CN104311407B - A kind of green preparation process of 3,5,5-trimethyl-3-cyclohexene-1-ketone - Google Patents
A kind of green preparation process of 3,5,5-trimethyl-3-cyclohexene-1-ketone Download PDFInfo
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- 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
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
A kind of 3,5, the synthesis technique of 5-trimethyl-3-cyclohexene-1-ketone, it is characterized in that: with 3,5,5-trimethyl-2-cyclohexene-1-ketone (α-IP) is raw material, with alkali ionic liquid for catalyst, reaction rectification technique is adopted to carry out isomerization reaction, preparation a kind of 3,5,5-trimethyl-3-cyclohexene-1-ketone (β-IP), reaction absolute pressure is 0.2 2Bar, reaction temperature 150-230 DEG C, the purity of product β-IP can reach 99.5wt%-99.8wt%, and reaction selectivity can reach 99.2%-99.9%.This technique has selectivity height, the advantages such as alkali analysis, catalyst are easily recycled does not occur, and is the synthesis technique of a kind of environmental protection.
Description
Technical field
The present invention relates to the green preparation process of a kind of 3,5,5-trimethyls-3-cyclohexene-1-ketone (β-IP), be specifically related to alkali ionic liquid and catalyze and synthesize the preparation technology of β-IP.
Background technology
3,5,5-trimethyl-3-cyclohexene-1-ketone (β-IP) is a kind of important intermediate of the natural products such as synthesising complex E, carotenoid, astaxanthin and spice, especially tea ketone musk (2 is prepared, 6,6-trimethyl-2-cyclohexene-Isosorbide-5-Nitrae-diketone, KIP) primary raw material, tea ketone musk is again the precursor preparing trimethylhydroquinone (VE main ring) simultaneously.
β-IP and 3，5，5-trimethylcyclohexen-2-one-1 (α-IP) are a pair isomerss, there is isomery balance under acid or base catalysis, and β-IP can be prepared by the isomerization reaction of α-IP.But owing to β-IP is a unstable structure, therefore its equilibrium concentration is very low, it is necessary to constantly extracting is to break balance.Currently, having many documents for isomerization reaction and reported, catalytic type is broadly divided into acid catalysis and base catalysis two kinds, and main technique is as follows:
DE Published Patent DE2457157 discloses and utilizes triethanolamine as catalyst, isomerization reaction is carried out for raw material with α-IP, reactant liquor tartaric acid and brine, prepare β-IP, the method major downside is that reaction yield is low, post processing is complicated, waste liquid is many.
US publication US4845303 utilizes transition-metal catalyst ferric acetyl acetonade, aluminium acetylacetonate etc., it is achieved that isomerization reaction.This technique main drawback is that 1) β-IP space-time yield is low；2) by-product accumulates in a large number；3) catalyst difficulty is separated from homogeneous catalyst system.
France publication FR1446246, US publication US5929285 and DE Published Patent DE2508779 etc. individually disclose a kind of isomerization reaction using organic acid as catalyst, being used for preparing β-IP, the solid acid related to is: to adipic acid, toluenesulfonic acid, aminoacid etc..This technique main drawback is that 1) conversion ratio is relatively low, and 2) by-product generates more, and 3) equipment corrosion is serious.
US publication US6005147 reports Co304The isomerization reaction of catalysis, reaction temperature is 216-217 DEG C, by reduce pressure distillation obtain β-IP method, this technique main drawback is that 1) reaction by-product more, it is obvious that isophorone self condenses product；2) low conversion rate；3) catalyst is not easily recycled utilization.
China publication CN1235954 and US publication US6265617 etc. use alkali metal or alkaline earth metal compound to be catalyst synthesis β-IP, and involved catalyst mainly has NaOH, Na2CO3Deng.This technique main drawback is that 1) owing to used catalyst is alkali metal or alkaline earth metal hydroxide, carbonate and bicarbonate etc., this quasi-alkali or highly basic salt are easily saltoutd, heavy corrosion consersion unit；2) heel produced in course of reaction is more, and catalyst is easily poisoning, and not easily regeneration cycle uses, and the by-product environmental pollution also ratio formed is more serious.
Chinese patent CN1660752A, with α-IP for raw material, with acid ceramic material for separating medium and catalyst material, carries out isomerization reaction in multistage reactor, and this technique main drawback is that 1) catalyst amount is big, and 2) pressure is of a relatively high.
The FeCl of catalytic amount3With under Grignard reagent RMgX synergism, the carrying out of equally possible promotion isomerization reaction, thus synthesizing β-IP, this technique main drawback is that 1) reaction condition is harsher, 2) catalyst is expensive, 3) post processing is more complicated.
Existing technique mostly also exists following weak point: 1) catalyst can not regeneration or consumption excessive；2) space-time yield is not high；3) byproducts build-up is more；4) inorganic base catalyst, is easily generated alkali analysis, and equipment corrosion is serious；5) transition-metal catalyst environmental pollution is serious.
It is, thus, sought for a kind of new technique, to solve the various deficiencies existed in prior art.
Summary of the invention
It is an object of the invention to provide the green preparation process of a kind of 3,5,5-trimethyl-3-cyclohexene-1-ketone (β-IP).This technique adopts alkali ionic liquid to be catalyst, have product yield height, catalyst easily reclaims, environmental protection, be easily achieved the advantages such as industrialized production, thoroughly solves that the catalyst that exists in prior art can not regeneration, space-time yield be not high, by-product is more, equipment corrosion is serious, the various problems such as big for environment pollution.
For realizing above goal of the invention, the technical solution used in the present invention is as follows:
A kind of 3,5, the preparation technology of 5-trimethyl-3-cyclohexene-1-ketone, with 3,5,5-trimethyl-2-cyclohexene-1-ketone (α-IP) is raw material, with alkali ionic liquid for catalyst, adopt reaction rectification technique, α-IP is carried out isomerization and prepares 3,5,5-trimethyls-3-cyclohexene-1-ketone (β-IP).
In the present invention, the structural formula of described alkaline ionic liquid catalyst is A+B?, wherein, A+For cation unit, including but not limited to pyrrolidines cation, alkyl quaternaries cation, quaternary salt cationoid, pyridines cation and alkyl imidazolium cation, its structural formula is respectively B?For alkali anion unit, include but not limited to OH?、CO3 2、HCO3 ?、H2PO4 ?、HPO4 2, carboxylic acid anion RCOO?With pyrroles's anionWherein, R, R', R ", R " ' can be the same or different, separately represent H, the chain-like alkyl containing 1-20 carbon atom or the cycloalkyl containing 3-20 carbon atom, it is preferred to the chain-like alkyl containing 4-8 carbon atom or the cycloalkyl containing 5-8 carbon atom.
Preferably, in preparation technology of the present invention, the alkali anion unit of described alkaline ionic liquid catalyst is OH?, carboxylic acid anion RCOO?Or pyrroles's anionWherein, R, R', R ", R " ' can be the same or different, separately represent H, the chain-like alkyl containing 1-20 carbon atom or the cycloalkyl containing 3-20 carbon atom, it is preferred to the chain-like alkyl containing 4-8 carbon atom or the cycloalkyl containing 5-8 carbon atom.
It is highly preferred that in the present invention, described alkaline ionic liquid catalyst is selected from In one or two or more, wherein, Bu is normal-butyl.
In the present invention, the consumption of described catalyst is the 0.001wt%-5wt% of raw material 3，5，5-trimethylcyclohexen-2-one-1 (α-IP), it is preferable that 0.01wt%-1wt%.
Reactive distillation process of the present invention is to carry out in tower reactor, and the reactor theory number of plates is 25-50, it is preferable that 30-40, and reflux ratio is 10:1-2:1.Under room temperature, alkali ionic liquid is mixed in advance with raw material α-IP, being entered tower reactor by tower reactor, then tower reactor is warming up to 150 DEG C-230 DEG C, and α-IP is under the catalytic action of alkali ionic liquid, there is isomerization reaction, the boiling point of the product β-IP owing to generating is 190 DEG C, and the boiling point lower than raw material α-IP is 215 DEG C, therefore, β-the IP that reaction generates constantly is distilled out of from tower top, so that the balance of isomerization reaction moves to the direction generating β-IP.
In reactive distillation processes, the absolute pressure of tower reactor is 0.2Bar 2Bar, it is preferable that 0.5Bar 1Bar, and reactive distillation temperature is 150 DEG C-230 DEG C, it is preferable that 170 DEG C-220 DEG C, and reaction time is 24-150h, it is preferable that 50-100h.β-IP the crude product that purity is 93wt%-95wt% is obtained in overhead collection,
β-IP the crude product obtained is collected through further rectification under vacuum product β-IP in reactive distillation tower reactor column top, and the absolute pressure of rectification under vacuum is 1.5KPa, and vacuum rectification tower theoretical cam curve is 25-40, and reflux ratio is 3:1-5:1, and tower top temperature is 62-69 DEG C.In preparation technology of the present invention, the purity of product β-IP can reach 99.5wt%-99.8wt%, and reaction selectivity can reach 99.2%-99.9%.
Alkali ionic liquid is applied to the isomerization reaction of catalysis α-IP by the present invention, compared with prior art, has the advantage that
1) alkali ionic liquid disperses with homogeneous form in the liquid phase, and alkali ionic liquid dissolves in α-IP, it is not necessary to increase other solvents, therefore overcomes inorganic base and is prone to the problem that alkali precipitates out, and selectivity of product is high；
2) alkali ionic liquid has recovery high temperature resistant, easy, environment has the characteristics such as friendly；
3) by changing the structure of anion and cationic unit, it is possible to the alkalescence of regulation and control catalyst and selectivity, compared with common inorganic alkali, the organic cation of such catalyst has bigger steric hindrance, and the reaction intermediate of this catalyst is:The wherein cation A of big steric hindrance+Serve as the effect of wall, block the combination of IP anion intermediate and other IP molecules, and then inhibit the generation of autohemagglutination product, therefore, there is high stereoselectivity；
4) adopting reaction rectification technique to react, operating process is simple, and reaction can continuously perform；
5) extract by washing, catalyst just recovery rapidly and efficiently from reaction system, it is possible to achieve alkaline ionic liquid catalyst and the sharp separation of reactant liquor, efficiently solve the separation problem of catalyst.Meanwhile, catalyst can regenerate use, thus reaching the purpose of catalyst recycling, decreasing the consumption of chemical reagent, decreasing the generation of " three wastes ", is the preparation technology of a kind of environmental protection.
Accompanying drawing explanation
Fig. 1 is gas chromatographic analysis spectrogram
Detailed description of the invention
Gas phase analysis condition: Agilent gas chromatogram on-line determination, chromatographic column: polysiloxanes post HP-5, vaporizer temperature is: 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
The preparation method of alkali ionic liquid used in the present invention
By anion potassium salt (K+B—, buy in lark prestige science and technology), join ionic liquid bromine salt (A+Br—, buy in upper marine origin victory Chemical Co., Ltd.) dichloromethane solution in, be vigorously mixed at room temperature for 10 hours, then precipitate potassium bromide (KBr) be filtered to remove.Filtrate is evaporated off solvent through rotation, then with washed with diethylether 3 times, finally dry 10h at 90 DEG C, namely obtains corresponding ionic liquid (A+B—)。
Embodiment 2
α-IP the raw material containing 0.05wt% alkaline ionic liquid catalyst IL-A is added to tower reactor tower reactor, 210 DEG C, 0.9Bar when carry out rectification process, there is α-IP isomerization reaction, time of staying 24hr, reaction selectivity is 99.7%, and overhead collection obtains thick product β-IP (purity is 94wt%).Thick product β-IP is 1.5KPa at pressure, and the number of plates is 30, and when reflux ratio is 3:1, further rectification under vacuum obtains the product β-IP that purity is 99.5wt%, and gas phase analysis spectrogram is shown in Fig. 1.
Embodiment 3-10
On the basis of example 2, change catalyst type and consumption, temperature, pressure, response time, the results detailed in Table 1.
Wherein, catalyst IL-F, IL-G, IL-H structural formula is respectively
Embodiment 11
For the catalyst IL-D in example 6, after utilizing water to carry out extraction and recovery, water is removed through decompression, repeat the condition of example 6: in tower reactor, add containing the α-IP raw material of 0.1wt%IL-D to tower reactor, 230 DEG C, 2.0Bar when stop 100hr, reaction selectivity is 99.6%, after catalyst reclaims, selectivity does not change, the results detailed in Table 1.
Table 1 embodiment 2-11
Above detailed description of the invention, not does any pro forma restriction to technical scheme.Every technical spirit according to the present invention, to any simple modification made for any of the above embodiments, equivalent variations and modification, each falls within protection scope of the present invention.
Claims (11)
1. the preparation technology of a trimethyl-3-cyclohexene-1-ketone, with 3,5,5-trimethyl-2-cyclohexene-1-ketone are raw material, with alkali ionic liquid for catalyst, adopt reaction rectification technique, 3，5，5-trimethylcyclohexen-2-one-1 is carried out isomerization and prepares 3,5,5-trimethyl-3-cyclohexene-1-ketone；
Described alkali ionic liquid structural formula is A+B?, wherein, A+For cation unit, selected from pyrrolidines cation, alkyl quaternaries cation, quaternary salt cationoid, pyridines cation and alkyl imidazolium cation, structural formula is respectivelyB?For alkali anion unit, selected from OH?、CO3 2-、HCO3 -、HPO4 2-, carboxylic acid anion RCOO?With pyrroles's anionWherein, R, R', R ", R " ' identical or different, separately represent H, the chain-like alkyl containing 1-20 carbon atom or the cycloalkyl containing 3-20 carbon atom.
2. preparation technology according to claim 1, it is characterised in that described R, R', R ", R " ' identical or different, separately represent containing 4-8 carbon atom chain-like alkyl or contain 5-8 carbon atom cycloalkyl.
3. preparation technology according to claim 1, it is characterised in that the alkali anion unit of described alkali ionic liquid is carboxylic acid anion RCOO?、OH?Or pyrroles's anionWherein, R, R', R ", R " ' identical or different, separately represent H, the chain-like alkyl containing 1-20 carbon atom or the cycloalkyl containing 3-20 carbon atom.
4. preparation technology according to claim 3, it is characterised in that described R, R', R ", R " ' separately represent containing 4-8 carbon atom chain-like alkyl or contain 5-8 carbon atom cycloalkyl.
5. preparation technology according to claim 3, it is characterised in that described alkaline ionic liquid catalyst isIn one or two or more, wherein, Bu is normal-butyl.
6. the preparation technology according to any one of claim 1-5, it is characterised in that the consumption of described catalyst is the 0.001wt%-5wt% of raw material 3，5，5-trimethylcyclohexen-2-one-1.
7. preparation technology according to claim 6, it is characterised in that the consumption of described catalyst is the 0.01wt%-1wt% of raw material 3，5，5-trimethylcyclohexen-2-one-1.
8. the preparation technology according to claim l, it is characterised in that described reactive distillation carries out in tower reactor, the reactor theory number of plates is 25-50；Reflux ratio is 10:1-2:1.
9. preparation technology according to claim 8, it is characterised in that described tower reactor theoretical cam curve is 30-40.
10. the preparation technology according to claim l or 8, it is characterised in that the absolute pressure of described reactive distillation is 0.2Bar 2Bar；Reaction temperature is 150 DEG C-230 DEG C；Reaction time is 24-150h.
11. preparation technology according to claim 10, it is characterised in that the absolute pressure of described reactive distillation is 0.5Bar 1Bar；Reaction temperature is 170 DEG C-220 DEG C；Reaction time is 50-100h.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104761443B (en) * | 2015-03-23 | 2016-05-18 | 万华化学集团股份有限公司 | A kind of method of continuous production BETA-IP |
| CN106278854B (en) * | 2015-06-05 | 2018-10-26 | 浙江新和成药业有限公司 | A kind of preparation method by α-isophorone isomery β-isophorone |
| CN107216244B (en) * | 2017-06-16 | 2020-07-28 | 万华化学集团股份有限公司 | Method for preparing 3,5, 5-trimethyl-3-cyclohexene-1-ketone |
| CN108218742B (en) * | 2017-12-11 | 2021-08-27 | 绍兴文理学院 | Preparation method of ketoxime |
| 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 |
| CN111804331A (en) * | 2019-12-09 | 2020-10-23 | 沈阳化工大学 | Homogeneous catalyst and heterogeneous catalyst based on ionic liquid, and preparation method and application thereof |
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| CN1660752A (en) * | 2004-12-10 | 2005-08-31 | 浙江大学 | Technique for synthesizing 3,5,5 trimethyl-olefin-1-ketone |
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2014
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| US4010205A (en) * | 1973-12-07 | 1977-03-01 | Firmenich S.A. | Process for the preparation of a diketone derivative |
| CN1914165A (en) * | 2004-01-29 | 2007-02-14 | 巴斯福股份公司 | Homogeneous isomerization of cis-2-pentene nitrile to form 3-pentene nitrile |
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