CN105801529B - A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester - Google Patents
A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester Download PDFInfo
- Publication number
- CN105801529B CN105801529B CN201610340126.2A CN201610340126A CN105801529B CN 105801529 B CN105801529 B CN 105801529B CN 201610340126 A CN201610340126 A CN 201610340126A CN 105801529 B CN105801529 B CN 105801529B
- Authority
- CN
- China
- Prior art keywords
- ester
- carbonic acid
- solution
- linalool oxide
- ethyl ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, include the following steps：1) solution for forming 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, dichloromethane and pyridine, is stirred until homogeneous, and the dichloromethane solution of ethyl chloroformate is added dropwise into solution, and after being stirred to react, reaction solution pH is adjusted to neutrality with aqueous hydrochloric acid solution；2) by neutral reaction liquid extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry, after next day filtering carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester crude product is obtained after evaporation, concentration；3) by crude product purified by silica gel post separation, the mixed solvent formed with petroleum ether and ethyl acetate makees eluent, is eluted to it, then rotary evaporation remove petroleum ether and ethyl acetate to get；Compared with the existing technology, raw material is easy to get the present invention, and preparation process is simple, easy to operate, and yield is high, is suitable for industrialized production.
Description
[technical field]
The present invention relates to the preparation method technical field of carbonic acid monoterpene alkoxide fragrance precursor, specifically a kind of carbonic acid
The preparation method of linalool oxide (pyranoid form and furan type) ester ethyl ester.
[background technology]
Carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester is a kind of carbonic acid monoterpene alcohol ester.Carbonic acid linalool oxygen
Compound (pyranoid form and furan type) ester ethyl ester is existed in the form of two kinds of cis and trans, and petit grain oil, rose are widely present in
It is a kind of particularly useful fragrance precursor, carbonic acid linalool oxide (pyrrole in rare oil, lavender oil and various plants essential oils
Type of muttering and furan type) under the effect of the external factors such as heating, pressurization, mechanical friction, slow release goes out to have special aroma ester ethyl ester.
Fragrance precursor has a wide range of applications in fragrance, foods and cosmetics industry.
It is both domestic and external from after Bouque and Bride in 1913 has found geranyl-β-D- pyrrole nanmu glucose glycosides in plant
Research is increasingly enhanced, especially in tealeaves, fruit, tobacco etc..It is fragrant that United States Patent (USP) announces FEMA3801 ethyls in 1988 for the first time
Lan Su-β-D- pyrrole nanmu glucose glycosides, are widely used in food, tealeaves and cigarette.
Carbonates release fragrance and carbon dioxide under lower pyrolysis temperature, environmentally friendly.Currently, carbonic acid is thin
The synthesis that lotus alcohol linalool mixes several carbonic esters such as the carbonic acid menthol of ester, ethylene glycol or sugar has a large amount of United States Patent (USP) report
Road.These carbonic esters are obtained with alcohol and acid or acyl chloride reaction.
2001, Givaudan companies of Switzerland D.Anderson etc. applied for United States Patent (USP), describes carbonates fragrance
The preparation method of precursor.It is reacted with chloro-formate using alcohols fragrance, carbonates fragrance is prepared under the conditions of alkali as a catalyst
Precursor.
Above method is all with alcohol and acid or acyl chloride reaction, under the conditions of alkali as a catalyst, before obtaining carbonates fragrance
Body.And the preparation of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, have no document report.
[invention content]
A kind of carbonic acid linalool oxide (pyranoid form and furan are provided present invention aim to solve above-mentioned deficiency
Mutter type) preparation method of ester ethyl ester, raw material is easy to get, and preparation process is simple, easy to operate, and yield is high, is suitable for industrialized production.
A kind of preparation side of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester is designed to achieve the above object
Method includes the following steps：
1) under ice-water bath, by the molten of 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, dichloromethane and pyridine composition
Liquid is stirred until homogeneous, and is obtained solution A, is added dropwise to the dichloromethane solution of ethyl chloroformate in 10min into solution A, stirs simultaneously
It mixes, after adding, continues to be stirred to react 10~20 hours in room temperature, after reaction, obtained reaction solution mass percent is dense
Degree adjusts reaction solution pH to neutrality for 5% aqueous hydrochloric acid solution, obtains neutral reaction liquid；
2) step 1) is washed into pH to neutral reaction solution extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry,
Next day is filtered with filter paper, the filtrate of gained evaporated with Rotary Evaporators, obtained after concentration carbonic acid linalool oxide (pyranoid form and
Furan type) ester ethyl ester crude product；
3) by carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester crude product purified by silica gel column obtained by step 2)
Separation, the mixed solvent formed with petroleum ether and ethyl acetate makees eluent, to carbonic acid linalool oxide (pyranoid form and furans
Type) ester ethyl ester crude product eluted, and until no product flows out, the method for then using rotary evaporation removes petroleum ether and second
Acetoacetic ester is to get colourless carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester.
Preferably, in step 1), 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, dichloromethane and pyridine
It is calculated by the amount and volume ratio of substance, i.e. 3,7- dimethyl -6,7- epoxy -2- octen-1-ols：Dichloromethane：Pyridine is 1mol：
1.20~3.20L：0.16~0.81L.
Preferably, in step 1), a concentration of 0.62~1.65mol/L of dichloromethane solution of the ethyl chloroformate.
Preferably, in step 1), the addition of the dichloromethane solution of the ethyl chloroformate, by the chloromethane contained by it
The molar ratio of acetoacetic ester and 3,7- dimethyl -6,7- epoxy -2- octen-1-ols in solution A calculates, i.e. ethyl chloroformate：3,
7- dimethyl -6,7- epoxy -2- octen-1-ols are 1.00~2.00：1.
Preferably, in step 3), example calculates the in the mixed solvent of the petroleum ether and ethyl acetate composition by volume,
That is petroleum ether：Ethyl acetate is 15~20:1.
Preferably, in step 3), example calculates the in the mixed solvent of the petroleum ether and ethyl acetate composition by volume,
That is petroleum ether：Ethyl acetate is 15:1.
Preferably, in carbonic acid linalool oxide (pyranoid form and furan type) the ester ethyl ester, the oxidation of carbonic acid linalool
Both object (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan type) ester ethyl ester mass ratio are 2：3.
The present invention compared with the existing technology, due to not being directly with linalool oxide (pyranoid form and furan in preparation process
Mutter type) product is obtained by the reaction with ethyl chloroformate, but 3,7- dimethyl -6,7- epoxy -2- octen-1-ols are in alkali as a catalyst
Under the conditions of, with ethyl chloroformate into rearrangement and esterification, obtain carbonic acid linalool oxide (pyranoid form and furan type) ester
Ethyl ester, both carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan type) ester ethyl ester mass ratio
It is 2：3, not only raw material be easy to get, preparation process is simple, easy to operate, and final crude product carbonic acid linalool oxide (pyrans
Type and furan type) ester ethyl ester yield up to 65.80-89.57%；In addition, dimethyl -6 3,7- used in the preparation method,
7- epoxy -2- octen-1-ol raw materials are easy to get, cheap, to carbonic acid linalool oxide (pyranoid form and the furans of the present invention
Type) ester ethyl ester preparation method production cost it is relatively low, be suitable for industrialized production, be worthy of popularization.
[specific implementation mode]
The present invention technical principle be：Be first 3,7- dimethyl -6,7- epoxy -2- octen-1-ols in acid condition
Epoxy addition obtains o-dihydroxy compound, then under alkaline condition, obtains negative oxygen ion, then negative oxygen ion attack double bond,
Pyranoid ring and furan nucleus are obtained, is further esterified, carbonic acid linalool oxide (pyranoid form) ester ethyl ester (II) and carbonic acid virtue are obtained
Camphor tree alcohol oxide (furan type) ester ethyl ester (I).As follows, reaction equation is as follows：
The preparation method of carbonic acid linalool oxide (pyranoid form and furan type) the ester ethyl ester, includes the following steps：
1) under ice-water bath, by the molten of 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, dichloromethane and pyridine composition
Liquid is stirred until homogeneous, and is obtained solution A, is added dropwise to the dichloromethane solution of ethyl chloroformate in 10min into solution A, stirs simultaneously
It mixes, after adding, continues to be stirred to react 10~20 hours in room temperature, after reaction, obtained reaction solution mass percent is dense
Degree adjusts reaction solution pH to neutrality for 5% aqueous hydrochloric acid solution, obtains neutral reaction liquid；Wherein, 3,7- dimethyl -6,7- ring
Oxygen -2- octen-1-ols, dichloromethane and pyridine are calculated by the amount and volume ratio of substance, i.e. 3,7- dimethyl -6,7- epoxies -2-
Octen-1-ol：Dichloromethane：Pyridine is 1mol：1.20~3.20L：0.16~0.81L；The dichloromethane of ethyl chloroformate is molten
A concentration of 0.62~1.65mol/L of liquid；The addition of the dichloromethane solution of ethyl chloroformate, by the ethyl chloroformate contained by it
It is calculated with the molar ratio of 3,7- dimethyl -6,7- epoxy -2- octen-1-ols in solution A, i.e. ethyl chloroformate：3,7- diformazans
Base -6,7- epoxy -2- octen-1-ols are 1.00~2.00：1；
2) step 1) is washed into pH to neutral reaction solution extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry,
Next day is filtered with filter paper, the filtrate of gained evaporated with Rotary Evaporators, obtained after concentration carbonic acid linalool oxide (pyranoid form and
Furan type) ester ethyl ester crude product；
3) by carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester crude product purified by silica gel column obtained by step 2)
Separation, the mixed solvent formed with petroleum ether and ethyl acetate makees eluent, to carbonic acid linalool oxide (pyranoid form and furans
Type) ester ethyl ester crude product eluted, and until no product flows out, the method for then using rotary evaporation removes petroleum ether and second
Acetoacetic ester is to get colourless carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester；Wherein, petroleum ether and ethyl acetate
Example calculates the in the mixed solvent of composition by volume, i.e. petroleum ether：Ethyl acetate is 15~20:1, preferably 15:1.
The present invention is made with reference to specific embodiment further explained below.
The model of various analytical instrument used in the present invention and the information of manufacturer are as follows：
Bruker AVANCE III 500MHz Nuclear Magnetic Resonance, the production of Bruker companies of Switzerland；
360 FT-IR type infrared spectrometers of Nicolet Avatar, the production of Nicolet companies of the U.S.；
6890N-5973 GC-MS, Agilent company of the U.S. production.
Equipment used in various embodiments of the present invention and the information of manufacturer are as follows：
Rotary Evaporators, model ZX-98, the production of Shanghai Yu Kang Science & Teaching Instrument equipment Co., Ltd；
Silicagel column, 2.5cm × 50cm, the production of Shanghai Zheng Hui Trade Co., Ltd.s.
Embodiment 1
A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, includes the following steps：
(1) by 2.11 grams of (98.90%, 12.28mmol) 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, 30ml bis-
The mixed solution of chloromethanes and 8ml pyridines composition is placed in three-necked flask, at 0-5 DEG C, is added dropwise into solution in 10min
The dichloromethane 10ml solution of 2.68 grams of ethyl chloroformates, is stirred simultaneously, after adding, continues to be stirred to react 18h in room temperature, reaction
After obtained reaction solution mass percent concentration be 5% aqueous hydrochloric acid solution adjust reaction solution pH to neutrality；
(2) step (1) pH is washed to neutral reaction solution extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry
Dry, next day is filtered with filter paper, and the filtrate of gained is evaporated with Rotary Evaporators, obtains carbonic acid linalool oxide (pyrans after concentration
Type and furan type) ester ethyl ester crude product 2.72g；It is detected through gas chromatographic analysis, purity 97.80%, yield 89.57%,
Wherein both carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan type) ester ethyl ester mass ratio
It is 2：3；
(3) carbonic acid linalool oxide (pyranoid form and furan type) the ester ethyl ester crude product purified by silica gel obtained step (2)
Post separation is petroleum ether by volume with petroleum ether and ethyl acetate：Ethyl acetate is 15：The mixed solvent of 1 ratio composition
Make eluent elution, until no product flows out, then steaming petroleum ether and ethyl acetate mixed solvent, finally obtain
1.96g colourless substance.
The GC-MS mass spectrometric datas of the colourless substance of above-mentioned gained are as follows：
Carbonic acid linalool oxide (pyranoid form) ester ethyl ester (II)：242(M+.),170,152,137,135,119,98,94,
84,81,68(100),59,43,41,39。
Carbonic acid linalool oxide (furan type) ester ethyl ester (I):
242(M+.),173,153,135,112,111(100),94,93,84,81,69,68,67,59,55,43,41,39。
The GC-MS mass spectrometric datas of colourless substance as obtained by above-mentioned are analyzed, the results showed that, above-mentioned gained it is colourless
Substance is carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, and through gas chromatographic analysis, purity is
98.00%, yield 72.20%.Carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furans
Type) both ester ethyl esters mass ratio is 2：3.
Embodiment 2
A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, includes the following steps：
(1) by 2.02 grams of (98.90%, 11.75mmol) 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, 30ml bis-
The mixed solution of chloromethanes and 10ml pyridines composition is placed in three-necked flask, at 0-5 DEG C, is added dropwise into solution in 10min
The dichloromethane 10ml solution of 2.55 grams of ethyl chloroformates, is stirred simultaneously, after adding, continues to be stirred to react 18h in room temperature, reaction
After obtained reaction solution mass percent concentration be 5% aqueous hydrochloric acid solution adjust reaction solution pH to neutrality；
(2) step (1) pH is washed to neutral reaction solution extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry
Dry, next day is filtered with filter paper, and the filtrate of gained is evaporated with Rotary Evaporators, obtains carbonic acid linalool oxide (pyrans after concentration
Type and furan type) ester ethyl ester crude product 2.44g；It is detected through gas chromatographic analysis, purity 98.10%, yield 84.28%,
Wherein both carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan type) ester ethyl ester mass ratio
It is 2：3；
(3) carbonic acid linalool oxide (pyranoid form and furan type) the ester ethyl ester crude product purified by silica gel obtained step (2)
Post separation is petroleum ether by volume with petroleum ether and ethyl acetate：Ethyl acetate is 15：The mixed solvent of 1 ratio composition
Make eluent elution, until no product flows out, then steaming petroleum ether and ethyl acetate solvent, finally obtain 1.71g's
Colourless carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, through gas chromatographic analysis, purity is more than
98.00%, yield 70.01%, wherein carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan
Mutter type) both ester ethyl esters mass ratio is 2：3.
Embodiment 3
A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, includes the following steps：
(1) by 1.92 grams of (98.90%, 11.17mmol) 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, 30ml bis-
The mixed solution of chloromethanes and 8ml pyridines composition is placed in three-necked flask, at 0-5 DEG C, is added dropwise into solution in 10min
The dichloromethane 10ml solution of 1.21 grams of ethyl chloroformates, is stirred simultaneously, after adding, continues to be stirred to react 20h in room temperature, reaction
After obtained reaction solution mass percent concentration be 5% aqueous hydrochloric acid solution adjust reaction solution pH to neutrality；
(2) step (1) is washed into pH to neutral reaction solution extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry
Dry, next day is filtered with filter paper, and the filtrate of gained is evaporated with Rotary Evaporators, obtains carbonic acid linalool oxide (pyrans after concentration
Type and furan type) ester ethyl ester crude product 2.14g；Through gas chromatographic detection, purity 96.18%, yield 76.23%,
Both middle carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan type) ester ethyl ester mass ratio is
2：3；
(3) carbonic acid linalool oxide (pyranoid form and furan type) the ester ethyl ester crude product purified by silica gel obtained step (2)
Post separation is petroleum ether by volume with petroleum ether and ethyl acetate：Ethyl acetate is 15：The mixed solvent of 1 ratio composition
Make eluent elution, until no product flows out, then steaming petroleum ether and ethyl acetate solvent, finally obtain 1.47g's
Colourless carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, through gas chromatographic analysis, its purity is more than 98.00%,
Yield is 69.99%, wherein carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan type) ester
Both ethyl esters mass ratio is 2：3.
Embodiment 4
A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester, includes the following steps：
(1) by 2.30 grams of (98.90%, 13.38mmol) 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, 30ml bis-
The mixed solution of chloromethanes and 8ml pyridines composition is placed in three-necked flask, at 0-5 DEG C, is added dropwise into solution in 10min
The dichloromethane 10ml solution of 2.90 grams of ethyl chloroformates, is stirred simultaneously, after adding, continues to be stirred to react 10h in room temperature, reaction
After obtained reaction solution mass percent concentration be 5% aqueous hydrochloric acid solution adjust reaction solution pH to neutrality；
(2) step (1) is washed into pH to neutral reaction solution extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry
Dry, next day is filtered with filter paper, and the filtrate of gained is evaporated with Rotary Evaporators, obtains carbonic acid linalool oxide (pyrans after concentration
Type and furan type) ester ethyl ester crude product 2.24g, through gas chromatographic analysis, purity 95.17%, yield 65.80%,
Both middle carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan type) ester ethyl ester mass ratio is
2：3；
(3) carbonic acid linalool oxide (pyranoid form and furan type) the ester ethyl ester crude product purified by silica gel obtained step (2)
Post separation is petroleum ether by volume with petroleum ether and ethyl acetate：Ethyl acetate is 15：The mixed solvent of 1 ratio composition
Make eluent elution, until no product flows out, then steaming petroleum ether and ethyl acetate mixed solvent, finally obtain
Colourless carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester of 1.52g, through gas chromatographic analysis, purity is more than
98.00%, yield 69.87%, wherein carbonic acid linalool oxide (pyranoid form) ester ethyl ester and carbonic acid linalool oxide (furan
Mutter type) both ester ethyl esters mass ratio is 2：3.
The present invention is simultaneously not limited to the embodiments described above, other any Spirit Essences and principle without departing from the present invention
Changes, modifications, substitutions, combinations, simplifications made by lower, should be equivalent substitute mode, be included in the protection model of the present invention
Within enclosing.
Claims (7)
1. the preparation method of a kind of pyranoid form and furan type carbonic acid linalool oxide ester ethyl ester, which is characterized in that including following
Step：
1) under ice-water bath, the solution that 3,7- dimethyl -6,7- epoxy -2- octen-1-ols, dichloromethane and pyridine are formed,
It is stirred until homogeneous, obtains solution A, be added dropwise to the dichloromethane solution of ethyl chloroformate in 10min into solution A, stir, add simultaneously
After complete, continue to be stirred to react 10~20 hours in room temperature, after reaction, obtained reaction solution is with mass percent concentration
5% aqueous hydrochloric acid solution adjusts reaction solution pH to neutrality, obtains neutral reaction liquid；
2) step 1) is washed into pH to neutral reaction solution extracted by ether, the anhydrous MgSO of the organic layer of gained4It is dry, next day
It is filtered with filter paper, the filtrate of gained is evaporated with Rotary Evaporators, obtains pyranoid form carbonic acid linalool oxygen shown in formula II after concentration
Furan type carbonic acid linalool oxide ester ethyl ester crude product shown in compound ester ethyl ester crude product and formula I；
3) it by the pyranoid form and furan type carbonic acid linalool oxide ester ethyl ester crude product purified by silica gel post separation obtained by step 2), uses
The mixed solvent of petroleum ether and ethyl acetate composition makees eluent, to pyranoid form and furan type carbonic acid linalool oxide ester ethyl ester
Crude product is eluted, and until no product flows out, the method for then using rotary evaporation removes petroleum ether and ethyl acetate, i.e.,
It is as follows to obtain colourless pyranoid form and furan type carbonic acid linalool oxide ester ethyl ester, reaction equation：
2. preparation method as described in claim 1, it is characterised in that：In step 1), 3,7- dimethyl -6,7- epoxy -
2- octen-1-ols, dichloromethane and pyridine are calculated by the amount and volume ratio of substance, i.e. 3,7- dimethyl -6,7- epoxies -2- is pungent
Alkene -1- alcohol：Dichloromethane：Pyridine is 1mol：1.20~3.20L：0.16~0.81L.
3. preparation method as described in claim 1, it is characterised in that：In step 1), the dichloromethane of the ethyl chloroformate
Solution concentration is 0.62~1.65mol/L.
4. preparation method as described in claim 1, it is characterised in that：In step 1), the dichloromethane of the ethyl chloroformate
The addition of solution, by 3,7- dimethyl -6,7- epoxy -2- octen-1-ols in the ethyl chloroformate and solution A contained by it
Molar ratio calculates, i.e. ethyl chloroformate：3,7- dimethyl -6,7- epoxy -2- octen-1-ols are 1.00~2.00：1.
5. preparation method as described in claim 1, it is characterised in that：In step 3), the petroleum ether and ethyl acetate composition
In the mixed solvent example calculates by volume, i.e. petroleum ether：Ethyl acetate is 15~20:1.
6. preparation method as described in claim 1, it is characterised in that：In step 3), the petroleum ether and ethyl acetate composition
In the mixed solvent example calculates by volume, i.e. petroleum ether：Ethyl acetate is 15:1.
7. preparation method as described in claim 1, it is characterised in that：The pyranoid form and furan type carbonic acid linalool oxide
In ester ethyl ester, both pyranoid form carbonic acid linalool oxide ester ethyl ester and furan type carbonic acid linalool oxide ester ethyl ester mass ratio
It is 2：3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610340126.2A CN105801529B (en) | 2016-05-22 | 2016-05-22 | A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610340126.2A CN105801529B (en) | 2016-05-22 | 2016-05-22 | A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801529A CN105801529A (en) | 2016-07-27 |
| CN105801529B true CN105801529B (en) | 2018-10-30 |
Family
ID=56451658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610340126.2A Expired - Fee Related CN105801529B (en) | 2016-05-22 | 2016-05-22 | A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801529B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625018A (en) * | 2020-12-10 | 2021-04-09 | 河南中烟工业有限责任公司 | 2, 3-dihydro-3-hydroxy-6-methyl-4H-pyran-4-one-5-O-linalyl carbonate and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59225176A (en) * | 1983-06-07 | 1984-12-18 | Taiyo Koryo Kk | Production of linalool oxide |
| CN101041647B (en) * | 2006-03-24 | 2011-03-16 | 杭州格林香料化学有限公司 | Novel production technique for linalool oxide |
-
2016
- 2016-05-22 CN CN201610340126.2A patent/CN105801529B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801529A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| SU433670A3 (en) | ||
| TWI240753B (en) | Process for the preparation of dihydroxy esters and derivatives thereof | |
| CN110467591A (en) | Rare earth metal complex promote one pot process cosmetic active object Bose because | |
| US8835670B2 (en) | Method for synthesis of lactic acid and its derivatives | |
| CN111333509A (en) | Apple flavor compound, preparation method thereof and food additive | |
| CN105801529B (en) | A kind of preparation method of carbonic acid linalool oxide (pyranoid form and furan type) ester ethyl ester | |
| Tsuboi et al. | Regio-and enantioselective reduction of. alpha., 2-dioxocycloalkaneacetates with fermenting baker's yeast. A new synthesis of (R)-(-)-hexahydromandelic acid | |
| CN102863419B (en) | Flavane 3-alcohol acetylate and its preparation method and application | |
| CN106800543A (en) | A kind of burnt fragrant and sweet type compound of furans alkoxide and its synthetic method | |
| CN106496112B (en) | The preparation method and applications of the latent fragrant monomer pyridine -3,5- diformic ester of cigarette | |
| CN110128385A (en) | A kind of quercetin derivative and its synthetic method by lauroyl chloride chemical modification | |
| CN106478418B (en) | The preparation method and applications of the latent fragrant monomer 3- cinnamic acid esters of cigarette | |
| CN107089957A (en) | A kind of preparation method of the furans ethanol of 2 methyl of 4H 5 (Methylethyl of 1 hydroxyl 1) 2 | |
| Ikejiri et al. | A novel and efficient method for inside selective esterification of terminal vic-diols | |
| CN101538202A (en) | Method for preparing ferulic acid ethylester by thionyl chloride catalysis | |
| CN106496149B (en) | The preparation method and applications of the latent fragrant monomer pyrazine -2- formate ester of cigarette | |
| CN107032971B (en) | Preparation method of 3, 7-dimethyl-6-carbonyl-2-octenal | |
| CN105037348B (en) | A kind of Retapamulin synthetic method | |
| CN107129475B (en) | A kind of preparation method of furan type linalool oxide | |
| CN104193601B (en) | A kind of novel method preparing 3-methyl-2-amylene-4-alkynes-1-aldehyde | |
| KR20160075922A (en) | Anhydrosugar alcohol ester with improved color and method for preparing the same | |
| CN108484586A (en) | A kind of preparation method of 2- [5- methyl -5- (epoxy -2- bases) tetrahydrofuran base] -2- propyl alcohol | |
| CN104844454B (en) | The preparation method of carbonic acid 1-(5-hydroxyl-2,6,6-trimethyl-2-cyclohexenyl group) methanol ester ethyl ester | |
| KR102657359B1 (en) | A novel compound having antioxidant activity and anti-inflammatory activity and a composition for antioxidant activity and anti-inflammatory according to thereof | |
| KR102672137B1 (en) | A synthesis method and synthesis kit for novel naringin compound having antioxidant activity and anti-inflammatory activity through enzymatic synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181030 Termination date: 20210522 |