CN107216244B - Method for preparing 3,5, 5-trimethyl-3-cyclohexene-1-ketone - Google Patents
Method for preparing 3,5, 5-trimethyl-3-cyclohexene-1-ketone Download PDFInfo
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- CN107216244B CN107216244B CN201710456091.3A CN201710456091A CN107216244B CN 107216244 B CN107216244 B CN 107216244B CN 201710456091 A CN201710456091 A CN 201710456091A CN 107216244 B CN107216244 B CN 107216244B
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- trimethyl
- cyclohexene
- azophoska
- catalyst
- ketone
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- 238000000034 method Methods 0.000 title claims description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000066 reactive distillation Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 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 3
- 239000007858 starting material Substances 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- -1 n-octyl Chemical group 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 239000001168 astaxanthin Substances 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0264—Phosphorus acid amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
-
- 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
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
3,5, 5-trimethyl-3-cyclohexene-1-ketone (α -IP) is used as a raw material, the former nitrogen phosphorus alkali is used as a catalyst, and a reaction rectification technology is adopted to carry out an isomerization reaction to prepare the 3,5, 5-trimethyl-3-cyclohexene-1-ketone (β -IP), the purity of the product β -IP can reach 99.5 wt% -99.8 wt%, and the reaction selectivity can reach 99.2% -99.9%.
Description
Technical Field
The invention relates to a preparation method of 3,5, 5-trimethyl-3-cyclohexene-1-ketone (β -IP), and particularly relates to a method for preparing 3,5, 5-trimethyl-3-cyclohexene-1-ketone by means of isomerization of 3,5, 5-trimethyl-2-cyclohexene-1-ketone (α -IP) under catalysis of azophoska.
Background
3,5, 5-trimethyl-3-cyclohexene-1-ketone (β -IP) is an important intermediate for synthesizing natural products such as vitamin E, carotenoid, astaxanthin and the like and perfumes, in particular to a main raw material for preparing tea-scented ketone (2,6, 6-trimethyl-2-cyclohexene-1, 4-dione, KIP), and the tea-scented ketone is also a precursor for preparing trimethylhydroquinone (VE main ring).
β -IP and α -IP are a pair of isomers, which have isomerization equilibrium under acid or alkali catalysis, β -IP can be prepared by isomerization of α -IP, but β -IP is an unstable structure, so the equilibrium concentration is very low, and continuous extraction is needed to break the equilibrium.
German patent DE 2457106 discloses a process for preparing β -IP by isomerizing α -IP as a raw material using triethanolamine as a catalyst, washing the reaction solution with tartaric acid and a salt solution, which has the main disadvantages of low reaction yield, complicated post-treatment, large amount of waste liquid, etc.
U.S. Pat. No. 4,489,303 utilizes transition metal catalysts such as iron acetylacetonate, aluminum acetylacetonate, etc. to effect isomerization, the major disadvantages of this process are 1) low space-time yield of β -IP, 2) large accumulation of by-products, and 3) difficulty in separating the catalyst from the homogeneous catalyst system.
French patent FR1446246, U.S. Pat. No. 5,285 and German patent DE2508779 respectively disclose an isomerization reaction using an organic acid as a catalyst for the preparation of β -IP, wherein the solid acid is selected from the group consisting of p-adipic acid, toluenesulfonic acid, amino acids, etc. the process has the main disadvantages of 1) low conversion, 2) high by-product formation, and 3) severe corrosion of equipment.
U.S. Pat. No. 5,6005147 reports on Co3O4The catalytic isomerization reaction is carried out at the reaction temperature of 216-217 ℃, and β -IP is obtained by reduced pressure distillation, and the process has the main defects of 1) more reaction byproducts and obvious isophorone self-condensation product, 2) low conversion rate and 3) difficult recycling of the catalyst.
Chinese patent CN1235954 and U.S. Pat. No. 4, 6265617, etc. use alkali metal or alkaline earth metal compound as catalyst to synthesize β -IP, and the related catalyst mainly includes NaOH and Na2CO3And the like. The main disadvantages of the process are: 1) because the used catalyst is alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate and the like, the strong base or the strong base salt is easy to salt out and seriously corrodes reaction equipment; 2) the leftover material produced in the reaction process isMoreover, the catalyst is easy to be poisoned and difficult to be regenerated and recycled, and the formed by-products have serious environmental pollution.
The Chinese patent CN 1660752A takes α -IP as raw material and takes acid ceramic material as separating agent and catalyst, and carries out isomerization reaction in a multi-stage reactor, and the process has the main defects that 1) the dosage of the catalyst is large, and 2) the pressure is relatively high.
Catalytic amount of FeCl3Under the synergistic action of the catalyst and a Grignard reagent RMgX, the catalyst can also promote the isomerization reaction to synthesize β -IP, and the process has the main disadvantages of 1) harsh reaction conditions and 2) complex post-treatment.
The prior art has the following defects: 1) the dosage of the catalyst is too large; 2) the space-time yield is not high; 3) the accumulation of byproducts is high; 4) the inorganic base catalyst is easy to generate alkali precipitation, and the equipment is seriously corroded; 5) the transition metal catalyst has serious environmental pollution.
Therefore, a new process is needed to solve the various deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a green preparation process of 3,5, 5-trimethyl-3-cyclohexene-1-ketone (β -IP), which adopts azophoska as a catalyst, has the advantages of less catalyst dosage, high yield, environmental protection, easy realization of industrial production and the like, and solves the problems of low space-time yield, excessive catalyst dosage, more byproducts, strong equipment corrosion and the like in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of 3,5, 5-trimethyl-3-cyclohexene-1-ketone uses 3,5, 5-trimethyl-2-cyclohexene-1-ketone (α -IP) as a raw material, uses former nitrogen phosphorus alkaloid as a catalyst, and adopts a reactive rectification technology to isomerize α -IP to prepare 3,5, 5-trimethyl-3-cyclohexene-1-ketone (β -IP).
In the invention, the structure of the azophoska catalyst is shown as a formula (1),
wherein R, R' are the same or different and each independently represents H, a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, cyclopentyl, n-octyl, benzyl, etc. Preferred R' is a chain alkyl group having 2 to 5 carbon atoms. The dosage of the azophoska is 0.0001-1 wt% of the raw material 3,5, 5-trimethyl-2-cyclohexene-1-one.
Preferably, the catalyst is a combination of fully substituted pro-azophospine (R ≠ H; R '≠ H) and disubstituted pro-azophospine (R ═ H; R' ≠ H), R and R 'in the fully substituted pro-azophospine are preferably chain alkyl with 2-5 carbon atoms, R' in the disubstituted pro-azophospine is preferably chain alkyl with 2-5 carbon atoms, the chain alkyl with 2-5 carbon atoms is such as ethyl, propyl, isopropyl, n-butyl and the like, wherein the molar ratio of the fully substituted pro-azophospine to the disubstituted pro-azophospine is 50:1-1:5, preferably 20:1-5:1, the amount of the catalyst is 0.0001-0.1 wt%, preferably 0.001-0.01 wt% of the raw material 3,5, 5-trimethyl-2-cyclohexene-1-one (α -IP), and the fine adjustment of the pre-azophospine can effectively reduce the generation of side products of the alkaline reaction and improve the selectivity of the system.
The reactive distillation is carried out in a tower reactor, the theoretical plate number of the tower reactor is 25-50, preferably 30-40, the reflux ratio is 10:1-2:1, under normal temperature, the former azophoska and the raw material α -IP are mixed in advance, the mixture enters the tower reactor from a tower kettle, then the temperature of the tower kettle is raised to 150-230 ℃, preferably 170-220 ℃, the absolute pressure of the tower reactor in the reactive distillation process is 0.2Bar-2Bar, preferably 0.5Bar-1Bar, the reaction residence time is 10-150h, preferably 20-80h, α -IP generates isomerization reaction under the catalytic action of the former azophoska, the boiling point of the generated product β -IP is 190 ℃ and is lower than the boiling point of the raw material α -IP 215 ℃, therefore, β -IP generated by the reaction is continuously distilled out from the tower top, so that the equilibrium of the isomerization reaction moves to the direction of generating β -IP, the crude product with the purity of 50-95 wt% and the crude product with the selectivity of 50-95% and 99.592% of the crude product.
The β -IP crude product collected from the tower top of the tower reactor is further decompressed and rectified in a decompression rectifying tower to obtain a product β -IP, the theoretical plate number of the decompression rectifying tower is 25-40, the absolute pressure is 1-20kPa, the reflux ratio is 1:1-5:1, the tower top temperature is 80-130 ℃, and the purity of the product β -IP can reach 99.5-99.8 wt% after further decompression and rectification.
Compared with the prior art, the scheme of the invention has the following advantages:
1) the azophoska before the catalyst is dispersed in a liquid phase in a homogeneous phase mode, and the azophoska can be dissolved in α -IP without adding other solvents, so that the problem that inorganic base is easy to separate out alkali is solved, and the product selectivity is high.
2) Compared with common inorganic base, the azophoska base has larger steric hindrance, prevents the combination of the IP negative ion intermediate and other IP molecules, and further inhibits the generation of self-polymerization products, so that the azophoska base has high isomeric selectivity, reduces the consumption of chemical reagents, and reduces the generation of three wastes.
3) In the preferred scheme, the pre-nitrogen phosphorus alkali mixed catalyst with double substitution and full substitution is adopted, so that the alkalinity of the system can be effectively finely adjusted, the generation of byproducts is reduced, and the selectivity of the reaction is improved.
4) The reaction rectification technology is adopted for reaction, the operation flow is simple, and the reaction can be continuously carried out.
Detailed Description
The catalyst can be prepared by adopting a conventional chemical synthesis method, and the specific reaction route is as follows:
synthesis of Compound III
Dissolving substance II (0.3mol) in 300m L toluene, dripping 0.15mol mixture of aldehyde I and 100m L toluene while stirring, reacting at room temperature for 24h, evaporating to remove solvent to obtain viscous liquid, adding 150m L methanol, cooling in ice water bath, and adding 8.8g NaBH4, reacting for 12h at room temperature, concentrating, adding equal volume of water, extracting with petroleum ether (50m L× 3), anhydrous Na2SO4Drying, and distilling under reduced pressure to obtain III.
Synthesis of Compound IV
0.1mol of NaOH (10%) is added to 0.1mol of III, 0.2mol of halohydrocarbon R' X is then added dropwise, after 2h reaction at room temperature, water is added for dilution, n-hexane extraction (50m L× 3), anhydrous Na2SO4 is dried, and the compound IV is obtained by distillation under reduced pressure.
Synthesis of Compound V
0.05mol of medium IV is dissolved in 50m L CH2Cl2Cooling to 0-5 deg.C in ice salt bath, and cooling to N2
Under protection, hexamethylphosphoramide (0.05mol) and CF are added dropwise successively3SO3H (0.05mol), after the addition, the reaction is continued for 2H at room temperature, the solvent is distilled off and washed with ether (30m L× 3) to obtain a viscous liquid V.
Synthesis of Compound VI
Dissolving 0.045mol of V in 50m L tetrahydrofuran, injecting t-BuOK (0.09mol) 40m L THF solution in portions under the protection of nitrogen, reacting for 2h, adding 120m L n-pentane, standing to separate supernatant, removing light components by rotary evaporation, and performing reduced pressure rectification to obtain the azophoska VI.
The different pro-NPCHUAN base catalysts used in the examples were as follows:
i L-A, R ═ H, R' ═ n-butyl
I L-B, R ═ H, R ═ ethyl
I L-C, R ═ isobutyl, R ═ isopropyl
I L-D, R ═ methyl, R' ═ n-pentyl
I L-E, R ═ propyl, R ═ cyclopentyl
I L-F, R ═ n-octyl, R ═ cyclopentyl
I L-G, R ═ H, R ═ n-propyl
I L-H, R ═ benzyl, R' ═ n-hexyl
Gas phase analysis conditions: an agilent gas chromatography on-line measurement, a chromatographic column: polysiloxane column HP-5, the gasification chamber temperature was: 250 ℃, detector temperature: temperature programming at 250 ℃ of: 50 ℃ for 1 min; at 80 ℃ for 1 min; 10 ℃/min to 250 ℃ for 10 min.
Example 1
Adding α -IP raw material containing 0.05 wt% of front nitrogen phosphorus alkali catalyst I L-A into a tower kettle of a tower reactor, carrying out reaction rectification under the conditions that the temperature of the tower kettle is 210 ℃, the theoretical plate number is 30, the reflux ratio is 3:1 and the absolute pressure of the tower reactor is 0.9Bar, carrying out α -IP isomerization reaction, the reaction selectivity is 99.7%, collecting a crude product β -IP (the gas phase purity is 70 wt%) at the top of the tower, further carrying out reduced pressure rectification on the crude product β -IP under the conditions that the absolute pressure is 1.5kPa, the theoretical plate number is 30 and the reflux ratio is 3:1 to obtain a product β -IP with the purity of 99.5 wt%, and the temperature of the top of the tower is 100 ℃.
Examples 2 to 10 and example 11 (comparative example)
On the basis of example 1, the type and amount of the catalyst, the theoretical plate number of the reactive distillation tower reactor, the temperature of the tower bottom, the pressure, the reflux ratio and the residence time are changed, and the results are detailed in table 1.
TABLE 1
The above embodiments are not intended to limit the technical solutions of the present invention in any manner. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (9)
1. A method for preparing 3,5, 5-trimethyl-3-cyclohexene-1-ketone is characterized in that 3,5, 5-trimethyl-2-cyclohexene-1-ketone is used as a raw material, and the former nitrogen phosphorus Sichuan alkali is used as a catalyst, and the reaction rectification is adopted to carry out isomerization to prepare 3,5, 5-trimethyl-3-cyclohexene-1-ketone;
the structure of the azophoska is shown as formula (I)
R, R 'are the same or different, R represents H, a chain alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R' represents a chain alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms; the pre-azophoska is the combination of fully substituted pre-azophoska and disubstituted pre-azophoska, and the molar ratio of the fully substituted pre-azophoska to the disubstituted pre-azophoska is 20:1-5: 1.
2. The method of claim 1, wherein the catalyst is used in an amount of 0.0001 wt% to 0.1 wt% based on the starting material 3,5, 5-trimethyl-2-cyclohexen-1-one.
3. The method of claim 1, wherein the catalyst is used in an amount of 0.001 wt% to 0.01 wt% based on the starting material 3,5, 5-trimethyl-2-cyclohexen-1-one.
4. The process of claim I, wherein the reactive distillation is carried out in a column reactor having a theoretical plate number of 25 to 50; the reflux ratio is 10:1-2: 1.
5. The process of claim i, wherein the reactive distillation is carried out in a column reactor having a theoretical plate number of 30 to 40; the reflux ratio is 10:1-2: 1.
6. A process according to claim 4, wherein the absolute pressure of the column reactor is 0.2Bar-2 Bar; the temperature of the tower kettle is 150-230 ℃.
7. A process according to claim 4, wherein the absolute pressure of the column reactor is 0.5Bar-1 Bar; the temperature of the tower kettle is 170-220 ℃.
8. The method as claimed in claim 4 or 6, characterized in that the crude 3,5, 5-trimethyl-3-cyclohexene-1-one with a purity of 50 wt% to 95 wt% is taken out from the top of the tower reactor.
9. The method as claimed in claim 8, wherein the 3,5, 5-trimethyl-3-cyclohexene-1-one crude product is subjected to vacuum rectification in a vacuum rectification tower to obtain the product 3,5, 5-trimethyl-3-cyclohexene-1-one, the theoretical plate number of the vacuum rectification tower is 25-40, and the reflux ratio is 1:1-5: 1.
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| CN104311407A (en) * | 2014-09-29 | 2015-01-28 | 万华化学集团股份有限公司 | Environmental-friendly preparation process of 3,5,5-trimethyl-3-cyclohexene-1-ketone |
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| US6265617B1 (en) * | 1998-05-13 | 2001-07-24 | Degussa-Huls Aktiengesellschaft | Process for the preparation of 3,5,5-trimethylcyclohexa-3-en-1-one (β-isophorone) by isomerization of 3,5,5- trimethylcyclohexa-2-en-1-one (α-isophorone) |
| CN104311407A (en) * | 2014-09-29 | 2015-01-28 | 万华化学集团股份有限公司 | Environmental-friendly preparation process of 3,5,5-trimethyl-3-cyclohexene-1-ketone |
Non-Patent Citations (1)
| Title |
|---|
| 二异丁基取代前氮磷川碱的合成及其促进的双键异构化反应;吴伟等;《化学通报》;20101231(第5期);第461-464页 * |
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