CN101234971A - Method for synthesizing phenylacetic acid ester derivatives and application for products thereof - Google Patents
Method for synthesizing phenylacetic acid ester derivatives and application for products thereof Download PDFInfo
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- CN101234971A CN101234971A CNA2008100492871A CN200810049287A CN101234971A CN 101234971 A CN101234971 A CN 101234971A CN A2008100492871 A CNA2008100492871 A CN A2008100492871A CN 200810049287 A CN200810049287 A CN 200810049287A CN 101234971 A CN101234971 A CN 101234971A
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Abstract
A synthesis method of phenyl acetic acid ester derivate is characterized in that the phenyl acetic acid ester derivate is directly prepared from phenyl acetic acid and alcohol via esterification synthesis reaction, wherein the prepared phenyl acetic acid ester derivate can be used as cigarette additive. The synthesis method of phenyl acetic acid ester derivate has the advantages that the synthesis method is simple with low cost, high synthesis efficiency and high product purity, the synthesis method realizes better cigarette taste via leading in characteristic carboxyl, aromatic acid and fatty acid groups. The phenyl acetic acid ester derivate added on cigarette pipe tobacco, proven via relative departments, can improve cigarette taste and quality. The invention can avoid modifying prior cigarette processing technology.
Description
Technical field
The present invention relates to the synthetic and application of spices, belong to the synthetic field of spices.Be specifically related to synthetic and their application in perfuming cigarette of a kind of phenylacetic acid ester derivatives, the phenylacetic acid ester material derivant that utilizes the present invention to obtain has good effect in perfuming cigarette.
Background technology
Toluylic acid is important fine-chemical intermediate, is widely used in fields such as medicine, agricultural chemicals, spices, dyestuff.Aspect spices, phenylacetate is the flavouring agent that China's regulation allows use, as the surrogate of indoles or civet, and the adjustable essence of allotting odor types such as Acacia, sweet osmanthus, rose.It is mainly used in productions such as food, washing composition, sanitising agent, makeup, tobacco, beverage.And phenylacetate has the perfume (or spice) treatment effect of restraining appetite, for the assisting therapy of obesity the good clinical effect arranged.According to pertinent data, phenylacetic acid ester spices occupies considerable status on the world market in ester perfume, and demand increases year by year.Find that in tobacco flavoring toluylic acid can be used for improving the fragrance of tobacco.The phenylacetic acid ester material has distinctive perfuming effect equally in tobacco, wherein, Phenylacetic acid ethylester is with its remarkable and happy rose scent acquisition perfumer's favor, and Chang Zuowei modifier and type-odor are applied in the industries such as tobacco, food, daily cosmetics.From the blending performance, carbochain is longer, and boiling point is higher, and long lasting quality is more lasting, and fragrance is more graceful.The applied research of toluylic acid long-chain ester analog derivative in cigarette has certain development research and is worth.Commercially available prod such as methyl phenylacetate, Phenylacetic acid ethylester, butyl phenylacetate etc. have been widely used in aspects such as tobacco, food, medicine, daily use chemicals at present.
Summary of the invention
The objective of the invention is to cater to the needs of present tobacco developing direction, seek the more characteristic spices in the tobacco, for the Chinese style cigarette flavors provides new source, and synthetic method of a kind of phenylacetic acid ester derivatives that provides and products thereof is used, and this method is realizing the mellow and full harmony of flue gas mouthfeel by introducing distinctive carboxyl and aromatic acid, fatty acid group.The phenylacetic acid ester derivatives that the present invention is prepared is applied on the cigarette shreds, can improve cigarette strength, increases the cigarette property sent out thoroughly, improves cigarette odor-absorbing, promote flavouring essence quality, and this The Application of Technology does not change the existing complete processing of cigarette.
The objective of the invention is to be achieved through the following technical solutions: the synthetic method of phenylacetic acid ester derivatives of the present invention adopts toluylic acid and pure direct esterification to synthesize and makes, and its reaction formula is as follows:
Wherein R is 6-10,12,14,16,18 straight chained alkyls or benzyl, styroyl;
Its reaction process is as follows:
The first step adds the band aqua in three-necked bottle, alcohol, and toluylic acid, catalyzer,
Wherein the mol ratio of each component is: toluylic acid: alcohol 1: 1-8
Catalyzer: toluylic acid 1: 10-100
Under mechanical stirring, in 2-10min, be warming up to 100-200 ℃, after back flow reaction 2-10 hour, when treating that water trap does not have the globule and takes out of, stop heating;
Second step added the back products therefrom in the separating funnel and added organic solvent diluting, with saturated solution of sodium bicarbonate or sodium hydroxide solution washing, vibration, extracting and demixing, discard lower aqueous layer, use the distilled water wash organic layer, till the pH value of solution value reaches neutrality, add anhydrous sodium sulphate or anhydrous magnesium sulfate after at room temperature dry 6 hours, filter, concentrate, the corresponding collection target compound of characteristics according to target compound promptly obtains target product of the present invention.
In the present invention, described catalyzer is sulfuric acid monohydrate hydrogen sodium or tosic acid; The synthetic used alcohol of esterification is n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, phenylethyl alcohol, phenylcarbinol, n-dodecanol, positive tetradecyl alcohol, positive hexadecanol, positive stearyl alcohol.
The band aqua that adopts is benzene, toluene or hexanaphthene; Described organic solvent is ethyl acetate, methylene dichloride, chloroform, tetracol phenixin, ether, sherwood oil, alkane, aromatic hydrocarbon.
Utilize the phenylacetic acid ester derivatives of synthetic method preparation of the present invention to can be used as the cigarette additive use, its consumption is the 0.0001-0.5% of pipe tobacco weight, earlier through adding on the pipe tobacco by spray pattern behind the alcohol dilution.As the application of cigarette additive, to improve cigarette Harmony, improve cigarette strength, the property sent out, the fragrance matter that strengthens cigarette have obvious effect thoroughly to increase cigarette.
Beneficial effect of the present invention and characteristics are: the synthetic method that is adopted is simple, and is with low cost, combined coefficient height, and synthetic product purity height.This method realizes the mellow and full harmony of flue gas mouthfeel by introducing distinctive carboxyl and aromatic acid, fatty acid group.The phenylacetic acid ester derivatives that the present invention is prepared is applied on the cigarette shreds, and tissue is smoked panel test through relevant department, thinks and can improve cigarette strength, increase the cigarette property sent out thoroughly, improve cigarette odor-absorbing, promote flavouring essence quality, and this The Application of Technology does not change the existing complete processing of cigarette.
Embodiment
To method afford further instruction of the present invention, but do not limit the present invention below by example.
Example one: the own ester of toluylic acid synthetic
In three-necked bottle, add 40ml toluene, the 13g toluylic acid, 2g sulfuric acid monohydrate hydrogen sodium dropwise adds the 40ml n-hexyl alcohol, electronic stirring, control is bathed warm 120-124 ℃, behind the about 3h of reflux, stops heating.In the mixed liquid impouring separating funnel of gained reaction, add the dilution of 20mL ethyl acetate, with saturated sodium bicarbonate solution washing three times, vibration, extracting and demixing discards lower aqueous layer, the adding distil water washing, the vibration layering is till water layer pH value of solution value is neutrality.Add anhydrous sodium sulphate, dry 6h under the room temperature filters, concentrate, and underpressure distillation, the cut of 93-95 ℃/15Pa of collection obtains achromaticity and clarification liquid, is the products benzene hexyl acetate, product purity 97.9%.
Example two: toluylic acid heptyl ester synthetic
In three-necked bottle, add 30ml benzene, the 8g toluylic acid, the 3g tosic acid dropwise adds the 34ml n-Heptyl alcohol, and under electronic stirring, control is bathed warm 110-114 ℃, behind the about 3.5h of reflux, stops heating.In the mixed liquid impouring separating funnel of gained reaction, add the dilution of 20mL methylene dichloride, with saturated sodium bicarbonate solution washing three times, vibration, extracting and demixing discards lower aqueous layer, the adding distil water washing, the vibration layering is till water layer pH value of solution value is neutrality.Add anhydrous magnesium sulfate, dry 6h under the room temperature filters, concentrate, and underpressure distillation, the cut of 102-104 ℃/25Pa of collection obtains achromaticity and clarification liquid, is the products benzene heptyl acetate, product purity 99.11%.
Example three: toluylic acid monooctyl ester synthetic
In three-necked bottle, add the 35ml hexanaphthene, the 20g toluylic acid, 4g sulfuric acid monohydrate hydrogen sodium dropwise adds the 40ml n-Octanol, and under electronic stirring, control is bathed warm 124-128 ℃, behind the about 4h of reflux, stops heating.In the mixed liquid impouring separating funnel of gained reaction, add the dilution of 30mL ether, with 5% sodium hydroxide solution washing three times, vibration, extracting and demixing discards lower aqueous layer, adding distil water washing organic layer, the vibration layering is till water layer pH value reaches neutrality.Add anhydrous sodium sulphate, dry 6h under the room temperature filters, concentrate, and underpressure distillation, the cut of 118-120 ℃/60Pa of collection obtains achromaticity and clarification liquid, is the products benzene octyl acetate, product purity 97.71%.
Example four: toluylic acid ester in the ninth of the ten Heavenly Stems synthetic
In three-necked bottle, add 40ml toluene, the 15g toluylic acid, 4g sulfuric acid monohydrate hydrogen sodium dropwise adds the 30ml nonanol-, and under electronic stirring, control is bathed warm 130-134 ℃, behind the about 3.5h of reflux, stops heating.In the mixed liquid impouring separating funnel of gained reaction, add the dilution of 25mL chloroform, with 5% sodium hydroxide solution washing three times, vibration, extracting and demixing discards lower aqueous layer, uses the distilled water wash organic layer, till water layer pH value of solution value is neutrality.Add anhydrous magnesium sulfate, dry 6h under the room temperature filters, concentrate, and underpressure distillation, the cut of 124-126 ℃/50Pa of collection obtains achromaticity and clarification liquid, is the products benzene nonyl acetate, product purity 96.34%.
Example five: toluylic acid hexadecyl ester synthetic
In three-necked bottle, add the 30ml hexanaphthene, the 8g toluylic acid, the 4g tosic acid dropwise adds the positive hexadecanol of 30ml, electronic stirring, control is bathed warm 110-114 ℃, behind the about 4h of reflux, stops heating.In the mixed liquid impouring separating funnel of gained reaction, add the dilution of 30mL methylene dichloride, with the washing of 5% sodium hydroxide solution, vibration, extracting and demixing discards lower aqueous layer, uses the distilled water wash organic layer, till water layer pH value of solution value is neutrality.Add anhydrous magnesium sulfate, dry 6h under the room temperature filters, and concentrates, and collects the products benzene cetyl acetate, product purity 98.4%.
Be applied in proportion in the cigarette shreds by the prepared product of above-mentioned example, all can reach and improve cigarette odor-absorbing, improve the purpose of cigarette quality.
The present invention no longer describes by embodiment one by one if the alcohol defined in employing toluylic acid and the claim (as nonylcarbinol, phenylethyl alcohol, phenylcarbinol, n-dodecanol, positive tetradecyl alcohol, positive stearyl alcohol etc.) utilizes aforesaid method all can obtain corresponding ester derivative.
Claims (7)
1, a kind of synthetic method of phenylacetic acid ester derivatives is characterized in that: it adopts toluylic acid and pure direct esterification to synthesize and makes, and its reaction formula is as follows:
Wherein R is 6-10,12,14,16,18 straight chained alkyls or benzyl, styroyl;
Its reaction process is as follows:
The first step adds the band aqua in three-necked bottle, alcohol, and toluylic acid, catalyzer,
Wherein the mol ratio of each component is: toluylic acid: alcohol 1: 0.2-8
Catalyzer: toluylic acid 1: 10-100
Under mechanical stirring, in 2-10min, be warming up to 100-200 ℃, after back flow reaction 2-10 hour, when treating that water trap does not have the globule and takes out of, stop heating;
Second step added the back products therefrom in the separating funnel and added organic solvent diluting, with saturated solution of sodium bicarbonate or sodium hydroxide solution washing, vibration, extracting and demixing, discard lower aqueous layer, use the distilled water wash organic layer, till the pH value of solution value reaches neutrality, add anhydrous sodium sulphate or anhydrous magnesium sulfate after at room temperature dry 6 hours, filter, concentrate, the corresponding collection product of characteristics according to target compound promptly obtains target product of the present invention.
2, the synthetic method of phenylacetic acid ester derivatives as claimed in claim 1 is characterized in that: described catalyzer is sulfuric acid monohydrate hydrogen sodium or tosic acid.
3, the synthetic method of phenylacetic acid ester derivatives as claimed in claim 1 is characterized in that: the synthetic used alcohol of esterification is n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, phenylethyl alcohol, phenylcarbinol, n-dodecanol, positive tetradecyl alcohol, positive hexadecanol, positive stearyl alcohol.
4, the synthetic method of phenylacetic acid ester derivatives as claimed in claim 1 is characterized in that: the band aqua that is adopted is benzene, toluene or hexanaphthene.
5, the synthetic method of phenylacetic acid ester derivatives as claimed in claim 1 is characterized in that: described organic solvent is ethyl acetate, methylene dichloride, chloroform, tetracol phenixin, ether, sherwood oil, alkane, aromatic hydrocarbon.
6, a kind of application of phenylacetic acid ester derivatives in cigarette that utilizes the described synthetic method preparation of claim 1 is characterized in that: phenylacetic acid ester derivatives of the present invention is used as cigarette additive.
7, the application of phenylacetic acid ester derivatives according to claim 6 in cigarette is characterized in that: the consumption of phenylacetic acid ester derivatives is the 0.0001-0.5% of pipe tobacco weight, through behind the alcohol dilution, adds in the pipe tobacco by spray pattern more earlier.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408335A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院福建物质结构研究所 | Synthetic method of p-fluorophenyl acetate |
| CN102993340A (en) * | 2012-12-21 | 2013-03-27 | 天津久日化学股份有限公司 | Photoinitiator for ultraviolet light curing agent and manufacturing method thereof |
| CN104628568A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Method for producing bifenthrin with clean synthesizing process |
| CN106255424A (en) * | 2014-01-17 | 2016-12-21 | R.J.雷诺兹烟草公司 | For the method producing spice and associated materials |
| CN110477338A (en) * | 2019-08-02 | 2019-11-22 | 安徽锦戎香料有限公司 | A kind of food flavor and preparation method thereof |
-
2008
- 2008-02-29 CN CN2008100492871A patent/CN101234971B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408335A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院福建物质结构研究所 | Synthetic method of p-fluorophenyl acetate |
| CN102993340A (en) * | 2012-12-21 | 2013-03-27 | 天津久日化学股份有限公司 | Photoinitiator for ultraviolet light curing agent and manufacturing method thereof |
| CN102993340B (en) * | 2012-12-21 | 2015-09-02 | 天津久日化学股份有限公司 | A kind of light trigger for ultraviolet curable agent and manufacture method thereof |
| CN104628568A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Method for producing bifenthrin with clean synthesizing process |
| CN106255424A (en) * | 2014-01-17 | 2016-12-21 | R.J.雷诺兹烟草公司 | For the method producing spice and associated materials |
| US10188137B2 (en) | 2014-01-17 | 2019-01-29 | R.J. Reynolds Tobacco Company | Process for producing flavorants and related materials |
| CN106255424B (en) * | 2014-01-17 | 2021-10-08 | R.J.雷诺兹烟草公司 | Process for producing fragrances and related materials |
| CN110477338A (en) * | 2019-08-02 | 2019-11-22 | 安徽锦戎香料有限公司 | A kind of food flavor and preparation method thereof |
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| CN101234971B (en) | 2010-10-13 |
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