CN103626641A - Preparation method for alpha-amyl cinnamic aldehyde dimethyl acetal - Google Patents
Preparation method for alpha-amyl cinnamic aldehyde dimethyl acetal Download PDFInfo
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- CN103626641A CN103626641A CN201310646178.9A CN201310646178A CN103626641A CN 103626641 A CN103626641 A CN 103626641A CN 201310646178 A CN201310646178 A CN 201310646178A CN 103626641 A CN103626641 A CN 103626641A
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Abstract
The invention discloses a preparation method for alpha-amyl cinnamic aldehyde dimethyl acetal. The preparation method comprises the following steps: adding alpha-amyl cinnamaldehyde and cyclohexane water-carrying agent to a reaction kettle in a vacuum intake manner; feeding nitrogen to displace vacuum; adding methanol and a catalyst; controlling the temperature of the reaction kettle to be 80-120 DEG C; 4 hours after the reaction, washing; layering by standing; transferring the upper oil layer of the reaction product to a fractionation kettle; recycling methanol which does not react at the normal pressure; under the condition that the pressure is 1000-3000 Pa, the temperature of the reaction kettle is 150-180 DEG C, and the reflux ratio is (2:1)-(1:10), fractionating out a crude alpha-amyl cinnamic aldehyde dimethyl acetal product. According to the invention, the alpha-amyl cinnamic aldehyde dimethyl acetal is synthetized in one step; the reaction conditions are mild; the purification treatment of the product is easy; the phenomena of equipment corrosion and generation of a great amount of waste acid liquid, caused when traditional concentrated acids such as sulfuric acid and hydrochloric acid are used as catalysts, are avoided; the purity of the end product reaches above 97%; the product has lasting fragrance, and is pure and mild.
Description
Technical field
The present invention relates to the preparation method of a kind of organic synthesis spices of technical field of fine chemical synthesis, be specifically related to a kind of preparation method of α amyl cinnamic aldehyde dimethylacetal.
Background technology
α amyl cinnamic aldehyde dimethylacetal, 2-(dimethoxy methyl)-1-heptenyl benzene, CAS 91-87-2, relative density (25 ℃) 0.955, refractive index (20 ℃) 1.508, water insoluble, almost be dissolved in ethanol and propylene glycol 300 ℃ of boiling points, 92 ℃ of flash-points, colourless to pale yellow oily liquid body, be soft fresh flowers fragrance.α amyl cinnamic aldehyde dimethylacetal can be used in daily chemical essence formula, is the good merchantable brand of modulation jasmine fragrance serial cosmetics essence.Its chemical property in alkaline medium is stable compared with α amyl cinnamic aldehyde, be difficult for oxidized, therefore be suitable for very much in soap compound formula, consumption can reach 10%, has non-discoloring advantage, in addition, because coordination performance is good, be widely used in corrective incense agent and the blender of α amyl cinnamic aldehyde, also can be used as the fixative of jasmine type essence, prepare other bouquet type compositions.
α amyl cinnamic aldehyde dimethylacetal has gentle Flower of Arabian Jasmine fragrance, and lasting is lasting, for trans and mixture cis-isomeride, by FEMA, regarded as GRAS, it is edible that FEMA numbers the approval of 2062 ，Bing Jing food and drug administrations (FDA), and the suggestion consumption in food is (FDA § 172.515,2000, mg/kg): soft drink 0.80; Cold drink 1.5～2.0; Candy 2.0; Bakery product 2.6.That China < < foodstuff additive are used hygienic standard (GB2760-2011) > > regulation to allow the food spice using.Council of Europe also by amyl group cinnamic aldehyde dimethyl acetal when consumption is 2mg/kg, list in and can add in food and in the harmless synthetic flavour material table of HUMAN HEALTH.
Traditional α amyl cinnamic aldehyde dimethylacetal synthetic method by α-Ji cinnamic aldehyde and anhydrous methanol at HCl or H
2sO
4condensation under catalysis and preparing, is used concentrated acid as catalyzer, due to concentrated acid corrosion production unit, need to carry out alkali cleaning, water washing process, its postprocessing working procedures is complicated, produces a large amount of acid waste liquids, contaminate environment, and side reaction is many, product colour is darker, reduces yield when affecting quality product.
Summary of the invention
Object of the present invention is exactly the environmental pollution existing for prior art, the restriction of simplifying aftertreatment technology and equipment corrosion, proposes a kind of environment green catalyst silica gel load zirconium sulfate (Zr (SO4)
2/ SiO
2) even load type solid acid is as preparing the method for α amyl cinnamic aldehyde dimethylacetal under the good katalysis of aldolization.
The preparation method of α amyl cinnamic aldehyde dimethylacetal of the present invention, its step comprises:
A) adopt vacuum intake mode to add α amyl cinnamic aldehyde in reactor, band aqua hexanaphthene, with the charging capacity of aqua hexanaphthene, be total charging capacity 1 ~ 5%, after charging finishes, pass into nitrogen replacement vacuum, add methyl alcohol and catalyzer, unlatching stirrer mixes, the mol ratio of methyl alcohol and α amyl cinnamic aldehyde is 1.5 ~ 3.0:1.0, and catalyst levels is total charging capacity 1 ~ 5%, described
Catalyzer is a kind of in silica gel load zirconium sulfate, silica gel load ferric sulfate, silica gel load cesium sulfate, silica gel load cerous sulfate;
B) control 80 ~ 120 ℃ of temperature of reaction kettle;
C), after 4 hours reaction times, gas chromatographic detection is carried out in sampling, when α amyl cinnamic aldehyde content is less than 2%, and cooling termination reaction;
D) after reaction finishes, wash stratification;
E) by d) oil reservoir is transferred in fractionation still in reaction product in step reactor, rises still temperature, controls 55～75 ℃ of temperature, and normal pressure reclaims unreacted methyl alcohol completely;
F) after Methanol Recovery finishes, at pressure 1000 ~ 3000Pa, 150 ~ 180 ℃ of still temperature, under the condition of reflux ratio 2:1 ~ 1:10, fractionation α amyl cinnamic aldehyde dimethylacetal crude product, when tower top temperature declines, during zero discharge, cooling presses still residual.
The reactor of above-mentioned a) step is the enamel reaction still of 500L ~ 2500L.
Above-mentioned e) separation column of step is filled with CY700 type filler.
Technique scheme adopts α amyl cinnamic aldehyde and methyl alcohol under solid acid catalyst exists, one-step synthesis α amyl cinnamic aldehyde dimethylacetal.Adopt normal pressure to reclaim organic solvent, reduced the waste of methyl alcohol, increased the number of times that Methanol Recovery is applied mechanically simultaneously.The inventive method reaction conditions is gentle, product is easy to purification process, and equipment corrosion and the generation of spent acid solutions in a large number of having avoided traditional concentrated acids such as sulfuric acid, hydrochloric acid to bring as catalyzer, the finished product purity reaches more than 97% simultaneously, control α amyl cinnamic aldehyde content in 3%, reduce to greatest extent the content of impurity, improve the purity of α amyl cinnamic aldehyde dimethylacetal, thereby make product fragrance lasting, pure soft.
Accompanying drawing explanation
Fig. 1 is the process device figure of the inventive method.
Embodiment
As seen from Figure 1, the process unit that the preparation method of α amyl cinnamic aldehyde dimethylacetal of the present invention adopts comprises vacuum intaking device 1, header tank 2, enamel reaction still 3, chemical pump 4, separation column 5, fractionation still 51, spiral-plate heat exchanger 6, gas-liquid separator 7, vacuum receiving tank 8, finished product is kept in tank 9, methyl alcohol is kept in Receiving bin 10, anti-explosion membrane pump 11, vacuum intaking device 1 is connected with enamel reaction still 3 by tetrafluoro flexible pipe, header tank 2 is connected with enamel reaction still 3 by pipeline, the bottom of enamel reaction still 3 is connected with fractionation still 5 with the chemical pump 4 being arranged on this pipeline by pipeline, separation column 51 is installed on fractionation still 5, the tower top of separation column 51 passes through pipeline and is connected with gas-liquid separator 7 through spiral-plate heat exchanger 6, gas-liquid separator 7 is connected and is connected with header tank 2 through anti-explosion membrane pump 11 by the temporary Receiving bin 10 of pipeline and methyl alcohol, gas-liquid separator 7 is connected through the temporary tank 9 of vacuum receiving tank 8 and finished product.
Embodiment 1
A) adopt vacuum intaking device 1 to add α amyl cinnamic aldehyde 200 ㎏ in 500L enamel reaction still 3, band aqua hexanaphthene 10 ㎏, after charging finishes, pass into nitrogen replacement vacuum, from header tank 2, add methyl alcohol 80 ㎏, from reactor hand hole, add catalyzer silica gel load zirconium sulfate 10 ㎏, open stirrer and mix;
B) open steam valve, enamel reaction still 3 is heated up, control 85 ~ 90 ℃ of temperature of reaction;
C), after 4 hours reaction times, gas chromatographic detection is carried out in sampling, when α amyl cinnamic aldehyde content is less than 2%, and cooling termination reaction;
D) after reaction finishes, add 75 ㎏ clear water, wash, stratification, after 2 hours, is observed and is separated lower layer of water by visor;
E) by d) oil reservoir is transferred in fractionation still 5 in reaction product in step enamel reaction still 3, rises still temperature, controls 65 ± 5 ℃ of temperature, and normal pressure reclaims unreacted methyl alcohol completely, when separation column 51 tower top temperatures decline, during tower top zero discharge, reclaims Methanol Recovery and finishes; The methyl alcohol reclaiming proceeds to header tank 2, as feeding intake of lower batch reaction;
F) after Methanol Recovery finishes, open vacuum, at pressure 1333Pa, 165 ~ 170 ℃ of still temperature, under the condition of reflux ratio 1:1 ~ 1:2, fractionation α amyl cinnamic aldehyde dimethylacetal crude product, when tower top temperature declines, during zero discharge, cooling presses still residual.α amyl cinnamic aldehyde dimethylacetal crude product obtains finished product after fractionation, made product is transparent liquid, there is gentle Flower of Arabian Jasmine fragrance, through gas chromatographic analysis product purity, can reach 97.8%(cis-trans-isomer sum), α amyl cinnamic aldehyde content is 1.5%, detecting refractive index (20 ℃) is 1.508, and relative density (25 ℃) is 0.956.
A) adopt vacuum intake mode to add α amyl cinnamic aldehyde 240 ㎏ in 500L enamel reaction still, band aqua hexanaphthene 12 ㎏, after charging finishes, pass into nitrogen replacement vacuum, from header tank, add methyl alcohol 100 ㎏, from reactor hand hole, add catalyzer silica gel load ferric sulfate 12 ㎏, open stirrer and mix;
B) open steam valve, reactor is heated up, control 85 ~ 90 ℃ of temperature of reaction;
C), after 4 hours reaction times, gas chromatographic detection is carried out in sampling, when α amyl cinnamic aldehyde content is less than 2%, and cooling termination reaction;
D) after reaction finishes, add clear water 80 ㎏, wash, stratification, after 2 hours, is observed and is separated lower layer of water by visor;
E) by d) oil reservoir is transferred in fractionation still in reaction product in step reactor, rises still temperature, controls 65 ± 5 ℃ of temperature, and normal pressure reclaims unreacted methyl alcohol completely, when tower top temperature declines, during tower top zero discharge, reclaims Methanol Recovery and finishes; The methyl alcohol reclaiming proceeds to methyl alcohol header tank, as feeding intake of lower batch reaction;
F) after Methanol Recovery finishes, open vacuum, at pressure 1333Pa, 165 ~ 170 ℃ of still temperature, under the condition of reflux ratio 1:1 ~ 1:2, fractionation α amyl cinnamic aldehyde dimethylacetal crude product, when tower top temperature declines, during zero discharge, cooling presses still residual.α amyl cinnamic aldehyde dimethylacetal crude product obtains finished product after fractionation, made product is transparent liquid, there is gentle Flower of Arabian Jasmine fragrance, through gas chromatographic analysis product purity, can reach 98.0%(cis-trans-isomer sum), α amyl cinnamic aldehyde content is 1.4%, detecting refractive index (20 ℃) is 1.508, and relative density (25 ℃) is 0.956.
Embodiment 3
A) adopt vacuum intake mode to add α amyl cinnamic aldehyde 1200 ㎏ in 2500L enamel reaction still, band aqua hexanaphthene 60 ㎏, after charging finishes, pass into nitrogen replacement vacuum, from header tank, add methyl alcohol 500 ㎏, from reactor hand hole, add catalyzer silica gel load ferric sulfate 55 ㎏, open stirrer and mix;
B) open steam valve, reactor is heated up, control 85 ~ 90 ℃ of temperature of reaction;
C), after 4 hours reaction times, gas chromatographic detection is carried out in sampling, when α amyl cinnamic aldehyde content is less than 2%, and cooling termination reaction;
D) after reaction finishes, add clear water 300 ㎏, wash, stratification, after 2 hours, is observed and is separated lower layer of water by visor;
E) by d) oil reservoir is transferred in fractionation still in reaction product in step reactor, rises still temperature, controls 65 ± 5 ℃ of temperature, and normal pressure reclaims unreacted methyl alcohol completely, when tower top temperature declines, during tower top zero discharge, reclaims Methanol Recovery and finishes; The methyl alcohol reclaiming proceeds to methyl alcohol header tank, as feeding intake of lower batch reaction;
F) after Methanol Recovery finishes, open vacuum, at pressure 1333Pa, 165 ~ 170 ℃ of still temperature, under the condition of reflux ratio 1:1 ~ 1:2, fractionation α amyl cinnamic aldehyde dimethylacetal crude product, when tower top temperature declines, during zero discharge, cooling presses still residual.α amyl cinnamic aldehyde dimethylacetal crude product obtains finished product after fractionation, made product is transparent liquid, there is gentle Flower of Arabian Jasmine fragrance, through gas chromatographic analysis product purity, can reach 97.6%(cis-trans-isomer sum), α amyl cinnamic aldehyde content is 1.5%, detecting refractive index (20 ℃) is 1.508, and relative density (25 ℃) is 0.956.
Embodiment 4
A) adopt vacuum intake mode to add α amyl cinnamic aldehyde 1200 ㎏ in 2500L enamel reaction still, band aqua hexanaphthene 60 ㎏, after charging finishes, pass into nitrogen replacement vacuum, from header tank, add methyl alcohol 500 ㎏, from reactor hand hole, add catalyzer silica gel load cerous sulfate 55 ㎏, open stirrer and mix;
B) open steam valve, reactor is heated up, control 85 ~ 90 ℃ of temperature of reaction;
C), after 4 hours reaction times, gas chromatographic detection is carried out in sampling, when α amyl cinnamic aldehyde content is less than 2%, and cooling termination reaction;
D) after reaction finishes, add clear water 300 ㎏, wash, stratification, after 2 hours, is observed and is separated lower layer of water by visor;
E) by d) oil reservoir is transferred in fractionation still in reaction product in step reactor, rises still temperature, controls 65 ± 5 ℃ of temperature, and normal pressure reclaims unreacted methyl alcohol completely, when tower top temperature declines, during tower top zero discharge, reclaims Methanol Recovery and finishes; The methyl alcohol reclaiming proceeds to methyl alcohol header tank, as feeding intake of lower batch reaction;
F) after Methanol Recovery finishes, open vacuum, at pressure 1333Pa, 165 ~ 170 ℃ of still temperature, under the condition of reflux ratio 1:1 ~ 1:2, fractionation α amyl cinnamic aldehyde dimethylacetal crude product, when tower top temperature declines, during zero discharge, cooling presses still residual.α amyl cinnamic aldehyde dimethylacetal crude product obtains finished product after fractionation, made product is transparent liquid, there is gentle Flower of Arabian Jasmine fragrance, through gas chromatographic analysis product purity, can reach 97.9%(cis-trans-isomer sum), α amyl cinnamic aldehyde content is 1.3%, detecting refractive index (20 ℃) is 1.508, and relative density (25 ℃) is 0.956.
GC condition is: chromatographic column HP-5(30m x 0.32mm x 2.65um); Detector FID, 250 ℃ of temperature; Sample introduction: the about 0.2ul of sample size, splitting ratio 1:50,250 ℃ of injector temperatures; Carrier gas: N2, flow velocity 20L/min, presses 90kPa before post; Chromatogram furnace temperature: linear temperature program is from 120 ℃ to 220 ℃, 10 ℃/min of speed.
Claims (3)
1. a preparation method for α amyl cinnamic aldehyde dimethylacetal, its step comprises:
A) adopt vacuum intake mode to add α amyl cinnamic aldehyde in reactor, band aqua hexanaphthene, the charging capacity of hexanaphthene is 1 ~ 5% of total charging capacity, after charging finishes, pass into nitrogen replacement vacuum, add methyl alcohol, catalyzer, unlatching stirrer mixes, the mol ratio of methyl alcohol and α amyl cinnamic aldehyde is 1.5 ~ 3.0:1.0, catalyst levels is 1 ~ 5% of total charging capacity, and described catalyzer is a kind of in silica gel load zirconium sulfate, silica gel load ferric sulfate, silica gel load cesium sulfate, silica gel load cerous sulfate;
B) control 80 ~ 120 ℃ of temperature of reaction kettle;
C), after 4 hours reaction times, gas chromatographic detection is carried out in sampling, when α amyl cinnamic aldehyde content is less than 2%, and cooling termination reaction;
D) after reaction finishes, wash stratification;
E) by d) oil reservoir is transferred in fractionation still in reaction product in step reactor, rises still temperature, controls 55～75 ℃ of temperature, and normal pressure reclaims unreacted methyl alcohol completely;
F) after Methanol Recovery finishes, at pressure 1000 ~ 3000Pa, 150 ~ 180 ℃ of still temperature, under the condition of reflux ratio 2:1 ~ 1:10, fractionation α amyl cinnamic aldehyde dimethylacetal crude product, when tower top temperature declines, during zero discharge, cooling presses still residual.
2. preparation method according to claim 1, is characterized in that: the enamel reaction still that a) reactor of step is 500L ~ 2500L.
3. preparation method according to claim 1 and 2, is characterized in that: e) separation column of step is filled with CY700 type filler.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965024A (en) * | 2014-04-21 | 2014-08-06 | 安徽华业香料股份有限公司 | Preparation method for 1-dimethoxyoctane synthetic perfume |
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- 2013-12-06 CN CN201310646178.9A patent/CN103626641A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| OPDYKE,D.L.J.: "Monographs on fragrance raw materials. α-Amylcinnamic aldehyde dimethyl acetal", 《FOOD AND COSMETICS TOXICOLOGY》 * |
| 严楠等: "硅胶负载硫酸锆催化合成苯乙醛缩乙二醇", 《精细石油化工》 * |
| 熊斌等: "硅胶负载硫酸铈催化合成苯乙醛缩乙二醇", 《日用化学工业》 * |
| 许招会等: "硅胶负载硫酸铁催化合成肉桂醛乙二醇缩醛", 《林产化学和工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965024A (en) * | 2014-04-21 | 2014-08-06 | 安徽华业香料股份有限公司 | Preparation method for 1-dimethoxyoctane synthetic perfume |
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Application publication date: 20140312 |