CN104529761B - A kind of preparation method of TMHQ two alkanoic acid esters - Google Patents
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- AYJXHIDNNLJQDT-UHFFFAOYSA-N CC(C)(CC(C=C1C)=O)C1=O Chemical compound CC(C)(CC(C=C1C)=O)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 description 1
- 0 Cc(cc(c(C)c1C)O*)c1O* Chemical compound Cc(cc(c(C)c1C)O*)c1O* 0.000 description 1
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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
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a kind of preparation method of TMHQ two alkanoic acid esters, under degradation property catalysis, reset acylation reaction by KIP and acylating agent and realize. Compared with traditional acid catalysis, this technique has catalyst and easily reclaims, environmental friendliness,, activity and selectivity advantages of higher little to equipment corrosion.
Description
Technical field
The preparation method who the present invention relates to TMHQ two alkanoic acid esters, urges at degradation propertyUnder the existence of agent, utilize KIP and acylation reaction to prepare 2,3,5-Trimethylhydroquine dialkanoates.
Background technology
TMHQ two alkanoic acid esters (TMHQ-DA) are the important centres of synthesising complex E main ringBody. Meanwhile, its hydrolysate TMHQ can be used as antioxidant, dyestuff and medicine intermediate,Rubber antioxidant, polymerization inhibitor, antioxidant, developer etc. Therefore, its prospects for commercial application is wide.
At present by KIP (4-ketoisophorone, tea ketone musk, KIP)Under existing, catalyst there are synthetic TMHQ two alkanoic acid esters of rearrangement reaction with acylating agent(TMHQ-DA) technique is mainly divided into two classes: 1) adopt liquid acid Catalytic processes,, major defect is:Equipment corrosion is serious; Catalyst can not separating cycle utilization; Post processing need to add in alkali and system, this behaviourWork can cause the decomposed of product; 2) adopt the general solid acid catalysis technique such as sulfonate resin and molecular sieve,Compared with liquid acid, although can reduce the corrosion to equipment, product selectively not satisfactory.
In american documentation literature US005969176A, mention that (KIP) and acylating agent are at Lewis acid and BronstedThe mixture as catalyst of acid, for example, under the mixture conditions of the concentrated sulfuric acid and boric acid, TMHQ is prepared in reactionDibasic acid ester (reaction equation is suc as formula shown in (1)); American documentation literature US6350897 be reported in sulfonating agent andFor example, under existing, strong acid (concentrated sulfuric acid) and acylating agent prepare TMHQ diester by KIP reaction. But,The liquid acid using as catalyst in these class methods, must neutralization after reaction completes. But, in neutralizationIn process, 1,4-diacetoxy-2,3,5-trimethylbenzene can be hydrolyzed, and causes productive rate to reduce. Meanwhile, due to liquid acid pairThe seriously corroded of metallic reactors, thus comparatively harsh to equipment requirement, cause industrialization cost to increase.
In Chinese patent literature CN102180793A, mention taking α-isophorone as raw material, itself and acidylateThe enol isomers carboxylate that obtains isophorone is reacted in agent under the existence of catalyst; The esterification of enol isomersIn thing, add solvent DMSO and heteropllyacids catalyst and alkali again, blast air, it is different that reaction obtains oxoThe mono-esterification product of phorone; Reclaim the solvent in described mono-esterification product, then at carboxylic acid anhydrides and catalystExistence under reaction obtain 1,4-diacetoxy-2,3,5-trimethylbenzene. In this invention with can realize from α-isophorone toThe preparation of 1,4-diacetoxy-2,3,5-trimethylbenzene, but it is more to react required step, and crystallization afterproduct purity is generally inclined to one sideLow, cannot meet the requirement of downstream reaction.
In European patent document EP850910A, be reported under solid catalyst existence condition 2,6,6-front three basic ringOwn-2-alkene-Isosorbide-5-Nitrae-diketone and acylation reaction are prepared 2,5,6-Trimethyl Hydroquinone dibasic acid esters, the method and liquid acidCatalyst is compared to a great extent equipment corrosion is reduced, and does not also need catalyst neutralisation, largely simultaneouslyOn slowed down the hydrolysis of TMHQ two alkanoic acid esters, for example, when adopting strong-acid ion exchange resinWhen " Amberlyst15 " makes catalyst, selectivity reaches 88%, Crystallization Separation yield 60%; Super when adoptingWhen strong-acid ion exchange resin " NafionNR50 " is made catalyst, selectivity reaches 85%, and Crystallization Separation is receivedRate 60%. But it is selective and crystallization yield is relatively low.
It is catalyst that Chinese patent literature CN101607896A uses acidic ion liquid, at-20 DEG C extremelyUnder the reaction temperature of 130 DEG C, make ketoisophorone reset acidylate and prepare TMHQ two alkanoic acid esters.Wherein the recovery of catalyst adopts the mode of extraction and distillation, and major defect is: 1) extraction process consumption is a large amount ofOrganic solvent (n-hexane), 2) distillation removal process bring a large amount of energy consumptions.
In summary it can be seen, the method for preparing at present TMHQ two alkanoic acid esters exists catalyst to establishingStandby corrosion or be difficult to recovery problem, and product yield is low, poor selectivity, therefore need to seek a kind of new 2,3,5-The preparation method of trimethylhydroquine dialkanoates solves the problems of the technologies described above.
Summary of the invention
The object of this invention is to provide a kind of little to equipment corrosion, react complete without catalyst neutralisation, keep awayExempted from product hydrolysis, reaction workable, be easy to the industrialized TMHQ dioxane of preparingThe method of acid esters, to overcome the defect of existing technique.
For reaching above goal of the invention, technical scheme of the present invention is as follows:
A preparation method for TMHQ two alkanoic acid esters, taking degradation property as catalyst,At 40 DEG C of-130 DEG C of temperature, there is ester by raw material KIP and acylating agentChange and rearrangement reaction and realize. After reaction finishes, can realize degradation property catalyst by filteringSeparate with the quick of reactant liquor, thereby reach the object that catalyst recovery recycles. Catalyst can repeatedly circulateUse, reactivity is almost without reducing.
The method according to this invention, TMHQ dioxane acrylate structure is as shown in the formula shown in (1):
Wherein, R represents alkyl, cycloalkyl or aryl. Preferably, R represents C1-3Alkyl, straight chain orThe C of chain4-10Alkyl (such as methyl, ethyl, propyl group, isopropyl etc.). R also can represent cyclopropyl, ringThe C such as hexyl3-10Cycloalkyl. In addition, R also can represent such as the C such as phenyl, o-methyl-phenyl-6-12Aryl.More preferably, R represent methylidene.
The method according to this invention, described catalyst is formed by the grafting of following two construction unit bondings. 1)Inorganic polymer carrier element: carrier is unformed SiO2, granularity 50-800 μ m, specific area is 50-500m3/ g; 2) acidic ionic liquid body unit: cationic moiety includes but not limited to quaternary ammonium salt, pyridines and miaowAzoles etc., anionicsite is AlCl4 －, such catalyst has strong Lewis; Preferably, carrier elementAnd between ionic liquid unit, pass through halo trialkoxy silane X (CH2)nSi(OR”’)3Carry out bridging, Qi ZhongqiMiddle R " ' be C1-10Alkane or C3-10Cycloalkane, n=1-8.
Preferably, the concrete structure formula of catalyst is as follows: wherein R, R', R ", R " ' independently represent C1-10AlkaneHydrocarbon or C3-10Cycloalkane; N=1-8.
The method according to this invention, described catalyst is by the side of chemical graft to carrier and ionic liquidMethod is prepared from. The preparation method of described degradation property catalyst comprises:
(1) adopt hydrochloric acid activation silica gel to obtain activated silica gel;
(2) by quaternary ammonium salt, pyridines or imidazoles material and halo trialkoxy silaneX(CH2)nSi(OR”’)3Under 100-200 DEG C and absolute pressure 1-3Bar, reaction 5-15h final vacuum is dry obtain fromSub-liquid; Wherein R " ' be C1-10Alkane or C3-10Cycloalkane, n=1-8;
(3) activated silica gel and step (2) are obtained to ionic liquid under solvent exists, 90-170 DEG C, absolute pressureUnder 1-3Bar, react 8-15h, except desolventizing, and unnecessary ionic liquid, vacuum drying are removed in extraction;
(4) organic solution of the aluminum trichloride (anhydrous) of step (3) products therefrom and equimolar amounts is existedAt 50-100 DEG C, react 3-8h final vacuum dry.
In the preparation method of catalyst of the present invention, mole proportioning of hydrochloric acid and silica gel is 5/1-2/1, ammonium salt class,Pyridines or imidazoles material and halo trialkoxy silane X (CH2)nSi(OR”’)3Mole proportioning be1/1-1/3, mole proportioning of activated silica gel and ionic liquid is 1/1-1/3, aluminum trichloride (anhydrous) and ionic liquidMole proportioning be 1/1-2/1.
In the preparation method of catalyst of the present invention, described hydrochloric acid activation silica gel is that silica gel is dense at 1-10mol/LIn the hydrochloric acid solution of degree, soak ultrasonic concussion 0.5-3h after 0.5-3h, then washing is to neutrality, at 100-120 DEG CDry 3-7h at temperature.
In the preparation method of catalyst of the present invention, in step (2), vacuum drying temperature is 40-80 DEG C, dryThe dry time is 2-7h; Step (3) and (4) vacuum drying temperature are 50-100 DEG C, and be 3-7h drying time;Solvent described in step (3) is aromatic solvent, preferably toluene or dimethylbenzene, solvent quality consumption be fromThe 0.5-2 of sub-liquid quality doubly; The organic solution of the aluminum trichloride (anhydrous) described in step (4) is anhydrous threeThe dichloromethane solution of aluminium chloride, concentration is 1-10mol/L.
Taking IL-C-1 catalyst as example, chemical equation prepared by catalyst as shown in Figure 1.
The method according to this invention, the 0.1-10% (wt) that catalyst amount is KIP, preferably 0.2-5% (wt).
The acylating agent using in the present invention has structure shown in following formula (2) or formula (3):
Wherein, R and the R ' in formula (2) can represent aliphatic group, alicyclic hydrocarbon radical or aromatic hydrocarbon group. Formula (2)Preferably contain C such as acetic anhydride, propionic andydride, butyric anhydride, isobutyric anhydride etc.2-6The acid anhydrides of aliphatic hydrocarbon group.Formula (3) represents carboxylic acid halides, and X represents halogen, and R can represent aliphatic group, alicyclic hydrocarbon radical or aromatic hydrocarbon group,R is preferably C1-4Aliphatic hydrocarbon group, more preferably chloroacetic chloride of formula (3).
The method according to this invention, the mol ratio of above-mentioned acylating agent and raw material KIP is all between 2:1-10:1Suitable, preferred molar ratio is 3:1-10:1, more preferably mol ratio is 3:1-5:1.
The inventive method is carried out between 40 DEG C-130 DEG C of reaction temperatures, and preferably 50 DEG C-100 DEG C itBetween. If reaction temperature is too low, reaction rate will be very slow; If reaction temperature is too high, selectivity of productTo decline to some extent.
The inventive method can be implemented having under solvent or condition of no solvent, and solvent is inertia in reaction system.Solvent is selected acetonitrile, DMF, methyl-sulfoxide etc. conventionally; If acylating agent is excessive, also can doFor the solvent of reaction system. The consumption of solvent can be between the 0-300% of KIP and acylating agent total amount (wt),Preferred solvent load is the 0-100% (wt) of KIP and acylating agent total amount.
Good effect of the present invention is: ionic liquid is that a class is made up of organic cation and inorganic anion, the salt being in a liquid state in certain temperature range; There is the spies such as liquid journey is wide, steam forces down, solvability is strongProperty. By be combined with inorganic macromolecule material immobilized after, on the basis of primary characteristic, also increased keepingThe new feature such as easily separated recovery, reusability are strong; And simple ionic liquid is in removal process, depositIn the loss of a large amount of extractants, and uneconomical environmental protection. In addition, because carrier has the shape of selecting function, i.e. carrierThe duct size of itself can selectively enter differential responses molecule, and therefore the ionic liquid after load hasHigher reaction selectivity. This catalyst also has suitable acidity simultaneously, acid between H2SO4WithCF3SO3Between H, both ensure carrying out smoothly of reaction, effectively suppressed again the pair that highly acid causes excessively anti-Should, therefore, adopt the method product selectivity of the present invention can be up to more than 97%, the total recovery after recrystallizationCan be up to more than 89%.
Brief description of the drawings
Fig. 1 is taking IL-C-1 catalyst as example, chemical equation prepared by catalyst.
Specific implementation method
The following examples will be further described method provided by the present invention, but the present invention does not limitIn listed embodiment, also should be included in other any known changing in interest field of the presently claimed inventionBecome.
Analytical conditions for gas chromatography: the polysiloxanes post HP-5 of Agilent gas-chromatography carries out on-line determination, gasChanging room temperature is 250 DEG C, 250 DEG C of detector temperatures, and column temperature is temperature programming: 50 DEG C, 1min; 80 DEG C, 1Min; 10 DEG C/min to 250 DEG C, 10min, sample size 0.2 μ L.
Embodiment 1
Catalyst is synthetic by the method for chemical graft, and this example is with catalyst I L-A-1, IL-B-1, IL-C-1For example is shown the preparation of three class catalyst.
The preparation of IL-C-1 as shown in Figure 1.
Silica gel activating: (granularity 700-800 μ m, specific area is 450m to take 1Kg silica gel3/ g), at 2.5LConcentration is in the hydrochloric acid of 6.0mol/L, to stir to soak 40min, sonic oscillation 40min, and with deionized water washing,Emerge in worm water rinses to neutral, checks without Cl with silver nitrate-Exist. Then dry 5h in 110 DEG C of baking ovens, putsFor subsequent use in drier.
Preparation IL-C-A: being furnished with in the flask of reflux condensing tube and inlet duct, add N-methylimidazole82.1g (1.0mol) and 3-chloropropyl triethoxysilane 240.8g (1.0mol), lower 120 DEG C of nitrogen protection,Under absolute pressure 1Bar, react 10h, wash for several times with acetoneand ethyl acetate, then in 60 DEG C of vacuum drying 4h.
Preparation IL-C-B: to the silicon that adds 62.1g (1.0mol) to process in synthetic ionic liquid IL-C-AGlue adds the toluene of 100mL simultaneously, and under nitrogen protection, the lower 90 DEG C of magnetic agitation 12h of absolute pressure 1Bar, revolveTurn evaporation and remove the ethanol of toluene and generation, taking carrene as solvent, use soxhlet's extractor extraction excessiveIonic liquid, 60 DEG C of vacuum drying 5h.
Preparation IL-C-1: in the ionic liquid IL-C-B after load, under nitrogen protection stirring condition, slowThe slow anhydrous AlCl of 0.2L that adds3Dichloromethane solution (5mol/L), rotary evaporation is removed 60 DEG C of carreneVacuum drying 5h.
The preparation of IL-A-1
The same IL-C-1 of preparation flow, just replaces to tri-butylamine by N-methylimidazole, 3-chloropropyl three ethoxiesBase silane replaces to 4-chlorobutyl triethoxysilane, silica gel granularity 50-100 μ m, and specific area is 50m3/g。
The preparation of IL-B-1
The same IL-C-1 of preparation flow, just replaces to pyridine by N-methylimidazole, 3-chloropropyl triethoxy siliconAlkane replaces to 8-chlorine octyl group trimethoxy silane, silica gel granularity 400-500 μ m, and specific area is 250m3/g。
Embodiment 2
By 666.7g (6.6mol) chloroacetic chloride and 5.0g degradation property catalyst I L-A-1 (granularity50-100 μ m, specific area is 50m3/ g) be placed in 500ml there-necked flask, and by 100.0g (0.66mol)KIP slowly adds in there-necked flask. This mixture reacts 1h at 100 DEG C,Filtering recovering catalyst. Extract reaction solution and carry out gas chromatographic analysis, can obtain raw material 2,6,6-3-methyl cyclohexanol-2-Alkene-Isosorbide-5-Nitrae-diketone conversion ratio 100%, product TMHQ-DA selective 95.2%.
Under 80 DEG C of conditions, add 130g water, be cooled to 20 DEG C and be recrystallized. Filter crystallize out, andWash filter cake with water for several times, vacuum drying at 60 DEG C of temperature. Can obtain light yellow solid 129.0g, purity99.96%, mp:109-110 DEG C, corresponding yield 85.1%.
By after catalyst recycling 10 times, selectivity of product 95.1%, visible catalyst activity keeps substantially.
Embodiment 3
By 133.3g (1.32mol) acetic anhydride and 10.0g degradation property catalyst I L-B-1 (granularity400-500 μ m, specific area is 250m3/ g) be placed in 500ml there-necked flask, and by 100.0g (0.66Mol) KIP slowly adds in there-necked flask. This mixture is 40 DEG C of reactions10h, filtering recovering catalyst. Extract reaction solution and carry out gas chromatographic analysis, can obtain raw material 2,6,6-front three basic ringOneself-2-alkene-Isosorbide-5-Nitrae-diketone conversion ratio 100%, product TMHQ-DA selective 96.0%.
Under 85 DEG C of conditions, add 126g water, be cooled to 20 DEG C and be recrystallized. Filter crystallize out, andWash filter cake with water for several times, vacuum drying at 60 DEG C of temperature. Can obtain light yellow solid 136.8g, purity99.96%, mp:109-110 DEG C, corresponding yield 88.1%.
By after catalyst recycling 10 times, selectivity of product remains on 95.8%.
Embodiment 4
By 200.0g (1.96mol) acetic anhydride and 0.1g degradation property catalyst I L-C-1 (granularity700-800 μ m, specific area is 450m3/ g) be placed in 500ml there-necked flask, and by 100.0g (0.66Mol) KIP slowly adds in there-necked flask. This mixture is 60 DEG C of stirringsUnder condition, react 10h, react complete, filtering recovering catalyst. Extract reaction solution and carry out gas chromatographic analysis,Can obtain raw material KIP conversion ratio 100%, product TMHQ twoAcetic acid esters selective 97.8%.
Under 75 DEG C of conditions, add 130g water, be cooled to 20 DEG C and be recrystallized. Filter crystallize out, andWash filter cake with water for several times, vacuum drying at 60 DEG C of temperature. Can obtain light yellow solid 138.3g, purity99.95%, mp:109-110 DEG C, corresponding yield 89.1%.
After catalyst recycling 5 times, selectivity of product still keeps 97.7%.
Embodiment 5
333.3g (3.3mol) acetic anhydride and 5.0g degradation property catalyst I L-C-1 are placed in to 500In ml there-necked flask, and 100.0g (0.66mol) KIP is slowly addedEnter in there-necked flask. This mixture is at 50 DEG C of reaction 8h, filtering recovering catalyst. Extract reaction solution and carry out gas phase lookAnalysis of spectrum, product TMHQ-DA selective 98.0%.
Under 80 DEG C of conditions, add 130g water, be cooled to 18 DEG C and be recrystallized. Filter crystallize out, andWash filter cake with water for several times, vacuum drying at 60 DEG C of temperature. Can obtain light yellow solid 138.3g, purity99.96%, mp:109-110 DEG C, corresponding yield 89.1%.
Embodiment 6
200.0g (2.64mol) acetic anhydride and 2.0g degradation property catalyst I L-C-1 are placed inIn 500ml there-necked flask, and 100.0g (0.66mol) KIP is slowSlowly add in there-necked flask. This mixture reacts 1h under 130 DEG C of stirring conditions, reacts complete, filtered and recycledCatalyst. Extract reaction solution and carry out gas chromatographic analysis, raw material KIP is wholeTransform product TMHQ-DA selective 97.2%.
Under 75 DEG C of conditions, add 130g water, be cooled to 20 DEG C and be recrystallized. Filter crystallize out, and waterWashing leaching cake several, vacuum drying at 60 DEG C of temperature. Can obtain light yellow solid 124.1g, purity 99.5%,Mp:109-110 DEG C, corresponding yield 89.0%.
Claims (19)
1. a preparation method for TMHQ two alkanoic acid esters, is characterized in that, at macroion liquidUnder body catalyst exists, by raw material KIP and acylating agent generation esterification withTMHQ two alkanoic acid esters are prepared in rearrangement reaction, described TMHQ two alkanoic acid ester knotsStructure formula is suc as formula shown in (1):
Wherein, R represents alkyl, cycloalkyl or aryl;
Described degradation property catalyst is formed by the grafting of following two construction unit bondings, and 1) nothingMachine macromolecule carrier unit: carrier is unformed SiO2, granularity 50-800 μ m, specific area is 50-500m3/ g; 2) acidic ionic liquid body unit: cationic moiety is quaternary ammonium salt, pyridines and imidazoles, cloudy fromSubdivision is AlCl4 －。
2. method according to claim 1, is characterized in that, in formula (1), R represents C1-3Alkyl,The C of straight or branched4-10Alkyl, or C3-10Cycloalkyl, or C6-12Aryl.
3. method according to claim 2, is characterized in that, R represent methylidene in formula (1).
4. method according to claim 1, is characterized in that, described degradation property catalystTwo construction units form by the grafting of halo trialkoxy silane bonding.
5. method according to claim 1, is characterized in that, degradation property catalyst concrete structureShown in IL-A, IL-B or IL-C:
Wherein, wherein R, R', R ", R " ' independently represent C1-10Alkane or C3-10Cycloalkane; N=1-8.
6. according to the method described in any one in claim 1-5, it is characterized in that, catalyst amount is 2,6,6-The 0.1-10wt% of 3-methyl cyclohexanol-2-alkene-Isosorbide-5-Nitrae-diketone consumption.
7. method according to claim 6, is characterized in that, catalyst amount is 2,6,6-3-methyl cyclohexanolThe 0.2-5wt% of-2-alkene-Isosorbide-5-Nitrae-diketone consumption.
8. according to the method for claim 1, it is characterized in that, described acylating agent has following formula (2) or formula (3)Shown in structure:
Wherein, the R in formula (2) and R ' represent aliphatic group, alicyclic hydrocarbon radical or aromatic hydrocarbon group; Formula (3) generationTable carboxylic acid halides, X represents halogen, R represents aliphatic group, alicyclic hydrocarbon radical or aromatic hydrocarbon group.
9. method according to Claim 8, is characterized in that, R and R ' in formula (2) represent respectively C2-6Aliphatic hydrocarbon group; In formula (3), R is C1-4Aliphatic hydrocarbon group.
10. according to the method for claim 9, it is characterized in that, described acylating agent is acetic anhydride or chloroacetic chloride.
11. according to the method described in claim 1 or 8, it is characterized in that acylating agent and 2,6,6-3-methyl cyclohexanolThe mol ratio of-2-alkene-Isosorbide-5-Nitrae-diketone is 2:1-10:1.
12. methods according to claim 11, is characterized in that, acylating agent and 2,6,6-3-methyl cyclohexanol-2-The mol ratio of alkene-Isosorbide-5-Nitrae-diketone is 3:1-10:1.
13. methods according to claim 12, is characterized in that, acylating agent and 2,6,6-3-methyl cyclohexanol-2-The mol ratio of alkene-Isosorbide-5-Nitrae-diketone is 3:1-5:1.
14. according to the method for claim 1, it is characterized in that, the reaction temperature of esterification and rearrangement reaction is 40 DEG C-130 DEG C, described esterification and rearrangement reaction are implemented having under solvent or condition of no solvent, solvent select acetonitrile,DMF, methyl-sulfoxide or KIP.
15. according to the method for claim 14, it is characterized in that, the reaction temperature of esterification and rearrangement reaction is 50 DEG C-100℃，
16. according to the method described in any one in claim 1-5, it is characterized in that described macroion liquidThe preparation method of body catalyst comprises:
(1) adopt hydrochloric acid activation silica gel to obtain activated silica gel;
(2) by quaternary ammonium salt, pyridines or imidazoles material and halo trialkoxy silane X (CH2)nSi(OR”’)3Under 100-200 DEG C and absolute pressure 1-3Bar, the dry ionic liquid that obtains of reaction 5-15h final vacuum; Wherein R " 'For C1-10Alkane or C3-10Cycloalkane, n=1-8;
(3) silica gel after activation and step (2) are obtained to ionic liquid under solvent exists, 90-170 DEG C, absolute pressureUnder 1-3Bar, react 8-15h, except desolventizing, and unnecessary ionic liquid, vacuum drying are removed in extraction;
(4) by the organic solution of the aluminum trichloride (anhydrous) of step (3) products therefrom and equimolar amounts at 50-100 DEG CLower reaction 3-8h final vacuum is dry.
17. methods according to claim 16, is characterized in that, mole proportioning of hydrochloric acid and silica gel is5/1-2/1, and ammonium salt class, pyridines or imidazoles material and halo trialkoxy silane X (CH2) nSi (OR " ') 3Mole proportioning be 1/1-1/3, mole proportioning of activated silica gel and ionic liquid is 1/1-1/3, anhydrous tri-chlorinationMole proportioning of aluminium and ionic liquid is 1/1-2/1.
18. methods according to claim 16, is characterized in that, vacuum drying temperature in step (2)For 40-80 DEG C, be 2-7h drying time; Step (3) and (4) vacuum drying temperature are 50-100 DEG C,Be 3-7h drying time; Solvent described in step (3) is aromatic solvent, and solvent quality consumption is ionThe 0.5-2 of liquid quality doubly; The organic solution of the aluminum trichloride (anhydrous) described in step (4) is anhydrous trichlorineThe dichloromethane solution of changing aluminium, concentration is 1-10mol/L.
19. methods according to claim 18, is characterized in that, the solvent described in step (3) is firstBenzene or dimethylbenzene.
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