CN101768510A - Method for improving trans-cinnamic aldehyde content in cassia oil - Google Patents
Method for improving trans-cinnamic aldehyde content in cassia oil Download PDFInfo
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- CN101768510A CN101768510A CN201010045639A CN201010045639A CN101768510A CN 101768510 A CN101768510 A CN 101768510A CN 201010045639 A CN201010045639 A CN 201010045639A CN 201010045639 A CN201010045639 A CN 201010045639A CN 101768510 A CN101768510 A CN 101768510A
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Abstract
The invention discloses a method for improving trans-cinnamic aldehyde content in cassia oil. The method takes cassia oil as the raw material, reduces o-methoxy trans-cinnamic aldehyde and cinnamyl acetate in the cassia oil by phonochemical reaction and acid-catalyzed hydrolysis, and improves the trans-cinnamic aldehyde content. The invention is characterized in that firstly, the method realizes short treatment time and low temperature and saves energy; secondly, the phosphoric acid solution used in the method can be recycled, avoiding waste water pollution; thirdly, the method can improve the trans-cinnamic aldehyde content by more than 10 percent when being used to treat the cassia oil with higher content of o-methoxy trans-cinnamic aldehyde and cinnamyl acetate.
Description
Technical field
The present invention relates to a kind of method that improves trans-cinnamic aldehyde content in cassia oil.
Background technology
Chinese cassia tree is famous and precious medicine food dual purpose plant, is widely used in medicine, food and chemical industry.The cinnamomic product mainly contains cassia bark and cinnamon essential oil two big classes.China is maximum in the world Oleum Cinnamomi production and export State, and wherein the Oleum Cinnamomi export volume in Guangdong and Guangxi accounts for more than 80% of Gross World Product.The height of trans-cinnamic aldehyde content is an important indicator of estimating the Oleum Cinnamomi quality.Different places of production Oleum Cinnamomi chemical ingredients is difference to some extent, and the content of trans-Cinnamylaldehyde fluctuates between 50-95%, and is better with the Oleum Cinnamomi quality that produce in Guangxi.(it is far away etc. that Xiao Kaijun, Li Lin, Guo offer sacriffices to the gods or the spirits of the dead, the exploitation of cinnamomic utilization and natural essential oil, Chinese oil, 2000,25 (5): 52).Major impurity in the Oleum Cinnamomi is O-methoxy trans-Cinnamylaldehyde, cinnamyl acetate etc.As Yunnan produce in the Oleum Cinnamomi the former content can reach 12% or more (Han Yaming, Jiang Lin, Huang Zhengen etc., the Oleum Cinnamomi chemical ingredients is produced in Guangxi, Yunnan and the molecular distillation technique purifying is studied, Central-South pharmacy, 2005,3 (4), 216-219).Adopt behind the refining Oleum Cinnamomi of molecular distillation technique in the nubbin content of O-methoxy trans-Cinnamylaldehyde, cinnamyl acetate higher.If can adopt certain method to be removed, or be converted into trans-Cinnamylaldehyde, can promote the quality of product, and resource is further made full use of.
Summary of the invention
The purpose of this invention is to provide a kind of method that improves trans-cinnamic aldehyde content in cassia oil.
The present invention is as follows for the technical scheme that solves the problems of the technologies described above:
A kind of method that improves trans-cinnamic aldehyde content in cassia oil, be to be raw material with the Oleum Cinnamomi, reduce O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate content in the Oleum Cinnamomi with phonochemical reaction method, complex acid catalytic hydrolysis, improve trans-cinnamic aldehyde content, the concrete operations step is as follows:
1. the phosphoric acid solution that with Oleum Cinnamomi and volumetric concentration is 5-10% is mixed in there-necked flask with volume ratio at 1: 4, and puts into one and stir magneton;
2. there-necked flask inserts sonochemistry reactor and reflux condensing tube respectively, place 20～40 ℃ of water-baths to be heated to relevant temperature there-necked flask after, open magnetic stirrer and sonochemistry reactor, irradiation is 20 minutes under 500～1000W power;
3. the reaction solution of step 2. is transferred to and told upper oil phase in the separating funnel, be the Oleum Cinnamomi that has improved trans-cinnamic aldehyde content in cassia oil after the processing;
4. adopt the wherein content of trans-cinnamic aldehyde content, cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde of gas chromatography determination.
The inventive method has following characteristics:
1. handle the higher Oleum Cinnamomi of content of O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate with the inventive method, its trans-cinnamic aldehyde content can improve more than 10%.
2. the inventive method treatment time is short, temperature is low, saves the energy.
3. recyclable the recycling of phosphoric acid solution that relate to of the inventive method can not produce contaminated wastewater.
Description of drawings
Fig. 1 is Chinese cassia tree oil sample gas chromatographic analysis result.
Fig. 2 is that the inventive method is handled back Oleum Cinnamomi gas chromatographic analysis result (example 1).
Among the figure: trans-Cinnamylaldehyde 1, cinnamyl acetate 2, O-methoxy trans-Cinnamylaldehyde 3.
Embodiment
The present invention be the using ultrasound amplitude according to and acid hydrolysis, reduce the content of O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate in the Oleum Cinnamomi, improve the yield of trans Oleum Cinnamomi.
Action of ultrasonic waves mainly contains two aspects: (1) ultrasonic wave has promoted mixing of water and oil phase, helps ester hydrolysis reaction; (2) sound cavitation effect (Cavitation) makes solution produce high temperature and hundreds of atmospheric high pressure more than the 5000K in utmost point short period of time and little space, and association intensive shockwave and high-speed micro-jet, in system, there are simultaneously a large amount of free radicals, formed a very special physical environment, thereby the chemical reaction that can not take place under some normal conditions can carry out (Chemical Industry Press's in April, 2002 first version " Green Chemistry chemical industry practical technique " 72-88 page or leaf) with this understanding.Phonochemical reaction has been successfully applied to a plurality of organic synthesis systems.
The raw material that the present invention adopts is as follows:
Oleum Cinnamomi (trans-cinnamic aldehyde content 71.7%, the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 11.13% and 15.74%).
Phosphoric acid is analytical reagent (Gansu Province, west, Shantou).
The sonochemistry reactor that the present invention adopts, model is the direct insertion reactor of SN-D type ultrasonic wave, operating frequency 40KHz, peak power 1000W, Guangzhou Xin Nuoke ultrasonic device company limited makes.
Experimental installation of the present invention is the 250mL there-necked flask.
Treatment condition are as follows to the influence of gained Oleum Cinnamomi:
The quality of Oleum Cinnamomi depends primarily on the content of its trans-Cinnamylaldehyde.Therefore, by the content of the trans-Cinnamylaldehyde in the gas Chromatographic Determination Oleum Cinnamomi, O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate, investigated the influence of ultrasonic irradiation time, power, temperature, phosphoric acid concentration etc.
1. the influence of ultrasonic power
25mL Oleum Cinnamomi and 100mL10% phosphoric acid solution are pressed working method, and setting ultrasonic power respectively is 0,100,500W, 1000W, ultrasound wave irradiation 20 minutes, isolate oil phase after leaving standstill, record the content such as the table 1 of trans-Cinnamylaldehyde in the Oleum Cinnamomi, O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate.
Table 1 ultrasonic power is to the influence of Oleum Cinnamomi result
| Ultrasonic power (W) | Trans-Cinnamylaldehyde % | Cinnamyl acetate % | O-methoxy trans-Cinnamylaldehyde % |
| ?0 | ??71.7 | ??11.1 | ??15.7 |
| ?100 | ??72.7 | ??10.7 | ??15.9 |
| ?500 | ??81.4 | ??7.6 | ??10.1 |
| Ultrasonic power (W) | Trans-Cinnamylaldehyde % | Cinnamyl acetate % | O-methoxy trans-Cinnamylaldehyde % |
| ?1000 | ??83.4 | ??7.2 | ??8.6 |
Improve ultrasonic power, help strengthening the acoustic cavitation effect, thereby promote the decomposition of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde.The result shows that through behind the ultrasonic irradiation, trans-cinnamic aldehyde content can improve about about 10% in the oil of bay.
2. Temperature Influence
Ultrasonic power is 1000W, 25mL Oleum Cinnamomi and 100mL10% phosphoric acid solution are pressed working method, respectively 20,30, ultrasound wave irradiation is 20 minutes in 40 and 50 ℃ of water-baths, isolate oil phase after leaving standstill, record the content such as the table 2 of trans-Cinnamylaldehyde in the Oleum Cinnamomi, O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate.
Table 2 bath temperature is to the influence of Oleum Cinnamomi result
By table 2 as seen, temperature is not obvious to result's influence.But more than 50 ℃ the time, ultrasonic wave can cause phenylacrolein and react, and forms yellow mercury oxide.Therefore, bath temperature should be controlled at below 40 ℃.
3. the influence of phosphoric acid concentration
Ultrasonic power is 1000W, 40 ℃ of temperature, with 25mL Oleum Cinnamomi and 100mL different concns (0,1%, 2%, 5 and 10%) phosphoric acid solution was pressed the working method ultrasound wave irradiation 20 minutes, isolated oil phase after leaving standstill, and recorded the content such as the table 3 of trans-Cinnamylaldehyde in the Oleum Cinnamomi, O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate.
Table 3 phosphoric acid concentration is to the influence of Oleum Cinnamomi result
| Phosphoric acid concentration (%, v/v) | Trans-Cinnamylaldehyde % | Cinnamyl acetate % | O-methoxy trans-Cinnamylaldehyde % |
| ?0 | ??80.5 | ??8.2 | ??10.3 |
| ?1 | ??81.5 | ??8.1 | ??10.7 |
| ?2 | ??81.2 | ??6.8 | ??9.9 |
| ?5 | ??83.0 | ??7.0 | ??9.1 |
| ?10 | ??83.4 | ??7.2 | ??8.6 |
As seen from Table 3, phosphoric acid concentration is little to the influence of result.But the phosphoric acid density of different concns differs bigger, can influence the separation of profit phase.When phosphoric acid concentration was lower than 5%, profit was compared difficult the separation, and too high phosphoric acid concentration can make sour consumption increase on the one hand, and cost all increases the weight of with polluting, and simultaneously, the increase of soltion viscosity also can reduce sound cavitation effect.Therefore, 10% phosphoric acid solution is proper.
4. the influence of ultrasonic wave action time
Ultrasonic power is 1000W, with 25mL Oleum Cinnamomi and 100mL10% phosphoric acid solution in 40 ℃ of water-baths by working method irradiation 20,40 and 60 minutes respectively, find that the composition of handling the back oil of bay changes little.Therefore, ultrasonic wave is very rapid to the transformation of cinnamyl acetate in the oil of bay and O-methoxy trans-Cinnamylaldehyde, selects 20 minutes can guarantee the better conversion effect.
Below in conjunction with embodiment and accompanying drawing the inventive method is further described.
25mL Oleum Cinnamomi (trans-cinnamic aldehyde content 71.7%, the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 11.13% and 15.74%) is mixed in the there-necked flask with the 100mL10% phosphoric acid solution, and puts into one and stir magneton.There-necked flask inserts sonochemistry reactor and reflux condensing tube respectively.There-necked flask is put into after 30 ℃ of water-baths are heated to relevant temperature, is opened magnetic stirrer and sonochemistry reactor, after 20 minutes, transfer to and tell upper oil phase in the separating funnel at irradiation under the 1000W power, the Oleum Cinnamomi of 25mL after handling.Employing gas chromatography determination wherein trans-cinnamic aldehyde content is 83.4%, and the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 7.2% and 8.6%, as shown in Figure 2.
25mL Oleum Cinnamomi (trans-cinnamic aldehyde content 71.7%, the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 11.13% and 15.74%) is mixed in the there-necked flask with the 100mL5% phosphoric acid solution, and puts into one and stir magneton.There-necked flask inserts sonochemistry reactor and reflux condensing tube respectively.There-necked flask is put into after 30 ℃ of water-baths are heated to relevant temperature, is opened magnetic stirrer and sonochemistry reactor, after 20 minutes, transfer to and tell lower floor's oil phase in the separating funnel at irradiation under the 1000W power, the Oleum Cinnamomi of 22mL after handling.Employing gas chromatography determination wherein trans-cinnamic aldehyde content is 83.0%, and the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 7.0% and 9.1%.
25mL Oleum Cinnamomi (trans-cinnamic aldehyde content 71.7%, the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 11.13% and 15.74%) is mixed in the there-necked flask with the 100mL10% phosphoric acid solution, and puts into one and stir magneton.There-necked flask inserts sonochemistry reactor and reflux condensing tube respectively.There-necked flask is put into after 30 ℃ of water-baths are heated to relevant temperature, is opened magnetic stirrer and sonochemistry reactor, after 20 minutes, transfer to and tell upper oil phase in the separating funnel at irradiation under the 500W power, the Oleum Cinnamomi of 25mL after handling.Employing gas chromatography determination wherein trans-cinnamic aldehyde content is 81.4%, and the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 7.6% and 10.1%.
Embodiment 4
25mL Oleum Cinnamomi (trans-cinnamic aldehyde content 71.7%, the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 11.13% and 15.74%) is mixed in the there-necked flask with the 100mL10% phosphoric acid solution, and puts into one and stir magneton.There-necked flask inserts sonochemistry reactor and reflux condensing tube respectively.There-necked flask is put into after 40 ℃ of water-baths are heated to relevant temperature, is opened magnetic stirrer and sonochemistry reactor, after 20 minutes, transfer to and tell upper oil phase in the separating funnel at irradiation under the 1000W power, the Oleum Cinnamomi of 24.8mL after handling.Employing gas chromatography determination wherein trans-cinnamic aldehyde content is 82.8%, and the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 7.4% and 8.8%.
Embodiment 5
25mL Oleum Cinnamomi (trans-cinnamic aldehyde content 71.7%, the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 11.13% and 15.74%) is mixed in the there-necked flask with the 100mL10% phosphoric acid solution, and puts into one and stir magneton.There-necked flask inserts sonochemistry reactor and reflux condensing tube respectively.There-necked flask is put into after 20 ℃ of water-baths are heated to relevant temperature, is opened magnetic stirrer and sonochemistry reactor, after 20 minutes, transfer to and tell upper oil phase in the separating funnel at irradiation under the 1000W power, the Oleum Cinnamomi of 24.9mL after handling.Employing gas chromatography determination wherein trans-cinnamic aldehyde content is 81.5%, and the content of cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde is respectively 7.3% and 9.9%.
Claims (1)
1. method that improves trans-cinnamic aldehyde content in cassia oil, it is characterized in that, with the Oleum Cinnamomi is raw material, use the phonochemical reaction method, the complex acid catalytic hydrolysis reduces O-methoxy trans-Cinnamylaldehyde and cinnamyl acetate content in the Oleum Cinnamomi, improve trans-cinnamic aldehyde content, the concrete operations step is as follows:
1) is that the phosphoric acid solution of 5-10% is mixed in there-necked flask with volume ratio at 1: 4 with Oleum Cinnamomi and volumetric concentration, and puts into one and stir magneton;
2) there-necked flask inserts sonochemistry reactor and reflux condensing tube respectively, place 20～40 ℃ of water-baths to be heated to relevant temperature there-necked flask after, open magnetic stirrer and sonochemistry reactor, irradiation is 20 minutes under 500～1000W power;
3) with step 2) reaction solution transfer to and tell upper oil phase in the separating funnel, be the Oleum Cinnamomi that has improved trans-cinnamic aldehyde content in cassia oil after the processing;
4) adopt the wherein content of trans-cinnamic aldehyde content, cinnamyl acetate and O-methoxy trans-Cinnamylaldehyde of gas chromatography determination.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342632A (en) * | 2013-06-24 | 2013-10-09 | 广西壮族自治区林业科学研究院 | Method for separating high-purity cinnamyl aldehyde and cinnamyl acetate from cinnamon oil |
| CN104194940A (en) * | 2014-09-03 | 2014-12-10 | 广西壮族自治区林业科学研究院 | Processing method for increasing content of essential oil in barks as well as branches and leaves of cinnamon |
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| US20120093952A1 (en) * | 2007-12-11 | 2012-04-19 | Frehner Marco | Use of essential oil compounds as histomonastat |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342632A (en) * | 2013-06-24 | 2013-10-09 | 广西壮族自治区林业科学研究院 | Method for separating high-purity cinnamyl aldehyde and cinnamyl acetate from cinnamon oil |
| CN104194940A (en) * | 2014-09-03 | 2014-12-10 | 广西壮族自治区林业科学研究院 | Processing method for increasing content of essential oil in barks as well as branches and leaves of cinnamon |
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