CN101417935B - Method for preparing oxo-isophorone by catalytic oxidation using metal free catalytic system - Google Patents
Method for preparing oxo-isophorone by catalytic oxidation using metal free catalytic system Download PDFInfo
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- CN101417935B CN101417935B CN2008101629956A CN200810162995A CN101417935B CN 101417935 B CN101417935 B CN 101417935B CN 2008101629956 A CN2008101629956 A CN 2008101629956A CN 200810162995 A CN200810162995 A CN 200810162995A CN 101417935 B CN101417935 B CN 101417935B
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- isophorone
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- hydroxyphthalimide
- ketoisophorone
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- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical compound CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 10
- 239000002184 metal Substances 0.000 title claims abstract description 10
- LKOKKQDYMZUSCG-UHFFFAOYSA-N 3,5,5-Trimethyl-3-cyclohexen-1-one Chemical compound CC1=CC(C)(C)CC(=O)C1 LKOKKQDYMZUSCG-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 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 abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 claims description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- -1 transition metal salt Chemical class 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 241001647745 Banksia Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a new method for preparing keto-isophorone, which utilizes metal free co-catalyst system to catalyze and oxidize Beta-isophorone. Beta-isophorone is used as the raw material; in the presence of an organic solvent, molecular oxygen or an oxygen rich gas is used as an oxidant; under the effect of the co-catalyst system composed by the main catalyst N-hydroxyphthalimide and the analogues of N-hydroxyphthalimide, and organic cocatalyst, keto-isophorone is prepared by catalytic oxidation; reaction temperature ranges from 0 to 120 DEG C; reaction time ranges from 5 to 50 hours; keto-isophorone with high selectivity can be generated. The method has the advantages that, the catalyst is metal free, cheap and easy to be obtained; reaction conditions are mild; operation is simple; the product has high selectively; recycling is easy, and multiple usage can be realized.
Description
Technical field
The present invention relates to a kind of novel method of utilizing the common catalystsystem catalyzed oxidation β-isophorone of no metal to prepare ketoisophorone; Particularly relate to method with preparing oxo-isophorone by catalytic oxidation using metal free catalytic system; It is characterized in that: raw material β-isophorone, in the presence of solvent, with N-hydroxyphthalimide and analogue and the common catalystsystem of organic promoter composition; Use molecular oxygen or oxygen rich gas to be oxygenant, oxidation generates ketoisophorone.
Background technology
Ketoisophorone is called for short KIP, is a kind of important chemical medicine intermediate, can be used as seasonings or spices in the foodstuff additive, also can be used for synthetic makeup.Ketoisophorone still prepares the important intermediate of VITAMINs and carrotenoid.Be a kind of weak yellow liquid or solid under the normal temperature, its pure article fragrance is strong, and lasting is lasting, and fragrance is that the close sweet banksia rose of little acid, dry fruit are fragrant, and various cigarette are all had significant perfuming effect.
Because the importance of ketoisophorone in fields such as chemical and medicine industry for a long time, is oxidized to the focus that ketoisophorone is chemical field research with α-isophorone or β-isophorone always.Particularly for the oxidation of β-isophorone, patent and the document reported at present are many.Generally speaking, the oxidation of β-isophorone at present mainly is that the organic coordination compounds with transition metal is a homogeneous catalyst, carries out oxidation with molecular oxygen or air, many times can add some additives (such as solubility promoter etc.).Different-phase catalyst also has application in reaction.
Catalyzer patent from reaction is adopted mainly contains transition metal salt catalyst, transition metal acetyl acetone complex catalyzer; Transition metal schiff bases complex catalyzer; In addition transition metal porphyrin or phthalocyanine complex catalyzer, also have all metal catalyst etc.Can find out that from these patents adopting transition metal is the catalyzer at center,, under the conditions such as solubility promoter, can generate ketoisophorone by catalyzed oxidation β-isophorone at suitable organic bases and solvent, have in addition have very high transformation efficiency and a productive rate.
In US 4046813, described a kind of in the presence of the organic bases pyridine; Use the acetyl acetone complex of lead, vanadium, chromium, manganese, iron, cobalt etc. to be catalyzer; Catalyzed oxidation β-isophorone prepares the method for ketoisophorone, though this method has about 100% transformation efficiency, reaction simultaneously also makes β-isophorone to α-isophorone isomerizing easily; And form the high by product that gathers in the reaction again easily, institute is so that reaction preference descends.
In US6297404 and US6300521, described a kind ofly in the presence of DMF or DMA and tripropyl amine, use the catalysis system catalyzed oxidation β-isophorone of Schiff's base and lithium acetate or ammonium acetate to prepare the method for ketoisophorone; The shortcoming of a maximum of this method is that reaction is easy to generate 3,5,5-trimethyl-cyclohex-2-en-4-hydroxyl-1-ketone; 2; 2,6-trimethyl-cyclohexane-1, by products such as 4-diketone; Because each side such as these by product molecular weight and character are similar with product, thereby it is quite difficult with separating of ketoisophorone.
And in US4898985; Described a kind ofly in the presence of triethylamine and glycol dimethyl ether, used the porphyrin of iron, cobalt, ketone, manganese or phthalocyanine complex to be catalyzer, catalyzed oxidation β-isophorone prepares the method for ketoisophorone; Though this method has very high yield; But the transition-metal catalyst of porphyrin class is quite expensive, and in reaction, also is destroyed easily, makes that this technology cost is higher.The alkaline environment of glycol dimethyl ether combination triethylamine formation is abnormally dangerous on oxidation operation in addition; Because the burning-point of this mixture is very low; So for security reasons, although this method has very high yield, it must just can be implemented on technical scale under preventive measures as safe as a house.
Situation from the above-identified patent summary; Transition metal-organic coordination compound the catalyzer that adopts at present carries out the reaction that oxidation of beta-isophorone prepares ketoisophorone; The problem that exists is that reaction is slow under cryogenic condition; The easy isomery of β-isophorone turns to α-isophorone and other by product under the high temperature, greatly reduces the selectivity of reaction and the productive rate of ketoisophorone; Though and employing porphyrin class catalyzer can overcome above-mentioned shortcoming, it is high a lot of that the price of synthetic porphyrin catalyst is wanted, and destroy catalyzer in reacting again easily or cause poisoning of catalyst etc., makes the reaction unstable increase greatly.Simultaneously; Homogeneous catalyst as transition metal-type;, reaction can not directly from reaction system, separate after accomplishing, recovery and reuse, and its result not only makes reaction solvent, product etc. separate difficulty to be increased; Portion of product also can polymerization form by product in the presence of catalyzer simultaneously, and the final a large amount of pin material that forms has also increased the pressure of environment.
Summary of the invention
The purpose of this invention is to provide a kind of novel method for preparing ketoisophorone.Especially, it is to have adopted N-hydroxyphthalimide and analogue thereof to be total to catalystsystem with other organic promoter bonded than the characteristics of above-mentioned catalyzer.Reaction can be carried out under the condition of gentleness, and reaction pin material rate is low, has good transformation efficiency and selectivity, and catalyzer can also reclaim and reuse simultaneously.
The method of preparing oxo-isophorone by catalytic oxidation using metal free catalytic system provided by the invention, reaction formula is:
β-IP is oxidized to KIP
The present invention is that (β-IP) is a raw material with β-isophorone; In the presence of organic solvent; Common catalystsystem with N-hydroxyphthalimide and analogue and organic promoter composition uses molecular oxygen or oxygen rich gas oxygenant, and catalyzed oxidation prepares ketoisophorone (KIP).Temperature of reaction is 0 ℃～120 ℃, and the reaction times is 5～50 hours, generates the high ketoisophorone of selectivity.
In the altogether catalystsystem of the present invention, Primary Catalysts is a N-hydroxyphthalimide, 3,4, a kind of in 5,6 tetrachloros-N-hydroxyphthalimide, the 4-alkoxyl formyl-N-hydroxyphthalimide; And preferred N-hydroxyphthalimide.
In the altogether catalystsystem of the present invention, promotor is Lucidol, anthraquinone and 1,4-diamino--2, and 3-dichloroanthraquinone, Tetrabutyl amonium bromide, 2,2 '-a kind of in Diisopropyl azodicarboxylate, phenanthrolene and the bromine; And preferred Lucidol, anthraquinone.
In the catalystsystem altogether of the present invention, the scope of the mol ratio of Primary Catalysts and promotor is between 200: 1 to 10: 1, and preferably between 80: 1 to 40: 1.
The mol ratio of β-isophorone of the present invention and Primary Catalysts can be in the variation range of a broad, usually between 100: 1 to 1: 5, and preferably between 25: 1 to 1: 2.
Oxygenant of the present invention can be pure oxygen, be rich in the gas of oxygen, air.In 1 kilogram of β-isophorone, oxygen-supply quantity hourly is 50～1000L normally, and preferably at 100～500L.Oxygenous for other, its air flow can be converted according to oxygen level accordingly.
Temperature of reaction of the present invention is between 0 ℃～120 ℃, and preferably between 20 ℃～80 ℃.
Reaction solvent of the present invention can be one or both in acetone, benzyl cyanide, ETHYLE ACETATE, acetate, acetonitrile, DMSO 99.8MIN., phenyl trichloromethane, N, toluene, THF, the pyridine, and ethyl acetate, acetone, acetonitrile.
The scope of β-isophorone of the present invention and reaction solvent mol ratio is between 5: 1 to 1: 50, and preferably between 2: 1 to 1: 10.
Reaction times of the present invention is between 5～50 hours, and preferably between 10～30 hours.
The N-hydroxyphthalimide of use of the present invention and analogue catalyzer thereof make catalyzer separate with solvent and ketoisophorone through recrystallization after reaction finishes, and the catalyzer that obtains is used for the oxidizing reaction of β-isophorone once more.
Compare with traditional method, the used catalyzer of the present invention is very novel, and this N-hydroxyphthalimide catalyst system has following characteristic: 1) it is the organic catalytic system that cheap no metal is participated in; 2) the reaction conditions needed is gentle; 3) product selectivity is high.Than the transition metal-type homogeneous catalyst, it can utilize through simple recovery again.Simultaneously, the by product like two clusters in the reaction significantly reduces, and reaction conditions is gentle, separate easily and control, and preparing ketoisophorone for catalyzed oxidation β-isophorone is a kind of good method and catalyzer separate easily and control, is easy to utilize again.
Embodiment:
Following embodiment will more comprehensively describe the present invention.
Embodiment 1
The N-hydroxyphthalimide catalyzer that in the 50ml flask with four necks,round bottom, adds 0.82g, the acetone of 40ml is put into 60 ℃ water-bath; β-the isophorone that adds 6.9g after 20 minutes again, the Lucidol of 0.02g, aerating oxygen reacts then; Reaction process is monitored with gc; With ethyl benzoate is that interior mark is demarcated, and the transformation efficiency of measuring β-isophorone behind the 20h is 93%, and the selectivity of ketoisophorone is 88.5%.
Embodiment 2
4-alkoxyl formyl-N-hydroxyphthalimide the catalyzer that in the 50ml flask with four necks,round bottom, adds 1.46g, the acetone of 40ml is put into 60 ℃ water-bath; β-the isophorone that adds 6.9g after 20 minutes again, the phenanthrolene of 0.02g, aerating oxygen reacts then; Reaction process is monitored with gc; With ethyl benzoate is that interior mark is demarcated, and the transformation efficiency of measuring β-isophorone behind the 20h is 97%, and the selectivity of ketoisophorone is 78.5%.
Embodiment 3-5
Be similar to embodiment 1, temperature of reaction is to carry out under 60 ℃ the condition, and the reaction times is 20h; Change the molar ratio of β-isophorone and N-hydroxyphthalimide, must be like following table after the reaction end:
Embodiment 6-8
Be similar to embodiment 1, temperature of reaction is to carry out under 60 ℃ the condition, and the reaction times is 20h; Select different solvents, must be like following table after reaction finishes:
Embodiment 9-12
Be similar to embodiment 1, temperature of reaction is to carry out under 60 ℃ the condition, and the reaction times is 20h; Select different common catalystsystem, must be like following table after reaction finishes:
Embodiment 13
Reaction conditions according to embodiment 1 reacts.Reaction is removed most of solvent through underpressure distillation after accomplishing, and puts into refrigerator and cooled then and freezes, and has the NHPI crystal to separate out, and filters washing, the NHPI catalyzer that drying obtains reclaiming.The catalyzer that reclaims is reused for β-isophorone oxidation, and oxidizing condition is according to embodiment 1, and measuring β-isophorone transformation efficiency behind the reaction 20h is 88%, and the ketoisophorone selectivity is 86%.
Claims (3)
1. the method for a preparing oxo-isophorone by catalytic oxidation using metal free catalytic system; It is characterized in that: with β-isophorone is raw material; In the presence of organic solvent; Use molecular oxygen or oxygen rich gas to be oxygenant, catalyzed oxidation prepares ketoisophorone under the common catalystsystem effect of being made up of the Primary Catalysts and the organic promoter of N-hydroxyphthalimide and analogue thereof; Described Primary Catalysts is: N-hydroxyphthalimide, 3,4, a kind of in 5,6 tetrachloros-N-hydroxyphthalimide, the 4-alkoxyl formyl-N-hydroxyphthalimide; Said organic promoter is: Lucidol, anthraquinone, 1, and 4-diamino--2,3-dichloroanthraquinone, Tetrabutyl amonium bromide, 2,2 '-a kind of in the Diisopropyl azodicarboxylate, phenanthrolene; The mol ratio of Primary Catalysts and promotor is between 200: 1 to 10: 1 in the said catalystsystem altogether; The mol ratio of said β-isophorone and Primary Catalysts is between 100: 1 to 1: 5; Said molecular oxygen or oxygen rich gas, in 1 kilogram of β-isophorone, oxygen-supply quantity hourly is 50～1000L; Temperature of reaction is 0 ℃～120 ℃, and the reaction times is 5～50 hours, generates the high ketoisophorone of selectivity.
2. according to the said method for preparing ketoisophorone of claim 1, it is characterized in that: organic solvent is one or both in acetone, benzyl cyanide, ETHYLE ACETATE, acetate, acetonitrile, DMSO 99.8MIN., phenyl trichloromethane, N, toluene, THF, the pyridine.
3. according to the said method for preparing ketoisophorone of claim 1; It is characterized in that: N-hydroxyphthalimide and analogue catalyzer thereof are after reaction finishes; Through recrystallization catalyzer is separated with solvent and ketoisophorone, the catalyzer that obtains is used for the oxidizing reaction of β-isophorone once more.
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| CN105601490B (en) * | 2014-11-13 | 2017-10-17 | 四川大学 | Efficiently catalyzing and oxidizing α isophorones prepare ketoisophorone |
| CN109456153B (en) * | 2018-11-26 | 2020-04-28 | 上虞新和成生物化工有限公司 | Synthesis method of oxoisophorone |
| CN115703702B (en) * | 2021-08-16 | 2024-05-28 | 安徽圣诺贝化学科技有限公司 | Method for preparing tea-flavored ketone by oxidizing alpha-isophorone |
| CN114797988B (en) * | 2022-05-16 | 2023-08-11 | 万华化学(四川)有限公司 | Synthesis of composite catalyst and method for preparing beta-isophorone |
| CN115677461A (en) * | 2022-10-27 | 2023-02-03 | 万华化学集团股份有限公司 | Method for continuously producing 4-oxoisophorone by using tower reactor |
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| CN1660753A (en) * | 2004-12-10 | 2005-08-31 | 浙江大学 | Method for preparing 3,5,5-trimethyl-hexamethylene-2-olefin-1,4 diketone |
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