or two or more mixture wherein: methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, cyclopentanone, pimelinketone, methyl propyl ketone, ether, propyl ether, isopropyl ether, butyl ether, sherwood oil, dithiocarbonic anhydride, Nitromethane 99Min., oil of mirbane.
Described organic solvent also can be the sherwood oil of 30～120 ℃ of boiling ranges.Sherwood oil is an oils, mainly is made up of pentane and hexane.Available platformate raffinate or straight-run spirit make through fractionation, hydrogenation or additive method.
Preferably, described organic solvent is one of following or two or more mixture wherein: 1. ethyl acetate, 2. butanone, 3. acetone, 4. ether, 5. sherwood oil, 6. tetrahydrofuran (THF), 7. 1,1-ethylene dichloride, 8. 1,2-ethylene dichloride.
The ratio of described unsaturated hydrocarbons, catalyzer, oxygen amount of substance is 1:0.1～4.0:1.0～1000, and described organic solvent quality is 1～100 times of catalyst quality.
Preferably, the ratio of described unsaturated hydrocarbons, catalyzer, oxygen amount of substance is 1:0.2～0.5:1.0～10.0, and described organic solvent quality is 10～15 times of catalyst quality.
Described oxidation reaction condition is 20～150 ℃ and reacted 1～24 hour down.
Concrete, described method is as follows:
(1) ratio with amount of substance is unsaturated hydrocarbons or the aromatic hydrocarbons and the catalyzer of 1:0.2～0.5, and quality is the initiator azo-bis-isobutyl cyanide of 0.01～0.5 times of catalyst quality, add quality and be in the mixed solvent of the ethyl acetate of 10～15 times of catalyst qualities and butanone volume ratio 1:1, be warmed up to 70～100 ℃, continue bubbling air, reacted 12～18 hours;
(2) reaction solution is cooled to 0 ℃, filtering recovering catalyst, add quality respectively do for oneself 0.1～1 times pyridine and ferrous sulfate of unsaturated hydrocarbons quality, be warming up to 70～100 ℃, stirred 24 hours, filtrate is washed with dilute hydrochloric acid, boil off solvent, through distillation or recrystallization, promptly get described alpha, beta-unsaturated ketone again.
Recyclable the applying mechanically of catalyzer that the present invention is used, recovery method is to be cooled to below 0 ℃ reacting the solution that finishes gained, separate out catalyzer, filtering and washing, get filter cake and reclaim catalyzer, the rate of recovery can reach 90～95%, and the recovery catalyzer need not further purification and can be directly used in the next round reaction.
Beneficial effect of the present invention is embodied in: 1. reaction yield height (generally more than 80%), production cost are low; 2. have operational path advanced person, reaction conditions gentleness; 3. few and recyclable the applying mechanically of catalyst levels; 4. cut-out source of pollution have been prevented the pollution to environment from the source, environmentally friendly.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
In thermometer and churned mechanically 2500ml four-hole bottle are housed, add ditan 168g (1mol), N-maloyl imines 60g, azo-bis-isobutyl cyanide (AIBN, 0.5g), with dissolving of 1800ml ethyl acetate/butanone (V/V=1:1) mixed solvent and stirring, be heated to 70 ℃, bubbling air V=1.5ml/min.Keep temperature of reaction and stirred 12 hours.Be cooled to below 0 ℃, and fully stir 30min, leave standstill 10min then, filter, get filter cake and reclaim catalyzer 55g.Filtrate is transferred to the 2500ml there-necked flask, adds triethylamine 10ml, and ferrous sulfate 15g is heated to 70 ℃ and stirred 24 hours.Cool to room temperature adds 5% dilute hydrochloric acid, makes pH value≤5, separatory, upper strata clear solution washing back concentrates, faint yellow solid, use 80% ethyl alcohol recrystallization, get pure product 166g, yield 90.5%, 48 ℃ of fusing points.
Embodiment 2:
In thermometer and churned mechanically 2500ml four-hole bottle are housed, add ditan 168g (1mol), N-hydroxyl maleimide 60g, azo-bis-isobutyl cyanide (AIBN, 0.5g), with dissolving of 1800ml ethyl acetate/butanone (V/V=1:1) mixed solvent and stirring, be heated to 70 ℃, bubbling air V=1.5ml/min.Keep temperature of reaction and stirred 12 hours.Be cooled to below 0 ℃, and fully stir 30min, leave standstill 10min then, filter, get filter cake and reclaim catalyzer 52.5g.Filtrate is transferred to the 2500ml there-necked flask, adds triethylamine 10ml, and ferrous sulfate 15g is heated to 70 ℃ and stirred 24 hours.Cool to room temperature adds 5% dilute hydrochloric acid, makes pH value≤5, separatory, upper strata clear solution washing back concentrates, faint yellow solid, use 80% ethyl alcohol recrystallization, get pure product 155g, yield 85%, 47 ℃ of fusing points.
Embodiment 3:
In thermometer and churned mechanically 2500ml four-hole bottle are housed, add ditan 168g (1mol), N-hydroxyphthalimide 85g, azo-bis-isobutyl cyanide (AIBN, 0.5g), with dissolving of 1800ml ethyl acetate/butanone (V/V=1:1) mixed solvent and stirring, be heated to 70 ℃, bubbling air V=1.5ml/min.Keep temperature of reaction and stirred 12 hours.Be cooled to below 0 ℃, and fully stir 30min, leave standstill 10min then, filter, get filter cake and reclaim catalyzer 82.5g.Filtrate is transferred to the 2500ml there-necked flask, adds triethylamine 10ml, and ferrous sulfate 15g is heated to 70 ℃ and stirred 24 hours.Cool to room temperature adds 5% dilute hydrochloric acid, makes pH value≤5, separatory, upper strata clear solution washing back concentrates, faint yellow solid, use 80% ethyl alcohol recrystallization, get pure product 146g, yield 81%, 49 ℃ of fusing points.
Embodiment 4:
In thermometer and churned mechanically 2500ml four-hole bottle are housed, add tetrahydrobenzene 82g (1mol), N-hydroxyl fourth dicarboximide 60g, azo-bis-isobutyl cyanide (AIBN, 0.5g), with dissolving of 1800ml ethyl acetate/butanone (V/V=1:1) mixed solvent and stirring, be heated to 70 ℃, bubbling air V=1.5ml/min.Keep temperature of reaction and stirred 12 hours.Be cooled to below 0 ℃, and fully stir 30min, leave standstill 10min then, filter, get filter cake and reclaim catalyzer 82.5g.Filtrate is transferred to the 2500ml there-necked flask, adds triethylamine 10ml, and ferrous sulfate 15g is heated to 70 ℃ and stirred 24 hours.Cool to room temperature adds 5% dilute hydrochloric acid, makes pH value≤5, separatory, upper strata clear solution washing back concentrates, weak yellow liquid, distill pure product 66g, yield 81%.
Embodiment 5:
Reaction solvent is changed to ethylene dichloride/butanone (V/V=1:1), and temperature of reaction is 80 ℃, and other is operated with example 1, yield 89%, 48 ℃ of fusing points, catalyst recovery yield 90%.
Embodiment 6:
Reaction solvent is changed to tetrahydrofuran (THF)/butanone (V/V=1:1), and temperature of reaction is 60 ℃, and other is operated with embodiment 1, yield 82%, 47.5 ℃ of fusing points, catalyst recovery yield 87%.
Embodiment 7:
Reaction solvent is changed to ethylene dichloride/ethyl acetate (V/V=1:1), and temperature of reaction is 65 ℃, and other is operated with embodiment 1, yield 80%, 48 ℃ of fusing points, catalyst recovery yield 88%.
Embodiment 8:
Reaction solvent is changed to ethylene dichloride/sherwood oil (V/V=1:1), and temperature of reaction is 90 ℃, and other is operated with embodiment 1, yield 86%, 49 ℃ of fusing points, catalyst recovery yield 95%.
Embodiment 9:
Catalyst n-maloyl imines consumption is 12g, and other is operated with embodiment 1, yield 75%, 46 ℃ of fusing points, catalyst recovery yield 93%.
Embodiment 10:
Catalyst n-maloyl imines consumption is 120g, and other is operated with embodiment 1, yield 90%, 48 ℃ of fusing points, catalyst recovery yield 96%.
Embodiment 11:
Catalyst n-maloyl imines consumption is 240g, and other is operated with embodiment 1, yield 91%, 48 ℃ of fusing points, catalyst recovery yield 94%.
Embodiment 12:
Oxidation time becomes 2h, and other is operated with embodiment 1, yield 70%, 45 ℃ of fusing points, catalyst recovery yield 92%.
Embodiment 13:
Oxidation time becomes 8h, and other is operated with embodiment 1, yield 75%, 47 ℃ of fusing points, catalyst recovery yield 90%.
Embodiment 14:
Oxidation time becomes 24h, and other is operated with embodiment 1, yield 90%, 49 ℃ of fusing points, catalyst recovery yield 90%.
Embodiment 15:
Initiator is benzoyl peroxide (BPO), and other is operated with embodiment 1, yield 90%, 49 ℃ of fusing points, catalyst recovery yield 93%.
Embodiment 16:
Bubbling air V=5ml/min, other is operated with embodiment 1, yield 92%, 48 ℃ of fusing points, catalyst recovery yield 90%.
Embodiment 17:
Bubbling air V=10ml/min, other is operated with embodiment 1, yield 93%, 48.5 ℃ of fusing points, catalyst recovery yield 91%.
Embodiment 18:
The ferrous sulfate consumption is 30g, and other is operated with embodiment 1, yield 94%, 48 ℃ of fusing points, catalyst recovery yield 93%.
Embodiment 19:
The ferrous sulfate consumption is 90g, and other is operated with embodiment 1, yield 95%, 49 ℃ of fusing points, catalyst recovery yield 90%.
Embodiment 20～37:
In thermometer and churned mechanically 2500ml four-hole bottle are housed, add alkene or aromatic hydrocarbons 1mol, N-maloyl imines 60g, azo-bis-isobutyl cyanide (AIBN, 0.5g), with dissolving of 1800ml ethyl acetate/butanone (V/V=1:1) mixed solvent and stirring, be heated to 70 ℃, bubbling air V=1.5ml/min.Keep temperature of reaction and stirred 12 hours.Be cooled to below 0 ℃, and fully stir 30min, leave standstill 10min then, filter, get filter cake and reclaim catalyzer.Filtrate is transferred to the 2500ml there-necked flask, adds triethylamine 10ml, and ferrous sulfate 15g is heated to 70 ℃ and stirred 24 hours.Cool to room temperature adds 5% dilute hydrochloric acid, makes pH value≤5, separatory, upper strata clear solution washing back concentrates, faint yellow solid, with 80% ethyl alcohol recrystallization or rectifying, get white or transparent pure product, the results are shown in Table 1.
Table 1: example 20～37 experimental results
Claims (8)
1. α, the green synthesis method of alpha, beta-unsaturated ketone or arone, it is characterized in that described method is is raw material with corresponding unsaturated hydrocarbons or aromatic hydrocarbons, with the imide is catalyzer, with azo-bis-isobutyl cyanide or benzoyl peroxide is initiator, carries out oxidizing reaction with oxygen in organic solvent, dewaters through dewatering agent, separation and purification obtains described alpha, beta-unsaturated ketone or arone; Described oxygen comes from air or oxygen-rich air or pure oxygen;
Described imide is one of following: 1. N-hydroxyl fourth dicarboximide, 2. N-hydroxyl maleic dicarboximide, 3. N-hydroxyphthalimide, 4. N-hydroxyl-2,3-naphthalimide;
Described organic solvent is one of following or the mixture of two or more arbitrary proportions wherein: 1. contain the halohydrocarbon of 1～4 carbon atom, 2. contain the ester of 1～7 carbon atom, do not comprise the situation of having only 1 carbon atom, 3. contain the ketone of 3～10 carbon atoms, 4. contain the ether of 2～6 carbon atoms, 5. carbonatoms is 5～6 stable hydrocarbon;
Described dewatering agent is the mixture of ferrous sulfate and pyridine or triethylamine;
Described alpha, beta-unsaturated ketone or arone structural formula are one of following formula:
Corresponding unsaturated hydrocarbons or aromatic hydrocarbons structural formula are one of following formula:
R in the formula
1For hydrogen or contain the alkyl of 1～6 carbon atom or contain acyl group or the benzoyl or the benzenesulfonyl of 2～4 carbon atoms or contain the silylation of 1～6 carbon atom;
R
2For hydrogen or contain the alkyl of 1～10 carbon atom;
R
3For containing the straight chained alkyl of 1～10 carbon atom;
R
5For hydrogen or contain the alkyl of 1～6 carbon atom;
R
6, R
7Independent separately is hydrogen or alkyl or the phenyl that contains 1～6 carbon atom.
2. α as claimed in claim 1, the green synthesis method of alpha, beta-unsaturated ketone or arone, it is characterized in that described organic solvent is one of following or wherein two or more mixture: methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, cyclopentanone, pimelinketone, methyl propyl ketone, ether, propyl ether, isopropyl ether, sherwood oil.
3. the green synthesis method of alpha, beta-unsaturated ketone as claimed in claim 1 or arone is characterized in that described organic solvent is the sherwood oil of 30～120 ℃ of boiling ranges.
4. α as claimed in claim 1, the green synthesis method of alpha, beta-unsaturated ketone or arone, it is characterized in that described organic solvent is one of following or wherein two or more mixture: 1. ethyl acetate, 2. butanone, 3. acetone, 4. ether, 5. sherwood oil, 6. tetrahydrofuran (THF), 7. 1,1-ethylene dichloride, 8. 1, the 2-ethylene dichloride.
5. α as claimed in claim 1, the green synthesis method of alpha, beta-unsaturated ketone or arone, the ratio that it is characterized in that described unsaturated hydrocarbons, catalyzer, oxygen amount of substance is 1:0.1～4.0:1.0～1000, and described organic solvent quality is 1～100 times of catalyst quality.
6. α as claimed in claim 5, the green synthesis method of alpha, beta-unsaturated ketone or arone, the ratio that it is characterized in that described unsaturated hydrocarbons, catalyzer, oxygen amount of substance is 1:0.2～0.5:1.0～10.0, and described organic solvent quality is 10～15 times of catalyst quality.
7. as the green synthesis method of described alpha, beta-unsaturated ketone of one of claim 1～3 or arone, it is characterized in that described oxidation reaction condition is 20～150 ℃ and reacted 1～24 hour down.
8. the green synthesis method of alpha, beta-unsaturated ketone as claimed in claim 1 or arone is characterized in that described method is as follows:
(1) ratio with amount of substance is unsaturated hydrocarbons or the aromatic hydrocarbons and the catalyzer of 1:0.2～0.5, and quality is the initiator azo-bis-isobutyl cyanide of 0.01～0.5 times of catalyst quality, add quality and be in the mixed solvent of the ethyl acetate of 10～15 times of catalyst qualities and butanone volume ratio 1:1, be warmed up to 70～100 ℃, continue bubbling air, reacted 12～18 hours;
(2) reaction solution is cooled to 0 ℃, filtering recovering catalyst, add quality respectively do for oneself 0.1～1 times pyridine and ferrous sulfate of unsaturated hydrocarbons or aromatic hydrocarbons quality, be warming up to 70～100 ℃, stirred 24 hours, filtrate is washed with dilute hydrochloric acid, boil off solvent, through distillation or recrystallization, promptly get described alpha, beta-unsaturated ketone or arone again.
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| CN102757376A (en) * | 2011-12-13 | 2012-10-31 | 大连理工大学 | Preparation method of b-heterocyclic ketone compound |
| CN105669813B (en) * | 2015-12-31 | 2017-11-07 | 厦门金达威维生素有限公司 | A kind of synthetic method of the ketone cholesterol acetate of intermediates of vitamin D_3 7 |
| CN107936077A (en) * | 2016-10-12 | 2018-04-20 | 浙江天新药业有限公司 | A kind of preparation method of 7 oxo cholesterol acetate |
| CN107903280B (en) * | 2017-09-22 | 2020-06-16 | 华东师范大学 | Synthesis method of acyl aryl boric acid compound |
| WO2021035382A1 (en) * | 2019-08-23 | 2021-03-04 | 辽宁凯莱英医药化学有限公司 | Method forcontinuous synthesis of 2-cyclopentene-1-one |
| CN110407678A (en) * | 2019-08-23 | 2019-11-05 | 辽宁凯莱英医药化学有限公司 | 2- cyclopentene-1-one is continuously synthesizing to method |
| CN111302925B (en) * | 2020-03-16 | 2023-05-30 | 万华化学集团股份有限公司 | Method for preparing cyclic alpha, beta-unsaturated ketone |
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