CN103087036B - Preparation method of 1,3-dioxolane compound and alcohol compound - Google Patents

Preparation method of 1,3-dioxolane compound and alcohol compound Download PDF

Info

Publication number
CN103087036B
CN103087036B CN201110342486.3A CN201110342486A CN103087036B CN 103087036 B CN103087036 B CN 103087036B CN 201110342486 A CN201110342486 A CN 201110342486A CN 103087036 B CN103087036 B CN 103087036B
Authority
CN
China
Prior art keywords
alkyl
raw material
zinc chloride
preparation
dox
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201110342486.3A
Other languages
Chinese (zh)
Other versions
CN103087036A (en
Inventor
谢伦嘉
郭顺
亢宇
赵思源
孙竹芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201110342486.3A priority Critical patent/CN103087036B/en
Publication of CN103087036A publication Critical patent/CN103087036A/en
Application granted granted Critical
Publication of CN103087036B publication Critical patent/CN103087036B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a preparation method of a 1,3-dioxolane compound and alcohol compound. The method comprises the following steps: allowing a first raw material epoxy compound having a structure represented by formula (II) and a second raw material aldehyde or ketone having a general formula of R5COR6 to contact with a catalyst under a cyclization reaction condition to obtain a mixture, and separating the mixture to obtain the 1,3-dioxolane compound having a structure represented by formula (I), wherein the catalyst contains anhydrous zinc chloride. The invention also provides a preparation method of an alcohol compound. The anhydrous zinc chloride used in the preparation method of the 1,3-dioxolane compound has a low price and slightly pollutes the environment, and the preparation method of the 1,3-dioxolane compound has a high conversion rate and allows the selectivity of the 1,3-dioxolane compound to be high under the catalytic action of the cheap anhydrous zinc chloride.

Description

The preparation method of a kind of DOX based compound and alcohol based compound
Technical field
The present invention relates to a kind of preparation method of DOX based compound and a kind of preparation method of alcohol based compound.
Background technology
The production technique of existing ethylene glycol, mainly at high temperature under high pressure, oxyethane and large water gaging are reacted, the two mass ratio is about 1: 10, and this technique glycol selectivity is low, long flow path, and energy consumption is large, and facility investment is also larger.Also have and first oxyethane and acetone are reacted generation 1,3-dioxolane compound, then the technique of ethylene glycol is prepared in hydrolysis, the energy consumption that this technique solves traditional oxyethane hydrolysis technique existence is large, the problem that facility investment is large, while reduction water consumption, by product glycol ether can be reduced.But the key of this technique is the preparation of DOX compounds.
At present, the method preparing DOX compounds has a lot, by reactant classification, generally have two kinds: the first, with vicinal diamines compounds and containing the compound (aldehydes or ketones) of carbonyl for reactant, reaction generates DOX compounds and water; The second, epoxy compounds and aldehydes or ketones react and generate DOX compounds.In organic synthesis field, first method is usually used in the protection of o-dihydroxy or carbonyl functional group and the gas chromatographic analysis of vicinal diamines compounds; Second method bibliographical information less, the example wherein with potential industrial application value is under catalyst action, oxyethane and acetone reaction preparation 2,2-dimethyl-DOX, is then hydrolyzed 2,2-dimethyl-DOX prepares ethylene glycol.The second method of bibliographical information typically has following several:
American Chemical Society's periodical literature (J.Org.Chem.1978,43,438-440) reports under anhydrous cupric sulfate catalyst action, and epoxy compounds (I) and acetone react preparation 2,2-dimethyl-DOX derivative.But the method is the epoxy compounds of (I) formula for general structure, works as R 1to R 4have in group 1 or 2 groups be alkyl, all the other for hydrogen atom time, the transformation efficiency that described epoxy compounds and acetone react is lower (5-50%), and reaction need use a large amount of acetone (acetone and epoxy compounds mol ratio are greater than 16).
CN101519397A discloses a kind of preparation method of DOX compounds, and the method comprises, and under the effect of catalyzer trifluoromethane sulfonic acid zinc, general formula is the epoxy compounds of (I) formula and general formula is R 5cOR 6aldehydes or ketones reaction, generate DOX compounds.Meanwhile, disclose and prepare ketal and hydrolysis preparing ethylene glycol process flow diagram thereof with oxyethane.When the molar ratio of oxyethane and acetone is 1: 3.7, the transformation efficiency 99% of oxyethane, generates the selectivity 99% of 2,2-dimethyl-DOX.
CN101993430A discloses a kind of preparation method of DOX compounds, and the method reports employing mesoporous material after load trifluoromethane sulfonic acid zinc, the reaction of catalytic epoxyethane and acetone is carried out as heterogeneous catalyst, achieve higher yield (when the molar ratio of oxyethane and acetone is 1: 3.7, oxyethane generates 2, the selectivity of 2-dimethyl-DOX is greater than 99.9%).
As can be seen here, the preparation 1 that current yield, selectivity are higher, the method of 3-dioxolane compound all needs to use trifluoromethane sulfonic acid zinc as catalyzer, but, trifluoromethanesulfonic acid zincon corrodibility is strong, is unfavorable for environmental protection, and expensive, therefore developing a kind of cheap, catalyzer being suitable for preparing DOX compounds that environmental pollution is little will be the emphasis of research in for some time or even very long one section from now on.
Summary of the invention
The object of the invention is to the preparation 1 overcoming prior art, the defect that catalyzer trifluoromethane sulfonic acid zinc is expensive, environmental pollution is comparatively serious of the use existed in the method for 3-dioxolane based compound, one is provided to supply reusable cheap catalyst, catalysis epoxidation compound and ketone or aldehyde reaction prepare the method for DOX based compound and a kind of preparation method of alcohol based compound.
The invention provides a kind of preparation method of DOX based compound, the method comprises: under cyclization condition, is R by the first the raw material epoxy compounds shown in formula (II) and general formula 5cOR 6the second raw material aldehydes or ketones and catalyst exposure obtain mixture, from described mixture be separated obtain the DOX based compound shown in formula (I), wherein, described catalyzer contains Zinc Chloride Anhydrous;
Wherein, R 1, R 2, R 3, R 4be straight chained alkyl, the branched-chain alkyl of C3-C20, the cycloalkyl of C3-C20, the alkyl-cycloalkyl of C4-C20, the cycloalkylalkyl of C4-C20, the aryl of C6-C20 of H, C1-C20 separately, or R 1-R 2in any one and R 3-R 4in any one be keyed to ring;
R 5, R 6be straight chained alkyl, the branched-chain alkyl of C3-C20, the cycloalkyl of C3-C20, the alkyl-cycloalkyl of C4-C20, the cycloalkylalkyl of C4-C20, the aryl of C6-C20 of H, C1-C20 separately, or R 5with R 6be keyed to ring.
The invention provides a kind of preparation method of alcohol based compound, the method comprises the following steps:
(1) DOX based compound is prepared;
(2) under acidic solid catalyst exists, under hydrolysising condition, described 1, the 3-dioxolane based compound prepared is contacted with water;
Wherein, the method preparing described DOX based compound is method of the present invention.
The anhydrous chlorides of rase zinc catalyst that method of the present invention uses is cheap, environmental pollution is little, and under the katalysis of cheap Zinc Chloride Anhydrous, the method transformation efficiency preparing DOX based compound of the present invention is higher, the selectivity of DOX based compound is higher.
In the preferred embodiment of the present invention, by adding ionic liquid 1-alkyl-3-methylimidazole salt in catalyzer of the present invention, make preparation 1 of the present invention, in the method for 3-dioxolane based compound, the transformation efficiency of reactant improves further, 1, the selectivity of 3-dioxolane based compound also improves further, and, on this basis, compared to independent Zinc Chloride Anhydrous as catalyzer, the preferred catalyzer containing Zinc Chloride Anhydrous and ionic liquid 1-alkyl-3-methylimidazole salt of the present invention can more effectively be reused.
Embodiment
The invention provides a kind of preparation method of DOX based compound, the method comprises: under cyclization condition, is R by the first the raw material epoxy compounds shown in formula (II) and general formula 5cOR 6the second raw material aldehydes or ketones and catalyst exposure obtain mixture, from described mixture be separated obtain the DOX based compound shown in formula (I), wherein, described catalyzer contains Zinc Chloride Anhydrous;
Wherein, R 1, R 2, R 3, R 4be straight chained alkyl, the branched-chain alkyl of C3-C20, the cycloalkyl of C3-C20, the alkyl-cycloalkyl of C4-C20, the cycloalkylalkyl of C4-C20, the aryl of C6-C20 of H, C1-C20 separately, or R 1-R 2in any one and R 3-R 4in any one be keyed to ring;
R 5, R 6be straight chained alkyl, the branched-chain alkyl of C3-C20, the cycloalkyl of C3-C20, the alkyl-cycloalkyl of C4-C20, the cycloalkylalkyl of C4-C20, the aryl of C6-C20 of H, C1-C20 separately, or R 5with R 6be keyed to ring.
Goal of the invention of the present invention can be realized according to the aforesaid method of the present invention, and in order to improve preparation 1 further, in the process of 3-dioxolane based compound, the transformation efficiency of reactant and target product 1, the selectivity of 3-dioxolane based compound, the present inventor, by further research, finds finally, adds the target that ionic liquid can realize the yield improving target product in the system of Zinc Chloride Anhydrous as catalyzer.Therefore, for the present invention, under preferable case, described catalyzer is also containing ionic liquid 1-alkyl-3-methylimidazole salt, and more preferably, the mol ratio of described 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous is 0.1-10: 1, is particularly preferably 1-4: 1.
In the present invention, described cyclization condition can be conventional cyclization condition, and for the present invention, under preferable case, described cyclization condition comprises: the temperature of contact is subzero 20 DEG C to 150 DEG C above freezing, is preferably 30 DEG C-80 DEG C; Pressure be normal pressure to 5MPa, be preferably normal pressure to 2MPa; More preferably, the mol ratio of the first raw material, the second raw material and Zinc Chloride Anhydrous is 1: 0.1-10: 0.1-1, is preferably 1: 1-4: 0.1-0.4.
According to method of the present invention, be R by the first the raw material epoxy compounds shown in formula (II) and general formula 5cOR 6the second raw material aldehydes or ketones and catalyst exposure prepare 1, in the process of 3-dioxolane based compound, the consumption increasing the second raw material aldehydes or ketones and Zinc Chloride Anhydrous can improve the transformation efficiency of the first starting Epoxide, and, the present inventor is also unexpected in research process to be found, the consumption increasing the second raw material aldehydes or ketones can also improve the selectivity of target product DOX based compound further.
According to the present invention, the range of choices of described ionic liquid 1-alkyl-3-methylimidazole salt is wider, and for the present invention, under preferable case, the alkyl in described ionic liquid 1-alkyl-3-methylimidazole salt is the one in the straight or branched alkyl of C1-C10; Negatively charged ion is halogen ion, PF 6 -, borate ion, tetrafluoroborate ion, sulfate ion, hydrogen sulfate ion, alkyl sulfonate ion, one in trifluoromethane sulfonic acid radical ion and tosic acid radical ion.More preferably in situation, described alkyl is the one in the straight chained alkyl of C1-C10, is more preferably the one in the straight chained alkyl of C1-C5.
According to one of the present invention preferred embodiment, the positively charged ion of described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-Methylimidazole, and negatively charged ion is the one in bromide anion, chlorion, trifluoromethane sulfonic acid radical ion, methanesulfonate ions, tosic acid radical ion.
Concrete, described ionic liquid 1-alkyl-3-methylimidazole salt can be 1-butyl-3-methylimidazolium bromide, chlorination 1-butyl-3-Methylimidazole, 1-butyl-3-methylimidazolium hydrogen sulphate salt, 1-butyl-3-Methylimidazole mesylate, 1-butyl-3-Methylimidazole fluoroform sulphonate, 1-butyl-3-Methylimidazole tosilate etc., and more preferably described ionic liquid is 1-butyl-3-methylimidazolium bromide.Above-described ionic liquid can prepare by means commonly known in the art (see " Green Reaction Media in Organic Synthesis " that Koichi Mikami edits, the documents such as 2005, Blackwell Publishing Ltd.).
According to one of the present invention preferred embodiment, described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-methylimidazolium bromide, and the mol ratio of 1-butyl-3-methylimidazolium bromide and Zinc Chloride Anhydrous is 1-4: 1, is preferably 2: 1.
The preferred embodiment of one according to the present invention, described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-methylimidazolium bromide, and the mol ratio of 1-butyl-3-methylimidazolium bromide and Zinc Chloride Anhydrous is 1-4: 1, is preferably 2: 1; The mol ratio of the first raw material described and the second raw material is 1: 1-4, is preferably 1-3.5-4.
The particularly preferred embodiment of one according to the present invention, the first raw material described, the second raw material, 1-butyl-3-methylimidazolium bromide and Zinc Chloride Anhydrous are 5: 20: 2: 1.
The present invention to the time of described contact without particular requirement, can adjust according to the temperature and pressure of contact, in general, under fixation reaction volume conditions (i.e. confined reaction condition), temperature of reaction is higher, and the required reaction times is fewer, such as, be under the condition of 30-80 DEG C in preferred temperature of reaction, the time of contact is generally 3-20 hour, is preferably 5-12 hour.
In the present invention, the temperature of described contact can be provided by the various known method in this area, and such as 11-100 DEG C of scope provides by water-bath or oil bath heating, and the temperature range of 100-150 DEG C provides by pressured steam.The pressure of described contact can be adjusted by the temperature of contact, and generally speaking, under the condition of fixation reaction volume (i.e. confined reaction condition), the temperature of contact is higher, and pressure is also higher, and these are common practise, and this is no longer going to repeat them.
In the present invention, the boiling-point difference of DOX based compound, the first raw material, the second raw material is comparatively large, therefore they can be separated by rectifying.
In order to utilize various reaction raw materials more fully, according to one of the present invention preferred embodiment, the mol ratio of the first raw material described and the second raw material is 1: 1-10, described mixture is obtained 1 by rectifying separation, the mixture of 3-dioxolane based compound, the first raw material and the second raw material, the catalyzer containing Zinc Chloride Anhydrous, will be separated the first raw material of obtaining and the mixture of the second raw material, catalyzer (catalyzer containing Zinc Chloride Anhydrous generally the stays tower bottom of rectifying tower) reuse containing Zinc Chloride Anhydrous.
According to method of the present invention, the first the raw material epoxy compounds shown in formula (II) and general formula are R 5cOR 6the second raw material aldehydes or ketones carry out contacting according to method of the present invention and all can realize goal of the invention of the present invention, for the present invention, under preferable case, described R 1, R 2, R 3, R 4for straight chained alkyl, the branched-chain alkyl of C3-C8, the cycloalkyl of C3-C9, the alkyl-cycloalkyl of C4-C9, the cycloalkylalkyl of C4-C9, the aryl of C6-C10 of H, C1-C8, or R 1-R 2in any one and R 3-R 4in any one be keyed to ring; Described R 5, R 6for straight chained alkyl, the branched-chain alkyl of C3-C8, the cycloalkyl of C3-C9, the alkyl-cycloalkyl of C4-C9, the cycloalkylalkyl of C4-C9, the aryl of C6-C10 of H, C1-C8, or R 5with R 6be keyed to ring.
More preferably in situation, described R 5, R 6for H, methyl, ethyl, propyl group, phenyl, or R 5with R 6be keyed to ring.
According to the first embodiment of the present invention, described R 5, R 6for H, methyl, ethyl, propyl group, phenyl, or R 5with R 6be keyed to ring, described R 1and R 3for H, R 2and R 4for the alkylidene group of C1-C5, be preferably methylene radical, ethylidene or propylidene, and R 2and R 4be keyed to ring, more preferably, described R 1and R 3for H, R 2and R 4be ethylidene, R 2and R 4be keyed to six-ring.
According to the second embodiment of the present invention, described R 1, R 2, R 3, R 4for H, methyl or ethyl, more preferably described R 1, R 2, R 3, R 4for H, described R 5, R 6be methyl or R 5for methyl, R 6for ethyl or R 5for ethylidene, R 6for propylidene, and R 5and R 6be keyed to six-ring.
According to the third embodiment of the present invention, wherein, described R 1, R 2, R 3for H, R 4for methyl or ethyl; More preferably, described R 1, R 2, R 3for H, R 4for methyl, R 5, R 6be methyl.
The invention provides a kind of preparation method of alcohol based compound, the method comprises the following steps:
(1) DOX based compound is prepared;
(2) under acidic solid catalyst exists, under hydrolysising condition, the described DOX based compound prepared is contacted with water;
Wherein, the method preparing described DOX based compound is method of the present invention.
According to the present invention, described acidic solid catalyst can be the acidic solid catalyst that this area routine uses, and for the present invention, under preferable case, described acidic solid catalyst is storng-acid cation exchange resin.
Of the present invention 1, the preparation method of 3-dioxolane based compound, by using Zinc Chloride Anhydrous as one of catalyzer or catalyst component in the reaction, under catalysis epoxidation compound and aldehydes or ketones react the prerequisite possessing higher conversion and highly selective, successfully instead of trifluoromethane sulfonic acid zinc with more cheap Zinc Chloride Anhydrous.Such as, the first the raw material epoxy compounds being (II) formula for general structure is oxyethane, when the second raw material is acetone, with Zinc Chloride Anhydrous as catalyzer, in the reaction process of catalytic epoxyethane and acetone, the transformation efficiency of oxyethane is up to 92%, product 1, the selectivity of 3-dioxolane based compound reaches 100%, and the amounts of acetone be oxidized required for every moles of ethylene oxide is by document (J.Org.Chem.1978,43,438 ~ 440) that reports is greater than 16, is reduced to 1-4;
Meanwhile, R is worked as 1or R 4group has that one or two group is alkyl, all the other are when being hydrogen atoms, with the reaction of acetone, also has very high selectivity (98-100%).For other epoxide of the present invention and the reaction of other ketone of the present invention or aldehyde, method of the present invention has very high selectivity (98-100%) and transformation efficiency (more than 90%) equally.
Method of the present invention, as compared to the preparation method that CN101519397A with CN101993430A reports, by introducing the catalyzer comprising Zinc Chloride Anhydrous in the reaction, under guarantee reaction possesses the prerequisite of high conversion and highly selective, successfully instead of strong, the expensive trifluoromethane sulfonic acid zinc of corrodibility with more cheap Zinc Chloride Anhydrous.Such as, to react preparation 2 at catalytic epoxyethane and acetone, 2-dimethyl-1, under the Optimal reaction conditions of 3-dioxolane, the catalyzer be made up of 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous, oxyethane transformation efficiency reaches 99%, 2, the selectivity of 2-dimethyl-DOX reaches 100%, higher than with trifluoromethane sulfonic acid zinc for selectivity of catalyst 99%.
Further, in the preferred embodiment of the present invention, by adding ionic liquid 1-alkyl-3-methylimidazole salt in catalyzer of the present invention, make preparation 1 of the present invention, in the method for 3-dioxolane based compound, the transformation efficiency of reactant improves further, 1, the selectivity of 3-dioxolane based compound also improves further, and, on this basis, compared to independent Zinc Chloride Anhydrous as catalyzer, the preferred catalyzer containing Zinc Chloride Anhydrous and ionic liquid 1-alkyl-3-methylimidazole salt of the present invention can more effectively be reused.
In the present invention, the mass spectrum provided according to gas chromatograph-mass spectrometer (GC-MS) and computer Plays spectrum library compare and determine various material, and those skilled in the art all can know this, do not repeat them here.
Adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation indexes such as the transformation efficiency of reactant, the yield of product and selectivity on this basis.
Below in conjunction with embodiment, the present invention is described in detail.
In embodiment and comparative example, if not otherwise specified, the chemical reagent of use is chemically pure reagent.
In comparative example and embodiment:
Such as:
Embodiment 1
Magnetic stir bar is put into 100mL teflon-lined reactor, add 0.2mol (11.6g) acetone, 0.05mol (2.2g) oxyethane, add 0.02mol (2.7g) Zinc Chloride Anhydrous, capping still, heat in 65 DEG C of oil baths, react 8 hours.Be cooled to room temperature, sampling analysis, the transformation efficiency of oxyethane is the selectivity of 92.5%, 2,2-dimethyl-DOX is 100%.
Embodiment 2
Magnetic stir bar is put into 25mL teflon-lined reactor, add 0.1mol (5.8g) acetone, 0.025mol (1.1g) oxyethane, add the catalyzer be made up of 0.01mol bromination 1-butyl-3-Methylimidazole ionic liquid and 0.005mol (0.68g) Zinc Chloride Anhydrous Homogeneous phase mixing again, capping still, under 65 DEG C of oil baths, stirring reaction 8 hours.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 99%, 2,2-dimethyl-DOX is 100%.
Comparative example 1
2,2-dimethyl-DOX is prepared according to the method for embodiment 1, unlike: the anhydrous trifluoromethane sulfonic acid zinc of Zinc Chloride Anhydrous same molar replaces.The transformation efficiency of oxyethane is the selectivity of 99%, 2,2-dimethyl-DOX is 99%.
Data as can be seen from embodiment 1-2 and comparative example 1: to react preparation 2 at catalytic epoxyethane and acetone, 2-dimethyl-1, in the method for 3-dioxolane, catalyzer is made with Zinc Chloride Anhydrous, or with the catalyzer be made up of 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous, the selectivity of its reaction product 2,2-dimethyl-DOX reach 100% higher than with trifluoromethane sulfonic acid zinc for selectivity of catalyst (99%).
Embodiment 3
By the reaction mixture that embodiment 2 obtains, distill under nitrogen protection, after product and the complete fractionation by distillation of raw material, the remaining ionic liquid be containing zinc chloride.By embodiment 2 method, with the catalyzer of the ionic liquid alternate embodiment 2 containing zinc chloride of this recovery, preparation 2,2-dimethyl-DOX.The transformation efficiency of oxyethane is the selectivity of 99%, 2,2-dimethyl-DOX is 98%.
Embodiment 4
By the reaction mixture that embodiment 1 obtains, distill under nitrogen protection, after product and the complete fractionation by distillation of raw material, residuum contains zinc chloride.By the method for embodiment 1, with the catalyzer of the distillation residuum alternate embodiment 1 containing zinc chloride of this recovery, preparation 2,2-dimethyl-DOX.After being cooled to room temperature, get fluid sample analysis, oxyethane transformation efficiency is 11%.
Comparative example 3 and 4 is known: the catalyzer of 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous composition, through first time catalytic epoxyethane and acetone to react preparation 2,2-dimethyl-1, after 3-dioxolane, after can reclaiming, catalytic epoxyethane and acetone react catalyzer again, and still keep high oxyethane transformation efficiency and the selectivity of 2,2-high dimethyl-DOX; And be catalyzer with Zinc Chloride Anhydrous, through first time catalytic epoxyethane and after acetone reacts, the catalyzer second time catalytic effect of recovery obviously reduces.This illustrates that 1-butyl-3-methylimidazolium bromide ionic liquid not only increases the katalysis of Zinc Chloride Anhydrous, and be conducive to catalyzer be cycled to repeat use.
Embodiment 5
Magnetic stir bar is put into 100mL teflon-lined reactor, add 0.4mol (23.2g) acetone, 0.1mol (4.4g) oxyethane, add 0.02mol (2.7g) anhydrous chlorides of rase zinc catalyst, capping still, heat in 65 DEG C of oil baths, stirring reaction 8 hours.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 77%, 2,2-dimethyl-DOX is 100%.
Embodiment 6
2,2-dimethyl-DOX is prepared according to the method for embodiment 5, unlike: the consumption of Zinc Chloride Anhydrous is 0.04mol (5.4g).React complete, after being cooled to room temperature, get fluid sample analysis, the selectivity of transformation efficiency 84%, 2, the 2-dimethyl-DOX of oxyethane is 100%.
Embodiment 7
2,2-dimethyl-DOX is prepared according to the method for embodiment 5, unlike: the consumption of Zinc Chloride Anhydrous is 0.01mol (1.36g), and the consumption of acetone is 0.2mol (11.6g).React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 67%, 2,2-dimethyl-DOX is 100%.
From the result data of embodiment 5-7, react preparation 2,2-dimethyl-1 at catalytic epoxyethane and acetone, in the process of 3-dioxolane, with Zinc Chloride Anhydrous as catalyzer, increase the consumption of Zinc Chloride Anhydrous and acetone, be conducive to the transformation efficiency improving oxyethane.
Embodiment 8
Magnetic stir bar is put into 100mL teflon-lined reactor, add 0.2mol (11.6g) acetone, 0.05mol (2.2g) oxyethane, add the catalyzer be made up of 0.02mol 1-butyl-3-methylimidazolium bromide ionic liquid and 0.01mol (1.36g) Zinc Chloride Anhydrous Homogeneous phase mixing again, capping still, under 65 DEG C of oil baths, stirring reaction 8 hours.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 99%, 2,2-dimethyl-DOX is 98%.
Embodiment 9
2,2-dimethyl-DOX is prepared according to the method for embodiment 8, unlike: the consumption of Zinc Chloride Anhydrous is 0.02mol.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 95%, 2,2-dimethyl-DOX is 90%.
Embodiment 10
2,2-dimethyl-DOX is prepared according to the method for embodiment 8, unlike: the consumption of Zinc Chloride Anhydrous is 0.005mol (0.68g).React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 56%, 2,2-dimethyl-DOX is 94%.
Embodiment 11
2,2-dimethyl-DOX is prepared according to the method for embodiment 8, unlike: the consumption of oxyethane is 0.1mol (4.4g).React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 87%, 2,2-dimethyl-DOX is 90%.
From the result data of embodiment 8-11, the catalyzer be made up of 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous Homogeneous phase mixing, its catalytic effect is relevant with the molar ratio of ionic liquid and Zinc Chloride Anhydrous.Particularly preferred molar feed ratio is: oxyethane: acetone: 1-butyl-3-methylimidazolium bromide: Zinc Chloride Anhydrous=5: 20: 2: 1.
Embodiment 12
2,2-dimethyl-DOX is prepared by the method for embodiment 11, unlike: ionic liquid is 1-butyl-3-Methylimidazole tosilate.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is 85%, 2,2-dimethyl-DOX selectivity is 100%.
Comparative example 11 is known with embodiment 12, and in catalyst component of the present invention, other ionic liquid (as 1-butyl-3-Methylimidazole tosilate) available substitutes 1-butyl-3-methylimidazolium bromide, and effect is without marked difference.
Comparative example 2
2,2-dimethyl-DOX is prepared by the method for embodiment 11, unlike: substitute 0.01mol (1.36g) Zinc Chloride Anhydrous with 0.01mol trifluoromethanesulfonic acid zinc.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of oxyethane is the selectivity of 83%, 2,2-dimethyl-DOX is 86%.
Comparative example 11 is known with comparative example 2, and after substituting Zinc Chloride Anhydrous with trifluoromethanesulfonic acid zinc in catalyst component, 2,2-dimethyl-DOX selectivity reduces.This illustrates that the catalyzer of 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous composition is superior to the catalyzer of 1-alkyl-3-methylimidazole salt and trifluoromethanesulfonic acid zinc composition.
Embodiment 13
Magnetic stir bar is put into 100mL teflon-lined reactor, add 0.3mol (17.4g) acetone, 0.1mol (5.8g) propylene oxide, add rapidly 0.04mol (5.4g) anhydrous chlorides of rase zinc catalyst, capping still, heat in 55 DEG C of oil baths, stirring reaction 12 hours.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of propylene oxide is the selectivity of 86%, 2,2,4-trimethylammonium-DOX is 100%.
Embodiment 14
Magnetic stir bar is put into 25mL teflon-lined reactor, add 0.1mol (5.8g) acetone, 0.025mol (1.45g) propylene oxide, add the catalyzer be made up of 0.01mol (2.19g) 1-butyl-3-methylimidazolium bromide ionic liquid and 0.005mol (0.68g) Zinc Chloride Anhydrous Homogeneous phase mixing again, capping still, under 65 DEG C of oil baths, stirring reaction 8 hours.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of propylene oxide is the selectivity of 94%, 2,2,4-trimethylammonium-DOX is 100%.
Embodiment 15
Magnetic stir bar is put into 100mL teflon-lined reactor, add 0.2mol (11.6g) acetone, 0.05mol (2.9g) propylene oxide, add the catalyzer be made up of 0.02mol 1-butyl-3-methylimidazolium bromide ionic liquid and 0.01mol (1.36g) Zinc Chloride Anhydrous Homogeneous phase mixing again, capping still, under 55 DEG C of oil baths, stirring reaction 12 hours.React complete, after being cooled to room temperature, get fluid sample analysis, the transformation efficiency of propylene oxide is the selectivity of 95%, 2,2,4-trimethylammonium-DOX is 99.5%.
Comparative example 3
2,2,4-trimethylammonium-DOX is prepared according to the method for embodiment 15, unlike: the anhydrous trifluoromethane sulfonic acid zinc of Zinc Chloride Anhydrous same molar replaces.The transformation efficiency of propylene oxide is the selectivity of 99%, 2,2,4-trimethylammonium-DOX is 81%.
Can be found out by the data of above embodiment 13-15 and comparative example 3: to react preparation 2 at catalyze propylene oxide and acetone, 2,4-trimethylammonium-1, in the method for 3-dioxolane, with Zinc Chloride Anhydrous or with the catalyzer be made up of 1-butyl-3-methylimidazolium bromide ionic liquid and Zinc Chloride Anhydrous as catalyzer, 2,2, the selectivity of 4-trimethylammonium-DOX reach 99-100% higher than with trifluoromethane sulfonic acid zinc for selectivity of catalyst (81%).
Embodiment 16
Magnetic stir bar is put into 100mL teflon-lined reactor, add 0.4mol (28.8g) butanone, 0.1mol (4.4g) oxyethane and 0.02mol (2.7g) Zinc Chloride Anhydrous, capping still, reaction 8 hours under 55 DEG C of oil bath heating.Be cooled to room temperature, sampling analysis.The transformation efficiency of oxyethane is 56%, and the selectivity of target product DOX based compound is 98%.

Claims (16)

1. a preparation method for DOX based compound, the method comprises: under cyclization condition, is R by the first the raw material epoxy compounds shown in formula II and general formula 5cOR 6the second raw material aldehydes or ketones and catalyst exposure obtain mixture, be separated from described mixture and obtain 1 shown in formula I, 3-dioxolane based compound, it is characterized in that, described catalyzer contains Zinc Chloride Anhydrous, described catalyzer is also containing ionic liquid 1-alkyl-3-methylimidazole salt, the mol ratio of 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous is 0.1-10:1, and the alkyl in described ionic liquid 1-alkyl-3-methylimidazole salt is the one in the straight or branched alkyl of C1-C10; Negatively charged ion is halogen ion, PF 6 -, borate ion, tetrafluoroborate ion, sulfate ion, hydrogen sulfate ion, alkyl sulfonate ion, one in trifluoromethane sulfonic acid radical ion and tosic acid radical ion;
Wherein, R 1, R 2, R 3, R 4be straight chained alkyl, the branched-chain alkyl of C3-C20, the cycloalkyl of C3-C20, the alkyl-cycloalkyl of C4-C20, the cycloalkylalkyl of C4-C20, the aryl of C6-C20 of H, C1-C20 separately, or R 1-R 2in any one and R 3-R 4in any one be keyed to ring;
R 5, R 6be straight chained alkyl, the branched-chain alkyl of C3-C20, the cycloalkyl of C3-C20, the alkyl-cycloalkyl of C4-C20, the cycloalkylalkyl of C4-C20, the aryl of C6-C20 of H, C1-C20 separately, or R 5with R 6be keyed to ring.
2. preparation method according to claim 1, wherein, the mol ratio of described 1-alkyl-3-methylimidazole salt and Zinc Chloride Anhydrous is 1-4:1.
3. according to the preparation method in claim 1-2 described in any one, wherein, described cyclization condition comprises: the temperature of contact is subzero 20 DEG C to 150 DEG C above freezing; Pressure is that normal pressure is to 5MPa; The mol ratio of the first raw material, the second raw material and Zinc Chloride Anhydrous is 1:0.1-10:0.1-1.
4. method according to claim 3, wherein, described cyclization condition comprises: the temperature of contact is 30 DEG C-80 DEG C; Pressure is that normal pressure is to 2MPa; The mol ratio of the first raw material, the second raw material and Zinc Chloride Anhydrous is 1:1-4:0.1-0.4.
5. method according to claim 1, wherein, the described alkyl in described ionic liquid 1-alkyl-3-methylimidazole salt is the one in the straight chained alkyl of C1-C10.
6. method according to claim 5, wherein, the described alkyl in described ionic liquid 1-alkyl-3-methylimidazole salt is the one in the straight chained alkyl of C1-C5.
7. method according to claim 1, wherein, the positively charged ion of described ionic liquid 1-alkyl-3-methylimidazole salt is 1-butyl-3-Methylimidazole, and negatively charged ion is the one in bromide anion, chlorion, trifluoromethane sulfonic acid radical ion, methanesulfonate ions, tosic acid radical ion.
8. method according to claim 3, wherein, the mol ratio of the first raw material described and the second raw material is 1:1-10, described mixture is carried out rectifying separation and obtains 1, the mixture of 3-dioxolane based compound, the first raw material and the second raw material, the catalyzer containing Zinc Chloride Anhydrous, will be separated the mixture of the first raw material and the second raw material obtained and the catalyst recirculation reuse containing Zinc Chloride Anhydrous.
9. preparation method according to claim 1, wherein, described R 1, R 2, R 3, R 4be straight chained alkyl, the branched-chain alkyl of C3-C8, the cycloalkyl of C3-C9, the alkyl-cycloalkyl of C4-C9, the cycloalkylalkyl of C4-C9, the aryl of C6-C10 of H, C1-C8 separately, or R 1-R 2in any one and R 3-R 4in any one be keyed to ring;
Described R 5, R 6be straight chained alkyl, the branched-chain alkyl of C3-C8, the cycloalkyl of C3-C9, the alkyl-cycloalkyl of C4-C9, the cycloalkylalkyl of C4-C9, the aryl of C6-C10 of H, C1-C8 separately, or R 5with R 6be keyed to ring.
10. preparation method according to claim 9, wherein, described R 5, R 6for H, methyl, ethyl, propyl group, phenyl, or R 5with R 6be keyed to ring.
11. preparation methods according to claim 10, wherein, described R 1and R 3for H, R 2and R 4for the alkylidene group of C1-C5, and R 2and R 4be keyed to ring.
12. preparation methods according to claim 11, wherein, described R 2and R 4for methylene radical, ethylidene or propylidene, and R 2and R 4be keyed to ring.
13. preparation methods according to claim 12, wherein, described R 1and R 3for H, R 2and R 4be ethylidene, R 2and R 4be keyed to six-ring.
14. preparation methods according to claim 10, wherein, described R 1, R 2, R 3for H, R 4for methyl or ethyl.
15. preparation methods according to claim 10, wherein, described R 1, R 2, R 3, R 4for H; Described R 5for methyl, R 6for ethyl, or R 5for ethylidene, R 6for propylidene, and R 5and R 6be keyed to six-ring.
The preparation method of 16. 1 kinds of alcohol based compounds, the method comprises the following steps:
(1) DOX based compound is prepared;
(2) under acidic solid catalyst exists, under hydrolysising condition, the described DOX based compound prepared is contacted with water;
It is characterized in that, prepare the method for described DOX based compound for the method in claim 1-15 described in any one.
CN201110342486.3A 2011-11-02 2011-11-02 Preparation method of 1,3-dioxolane compound and alcohol compound Active CN103087036B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110342486.3A CN103087036B (en) 2011-11-02 2011-11-02 Preparation method of 1,3-dioxolane compound and alcohol compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110342486.3A CN103087036B (en) 2011-11-02 2011-11-02 Preparation method of 1,3-dioxolane compound and alcohol compound

Publications (2)

Publication Number Publication Date
CN103087036A CN103087036A (en) 2013-05-08
CN103087036B true CN103087036B (en) 2015-03-11

Family

ID=48200217

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110342486.3A Active CN103087036B (en) 2011-11-02 2011-11-02 Preparation method of 1,3-dioxolane compound and alcohol compound

Country Status (1)

Country Link
CN (1) CN103087036B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0448157A1 (en) * 1990-03-15 1991-09-25 Shell Internationale Researchmaatschappij B.V. A two-step monoethylene glycol preparation process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0448157A1 (en) * 1990-03-15 1991-09-25 Shell Internationale Researchmaatschappij B.V. A two-step monoethylene glycol preparation process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
B.N.Blackett,et al..The Mechanism of 1,3-Dioxolane Formation from the BF3-Catalysed Reaction of Epoxides with Carbonyl Compounds.《Tetrahedron》.1970,第26卷第1311页第1段及图1. *

Also Published As

Publication number Publication date
CN103087036A (en) 2013-05-08

Similar Documents

Publication Publication Date Title
CN100344596C (en) Method for preparing methylal using combined continuous distillation and liquid-liquid extraction
TWI745381B (en) Production method of isopropanol and isopropanol with reduced impurities
CN103172607B (en) Method for synthesizing cyclic carbonate from carbon dioxide and epoxy compound
CN108570019B (en) Acidic ionic liquid and catalytic application thereof
CN103508875A (en) 2,3,3,3-tetrafluoro propionic acid (I) synthesis method
CN106866331A (en) A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol
CN104892364A (en) Method for preparing trimethylolpropane by adopting hydrogenation method
Yang et al. Synthesis of Polyoxymethylene Dimethyl Ethers Catalyzed by Pyrrolidinonium‐Based Ionic Liquids
Hu et al. Metal‐and Solvent‐Free Transesterification and Aldol Condensation Reactions by a Homogenous Recyclable Basic Ionic Liquid Based on the 1, 3, 5‐Triazine Framework
CN102503774A (en) Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis
CN103087036B (en) Preparation method of 1,3-dioxolane compound and alcohol compound
US20170001941A1 (en) Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate
CN103214328B (en) Synthesis method for alpha-bromo-aromatic ketone compounds
CN103819426B (en) A kind of molybdenum multi-metal oxygen hydrochlorate catalyzing expoxidation of olefines method
CN104693016B (en) Method for preparing 4-methylbenzaldehyde from isoprene and acrolein
Jovanović et al. Acid-Catalyzed [3+ 2] Cycloaddition of Enones with Azomethine Imines for Easy Access to Tetrahydropyrazolopyrazolones
CN103087035B (en) Preparation methods of 2,2-dimethyl-1,3-dioxolane and ethylene glycol
CN102076647B (en) Process for producing bisphenol-a
CN105688983B (en) A kind of preparation method and purposes of ring-type quinine quarternary ammonium salt compound
CN104817513B (en) The preparation method of heteropoly acid tridemorph quaternary ammonium salt
CN103087034B (en) Preparation methods of 2,2,4-trimethyl-1,3-dioxolane and 1,2-propanediol
CN103435433A (en) Method for synthesizing isolongifolene by catalytically isomerizing longifolene with solid acid
CN112898156B (en) Method for recovering 1- (3, 3-dimethylcyclohexyl) ethanol and method for preparing musk eden
CN103922896B (en) Method for preparation of o-phenyl phenol from dibenzofuran
CN108727192B (en) Preparation method of diphenyl carbonate compound

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant