CN102701924B - The preparation method of cinnamaldehyde diethylacetal - Google Patents
The preparation method of cinnamaldehyde diethylacetal Download PDFInfo
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- CN102701924B CN102701924B CN201210166400.0A CN201210166400A CN102701924B CN 102701924 B CN102701924 B CN 102701924B CN 201210166400 A CN201210166400 A CN 201210166400A CN 102701924 B CN102701924 B CN 102701924B
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Abstract
The invention provides a kind of preparation method of cinnamaldehyde diethylacetal, with bromo-1, the 1-diethoxyethane of 2-and phenyl aldehyde for raw material, under the effect being catalyzer and solid carrier with triphenyl phosphorus, by microwave irradiation synthesis cinnamaldehyde diethylacetal, described solid carrier is basic macroporous resin.The present invention adopts cost of material to be cheaply easy to get, and catalyzer is that solid catalyst is easy to removing, and reaction conditions is gentle simple, and side reaction is few, and aftertreatment is easy, product yield and purity high, cost reduces greatly, can be continuously produced.<!--1-->
Description
Technical field
The present invention relates to and belong to fine-chemical intermediate synthesis technical field, specifically refer to a kind of preparation method of cinnamaldehyde diethylacetal.
Background technology
Cinnamaldehyde diethylacetal, also known as phenylacrolein diethyl acetal, is colourless transparent liquid, has the fragrance of similar phenylacrolein, but fragrance is softer, nature.Cinnamaldehyde diethylacetal can be used as floral type soap use, the head pastil of detergent essence and modifier; Also can be used in oranges and tangerines type food flavour, China (GB2760-96) is defined as the flavouring agent allowing to use.As the application quantity of blending spices in food flavouring up to 130ppm.
The classical mode of cinnamaldehyde diethylacetal synthesis be phenylacrolein and triethyl orthoformate or ethanol under inorganic liquid acid or lewis acidic katalysis, obtained by condensation.The price of the raw materials used phenylacrolein of this method is very high, and triethyl orthoformate is easily hydrolyzed; Moreover aldolization is a reversible reaction, when reaction reaches balance, be difficult to proceed; General productive rate is not high, is not suitable for suitability for industrialized production.Therefore, the synthetic method of an applicable suitability for industrialized production need be looked for, production cinnamaldehyde diethylacetal product is had great significance.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of preparation method of cinnamaldehyde diethylacetal of applicable suitability for industrialized production is provided.
For achieving the above object, the preparation method of cinnamaldehyde diethylacetal of the present invention, with bromo-1, the 1-diethoxyethane of 2-and phenyl aldehyde for raw material, with triphenyl phosphorus (PPh
3) under the effect of catalyzer and solid carrier, by microwave irradiation synthesis cinnamaldehyde diethylacetal, reaction formula is as follows:
Wherein, described solid carrier is basic macroporous resin.Described basic macroporous resin is preferably the macroporous resin of supported solid, and wherein solid alkali is NaOH, KOH, K
2cO
3, MgO or Na
3pO
4.
The method concrete steps comprise: by bromo-for 2-1,1-diethoxyethane, phenyl aldehyde, triphenyl phosphorus (PPh
3) and after solvent fully mixes, add solid carrier, under microwave radiation, be warmed up to 85 ~ 90 DEG C, and insulation reaction 1 ~ 2h, reaction terminates rear cool to room temperature, and obtain reaction solution, then air distillation goes out solvent, filter out triphenyl phosphorus, then by molecular distillation, obtain product cinnamaldehyde diethylacetal.
In the present invention, the mol ratio of bromo-1, the 1-diethoxyethane of described 2-and phenyl aldehyde is 1:1 ~ 1.5.
In the present invention, described triphenyl phosphorus (PPh
3) the consumption mass percent that accounts for benzene feedstock formaldehyde and bromo-1, the 1-diethoxyethane total amount of 2-be 5 ~ 15%.
In the present invention, solvent for use is toluene, and the mass ratio of the consumption of solvent and benzene feedstock formaldehyde and bromo-1, the 1-diethoxyethane total amount of 2-is 1:1.
In the present invention, the power of microwave radiation used is 500 ~ 600W.
The reaction mechanism that the present invention synthesizes cinnamaldehyde diethylacetal is:
The present invention synthesizes in the method for cinnamaldehyde diethylacetal, adopts the macroporous resin of solid alkali greatly can increase the contact surface with reactant.Reaction carries out under the condition of microwave radiation, microwave oven used be above with the microwave oven of perforate.Microwave heating has inner heating, rapid heating, selectivity heating and the advantage such as energy-conservation, reaction system is heated evenly, reduces the generation of side reaction, the purity of raising product.
Molecular distillation is a kind of special liquid-liquid separation technology, and it is different from Conventional espresso and relies on boiling-point difference separation principle, but realizes being separated by the difference of different substances molecular tools.Molecular distillation operates at the temperature far below material boiling point, and residence time of material is short.Effectively can reduce the thermal damage of material, protect the not contaminated and infringement of separated material, improve product yield and purity, reduce product cost.
Beneficial effect of the present invention: adopt cost of material to be cheaply easy to get, catalyzer is that solid catalyst is easy to removing, and reaction conditions is gentle simple, and side reaction is few, and aftertreatment is easy, product yield and purity high, cost reduces greatly, can be continuously produced.
Embodiment
The present invention is set forth further below in conjunction with specific embodiment.Following examples are only for further specific descriptions of the present invention, instead of for the restriction to application claims protection domain.
Embodiment 1
By triphenyl phosphorus 10g, toluene 101.5g, phenyl aldehyde (M=106) 0.4mol and 2-bromo-1,1-diethoxyethane (M=197) 0.3mol joins in Florence flask, pour into after abundant mixing in the tubular reactor of the macroporous resin carrier that load NaOH is housed, put into microwave oven, load onto thermometer and condenser.Under stirring atmospheric pressure state, carry out microwave irradiation, power 600W, be warming up to 85 DEG C, and insulation backflow 1.5h.React complete, reaction terminates rear cool to room temperature, and obtain reaction solution, then air distillation goes out solvent toluene, filters out catalyzer triphenyl phosphorus, and then reaction solution distills out product cinnamaldehyde diethylacetal further across scraper-type molecular distillation apparatus.Product purity 99%, productive rate 92.8%.
Example 2
By triphenyl phosphorus 10g, toluene 111g, phenyl aldehyde 0.4mol and 2-bromo-1,1-diethoxyethane 0.35mol joins in Florence flask, pour in the tubular reactor of the macroporous resin carrier that load KOH is housed after abundant mixing, put into microwave oven, load onto thermometer and condenser.Under stirring atmospheric pressure state, carry out microwave irradiation, power 550W, be warming up to 88 DEG C, and insulation backflow 1.5h.React complete, reaction terminates rear cool to room temperature, and obtain reaction solution, then air distillation goes out solvent toluene, filters out catalyzer triphenyl phosphorus, and then reaction solution distills out product cinnamaldehyde diethylacetal further across scraper-type molecular distillation apparatus.Product purity 99%, productive rate 93.3%.
Example 3
Triphenyl phosphorus 10g, toluene 117g, bromo-1, the 1-diethoxyethane 0.38mol of phenyl aldehyde 0.4mol and 2-are joined in Florence flask, fully pours into after mixing and load K is housed
2cO
3macroporous resin carrier tubular reactor in, put into microwave oven, load onto thermometer and condenser.Under stirring atmospheric pressure state, carry out microwave irradiation, power 500W, be warming up to 90 DEG C, and insulation backflow 2h.React complete, reaction terminates rear cool to room temperature, and obtain reaction solution, then air distillation goes out solvent toluene, filters out catalyzer triphenyl phosphorus, and then reaction solution distills out product cinnamaldehyde diethylacetal further across scraper-type molecular distillation apparatus.Product purity 99%, productive rate 93%.
Example 4
By triphenyl phosphorus 8g, toluene 107g, phenyl aldehyde 0.45mol and 2-bromo-1,1-diethoxyethane 0.3mol joins in Florence flask, pour in the tubular reactor of the macroporous resin carrier that load MgO is housed after abundant mixing, put into microwave oven, load onto thermometer and condenser.Under stirring atmospheric pressure state, carry out microwave irradiation, power 600W, be warming up to 90 DEG C, and insulation backflow 2h.React complete, reaction terminates rear cool to room temperature, and obtain reaction solution, then air distillation goes out solvent toluene, filters out catalyzer triphenyl phosphorus, and then reaction solution distills out product cinnamaldehyde diethylacetal further across scraper-type molecular distillation apparatus.Product purity 99%, productive rate 92.9%.
Example 5
Triphenyl phosphorus 5g, toluene 91g, bromo-1, the 1-diethoxyethane 0.3mol of phenyl aldehyde 0.3mol and 2-are joined in Florence flask, fully pours into after mixing and load Na is housed
3pO
4macroporous resin carrier tubular reactor in, put into microwave oven, load onto thermometer and condenser.Under stirring atmospheric pressure state, carry out microwave irradiation, power 500W, be warming up to 90 DEG C, and insulation backflow 1h.React complete, reaction terminates rear cool to room temperature, and obtain reaction solution, then air distillation goes out solvent toluene, filters out catalyzer triphenyl phosphorus, and then reaction solution distills out product cinnamaldehyde diethylacetal further across scraper-type molecular distillation apparatus.Product purity 99%, productive rate 92.6%.
Comparative example 1
Take sodium pyrosulfate as catalyzer, enanthaldehyde and ethanol are that enanthal diethyl acetal prepared by raw material.
In the 250ml four-hole boiling flask being configured with mechanical stirring, constant pressure funnel and reflux condensing tube (above having moisture eliminator), add 34ml ethanol and 0.16g sodium pyrosulfate, heated and stirred, temperature controlled at about 68 DEG C and slowly drip 10ml enanthaldehyde, the color of reaction solution has and colourlessly to turn yellow gradually, deep yellow is gradually become along with the growth of time, heated and stirred reaction 15h, generate liquid and be neutralized to neutrality through anhydrous sodium carbonate, filter, with anhydrous sodium sulfate drying, refilter, filtrate decompression is distilled, and collects the cut of 76.8 DEG C/0.4kPa.Productive rate is 85%, and in reaction, the mol ratio of enanthaldehyde and ethanol is 1:8, reaction times about 15h.
Can find out from comparative example 1, the reaction times is long, reaches about 15h.The mol ratio of raw material enanthaldehyde and ethanol is 1:8, and ethanol is greatly excessive, and power consumption feed consumption, overall economic benefit is not high.
Comparative example 2
Take tosic acid as catalyzer, citral and triethyl orthoformate are that citral diethyl acetal prepared by raw material.
Thermometer is being housed, 30ml dehydrated alcohol is added in the flask of dropping funnel, 17.6 (0.12mol) triethyl orthoformate, 0.1g p-methyl benzenesulfonic acid, 0.1g phase-transfer catalyst, induction stirring, 0-5 DEG C is cooled to ice-water bath, drip 15.7 (0.1mol) citric acid (97%), along with the dropping of citric acid, reaction solution becomes red-purple from yellow, 0 ~ 5 DEG C is continued stirring reaction 1h, neutralize with 0.1g solid sodium hydroxide, reaction solution becomes faint yellow from red-purple, dry with Anhydrous potassium carbonate, after air distillation goes out low boiling point solvent, underpressure distillation, collect 114-118 DEG C/1.33kPa cut.Productive rate is 65%, and it is necessary for entering phase-transfer catalyst in reaction, otherwise productive rate is less than 50%.
Can find out from comparative example 2, adopt dehydrated alcohol to make solvent, otherwise triethyl orthoformate easily be hydrolyzed, and causes productive rate to reduce.Acid is catalyzer, and subsequent disposal will neutralize, and catalyzer is liquid acid, etching apparatus.Also phase-transfer catalyst will be added, otherwise productive rate is less than 50%.Phase-transfer catalyst is most important.
The present invention is compared with above-mentioned comparative example, and bromo-1, the 1-diethoxyethane of 2-that raw material adopts low price to be easy to get, catalyzer is solid catalyst, is easy to removing, and reaction conditions is gentle simple, and can be continuously produced, product yield is high.
Claims (1)
1. a preparation method for cinnamaldehyde diethylacetal, reaction formula is as follows:
By triphenyl phosphorus 10g, toluene 111g, phenyl aldehyde 0.4mol and 2-bromo-1,1-diethoxyethane 0.35mol joins in Florence flask, pour in the tubular reactor of the macroporous resin carrier that load KOH is housed after abundant mixing, put into microwave oven, load onto thermometer and condenser; Under stirring atmospheric pressure state, carry out microwave irradiation, power 550W, be warming up to 88 DEG C, and insulation backflow 1.5h; React complete, reaction terminates rear cool to room temperature, and obtain reaction solution, then air distillation goes out solvent toluene, filters out catalyzer triphenylphosphine, and then reaction solution distills out product cinnamaldehyde diethylacetal further across scraper-type molecular distillation apparatus.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740145A (en) * | 2005-07-29 | 2006-03-01 | 浙江大学 | Cinnamide compound synthesizing process |
| CN102311320A (en) * | 2011-06-30 | 2012-01-11 | 绍兴文理学院 | Method for preparing 2,6,10-trimethyl-1,1-dialkoxyl-3,5,9-undecatriene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740145A (en) * | 2005-07-29 | 2006-03-01 | 浙江大学 | Cinnamide compound synthesizing process |
| CN102311320A (en) * | 2011-06-30 | 2012-01-11 | 绍兴文理学院 | Method for preparing 2,6,10-trimethyl-1,1-dialkoxyl-3,5,9-undecatriene |
Non-Patent Citations (3)
| Title |
|---|
| Direct synthesis of 3-arylpropionic acids by tetraphosphine/palladium catalyzed Heck reactions of aryl halides with acrolein ethylene acetal;M. Lemhadri et al.;《Tetrahedron》;20041006;第60卷(第50期);11533-11540 * |
| α,β-不饱和酮及酯的简易合成法;郑钦国等;《杭州大学学报》;19890430;第16卷(第2期);230-231 * |
| 微波干法合成4-(3-吡啶基)-3-丁烯-2-酮的研究;夏凉等;《精细与专用化学品》;20060121;第14卷(第2期);12-13 * |
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