CN101698645B - Method for synthesizing beta-cyclized ethyl geranate - Google Patents
Method for synthesizing beta-cyclized ethyl geranate Download PDFInfo
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- CN101698645B CN101698645B CN 200910197781 CN200910197781A CN101698645B CN 101698645 B CN101698645 B CN 101698645B CN 200910197781 CN200910197781 CN 200910197781 CN 200910197781 A CN200910197781 A CN 200910197781A CN 101698645 B CN101698645 B CN 101698645B
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Abstract
The invention discloses a method for synthesizing beta-cyclized ethyl geranate, which takes phosphoric acid as cyclizingagent, cyclohexane or methyl alcohol as solvent, performs cyclization on ethyl geranate to obtain the beta-cyclized ethyl geranate. The method for synthesizing beta-cyclized ethyl geranate has easily obtained raw materials, mild reaction condition, environment protection, high product yield which is up to 80-85%, and high purity of 98%. The product has fresh oil fragrance, vegetable and fruits fragrance like apple fragrance, can be widely used in daily heath essence such as soaps, detergents and the like and is a very important daily health essence and raw material in preparing top-grade perfume.
Description
Technical field
The present invention relates to a kind of synthetic method of β-beta-cyclized ethyl geranate.
Background technology
β-beta-cyclized ethyl geranate has the vegetables and fruits fragrance of the blue or green perfume of fresh grease, apple sample, not only can be widely used in the daily chemical essences such as soap, washing composition, and be very important daily use chemicals perfume material when preparing high-grade perfume.
β-beta-cyclized ethyl geranate chemistry is by name: 2,6,6-trimethylammonium-hexamethylene-1-alkene-1-base ethyl formate.The synthetic method of at present common β-beta-cyclized ethyl geranate is carried out cyclization take ethyl geranate as raw material and is made β-beta-cyclized ethyl geranate.When carrying out cyclization, take benzene as solvent, boron trifluoride is catalyzer [patent documentation Helv.Chim.Acta., 42,2598 (1959)].Because take benzene as solvent, in view of the industrial hygiene reason, benzene had cumulative toxicity to human body, and very high toxicity is arranged when cyclization prepared β-beta-cyclized ethyl geranate.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of mild condition, easy handling, environmentally safe close friend, β-beta-cyclized ethyl geranate that the reaction yield is high.
The reaction mechanism of synthetic method of the present invention is as follows:
Take phosphoric acid as cyclizing agent, hexanaphthene or methyl alcohol are solvent, ethyl geranate is carried out cyclization make β-beta-cyclized ethyl geranate;
The reaction formula of β of the present invention-beta-cyclized ethyl geranate synthetic method is as follows:
Technical scheme of the present invention
A kind of synthetic method of β-beta-cyclized ethyl geranate comprises the steps:
(1), the hybrid reaction of raw material
In reaction vessel, with the mass ratio of ethyl geranate and solvent by ethyl geranate: solvent is to join wherein at 2～4: 1, the control mixing speed is 120r/min, being heated to temperature and being 50～85 ℃, to begin to drip concentration be 85% phosphoric acid, the control drop rate is 0.8g/min, dropwise, insulation reaction 2h gets reaction solution;
Above-mentioned said solvent is hexanaphthene or methyl alcohol;
The concentration that wherein drips is that the amount of 85% phosphoric acid is that concentration is 85% phosphoric acid by itself and ethyl geranate in mass ratio: ethyl geranate is 144g: 180g;
(2), the separating and extracting of reaction solution
The reaction solution of step (1) gained is cooled to 20～25 ℃, standing demix, two-layer altogether, being respectively sour layer, the oil reservoir of phosphoric acid, is after its cyclohexane solvent of 1.25 times extracts once, to merge oil reservoir and extraction liquid with the acid layer with volume, and wash with tap water, standing demix is divided into as two-layer, discards the water layer of lower floor, it is 7 that the oil reservoir on upper strata is neutralized to pH with 10% yellow soda ash, standing demix again discards the water layer of lower floor, and the oil reservoir on upper strata is slightly oil of beta-cyclized ethyl geranate;
(3), vacuum fractionation
The beta-cyclized ethyl geranate of step (2) gained is slightly oily, normal pressure reclaims vacuum fractionation behind hexanaphthene or a small amount of methanol solvate, first paragraph is the chieftain of 70～90 ℃/5～6mmHg, second segment is finished product β-beta-cyclized ethyl geranate of 90～92 ℃/5～6mmHg, and finished product β-beta-cyclized ethyl geranate is 98% through gas chromatographic analysis content.
Beneficial effect of the present invention
The synthetic method of β-beta-cyclized ethyl geranate of the present invention, raw material are easy to get, reaction conditions gentleness, environmental friendliness, product yield are high, and yield is 80～85%, and purity reaches 98%.Product has the vegetables and fruits fragrance of the blue or green perfume of fresh grease, apple sample, not only can be widely used in the daily chemical essences such as soap, washing composition, and be very important daily use chemicals perfume material when preparing high-grade perfume.
Description of drawings
Fig. 1, the reaction formula of β-beta-cyclized ethyl geranate synthetic method
Embodiment
Embodiment 1
Synthesizing of β-beta-cyclized ethyl geranate
In the 500mL there-necked flask of agitator, thermometer, dropping funnel and spherical condensation tube is housed, adding 180g content is 97% ethyl geranate and 90g cyclohexane solvent, the control mixing speed is 120r/min, be heated to temperature and be 85 ℃ and begin to drip 144g phosphoric acid, the control drop rate is 0.8g/min, dropwise, continue insulation reaction 2h.Gas chromatographic analysis raw material ethyl geranate content is below 0.5%, and reaction finishes, and is cooled to 20～25 ℃, and standing demix is two-layer altogether, is respectively sour water layer, the oil reservoir of phosphoric acid.After the sour water layer extracts once with the 100mL hexanaphthene, merge oil reservoir and extraction liquid and use 500mL water washing, standing demix, be divided into as two-layer, discard the water layer of lower floor, it is 7 that the oil reservoir on upper strata is neutralized to pH with 10% yellow soda ash, standing demix again, the oil reservoir on upper strata are slightly oil of beta-cyclized ethyl geranate.Behind the thick oily normal pressure recovery cyclohexane solvent of beta-cyclized ethyl geranate with gained, vacuum fractionation, first paragraph is chieftain's 24 grams of 70～90 ℃/5～6mmHg, second segment is the finished product β-beta-cyclized ethyl geranate 151.5g (gas-chromatography content is 98.02%) of 90～92 ℃/5～6mmHg of interior temperature, and the reaction yield is 85.05% (in ethyl geranate).
Embodiment 2
Synthesizing of β-beta-cyclized ethyl geranate
In the 500mL there-necked flask of agitator, thermometer, dropping funnel and spherical condensation tube is housed, adding 180g content is 97% ethyl geranate and 90g cyclohexane solvent, the control mixing speed is 120r/min, be heated to temperature and be 50 ℃ and begin to drip 144g phosphoric acid, the control drop rate is 0.8g/min, dropwise, continue insulation reaction 2h.Gas chromatographic analysis raw material ethyl geranate content is below 0.5%, and reaction finishes, and is cooled to 20～25 ℃, and standing demix is two-layer altogether, is respectively sour water layer, the oil reservoir of phosphoric acid.After the sour water layer extracts once with the 100mL hexanaphthene, merge oil reservoir and extraction liquid and use 500mL water washing, standing demix, be divided into as two-layer, discard the water layer of lower floor, it is 7 that the oil reservoir on upper strata is neutralized to pH with 10% yellow soda ash, standing demix again, the oil reservoir on upper strata are slightly oil of beta-cyclized ethyl geranate.Behind the thick oily normal pressure recovery cyclohexane solvent of beta-cyclized ethyl geranate with gained, vacuum fractionation, first paragraph is chieftain's 25 grams of 70～90 ℃/5～6mmHg, second segment is the finished product β-beta-cyclized ethyl geranate 150.5g (gas-chromatography content is 98.1%) of 90～92 ℃/5～6mmHg of interior temperature, and the reaction yield is 84.56% (in ethyl geranate).
Embodiment 3
Synthesizing of β-beta-cyclized ethyl geranate
In the 500mL there-necked flask of agitator, thermometer, dropping funnel and spherical condensation tube is housed, adding 180g content is 97% ethyl geranate and 45g methanol solvate, the control mixing speed is 120r/min, be heated to temperature and be 60 ℃ and begin to drip 144g phosphoric acid, the control drop rate is 0.8g/min, dropwise, continue insulation reaction 2h.Gas chromatographic analysis raw material ethyl geranate content is below 0.5%, and reaction finishes, and is cooled to 20～25 ℃, and standing demix is two-layer altogether, is respectively methanol layer, the oil reservoir of phosphoric acid.It is 7 that the oil reservoir on upper strata is neutralized to pH with 10% yellow soda ash, and standing demix again, the oil reservoir on upper strata are slightly oil of beta-cyclized ethyl geranate.The beta-cyclized ethyl geranate of gained is slightly oily, vacuum fractionation, first paragraph is chieftain's 25.5 grams (containing a small amount of methyl alcohol) of 70～90 ℃/5～6mmHg, second segment is the finished product β-beta-cyclized ethyl geranate 145.2g (gas-chromatography content is 98.2%) of 90～92 ℃/5～6mmHg of interior temperature, and the reaction yield is 81.66% (in ethyl geranate).
The catalyzer (being the methanol solution of phosphoric acid) that reclaims is capable of circulation for above-mentioned reaction six times, and reaction result is as shown in the table:
Claims (1)
1. the synthetic method of a β-beta-cyclized ethyl geranate is characterized in that comprising the steps:
(1), the hybrid reaction of raw material
In reaction vessel, with the mass ratio of ethyl geranate and solvent by ethyl geranate: solvent is to join wherein at 2～4: 1, the control mixing speed is 120r/min, being heated to temperature and being 50～85 ℃, to begin to drip concentration be 85% phosphoric acid, the control drop rate is 0.8g/min, dropwise, insulation reaction 2h gets reaction solution;
Above-mentioned said solvent is hexanaphthene or methyl alcohol;
The concentration that wherein drips is that the amount of 85% phosphoric acid is that concentration is 85% phosphoric acid by itself and ethyl geranate in mass ratio: ethyl geranate is 144g: 180g;
(2), the separating and extracting of reaction solution
The reaction solution of step (1) gained is cooled to 20～25 ℃, standing demix, two-layer altogether, being respectively sour layer, the oil reservoir of phosphoric acid, is after its cyclohexane solvent of 1.25 times extracts once, to merge oil reservoir and extraction liquid with the acid layer with volume, and wash with tap water, standing demix is divided into as two-layer, discards the water layer of lower floor, it is 7 that the oil reservoir on upper strata is neutralized to pH with 10% yellow soda ash, standing demix again discards the water layer of lower floor, and the oil reservoir on upper strata is slightly oil of beta-cyclized ethyl geranate;
(3), vacuum fractionation
With the beta-cyclized ethyl geranate of step (2) gained oil slightly, normal pressure reclaims vacuum fractionation behind hexanaphthene or a small amount of methanol solvate, and first paragraph is the chieftain of 70～90 ℃/5～6mmHg, and second segment is finished product β-beta-cyclized ethyl geranate of 90～92 ℃/5～6mmHg.
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| CN 200910197781 CN101698645B (en) | 2009-10-28 | 2009-10-28 | Method for synthesizing beta-cyclized ethyl geranate |
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| CN 200910197781 CN101698645B (en) | 2009-10-28 | 2009-10-28 | Method for synthesizing beta-cyclized ethyl geranate |
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| CN101698645B true CN101698645B (en) | 2013-02-20 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727319A (en) * | 2005-07-28 | 2006-02-01 | 浙江大学 | Device in category of substitution tricyclo-diterpene-orthodiphenol, preparation method and application |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727319A (en) * | 2005-07-28 | 2006-02-01 | 浙江大学 | Device in category of substitution tricyclo-diterpene-orthodiphenol, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| H. Kappelerl, et.al.Zur Cyclisation von trans- und cis-Verbindungen der Geranylreihe.《Helvetica Chimica Acta》.1953,第36卷第1862-1876页. * |
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