CN1923783A - Method of preparing 3,5,5-trimethyl-cyclohex-2-en-1,4-dione by heterophase oxidation - Google Patents
Method of preparing 3,5,5-trimethyl-cyclohex-2-en-1,4-dione by heterophase oxidation Download PDFInfo
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- CN1923783A CN1923783A CNA2006100535261A CN200610053526A CN1923783A CN 1923783 A CN1923783 A CN 1923783A CN A2006100535261 A CNA2006100535261 A CN A2006100535261A CN 200610053526 A CN200610053526 A CN 200610053526A CN 1923783 A CN1923783 A CN 1923783A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 title claims description 19
- 230000003647 oxidation Effects 0.000 title claims description 14
- 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 description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 4
- 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 description 38
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- -1 nitrogen heterocyclic ring class organic bases Chemical class 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 150000007530 organic bases Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 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 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 4
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 230000001052 transient effect Effects 0.000 abstract 2
- 150000004820 halides Chemical class 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 7
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 6
- 230000009466 transformation Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NQIBQILAMKZKFE-UHFFFAOYSA-N 2-(5-bromo-2-fluorophenyl)-3-fluoropyridine Chemical compound FC1=CC=C(Br)C=C1C1=NC=CC=C1F NQIBQILAMKZKFE-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- 239000000203 mixture Substances 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
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical class [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 1
- 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 230000005587 bubbling Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FZFRXOAVALDVBJ-UHFFFAOYSA-N nitric acid;piperidine Chemical class O[N+]([O-])=O.C1CCNCC1 FZFRXOAVALDVBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 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
- 238000003746 solid phase reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000007704 transition Effects 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
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a new preparing method of 3, 5, 5-trimethyl-cyclic-2-alkylene-1, 4-diketone, which is characterized by the following: adopting activated porous carrier acetate or halide of transient metal as catalyst; preparing the product under 50-100 deg.c through molecular oxygen or oxygen-rich gas; making terminal transient rate reach more than 98%.
Description
Technical field
The present invention relates to a kind of heterogeneous oxidization preparation 3,5,5-trimethyl-cyclohex-2-en-1,4-diketone (ketoisophorone, novel method OIP), this method is a raw material 3,5, and 5-trimethylammonium-hexamethylene-3-alkene-1-ketone (β-isophorone, β-IP) in the presence of amine or nitrogen heterocycles organic bases and non-protonic solvent etc., use molecular oxygen or oxygen rich gas, generate ketoisophorone 50～100 ℃ of following heterocatalysis oxidations.Use therein catalyzer is acetate or the halogenide with the immobilized metallic copper of active porous carrier, iron, cobalt, manganese.
Background technology
Ketoisophorone 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 VITAMIN and carotenoid.
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.From these patents as can be seen, adopting transition metal is the catalyzer at center, at suitable organic bases and solvent, under the conditions such as solubility promoter, can generate ketoisophorone by catalyzed oxidation β-isophorone, have in addition have very high transformation efficiency and a productive rate.
In US4046813, 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, but reaction also makes β-isophorone to α-isophorone isomerization easily simultaneously, and form high poly-by product in the reaction again easily, institute is so that reaction preference descends.
In US6297404 and US6300521, described a kind of in the presence of DMF or DMA and tripropyl amine, the catalysis system catalyzed oxidation β-isophorone of use Schiff's base and lithium acetate or ammonium acetate prepares 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 to product, thereby it is quite difficult with separating of ketoisophorone.
And in US4898985, described a kind of in the presence of triethylamine and glycol dimethyl ether, use the porphyrin or the phthalocyanine complex of iron, cobalt, ketone, manganese 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 also destroyed easily in reaction, 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 carries out the reaction that oxidation of beta-isophorone prepares ketoisophorone at present, 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 again easily or cause poisoning of catalyst etc. in reacting, and makes the reaction unstable increase greatly.Simultaneously, as homogeneous catalyst, after finishing, reaction can not directly from reaction system, separate, recovery and reuse, 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 novel method that the purpose of this invention is to provide a kind of oxo isophorone by heterogeneous oxidization.Especially, it is than general different-phase catalyst, and reactive behavior and selectivity all improve greatly.And than homogeneous catalyst, it can utilize by simple recovery again.Simultaneously, the by product as two clusters in the reaction significantly reduces, the reaction conditions gentleness, and separate easily and control, preparing ketoisophorone for catalyzed oxidation β-isophorone is a kind of good method.
Compare with traditional method, the total technical scheme of the present invention is, used catalyzer mainly is under the organic bases effect, metal-salt is immobilized on active porous inorganic carrier, it is gas-liquid-solid phase reaction, adopting pure oxygen, the gas that is rich in oxygen, air is oxygenant, and immobilized metal-salt is a different-phase catalyst, reacts in the mode of heterocatalysis.
Heterogeneous oxidization preparation 3 of the present invention, 5,5-trimethyl-cyclohex-2-en-1, the method of 4-diketone, this method are raw materials 3,5,5-trimethylammonium-hexamethylene-3-alkene-1-ketone, in the presence of organic bases and solvent, the gas, the air that use pure oxygen, are rich in oxygen are oxygenant, generate ketoisophorones-30 ℃～150 ℃ following heterocatalysis oxidations.Use therein immobilized metal salt catalyst, it is metal-salt with the transition metal of IIIb～IIb in the immobilized active ingredient periodictable of active porous inorganic carrier, catalyst system therefor basic structure is: metal-salt-nitrogen heterocyclic ring or anion ligand/carrier, and reaction formula is as follows:
β-IP is oxidized to KIP in the formula.
Immobilized metal salt catalyst of the present invention with active porous inorganic carrier is: zeolite, and molecular sieve, gac, main component is the carbon black of C, main component is SiO
2White carbon black a kind of.
The catalyzer of immobilized metal-salt of the present invention, its catalytic center are the transition metal of IIIb～IIb in the periodictable, wherein preferred iron (Fe), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc metal-salts such as (Zn).
Metal-salt of the present invention mainly adopts transition metal halide, acetate, vitriol, nitrate, phosphoric acid salt.
In the immobilized process of metal salt catalyst of the present invention, the solvent of employing is a methyl alcohol, ethanol, toluene, butanone, DMF, THF, DMSO, one or both in the methylene dichloride.
The additive that the immobilized metal-salt of the present invention adopts is a nitrogen-containing heterocycle compound, wherein preferred imidazoles, pyridine, piperidines, a kind of in pyrimidine, the piperazine.
Employed organic bases is one or both in quadrol, triethylamine, tripropyl amine, pyridine, the pyrimidine in the oxidizing reaction of the present invention.
Range of reaction temperature of the present invention is between-30 ℃～150 ℃, and preferably between 50 ℃～100 ℃.
The mol ratio of β-isophorone and transition metal salt can be in the variation range of a broad in the present invention, and is general common between 200: 1 to 5: 1, and preferably between between 50: 1 to 10: 1.
The ratio of raw material β-isophorone and organic bases is between 50: 1 to 1: 2, and preferably between 5: 1 to 1: 1.
Employed in the present invention oxygenant can be pure oxygen, be rich in gas, the air of oxygen.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 accordingly according to oxygen level.
The present invention is than general different-phase catalyst, and reactive behavior and selectivity improve greatly.And than homogeneous catalyst, its reaction temperature and, the by product of two clusters significantly reduces, and catalyzer separate easily and control, is easy to utilize again.
Following embodiment will more comprehensively describe the present invention.
Embodiment
Catalyst system therefor basic structure is: metal-salt-part/carrier, wherein:
1#: cupric chloride-imidazoles/molecular sieve 2#: iron bromide-imidazoles/molecular sieve
3#: Manganous chloride tetrahydrate-imidazoles/molecular sieve 4#: cupric nitrate-piperidines/zeolite
5#: zinc nitrate-piperidines/zeolite 6#: nickelous nitrate-piperidines/zeolite
7#: neutralized verdigris-piperidines/gac 8#: ferric sulfate-than pyridine/gac
9#: manganese acetate-pyridine/gac 10#: cobaltous phosphate-quadrol/white carbon black
Embodiment 1:
Take by weighing 1g catalyzer (1#), join in the 250ml four neck flasks.Add 50g β-isophorone then successively, 20ml pyridine and 30mlDMF, under 80 ℃ of water-baths, bubbling air, the while vigorous stirring, afterreaction finished in 15 hours, and transformation efficiency is 98.2%, and selectivity reaches 85.5%.
Embodiment 2:
Taking by weighing 2g catalyzer (2#) joins in the 250ml four-necked bottle.Add 50g β-isophorone then successively, 20ml pyridine and 30ml toluene under 60 ℃ of water-baths, feed pure oxygen, the while vigorous stirring, and afterreaction finished in 18 hours, and transformation efficiency is 98.7%, and selectivity reaches 88.5%.
Embodiment 3-10
Be similar to embodiment 1,2, with the catalyzer of different metal and carrier composition, get as follows after reaction finishes respectively:
| Embodiment | β-IP (g) | Catalyzer (g) | Organic bases (ml) | Solvent (ml) | Temperature (℃) | Total time (h) | Transformation efficiency (%) | Selectivity (%) |
| 3 | 50 | 3#1.0 | Quadrol 10 | THF30 | 80 | 17 | 92.5 | 65.6 |
| 4 | 50 | 4#1.0 | Triethylamine 10 | THF30 | 80 | 19 | 94.5 | 78.5 |
| 5 | 50 | 5#2.0 | Pyridine 10 | DMF30 | 60 | 21 | 96.5 | 82.6 |
| 6 | 50 | 6#2.0 | Quadrol 20 | DMF30 | 60 | 18 | 97 | 86.1 |
| 7 | 50 | 7#2.0 | Triethylamine 20 | Butanone 30 | 80 | 24 | 97.8 | 83.2 |
| 8 | 50 | 8#4.0 | Pyridine 30 | Butanone 30 | 80 | 26 | 97.5 | 85.6 |
| 9 | 50 | 9#4.0 | Quadrol 30 | Toluene 30 | 60 | 32 | 98.6 | 87.2 |
| 10 | 50 | 10#4.0 | Triethylamine 30 | Toluene 30 | 60 | 29 | 97.6 | 89.5 |
Claims (10)
1, a kind of heterogeneous oxidization preparation 3,5,5-trimethyl-cyclohex-2-en-1, the method of 4-diketone, this method is a raw material 3,5,5-trimethylammonium-hexamethylene-3-alkene-1-ketone, in the presence of amine or nitrogen heterocyclic ring class organic bases and non-protonic solvent, use pure oxygen, be rich in the gas of oxygen, air is an oxygenant, generates ketoisophorone-30 ℃～150 ℃ following heterocatalysis oxidations, use therein immobilized metal salt catalyst, be that catalyst system therefor basic structure is with the metal-salt of the transition metal of IIIb～IIb in the immobilized active ingredient periodictable of active porous inorganic carrier: metal-salt-nitrogen heterocyclic ring or anion ligand/carrier, reaction formula is as follows:
β-IP is oxidized to KIP in the formula.
2,, it is characterized in that the active porous inorganic carrier of metal salt catalyst is according to the described method of claim 1: zeolite, molecular sieve, gac, main component is the carbon black of C, main component is SiO
2White carbon black a kind of.
3, according to the described method of claim 1, it is characterized in that the transition metal that synthetic solid supported type metal salt catalyst adopts is: manganese, iron, cobalt, nickel, copper, zinc a kind of.
4,, it is characterized in that the metal-salt that synthetic solid supported type metal salt catalyst adopts is according to the described method of claim 3: halogenide, acetate, vitriol, nitrate, phosphatic a kind of.
5,, it is characterized in that the solvent that synthetic solid supported type metal salt catalyst adopts is a methyl alcohol, ethanol, toluene, butanone, DMF, THF, DMSO, a kind of in the methylene dichloride according to the described method of claim 3.
6, according to the described method of claim 3, it is characterized in that the additive that synthetic solid supported type metal salt adopts is the nitrogen heterocyclic ring compounds, comprise imidazoles, pyridine, piperidines, pyrimidine, a kind of in the piperazine.
7,, it is characterized in that the non-protonic solvent that adopts in the oxidizing reaction is a toluene, butanone, DMF, one or both among THF and the DMSO according to the described method of claim 1.
8, according to the described method of claim 1, it is characterized in that the organic bases that uses is amine or heterocyclic nitrogen compound in the oxidizing reaction, comprise in quadrol, triethylamine, tripropyl amine, pyridine, the piperidines one or both.
9, according to the described method of claim 1, the mol ratio of raw material β-isophorone and solid-carried catalyst is between 50: 1 to 10: 1 in it is characterized in that reacting, and the mol ratio of raw material β-isophorone and organic bases is between 5: 1 to 1: 1.
10,, it is characterized in that temperature of reaction is between 50 ℃～100 ℃ according to the described method of claim 1.
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| CNA2006100535261A CN1923783A (en) | 2006-09-22 | 2006-09-22 | Method of preparing 3,5,5-trimethyl-cyclohex-2-en-1,4-dione by heterophase oxidation |
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| CNA2006100535261A CN1923783A (en) | 2006-09-22 | 2006-09-22 | Method of preparing 3,5,5-trimethyl-cyclohex-2-en-1,4-dione by heterophase oxidation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446074A (en) * | 2013-08-08 | 2013-12-18 | 上海海虹实业(集团)巢湖今辰药业有限公司 | Clarithromycin capsule and preparation method thereof |
| CN104649878A (en) * | 2013-11-21 | 2015-05-27 | 浙江新和成药业有限公司 | Continuous synthesis technology of 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 |
-
2006
- 2006-09-22 CN CNA2006100535261A patent/CN1923783A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446074A (en) * | 2013-08-08 | 2013-12-18 | 上海海虹实业(集团)巢湖今辰药业有限公司 | Clarithromycin capsule and preparation method thereof |
| CN104649878A (en) * | 2013-11-21 | 2015-05-27 | 浙江新和成药业有限公司 | Continuous synthesis technology of beta-isophorone |
| CN104649878B (en) * | 2013-11-21 | 2017-01-04 | 浙江新和成药业有限公司 | A kind of technique of continuous synthesis β-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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