CN101851159B - Method for synthetizing alcohol ester acetate by single step of ethyl acetate and alcohol ester exchange - Google Patents
Method for synthetizing alcohol ester acetate by single step of ethyl acetate and alcohol ester exchange Download PDFInfo
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- CN101851159B CN101851159B CN2010101721339A CN201010172133A CN101851159B CN 101851159 B CN101851159 B CN 101851159B CN 2010101721339 A CN2010101721339 A CN 2010101721339A CN 201010172133 A CN201010172133 A CN 201010172133A CN 101851159 B CN101851159 B CN 101851159B
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Abstract
The invention discloses a method for synthetizing alcohol ester acetate by a single step of ethyl acetate and alcohol ester exchange, which relates to a synthesis method of the alcohol ester acetate. The method obtains a finished product by taking various alcohol ester acetates as raw materials, carbonate as a catalyst and ethyl acetate as an esterification reagent through single-step ester exchange reaction and concentration and purification. The invention has the characteristics of simple method, simple and convenient operation, energy source saving, low production cost, convenient popularization and application and the like, and diversified alcohol ester products with high yield and good quality can be prepared by adopting the method. The method can be widely applied to the industrial production of the alcohol ester acetate; the products prepared by adopting the method can be widely used as various flavor types of food essences and cosmetic essences, the essences of fancy soaps, washing powders and laundry detergents, the good solvents of dyes and printing ink and the like, and thereby, the demands of high amount due to wide market plane are satisfied.
Description
Technical field
The invention belongs to the organic chemistry synthesis technical field, be specifically related to the compound method of acetic acid alcohol ester.
Background technology
The acetic acid alcohol ester is found to be structural unit important in the natural product of biologically active widely; Many acetic acid alcohol esters all have higher using value simultaneously; Has the distinctive fragrance of jasmine appearance like Benzyl Acetate FFC; Be used to allocate food flavours such as apple, banana, pineapple, also be used as the fine solvent of Synolac, nitrocellulose, dyestuff, grease, printing-ink.Phenylethyl acetate is used for preparing perfumed soap, daily cosmetics essence, can be used as the surrogate of heptynoic acid methyl esters, and it has the fragrant fragrance of peach, also is usually used in allocating essence and fruity flavors such as rose, flores aurantii, VT, Tuberose, Flos rosae multiflorae.The acetic acid lauryl belongs to the fragrant raw material of cheap ester class adipocere, in the perfume formulation of low grade, can be used as solvent, thinner or and mixture use, because of its chemical property stable; Be again the composition of some natural essential oils, so the application safety sense is better, at the citrus of food flavour; Coco group; The fruital compound, close fragrant class often has adapted, and rose, the Tuberose of floral type all made the essence adapted.Geranyl acetate is used to prepare type essence such as rose, flores aurantii, sweet osmanthus or the like, and market application foreground is good, and demand has a large capacity and a wide range.
The compound method of ester is numerous, and the development of ester compound probability, transesterify also become very important reaction in the organic synthesis, and the organic chemist is easy to utilize the synthetic ester that needs of this type of reaction.Because transesterify is a reversing process,, thereby need extra some separating devices that increase so the catalysis process of much having reported all need remove the alcohol that reaction generates synchronously.The method of the existing acetic acid synthesized alcohol ester of transesterify; It like the patent No. ' the ritalin transesterify prepares the method for amyl acetate fatty alcohol ' patent of 02136050.2; Disclosed method is to be raw material with ritalin and Fatty Alcohol(C12-C14 and C12-C18); Prepare the acetic acid Fatty Alcohol(C12-C14 and C12-C18) through transesterification reaction, the catalyzer that is adopted is sulfuric acid, tosic acid or sal enixum.This method is being very effective aspect the production amyl acetate fatty alcohol; In time remove the methyl alcohol of generation through evaporation, condensation, extraction; The ritalin that steams simultaneously is back to the transesterification reaction system; To guarantee that reactant ritalin concentration maintains enough levels, improve the forward impellent of transesterification reaction, but mainly there is following deficiency in this method:
(1) esterifying reagent of this method employing is a ritalin, and its relative vinyl acetic monomer is more expensive, has improved production cost.
(2) structure of the synthetic ester output of this method can only be an acetic acid fat alcohols material, can not synthesize the acetic acid alcohol ester products of the above higher alcohols of octanol, cyclic alcohol, aromatic alcohol, enol etc., is of limited application.
(3) this method adopts timely extraction process to remove the methyl alcohol that produces in the exchange process, and backflow ritalin entering reaction system, and this needs additional apparatus and power, thereby has further increased production cost.
(4) this method adopts strong acid tart catalyzer, and stronger for the corrosion on Equipment effect, environmental pollution is bigger, the cost height that depollutes, and inconvenience is applied.
Summary of the invention
The objective of the invention is weak point, the method for a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester is provided to the existing acetic acid synthesized alcohol ester method of transesterify.Advantages such as present method has the preparation feedback production safety, and processing condition are not harsh, production unit is required low, and technology is simple, raw material is easy to get, and preparation cost is low, and product do not contain harmful impurity basically, and it is simple to purify, and environmental pollution is little.
Mechanism of the present invention: the present invention has adopted common nontoxic, and is eco-friendly, and cheap vinyl acetic monomer provides a kind of simple, green relatively cleaning, the novel method of economical and practical synthetic new ester.Carbonate is as catalyzer, and it is relatively stable, cheaply is easy to get.
Carbonate has played the effect of dual-function catalyst, metal ions M in catalytic process
+The proton interaction activation of carbanion and alcoholic extract hydroxyl group alcohol in the activation ester group; The alcoholic extract hydroxyl group oxygen attack ester group generation nucleophilic substitution reaction that is activated generates new alcohol ester and an ethanol molecule; Carbonate dissociates out and accomplishes catalytic chain one time, then gets into identical catalytic chain of second step.
The technical scheme that realizes the object of the invention is: the method for a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester; With various alcohol is raw material; Use carbonate to be catalyzer; With the vinyl acetic monomer is esterifying reagent and double as solvent, and one step of warp transesterification reaction gets finished product with the simple process that concentrates, purifies.Its concrete grammar step is following:
(1) carries out transesterification reaction
With alcohol is raw material, is catalyzer with carbonate (comprising basic metal class carbonate such as salt of wormwood or cesium carbonate), is esterifying reagent with the vinyl acetic monomer; And the double solvent of doing, according to alcohol (mmole): carbonate (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: (0.01～3): the ratio of (0.208～2.439), earlier adding carbonate catalyst and vinyl acetic monomer solvent in reactor drum; Stir down; Add alcohol again, finish, be warming up to 85～205 ℃; Lasting stirring was carried out transesterify 2～26 hours, just prepared acetic acid alcohol ester reaction solution.
Described alcohol is a kind of in aliphatic chain primary alcohol, cycloaliphatic ring secondary alcohol, fragrant primary alcohol such as benzylalcohol, fragrant secondary alcohol such as 1-phenylethyl alcohol or benzhydrol, allyl alcohol such as styryl carbinol, the Geraniol.
(2) carry out that product concentrates, purifying
After (1) step accomplished, the acetic acid alcohol ester reaction solution that (1) step was prepared, naturally cooling in air, with the condenser system of dichloromethane rinse reactor drum, washings is incorporated the reaction solution in the reactor drum into.Through mixed solution in the rotary evaporation concentration response device, collect liquid concentrator and distillate respectively then.Distillate is a vinyl acetic monomer, can recycle, and liquid concentrator through purification by silica gel column chromatography, is carried out wash-out with elutriant, to the effluent of silica gel column chromatography through rotary evaporation concentrate, drain product.
Described elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: the mixed solution of (70～100).
After the present invention adopts technique scheme, mainly contain following effect:
(1) raw polyol wide material sources, structure is abundant, is easy to obtain the alcohol ester of various functionalization, can satisfy the multifarious demand of ester kind.
(2) vinyl acetic monomer cheaply is easy to get, and preparation technology is simple, and toxicity is low, pollutes for a short time, helps environment protection, and can reduce production costs, and is easy to utilize.
(3) the catalyst carbon hydrochlorate is weakly alkaline, and little to the production unit corrosion, environmental pollution is little, cheaply is easy to get, further reduce production costs, and environmental requirement.
(4) catalyzer shows as the heterogeneous catalysis effect in catalytic process, is convenient to Separation and Recovery, can use repeatedly, and this has not only made full use of resource, has reduced ' three wastes ' discharging again, helps environment protection.
(5) reaction conditions is gentle, save energy; Synthetic operation is easy, need not the anhydrous and oxygen-free condition, and aftertreatment is easy; With low cost, belong to green production.
(6) the present invention only need a step transesterify and concentrate purify finished product, yield is higher, need not to consider that the influence of chemical equilibrium in time removes the ethanol of generation.Good product quality is convenient to suitability for industrialized production, can satisfy the demand that has a large capacity and a wide range in market.
The inventive method can be widely used in the suitability for industrialized production of acetic acid alcohol ester.The product that adopts the inventive method to prepare can be widely used as the food flavor(ing) of various odor types, cosmetic essence, and the essence of perfumed soap, washing powder, washing liquid and be used for dyestuff and the fine solvent of printing ink or the like satisfies market demand large in number and widely distributed.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are following:
(1) being raw material with the Geraniol, using cesium carbonate to be catalyzer, is esterifying reagent with the vinyl acetic monomer, and the double solvent of doing; According to Geraniol (mmole): cesium carbonate (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 0.05: 1 a ratio, in reactor drum, adds cesium carbonate (32.6mg, 0.1mmol) catalyzer and vinyl acetic monomer solvent (2.0mL) earlier; Stir down, add again Geraniol (308.5mg, 2.0mmol); Finish, be warming up to 125 ℃, lasting stirring was carried out transesterify 25 hours.
After (2) (1) steps accomplished, the acetic acid alcohol ester reaction solution that (1) step was prepared, naturally cooling in air, with the condenser system of dichloromethane rinse reactor drum, washings is incorporated the reaction solution in the reactor drum into.Through mixed solution in the rotary evaporation concentration response device, collect liquid concentrator and distillate respectively then, distillate is a vinyl acetic monomer, recyclable utilization; Liquid concentrator is used purification by silica gel column chromatography, carries out wash-out with elutriant, to the effluent of silica gel column chromatography, through rotary evaporation concentrate, drain colourless transparent liquid geranyl acetate (373.0mg, yield 95%).
Described elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 100 a mixed solution.
Embodiment 2
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are with embodiment 1, wherein:
In the step (1), be raw material, use cesium carbonate to be catalyzer with the phenylethyl alcohol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to phenylethyl alcohol (mmole): cesium carbonate (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 0.01: 1 a ratio; (32.6mg 0.1mmol) with vinyl acetic monomer (10.0mL), stirs and adds phenylethyl alcohol (1.2216g down again in reactor drum, to add earlier cesium carbonate; 10.0mmol), lasting stirring was carried out transesterify 16 hours.
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 80 a mixed solution, gets colourless transparent liquid phenylethyl acetate (1.5382g, yield 94%).
Embodiment 3
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are with embodiment 1, wherein:
In the step (1), be raw material, use cesium carbonate to be catalyzer with the n-Octanol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to n-Octanol (mmole): cesium carbonate (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 0.025: 0.75 a ratio; (162.9mg 0.5mmol) with vinyl acetic monomer (15.0mL), stirs and adds n-Octanol (2.6046g down again in reactor drum, to add earlier cesium carbonate; 20.0mmol), lasting stirring was carried out transesterify 6 hours.
Get colourless transparent liquid n-octyl acetate (3.1006g, yield 90%) in the step (2).
Embodiment 4
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are with embodiment 1, wherein:
In the step (1), be raw material, use salt of wormwood to be catalyzer with the phenylcarbinol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to phenylcarbinol (mmole): salt of wormwood (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 0.15: 1 a ratio; (41.5mg 0.3mmol) with vinyl acetic monomer (2.0mL), stirs and adds phenylcarbinol (207.9 μ L down again in reactor drum, to add earlier salt of wormwood; 2.0mmol), lasting stirring was carried out transesterify 10 hours.
In the step (2), the elutriant vinyl acetic monomer: the volume ratio of sherwood oil is 1: 70, gets colourless transparent liquid Benzyl Acetate FFC (202.7g, yield 67%).
Embodiment 5
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, it amplifies synthetic concrete steps with embodiment 1, wherein:
In the step (1), be raw material, use salt of wormwood to be catalyzer with the phenylcarbinol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to phenylcarbinol (mmole): salt of wormwood (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 0.15: 0.208 a ratio; (1.9938g 14.4mmol) with vinyl acetic monomer (20mL), stirs and adds phenylcarbinol (10.0mL down again in reactor drum, to add earlier salt of wormwood; 96.2mmol), lasting stirring was carried out transesterify 13 hours.
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 70 a mixed solution, gets colourless transparent liquid Benzyl Acetate FFC (8.1791g, yield 57%).
Embodiment 6
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are with embodiment 1, wherein:
In the step (1), be raw material, use salt of wormwood to be catalyzer with the phenylcarbinol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to phenylcarbinol (mmole): salt of wormwood (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 3: 1 a ratio; In reactor drum, add salt of wormwood (829.3mg earlier; 6mmol), temperature of reaction is 85 ℃, and lasting stirring was carried out transesterify 2 hours.
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 70 a mixed solution, gets colourless transparent liquid Benzyl Acetate FFC (30.0mg, yield 10%).
Embodiment 7
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are with embodiment 1, wherein:
In the step (1), be raw material, use salt of wormwood to be catalyzer with the phenylcarbinol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to phenylcarbinol (mmole): salt of wormwood (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 3: 1 a ratio; In reactor drum, add salt of wormwood (829.3mg earlier; 6mmol), temperature of reaction is 205 ℃, and lasting stirring was carried out transesterify 2 hours.
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 70 a mixed solution, gets colourless transparent liquid Benzyl Acetate FFC (111.1mg, yield 37%).
Embodiment 8
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are with embodiment 1, wherein:
In the step (1), be raw material, use cesium carbonate to be catalyzer with the lauryl alcohol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to lauryl alcohol (mmole): salt of wormwood (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 0.01: 1 a ratio; (32.6mg 0.1mmol) with ETHYLE ACETATE (10mL), stirs and adds lauryl alcohol (1.8633g down again in reactor drum, to add earlier cesium carbonate; 10.0mmol), temperature of reaction is 125 ℃, lasting stirring was carried out transesterify 26 hours.
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 100 a mixed solution, gets colourless transparent liquid acetic acid lauryl (1.8032g, yield 79%).
Embodiment 9
The method of a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, its concrete steps are with embodiment 1, wherein:
In the step (1),, use salt of wormwood to be catalyzer to be raw material to methylbenzyl alcohol; With the vinyl acetic monomer is esterifying reagent, and the double solvent of doing, and according to methylbenzyl alcohol (mmole): salt of wormwood (mmole): the ratio of vinyl acetic monomer (milliliter) is 1: 0.15: 2.439 a ratio; In reactor drum, add salt of wormwood (17.0mg earlier; 0.123mmol) and ETHYLE ACETATE (2mL), stir add again down to methylbenzyl alcohol (100.0mg, 0.82mmol); Temperature of reaction is 125 ℃, and lasting stirring was carried out transesterify 11 hours.
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 70 a mixed solution, gets colourless transparent liquid acetic acid to methylbenzene methyl esters (71.4mg, yield 53%).
Embodiment 10-18
The concrete steps of the method for a kind of vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester, with embodiment 1, different piece wherein is as shown in the table.
Table 1
Claims (4)
1. the method for a vinyl acetic monomer and pure transesterify one-step synthesis acetic acid alcohol ester is characterized in that concrete method steps is following:
(1) carries out transesterification reaction
With alcohol is raw material, uses salt of wormwood or cesium carbonate to be catalyzer, is esterifying reagent with the vinyl acetic monomer; And the double solvent of doing, according to pure mmole: the carbonate mmole: the ratio of vinyl acetic monomer milliliter is 1: (0.01～3): the ratio of (0.208～2.439) adds carbonate catalyst and vinyl acetic monomer solvent earlier in reactor drum; Stir down, add alcohol again, finish; Be warming up to 85～205 ℃, lasting stirring was carried out transesterify 2～26 hours;
Described alcohol is that aliphatic chain primary alcohol, cycloaliphatic ring secondary alcohol, fragrant primary alcohol are that benzylalcohol, fragrant secondary alcohol are that 1-phenylethyl alcohol or benzhydrol, allyl alcohol are a kind of in styryl carbinol, the Geraniol;
(2) carry out that product concentrates, purifying
After the completion of (1) step; Go on foot the acetic acid alcohol ester reaction solution of preparing to (1); Naturally cooling in air, with the condenser system of dichloromethane rinse reactor drum, washings is incorporated the reaction solution in the reactor drum into; Through mixed solution in the rotary evaporation concentration response device, collect liquid concentrator and distillate respectively then; Liquid concentrator through purification by silica gel column chromatography, is carried out wash-out with elutriant, the effluent of silica gel column chromatography is concentrated, drains through rotary evaporation;
Described elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: the mixed solution of (70～100).
2. according to the method for described a kind of vinyl acetic monomer of claim 1 and pure transesterify one-step synthesis acetic acid alcohol ester; It is characterized in that: in the step (1); Raw material is a Geraniol, and catalyzer is a cesium carbonate, the Geraniol mmole: the cesium carbonate mmole: the ratio of vinyl acetic monomer milliliter is 1: 0.05: 1; Be warming up to 125 ℃, lasting stirring was carried out transesterify 10 hours;
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 100 a mixed solution, gets the colourless transparent liquid geranyl acetate.
3. according to the method for described a kind of vinyl acetic monomer of claim 1 and pure transesterify one-step synthesis acetic acid alcohol ester; It is characterized in that: in the step (1); Raw material is a phenylethyl alcohol, and catalyzer is a cesium carbonate, the phenylethyl alcohol mmole: the cesium carbonate mmole: the ratio of vinyl acetic monomer milliliter is 1: 0.01: 1; Be warming up to 125 ℃, lasting stirring was carried out transesterify 16 hours;
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 80 a mixed solution, gets the colourless transparent liquid phenylethyl acetate.
4. according to the method for described a kind of vinyl acetic monomer of claim 1 and pure transesterify one-step synthesis acetic acid alcohol ester; It is characterized in that: in the step (1); Raw material is a n-Octanol, and catalyzer is a cesium carbonate, the n-Octanol mmole: the cesium carbonate mmole: the ratio of vinyl acetic monomer milliliter is 1: 0.025: 0.75; Be warming up to 125 ℃, lasting stirring was carried out transesterify 6 hours;
In the step (2), elutriant is a vinyl acetic monomer: the volume ratio of sherwood oil is 1: 100 a mixed solution, gets the colourless transparent liquid n-octyl acetate.
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| CN102993003B (en) * | 2011-09-13 | 2016-01-06 | 湖南长岭石化科技开发有限公司 | A kind of preparation method of acetic ester |
| CN102796145B (en) * | 2012-06-19 | 2015-04-15 | 天津北方食品有限公司 | Preparation method of sucrose-6-benzoate |
| CN104710306A (en) * | 2015-01-12 | 2015-06-17 | 吉林化工学院 | Method for preparing acetate through ester interchange-adsorption ethanol removal combined technology |
| CN105924347A (en) * | 2016-04-22 | 2016-09-07 | 盐城市春竹香料有限公司 | Technology for preparing isogalbanate |
| CN107879931B (en) * | 2017-11-27 | 2021-03-26 | 盐城市春竹香料有限公司 | Preparation method of cinnamic acid cinnamate |
| CN108250076A (en) * | 2018-03-13 | 2018-07-06 | 上海贝通色彩科技有限公司 | The method for synthesizing 3- difluoromethyls -3 acrylic acid ethyl ester compound |
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| CN1197790A (en) * | 1997-04-30 | 1998-11-04 | 石伟 | Preparation of acetate product |
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