CN102633638A - Benzyl cinnamate preparation method - Google Patents
Benzyl cinnamate preparation method Download PDFInfo
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- CN102633638A CN102633638A CN2012100776564A CN201210077656A CN102633638A CN 102633638 A CN102633638 A CN 102633638A CN 2012100776564 A CN2012100776564 A CN 2012100776564A CN 201210077656 A CN201210077656 A CN 201210077656A CN 102633638 A CN102633638 A CN 102633638A
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- phenyl aldehyde
- jasmal
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Abstract
The invention provides a benzyl cinnamate preparation method, which includes: mixing dimethyl sulfoxide serving as solvent, NaOH-K2CO3 mixed aqueous solution serving as catalyst and tetrabutylammonium bromide serving as phase transfer catalyst with benzyl acetate, slowly dropwise adding benzaldehyde while stirring, and leading the temperature to be kept lower than 5 DEG C; after dropwise adding, keeping the temperature at 25 DEG C-30 DEG C for 3-5h, slowly dropwise adding sulfuric acid with the mass percent of 10%, and regulating reaction liquid pH (potential of hydrogen) between 6.8 and 7.2; and filtering the solution, recovering the solvent and excessive benzaldehyde by means of pressure reduction, rinsing and drying obtained solid to obtain a crude product, and recrystallizing with absolute ethyl alcohol so that benzyl cinnamate is obtained. The benzyl cinnamate is prepared by the method through one-step reaction, and yield is high. The benzyl cinnamate preparation method is simple, low in raw material cost, convenient in operation, high in yield, free from environmental pollution and green.
Description
Technical field
The present invention relates to a kind of preparation method of organic synthesis intermediate, specifically be meant a kind of preparation method of cinnamein.
Background technology
Cinnamein is called the beta-phenyl benzyl acrylate again.Cinnamein is natural to be present in the fragrant ester of Peru and tolu balsam and st-yrax, the styrax oil, also is the staple of fragrant ester.Cinnamein mainly is used in the preparation essence as fixative, as in the type essence grane ambra in the Orient as fixative, also make the blending raw material of soap with, makeup and edible fruit flavour type essence.
The method of synthesizing cinnamic acid benzyl ester is a lot, and compound method commonly used at present has:
1, be raw material with Sodium.beta.-phenylacrylate (potassium) with Benzyl Chloride, triethylamine, quadrol, pyridine, N, dinethylformamide are that catalyzer generation substitution reaction makes; Because organic amine catalyzer cost is high; Toxicity is big, and environmental pollution is serious, and catalyst levels is big; Long reaction time, economic benefit is relatively poor;
2, be raw material with styracin and benzylalcohol, the vitriol oil is that catalyzer generation esterification makes, because vitriol oil poor selectivity; There are side reactions such as esterification, oxidation, dehydration to take place simultaneously; Yield is low, brings very big difficulty for simultaneously the refining recovery with raw material of product, and severe corrosion equipment; Replace the vitriol oil with solid-carrying heteropolyacid salt, inorganic acid salt or Lewis acid, though production technique has certain improvement, but still exist Preparation of Catalyst complicated, long reaction time, the high deficiency of cost;
3, be raw material with jasmal and phenyl aldehyde, get, but traditional Claisen-Schmidt condensation reaction condition is to be solvent with the absolute ethyl alcohol through condensation reaction; 10%NaOH is a catalyzer; No phase-transfer catalyst, synthesizing cinnamic acid benzyl ester according to said method, long reaction time; By product is many, and normal yield is about 60%;
4, react with aceticanhydride or propanedioic acid with phenyl aldehyde earlier and make styracin, obtain two of cinnamein with benzylalcohol or Benzyl Chloride esterification again and go on foot synthesis methods, this technological operation step is many; Working condition is poor; Product yield is low, and cost is high and seriously polluted, does not meet the green production requirement;
5, in above-mentioned reaction, when being catalyzer, introduce microwave irradiation technology again with phase-transfer catalyst or solid acid; Reaction times is shortened; Yield makes moderate progress, but since microwave technology to be applied to organic synthesis still under test, that is that all right is ripe in the production technology industriallization; And apparatus expensive, further research and exploration await.
Summary of the invention
The objective of the invention is to provides the method for the cinnamein that a kind of cost is low, reaction conditions is gentle, easy and simple to handle to the deficiency that exists in the prior art.
For realizing the foregoing invention purpose, the preparation method of cinnamein provided by the present invention may further comprise the steps:
1) with the methyl-sulphoxide is solvent, NaOH-K
2CO
3Mixed aqueous solution is that catalyzer, Tetrabutyl amonium bromide are that phase-transfer catalyst mixes with jasmal, slowly drips phenyl aldehyde more while stirring, and temperature is remained on below 5 ℃;
2) drip and finish, remain on 25 ℃～30 ℃ reaction 3～5h after, slowly drip mass percent and be 10% sulfuric acid, make reaction solution pH regulation and control between 6.8～7.2;
3) above-mentioned solution is filtered, filtrating is through decompression and solvent recovery and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein.
Among the present invention, the mol ratio of said phenyl aldehyde and jasmal is 1.15～1.5: 1.
Among the present invention, the consumption of said methyl-sulphoxide (DMSO) is 10～65% of a reactant total mass.
Among the present invention, said catalyst n aOH-K
2CO
3In the mixed aqueous solution, the mass percent of NaOH is 5%, K
2CO
3Mass percent be 15%.
Among the present invention, said catalyst n aOH-K
2CO
3The consumption of mixed aqueous solution is 15～75% of a reactant total mass.
Among the present invention, the consumption of said phase-transfer catalyst Tetrabutyl amonium bromide (TBAB) is 1.5～12.5% of a reactant total mass.
Cinnamein building-up reactions formula of the present invention is following:
The present invention is to be raw material with phenyl aldehyde and jasmal, and DMSO is solvent, NaOH-K
2CO
3Mixed aqueous solution is that catalyzer, TBAB are phase-transfer catalyst, forms through Claisen-Schmidt reaction condensation.The inventive method makes cinnamein through single step reaction, and productive rate is about 80% (in jasmal).
Beneficial effect of the present invention: the present invention is relative, and prior art has the following advantages:
1, the DMSO that adopts of the present invention is the non-proton type solvent of a kind of strong polar, and it can the solubilizing reaction thing, does not have the effect of hydrogen bond again with OH-, more helps the exposure of OH-, and is stronger to the promoter action of reaction; And, the stronger DMSO of polarity can also with the complexing of proton type aqueous solvent, weaken its passivation to OH-; Make solvent than absolute ethyl alcohol, productive rate increases greatly.
2, the concentration of NaOH is excessive in reaction, produces by product and increases, if low excessively, reaction is difficult to again carry out, and the present invention adopts 5%NaOH-15%K
2CO
3Mixed aqueous solution is a catalyzer, has both guaranteed alkaline requirement, has reduced by product again; The adding of phase-transfer catalyst TBAB impels catalyzer to get into organic phase and gives full play to katalysis, has accelerated speed of response greatly, improves product yield.
3, the suitably excessive raising that helps reaction yield of phenyl aldehyde, and the excessive productive rate of jasmal descends on the contrary; Because excessive jasmal is prone to carry out the Claisen ester condensation reaction under the highly basic effect, produce a large amount of by products, product yield reduced, so the phenyl aldehyde that the present invention has adopted is the overfeeding method slightly.
4, the overall advantage of this inventive method is that its industrial applications is worth, and raw materials cost is cheap, and catalyst activity is high; Reaction conditions is gentle, and is easy to operate, stable and reliable product quality; The cinnamein yield of producing is high, and environmentally safe is a kind of compound method of green.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Following examples only are to be used for further specific descriptions of the present invention, rather than are used for the qualification to requirement protection domain of the present invention.
Embodiment 1
In three-necked bottle, add the DMSO of 1.4g, the 5%NaOH-15%K of 2.0g
2CO
3Mixed aqueous solution, the jasmal of the TBAB of 0.2g and 7.5g (0.05mol).Under ice-water bath, slowly drip the phenyl aldehyde of 6.1g (0.0575mol) while stirring, temperature is remained on below 5 ℃.Drip to finish, remain on 25 ℃～30 ℃ reaction 3h after, slowly dripping mass percent is 10% sulfuric acid, makes reaction solution pH regulation and control between 6.8～7.2.Filter, filtrating is through reclaim under reduced pressure DMSO and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein finished product 9.3g, 34.7 ℃ of fusing points, and purity is 98.4%, yield is 76.8% (in jasmal).
Embodiment 2
In three-necked bottle, add the DMSO of 4.7g, the 5%NaOH-15%K of 5.8g
2CO
3Mixed aqueous solution, the jasmal of the TBAB of 0.8g and 15.0g (0.1mol).Under ice-water bath, slowly drip the phenyl aldehyde of 12.7g (0.12mol) while stirring, temperature is remained on below 5 ℃.Drip to finish, remain on 25 ℃～30 ℃ reaction 3.5h after, slowly dripping mass percent is 10% sulfuric acid, makes reaction solution pH regulation and control between 6.8～7.2.Filter, filtrating is through reclaim under reduced pressure DMSO and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein finished product 20.2g, and 34.8 ℃ of purity of fusing point are 98.8%, and yield is 83.8% (in jasmal).
Embodiment 3
In three-necked bottle, add the DMSO of 11.3g, the 5%NaOH-15%K of 14.2g
2CO
3Mixed aqueous solution, the jasmal of the TBAB of 2.1g and 22.5g (0.15mol).Under ice-water bath, slowly drip the phenyl aldehyde of 20.7g (0.195mol) while stirring, temperature is remained on below 5 ℃.Drip to finish, remain on 25 ℃～30 ℃ reaction 4h after, slowly dripping mass percent is 10% sulfuric acid, makes reaction solution pH regulation and control between 6.8～7.2.Filter, filtrating is through reclaim under reduced pressure DMSO and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein finished product 30.8g, 35.0 ℃ of fusing points, and purity is 99.5%, yield is 85.7% (in jasmal).
Embodiment 4
In three-necked bottle, add the DMSO of 23.4g, the 5%NaOH-15%K of 29.3g
2CO
3Mixed aqueous solution, the jasmal of the TBAB of 4.7g and 30.0g (0.2mol).Under ice-water bath, slowly drip 29.7g (0.28mol) phenyl aldehyde while stirring, temperature is remained on below 5 ℃.Drip to finish, remain on 25 ℃～30 ℃ reaction 4.5h after, slowly dripping mass percent is 10% sulfuric acid, makes reaction solution pH regulation and control between 6.8～7.2.Filter, filtrating is through reclaim under reduced pressure DMSO and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein finished product 40.1g, 34.9 ℃ of fusing points, and purity is 99.1%, yield is 83.4% (in jasmal).
Embodiment 5
In three-necked bottle, add the DMSO of 50.2g, the 5%NaOH-15%K of 58.0g
2CO
3Mixed aqueous solution, the jasmal of the TBAB of 9.7g and 37.5g (0.25mol).Under ice-water bath, slowly drip 39.8g (0.375mol) phenyl aldehyde while stirring, temperature is remained on below 5 ℃.Drip to finish, remain on 25 ℃～30 ℃ reaction 5h after, slowly dripping mass percent is 10% sulfuric acid, makes reaction solution pH regulation and control between 6.8～7.2.Filter, filtrating is through reclaim under reduced pressure DMSO and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein finished product 48.4g, 34.8 ℃ of fusing points, and purity is 98.6%, yield is 80.1% (in jasmal).
Embodiment 6
In three-necked bottle, add the DMSO of 22.7g, the 5%NaOH-15%K of 28.4g
2CO
3Mixed aqueous solution, the jasmal of the TBAB of 4.3g and 45.1g (0.3mol).Under ice-water bath, slowly drip the phenyl aldehyde of 41.4g (0.39mol) while stirring, temperature is remained on below 5 ℃.Drip to finish, remain on 25 ℃～30 ℃ reaction 4h after, slowly dripping mass percent is 10% sulfuric acid, makes reaction solution pH regulation and control between 6.8～7.2.Filter, filtrating is through reclaim under reduced pressure DMSO and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein finished product 61.8g, 34.9 ℃ of fusing points, and purity is 99.4%, yield is 85.9% (in jasmal).
Comparative Examples 1
In three-necked bottle, add the 22.7g absolute ethyl alcohol, the 28.4g mass percent is a 10%NaOH solution, 45.1g (0.3mol) jasmal.Under ice-water bath, slowly drip 41.4g (0.39mol) phenyl aldehyde while stirring, temperature is remained on below 5 ℃.Drip to finish, remain on 25 ℃～30 ℃ thermotonus 12h after, slowly dripping mass percent is 10% sulfuric acid, makes reaction solution pH regulation and control between 6.8～7.2.Filter, filtrating is through decompression recycling ethanol and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein finished product 44.9g, 34.7 ℃ of fusing points, and purity is 98.7%, yield is 62.0% (in jasmal).
Comparative Examples 1 is traditional Claisen-Schmidt condensation reaction, is solvent with the absolute ethyl alcohol, and 10%NaOH is catalyzer (no phase-transfer catalyst), synthesizing cinnamic acid benzyl ester according to said method, and long reaction time, by product is many, and normal yield is about 60%.
Claims (6)
1. the preparation method of a cinnamein may further comprise the steps:
1) with the methyl-sulphoxide is solvent, NaOH-K
2CO
3Mixed aqueous solution is that catalyzer, Tetrabutyl amonium bromide are that phase-transfer catalyst mixes with jasmal, slowly drips phenyl aldehyde more while stirring, and temperature is remained on below 5 ℃;
2) drip and finish, remain on 25 ℃～30 ℃ reaction 3～5h after, slowly drip mass percent and be 10% sulfuric acid, make reaction solution pH regulation and control between 6.8～7.2;
3) above-mentioned solution is filtered, filtrating is through decompression and solvent recovery and excessive phenyl aldehyde, and the gained solid is used the absolute ethyl alcohol recrystallization again through washing, the dry bullion that gets, and gets cinnamein.
2. method according to claim 1 is characterized in that: the mol ratio of said phenyl aldehyde and jasmal is 1.15～1.5: 1.
3. method according to claim 1 is characterized in that: the consumption of said methyl-sulphoxide is 10～65% of a reactant total mass.
4. method according to claim 1 is characterized in that: said catalyst n aOH-K
2CO
3In the mixed aqueous solution, the mass percent of NaOH is 5%, K
2CO
3Mass percent be 15%.
5. method according to claim 1 is characterized in that: said catalyst n aOH-K
2CO
3The consumption of mixed aqueous solution is 15～75% of a reactant total mass.
6. method according to claim 1 is characterized in that: the consumption of said phase-transfer catalyst Tetrabutyl amonium bromide is 1.5～12.5% of a reactant total mass.
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| CN201210077656.4A CN102633638B (en) | 2012-03-22 | 2012-03-22 | Benzyl cinnamate preparation method |
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| CN201210077656.4A CN102633638B (en) | 2012-03-22 | 2012-03-22 | Benzyl cinnamate preparation method |
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| CN102633638B CN102633638B (en) | 2014-04-02 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618698A (en) * | 1984-06-16 | 1986-10-21 | Bayer Aktiengesellschaft | Process for the preparation of a mixture of an optionally substituted cinnamic acid ester and an optionally substituted β-alkoxy-β-phenyl-propionic acid ester, and a process for the preparation of optionally substituted cinnamic acid |
| CN101323567A (en) * | 2008-07-30 | 2008-12-17 | 华中师范大学 | Process for preparing cinnamate and derivates thereof |
-
2012
- 2012-03-22 CN CN201210077656.4A patent/CN102633638B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618698A (en) * | 1984-06-16 | 1986-10-21 | Bayer Aktiengesellschaft | Process for the preparation of a mixture of an optionally substituted cinnamic acid ester and an optionally substituted β-alkoxy-β-phenyl-propionic acid ester, and a process for the preparation of optionally substituted cinnamic acid |
| CN101323567A (en) * | 2008-07-30 | 2008-12-17 | 华中师范大学 | Process for preparing cinnamate and derivates thereof |
Non-Patent Citations (3)
| Title |
|---|
| DHEVALAPALLY B.RAMACHARY等: "Direct organocatalytic in situ generation of novel push-pull dienamines: application in tandem Claisen-Schmidt/iso -aromatization reactions", 《TETRAHEDRON LETTERS》 * |
| 照那斯图等: "相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究", 《化学研究与应用》 * |
| 范成有: "《香料及其应用》", 30 September 1990, 化学工业出版社 * |
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