CN107216244A - A kind of method for preparing the ketone of 3,5,5 trimethyl, 3 cyclohexene 1 - Google Patents
A kind of method for preparing the ketone of 3,5,5 trimethyl, 3 cyclohexene 1 Download PDFInfo
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- CN107216244A CN107216244A CN201710456091.3A CN201710456091A CN107216244A CN 107216244 A CN107216244 A CN 107216244A CN 201710456091 A CN201710456091 A CN 201710456091A CN 107216244 A CN107216244 A CN 107216244A
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- Prior art keywords
- ketone
- cyclohexene
- trimethyl
- nitrogen phosphorus
- alkali
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- 238000000034 method Methods 0.000 title claims abstract description 34
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 150000002576 ketones Chemical class 0.000 title abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 31
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- FFIDVTCKFVYQCZ-UHFFFAOYSA-N 1,3,3-trimethylcyclohexene Chemical compound CC1=CC(C)(C)CCC1 FFIDVTCKFVYQCZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000000066 reactive distillation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- UBMLKGCOROJNMF-UHFFFAOYSA-N 1,6,6-trimethylcyclohexene Chemical compound CC1=CCCCC1(C)C UBMLKGCOROJNMF-UHFFFAOYSA-N 0.000 claims 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 1
- ZSLXQCBRHBLQDX-UHFFFAOYSA-N 3,4,4-trimethylcyclohexene Chemical compound CC1C=CCCC1(C)C ZSLXQCBRHBLQDX-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 description 7
- 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
- 239000000126 substance Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- CHOOCIQDWNAXQQ-UHFFFAOYSA-N 1,5,5-trimethylcyclohexene Chemical compound CC1=CCCC(C)(C)C1 CHOOCIQDWNAXQQ-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
- 241001122767 Theaceae Species 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 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
- 239000006227 byproduct Substances 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
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000002304 perfume Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012805 post-processing 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 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
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 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
- 150000001450 anions Chemical class 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
- 239000001168 astaxanthin Substances 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- 239000012267 brine 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
- 239000003153 chemical reaction reagent 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
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 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
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons 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
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 239000000463 material Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 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
- -1 n-octyl Chemical group 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 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
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 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
- 238000009966 trimming Methods 0.000 description 1
- 238000010792 warming Methods 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
A kind of preparation method of the ketone of 3,5,5 trimethyl, 3 cyclohexene 1：With 3,5, the ketone of 5 trimethyl, 2 cyclohexene 1 (α IP) is raw material, nitrogen phosphorus river alkali was catalyst in the past, and isomerization reaction is carried out using reaction rectification technique, prepared 3,5, the ketone of 5 trimethyl, 3 cyclohexene 1 (β IP), product β IP purity can reach 99.5wt% 99.8wt%, and reaction selectivity can reach 99.2% 99.9%.The technique has the advantages that catalyst amount is few, selectivity is high, alkali analysis does not occur, high-boiling components are few, is a kind of efficient synthesis technique.
Description
Technical field
The present invention relates to a kind of preparation method of 3,5,5- trimethyl -3- cyclohexene -1- ketone (β-IP), and in particular to by preceding
The river base catalysis of nitrogen phosphorus 3,5,5- trimethyls -2- cyclohexene -1- ketone (α-IP) isomerization preparation 3,5,5- trimethyl -3- cyclohexene -
The method of 1- ketone.
Background technology
3,5,5- trimethyl -3- cyclohexene -1- ketone (β-IP) is that synthesising complex E, carotenoid, astaxanthin etc. are natural
A kind of important intermediate of product and spices, especially prepare tea perfume ketone (2,6,6- trimethyl -2- cyclohexene-Isosorbide-5-Nitrae-diketone,
KIP primary raw material), tea perfume ketone is again simultaneously the precursor for preparing TMHQ (VE main rings).
β-IP and α-IP are a pair of isomers, there is isomery balance under acid or base catalysis, β-IP can by α-
IP isomerization reaction and be made.But because β-IP are a unstable structures, therefore its equilibrium concentration is very low, it is necessary to constantly
Extract to break balance.Currently, reported that catalytic type is broadly divided into acid and urged for the existing many documents of isomerization reaction
Change and two kinds of base catalysis, main technique is as follows:
German patent DE 2457157 is disclosed by the use of triethanolamine as catalyst, and isomerization is carried out by raw material of α-IP
Reaction, reaction solution tartaric acid and brine, the method to prepare β-IP, the major defect of this method is that reaction is received
Rate is low, post processing is complicated, waste liquid is more etc..
United States Patent (USP) US4845303 realizes isomery using transition-metal catalyst ferric acetyl acetonade, aluminium acetylacetonate etc.
Change reaction.The technique major defect is：1) β-IP space-time yields are low；2) accessory substance is largely accumulated；3) catalyst is difficult from homogeneously urging
Separated in agent system.
French Patent (FRP) FR1446246, United States Patent (USP) US5929285 and German patent DE 2508779 etc. individually disclose one
The isomerization reaction using organic acid as catalyst is planted, for preparing β-IP, the solid acid being related to is:To adipic acid, toluene sulphur
Acid, amino acid etc..The technique major defect is：1) conversion ratio is relatively low, 2) accessory substance generation is more, 3) equipment corrosion is serious.
United States Patent (USP) US6005147 reports Co3O4The isomerization reaction of catalysis, reaction temperature is 216-217 DEG C, is passed through
The method that vacuum distillation obtains β-IP, the technique major defect is：1) reaction by-product is more, and it is bright that isophorone self condenses product
It is aobvious；2) conversion ratio is low；3) catalyst is not easily recycled utilization.
Chinese patent CN1235954 and the grades of United States Patent (USP) US 6265617 are to urge using alkali metal or alkaline earth metal compound
Agent synthesizes β-IP, and involved catalyst mainly has NaOH, Na2CO3Deng.The technique major defect is：1) due to catalysis used
Agent is alkali metal or alkaline earth metal hydroxide, carbonate and bicarbonate etc., and the quasi-alkali or highly basic salt are easily saltoutd, serious rotten
Lose consersion unit；2) heel produced in course of reaction is more, and catalyst is easily poisoned, and is difficult regeneration cycle and uses, institute's shape
Into accessory substance environmental pollution also than more serious.
Chinese patent CN 1660752A are using α-IP as raw material, using acid ceramic material as release agent and catalyst, in multistage
Isomerization reaction is carried out in reactor, the technique major defect is：1) catalyst amount is big, 2) pressure is of a relatively high.
The FeCl of catalytic amount3With under RMgBr RMgX synergies, can equally promote the progress of isomerization reaction, from
And synthesizing β-IP, the major defect of the technique is：1) reaction condition is harsher, 2) post processing is more complicated.
Existing process mostly has following weak point：1) catalyst amount is excessive；2) space-time yield is not high；3) by-product
Thing accumulation is more；4) inorganic base catalyst, is also easy to produce alkali analysis, and equipment corrosion is serious；5) transition-metal catalyst environmental pollution
Seriously.
It is, thus, sought for a kind of new technique, to solve various deficiencies present in prior art.
The content of the invention
It is an object of the invention to provide a kind of green preparation process of 3,5,5- trimethyls -3- cyclohexene -1- ketone (β-IP).
The technique uses preceding nitrogen phosphorus river alkali for catalyst, with product catalyst consumption is few, high income, environmental protection, is easily achieved work
The advantages of industry metaplasia is produced, solve that space-time yield present in prior art is not high, catalyst amount is excessive, accessory substance is more,
The various problems such as equipment deep-etching is serious.
To realize above goal of the invention, the technical solution adopted by the present invention is as follows：
The preparation method of one kind 3,5,5- trimethyl -3- cyclohexene -1- ketone, with Isophorone
(α-IP) is raw material, and former nitrogen phosphorus river alkali is catalyst, using reaction rectification technique, carries out isomerization to α-IP and prepares 3,5,5-
Trimethyl -3- cyclohexene -1- ketone (β-IP).
In the present invention, shown in the structure such as formula (1) of the preceding nitrogen phosphorus river base catalyst,
Wherein, R, R' are identical or different, separately represent H, the chain-like alkyl containing 1-10 carbon atom, contain 3-
The cyclic alkyl of 10 carbon atoms or the aryl containing 6-10 carbon atom, such as methyl, ethyl, propyl group, isopropyl, positive fourth
Base, cyclopenta, n-octyl, benzyl etc..It is preferred that R' be the chain-like alkyl containing 2-5 carbon atom.The preceding nitrogen phosphorus river alkali
Consumption is the 0.0001-1wt% of raw material 3,5,5- trimethyl -2- cyclohexene -1- ketone.
As preferred scheme, catalyst of the present invention is the preceding nitrogen phosphorus river alkali (R ≠ H replaced entirely；R' ≠ H) with it is disubstituted before
Nitrogen phosphorus river alkali (R=H；R' ≠ H) combination, the chain alkane of the preferred 2-5 carbon atom of R and R' in the preceding nitrogen phosphorus river alkali replaced entirely
R ' is preferably the chain-like alkyl of 2-5 carbon atom in base, disubstituted preceding nitrogen phosphorus river alkali；The chain alkane of the 2-5 carbon atom
Base such as ethyl, propyl group, isopropyl, normal-butyl etc..Wherein, the preceding nitrogen phosphorus river alkali replaced entirely and disubstituted preceding nitrogen phosphorus river alkali mole
Than for 50:1-1:5, preferably 20:1-5:1；The consumption of catalyst is raw material 3,5,5- trimethyl -2- cyclohexene -1- ketone (α-IP)
0.0001wt%-0.1wt%, preferably 0.001wt%-0.01wt%.Using the preceding nitrogen phosphorus river alkali of combination, can effectively it finely tune
The alkalescence of system, reduces the generation of accessory substance, improves the selectivity of reaction.
Reactive distillation of the present invention is carried out in tower reactor, and the theoretical cam curve of the tower reactor is
25-50, preferably 30-40；Reflux ratio is 10:1-2:1.Under normal temperature, preceding nitrogen phosphorus river alkali is mixed in advance with raw material α-IP, by
Tower reactor enters tower reactor, and then tower reactor is warming up to tower in 150 DEG C -230 DEG C, preferably 170 DEG C -220 DEG C, reactive distillation processes
The absolute pressure of formula reactor is 0.2Bar -2Bar, preferably 0.5Bar -1Bar.Reaction time 10-150h, preferably 20-
80h.Under the catalytic action of preceding nitrogen phosphorus river alkali isomerization reaction occurs for α-IP, because the product β-IP of generation boiling point is 190
DEG C, 215 DEG C of the boiling point less than raw material α-IP, therefore, the β-IP of reaction generation are constantly distilled out of from tower top, so that isomerization is anti-
The balance answered is moved to generation β-IP direction.In the β-IP crude products that overhead extraction purity is 50wt%-95wt%, selecting response
Property can reach 99.2%-99.9%.
β-IP the crude products of tower reactor overhead extraction obtain product in vacuum rectification tower by further rectification under vacuum
β-IP, vacuum rectification tower theoretical cam curve is 25-40, and absolute pressure is 1-20kPa, and reflux ratio is 1:1-5:1, tower top temperature is
80-130℃.After further rectification under vacuum, product β-IP purity can reach 99.5wt%-99.8wt%.
The solution of the present invention compared with prior art, with advantages below：
1) nitrogen phosphorus river alkali is scattered in homogeneous form in the liquid phase before catalyst, and preceding nitrogen phosphorus river alkali is dissolved in α-IP, without
Increase other solvents, therefore overcome inorganic base and be easy to the problem of alkali is separated out, selectivity of product is high.
2) compared with common inorganic alkali, preceding nitrogen phosphorus river alkali have bigger steric hindrance, block IP anions intermediate with it is other
The combination of IP molecules, and then the generation of autohemagglutination product is inhibited, therefore, with high stereoselectivity, reduce chemical reagent
Consumption, reduce the generation of " three wastes ".
3), can effective trimming body using disubstituted with preceding nitrogen phosphorus river alkali mixed catalyst that is replacing entirely in preferred scheme
The alkalescence of system, reduces the generation of accessory substance, improves the selectivity of reaction.
4) reacted using reaction rectification technique, operating process is simple, and reaction can be carried out continuously.
Embodiment
Catalyst of the present invention can be prepared using the method for conventional chemical synthesis, and specific reaction scheme is as follows：
Compound III synthesis
Material II (0.3mol) is taken to be dissolved in 300mL toluene, the lower aldehyde I for instilling 0.15mol of stirring is mixed with 100mL toluene
Liquid is closed, 24h is reacted at room temperature.It is evaporated off after solvent adding 150mL methanol in gained thick liquid, is added portionwise altogether under ice-water bath cooling
8.8g NaBH4, room temperature continues to react 12h, isometric water is added after concentration, with petroleum ether extraction (50mL × 3), anhydrous Na2SO4
Dry, vacuum distillation obtains III.
Compound IV synthesis
0.1mol NaOH (10%) is added into 0.1mol III, 0.2mol halogenated hydrocarbons R'X, room temperature is then added dropwise
React after 2h, be diluted with water, with n-hexane extraction (50mL × 3), anhydrous Na 2SO4 is dried, and vacuum distillation obtains compound IV.
Compound V synthesis
0.05mol middle IV is dissolved in 50mL CH2Cl2In, ice salt bath is cooled to 0-5 DEG C, N2
Under protection, hexamethyl phosphoramide (0.05mol) and CF are successively instilled3SO3H (0.05mol), after adding at room temperature
Continue to react 2h.It is evaporated off after solvent washing (30mL × 3) with ether, obtains thick liquid V.
Compound VI synthesis
0.045mol V is dissolved in 50mL tetrahydrofurans, the lower injection t-BuOK's (0.09mol) by several times of nitrogen protection
40mL THF solutions；React and 120mL pentanes, standing separation supernatant liquor are added after 2h；Rotary evaporation is removed after light component, is subtracted
Nitrogen phosphorus river alkali VI before pressure rectifying is obtained.
The different preceding nitrogen phosphorus river base catalysts used in embodiment are as follows：
IL-A：R=H；R'=normal-butyls
IL-B：R=H；R'=ethyls
IL-C：R=isobutyl groups；R'=isopropyls
IL-D：R=methyl；R'=n-pentyls
IL-E：R=propyl group；R'=cyclopenta
IL-F：R=n-octyls；R'=cyclopenta
IL-G：R=H；R'=n-propyls
IL-H：R=benzyls；R'=n-hexyls
Gas phase analysis condition：Agilent gas-chromatography on-line determination, chromatographic column：Polysiloxanes post HP-5, gasify room temperature
For：250 DEG C, detector temperature：250 DEG C, temperature programming：50 DEG C, 1min；80 DEG C, 1min；10 DEG C/min to 250 DEG C, 10min.
Embodiment 1
α-IP the raw materials containing nitrogen phosphorus river base catalyst IL-A before 0.05wt% are added to tower reactor tower reactor, in tower reactor
210 DEG C of temperature, theoretical cam curve are 30, and reflux ratio is 3:Reacted under conditions of 1, tower reactor absolute pressure 0.9Bar
Rectifying, occurs α-IP isomerization reactions, reaction selectivity is 99.7%, and overhead collection obtains crude product β-IP, and (gas phase purity is
70wt%).Crude product β-IP are 1.5kPa in absolute pressure, and theoretical cam curve is 30, and reflux ratio is 3:Under the conditions of 1, further
Rectification under vacuum obtains the product β-IP that purity is 99.5wt%, and tower top temperature is 100 DEG C.
Embodiment 2-10 and embodiment 11 (comparative example)
On the basis of example 1, the theoretical cam curve of change catalyst type and the tower reactor of consumption, reactive distillation,
Bottom temperature, pressure, reflux ratio, residence time, the results detailed in Table 1.
Table 1
Above embodiment, not makees any formal limitation to technical scheme.Every foundation is originally
The technical spirit of invention each falls within the guarantor of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification
Within the scope of shield.
Claims (10)
1. the method that one kind prepares 3,5,5- trimethyl -3- cyclohexene -1- ketone, it is characterised in that with 3,5,5- trimethyl -2- rings
Hexene -1- ketone is raw material, and former nitrogen phosphorus river alkali is catalyst, using reactive distillation, carry out isomerization prepare 3,5,5- trimethyls -
3- cyclohexene -1- ketone.
2. the method according to claim l, it is characterised in that described preceding nitrogen phosphorus river alkali structure is formula (I)
Wherein, R, R' are identical or different, separately represent H, the chain-like alkyl containing 1-10 carbon atom, containing 3-10
The cyclic alkyl of carbon atom or the aryl containing 6-10 carbon atom.
3. method according to claim 1 or 2, it is characterised in that the consumption of the preceding nitrogen phosphorus river alkali is raw material 3,5,5-
The 0.0001-1wt% of trimethyl -2- cyclohexene -1- ketone.
4. the method according to claim any one of 1-3, it is characterised in that the preceding nitrogen phosphorus river alkali is the preceding nitrogen replaced entirely
The combination of phosphorus river alkali and disubstituted preceding nitrogen phosphorus river alkali.
5. method according to claim 4, it is characterised in that the preceding nitrogen phosphorus river alkali replaced entirely and disubstituted preceding nitrogen phosphorus river alkali
Mole ratio be 50:1-1:5, preferably 20:1-5:1.
6. the method according to claim 4 or 5, it is characterised in that the consumption of the catalyst is the front three of raw material 3,5,5-
The 0.0001wt%-0.1wt%, preferably 0.001wt%-0.01wt% of base -2- cyclohexene -1- ketone.
7. the method according to claim any one of l-6, it is characterised in that the reactive distillation enters in tower reactor
OK, tower reactor theoretical cam curve is 25-50, preferably 30-40；Reflux ratio is 10:1-2:1.
8. method according to claim 7, it is characterised in that the absolute pressure of the tower reactor is 0.2Bar-
2Bar, preferably 0.5Bar-1Bar；Bottom temperature is 150 DEG C -230 DEG C, preferably 170 DEG C -220 DEG C.
9. the method according to claim 7 or 8, it is characterised in that tower reactor overhead extraction purity is 50wt%-
95wt% 3,5,5- trimethyl -3- cyclohexene -1- ketone crude products.
10. method according to claim 9, it is characterised in that 3,5,5- trimethyl -3- cyclohexene -1- ketone crude products are subtracting
In pressure rectifying column the trimethyl -3- cyclohexene -1- ketone of product 3,5,5-, vacuum rectification tower theoretical cam curve are obtained by rectification under vacuum
For 25-40, reflux ratio is 1:1-5:1.
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| CN108046498A (en) * | 2017-12-15 | 2018-05-18 | 江苏焕鑫新材料股份有限公司 | A kind of green pretreating process of ketone polymer waste liquid |
| CN112920032A (en) * | 2019-12-06 | 2021-06-08 | 万华化学集团股份有限公司 | Preparation method of beta-isophorone |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108046498A (en) * | 2017-12-15 | 2018-05-18 | 江苏焕鑫新材料股份有限公司 | A kind of green pretreating process of ketone polymer waste liquid |
| CN108046498B (en) * | 2017-12-15 | 2020-11-13 | 江苏焕鑫新材料股份有限公司 | Green pretreatment process of ketone polymer waste liquid |
| CN112920032A (en) * | 2019-12-06 | 2021-06-08 | 万华化学集团股份有限公司 | Preparation method of beta-isophorone |
| CN112920032B (en) * | 2019-12-06 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method of beta-isophorone |
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