CN107129475A - A kind of preparation method of furan type linalool oxide - Google Patents
A kind of preparation method of furan type linalool oxide Download PDFInfo
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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Abstract
The invention discloses a kind of preparation method of furan type linalool oxide.It is comprised the following steps that：First at room temperature, the furans ethanol of 4H 5 (Methylethyl of 1 hydroxyl 1) 2 methyl 2, paratoluensulfonyl chloride and alkali are mixed into reaction, after reaction terminates, pH is adjusted to neutrality with acid solution, extracts, dry, filter；Filtrate is concentrated by evaporation and obtains sulphonic acid ester.Then, reaction obtains crude product at a temperature of potassium tert-butoxide and the tert-butyl alcohol, 70~80 DEG C are added in sulphonic acid ester；The purified processing of crude product obtains furan type linalool oxide.The preparation method raw material of the present invention is easy to get, preparation process is simple and convenient to operate, and production cost is relatively low, suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of technical field of organic synthesis, a kind of system of furan type linalool oxide is particularly related to
Preparation Method.
Background technology
Linalool oxide, also known as epoxylinalol, are colourless to weak yellow liquid, are essential oil, fruit peel volatile oil and white
The important composition composition of grape wine etc..It includes the isomer of four kinds of structures, with furan type linalool oxide and pyranoid form
Two kinds of forms of linalool oxide are present, and two kinds of linalool oxide is the mixture of two kinds of isomers of cis and trans.
Most commonly furan type linalool oxide, pyranoid form is not common.Fragrance has the strong banksia rose, the fragrance of a flower based on furan type
Feature, or light lavender is fragrant, is a kind of good spices.Pyranoid form then has strong camphor smell, tea smell.My god
Right linalool oxide is the mixture of furan type and pyranoid form linalool oxide, and wherein furan type linalool oxide is accounted for
90%.It is a kind of particularly useful spices, especially in spices, foods and cosmetics industry, has a wide range of applications.On this
The preparation of compound, has substantial amounts of document report, most of is all that geraniol and nerol are raw material, with oxidation with linalool
Agent is aoxidized, and obtained product is the mixture of furan type and pyranoid form linalool oxide.
, Japanese the palace side of body clear grade of English (Production of linalool oxide [P], Jap.225176 in 1984
(1984) linalool and 40.00% formic acid) are heated to 60~65 DEG C, 30.00% Peracetic acid, temperature is added dropwise in 1.00h or so
Degree is maintained at after 65~75 DEG C, stirring reaction 2h, and the mixing of furan type and pyranoid form linalool oxide is obtained after being post-processed
Thing, cis and trans furan type linalool oxide 58.70%；Cis and trans pyranoid form linalool oxide 34.30%.
, (the Straightforward diastereoselective synthesis of such as Garcia M A in 1994
trans-linalyl oxide by an untramolecular SN2’reaction[J],Synlett.,1994(11):
It is 911-912) raw material with nerol, is first acylated with acyl chlorides, then carries out double bond epoxidation with organic peroxide acid, then not
Intramolecular cyclization under same Lewis acid catalysis, exclusively obtains trans furan type linalool oxide.Although this method is exclusively
Trans furan type linalool oxide, but severe reaction conditions are obtained, reaction scheme is long.
, (Palladium (0)-catalysed synthesis of cis-and such as Nguefack C.F in 1997
trans-linalyl oxides[J],Tetrahedron,1997,53(12):4353-4362) using geraniol as raw material, carry out
The three-dimensional synthesis of linalool oxide.Geraniol and ethyl chloroformate are reacted, obtaining allyl carbonate, (yield is
82.00%).The carbonic ester is hydrolyzed again through bromo is transformed into dihydroxy compounds (yield is 68.00%).Then, in THF,
Pb (0) class catalyst of certain catalytic amount is added at 50 DEG C, dihydroxy compounds is cyclized, obtained cis, trans (20/80)
Furan type linalool oxide mixture, yield is 52.00%.Although this method has obtained single furan type oxidation virtue
Camphor tree alcohol, but reaction scheme is long, and severe reaction conditions, yield is not high.
2013, the bright grade of paddy fortune (synthesis [J] of linalool oxide, fragrance flavor and cosmetic, supplementary issue, 2013 (ZL),
28-31) using linalool as raw material, it is respectively oxidizing linalool with Peracetic acid and hydrogen peroxide, carries out linalool oxide
Synthesis.With Peracetic acid method linalool oxide, the mixture of furan type and pyranoid form linalool oxide is obtained, yield is
61.00%.The ratio of furan type and pyranoid form linalool oxide is 6：1.Peroxide passivation linalool oxide is used, furan type is also obtained
With the mixture of pyranoid form linalool oxide, yield is 64.20%, and the ratio of furan type and pyranoid form linalool oxide is 4：1.
Above several method is all that geraniol and nerol are raw material, are aoxidized, had with organic peroxide acid with linalool
Machine peroxy acid is a kind of material of explosive, explosive, severe reaction conditions；In addition, reaction scheme is long, yield is not high, obtains
Be furan type and pyranoid form linalool oxide mixture.
The content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of preparation of furan type linalool oxide
Method.The present invention preparation method it is raw materials used be easy to get, preparation process is simple and convenient to operate, suitable for industrialized production.
Technical scheme is specifically described as follows.
A kind of preparation method of furan type linalool oxide, is comprised the following steps that：
(1) 4H-5- (1- hydroxyl -1- Methylethyls) -2- methyl -2- furans ethanol, paratoluensulfonyl chloride and alkali are mixed
Afterwards, 20~25h of stirring reaction at room temperature, after reaction terminates, with the pH of sour regulation system to neutrality, then is extracted, organic phase drying,
It is concentrated to give sulphonic acid ester；
(2) sulphonic acid ester and potassium tert-butoxide are dissolved in the tert-butyl alcohol, reaction 5~7 hours at a temperature of 70~80 DEG C, instead
After should terminating, with the pH of sour regulation system to neutrality, then extract, organic phase is dried, is concentrated to give crude product；Crude product is carried out again pure
Change processing obtains furan type linalool oxide.
In the present invention, in step (1), 4H-5- (1- hydroxyl -1- Methylethyls) -2- methyl -2- furans ethanol and to toluene
The mol ratio of sulfonic acid chloride is 1:1.0~1：3.0.
In the present invention, in step (1), alkali is pyridine or sodium hydroxide.
In the present invention, in step (1) and step (2), acid is hydrochloric acid.
In the present invention, in step (2), the rate of charge of sulphonic acid ester, potassium tert-butoxide and the tert-butyl alcohol is 1mol:(1.0~3.0)
mol：(2.00~4.00) L.
In the present invention, in step (2), purification process is carried out using column chromatography.
Compared to the prior art, the beneficial effects of the present invention are：
The preparation method of a kind of furan type linalool oxide of the present invention, due to raw material used in preparation process and synthesis
The difference of route, has solely synthesized furan type linalool oxide.It is easy to get there is provided a kind of raw material, preparation process is simple, operation
The preparation method of convenient furan type linalool oxide.The yield of final crude product furan type linalool oxide up to 72.90~
82.39%.
Further, 4H-5- (1- hydroxyl -1- methyl used in the preparation method of furan type linalool oxide of the invention
Ethyl) -2- methyl -2- furans ethanol raw materials are easy to get, cheap, so the preparation side of the furan type linalool oxide of the present invention
Method production cost is relatively low, suitable for industrialized production.
Embodiment
The present invention is described in further detail below by embodiment, but is not intended to limit the present invention.
The model of various analytical instrument used in the present invention and the information of manufacturer are as follows：
Bruker AVANCE III 500MHz NMRs, the production of Bruker companies of Switzerland；
The FT-IR type infrared spectrometers of Nicolet Avatar 360, the production of Nicolet companies of the U.S.；
6890N-5973 GC-MS, Agilent company of the U.S. production；
Equipment used and the information of manufacturer are as follows in various embodiments of the present invention：
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.
A kind of preparation method of furan type linalool oxide, the equation of its course of reaction is as follows：
Embodiment 1
A kind of preparation method of furan type linalool oxide, comprises the following steps：
(1), at room temperature, by 1.01 grams of (98.90%, 5.31mmol) 4H-5- (1- hydroxyl -1- Methylethyls) -2- first
The mixed solution A of base -2- furans ethanol, 1.01 grams of (5.31mmol) paratoluensulfonyl chlorides and 6mL anhydrous pyridines composition, stirring is anti-
Answer after 24h, the reaction solution of gained is washed with mass percent concentration for 10% HCl/water solution, pH is to neutrality for washing, uses acetic acid
Ethyl ester extractive reaction liquid, the anhydrous MgSO of organic layer of gained4Dry, next day is filtered with filter paper, the filtrate of gained is steamed with rotation
Intermediate sulfonic acid ester crude product I is obtained after the evaporation of hair instrument, concentration.In this crude product, 0.60 gram is further added
(5.36mmol) potassium tert-butoxide, the 20.00mL tert-butyl alcohols, obtain solution B, rise to 70~80 DEG C of reflux temperature, continue to be stirred at reflux
6h is reacted, the HCl/water solution that cooling adds 10% washs pH to neutrality；
(2), step (1) pH is washed to neutral reaction solution extracted by ether, the anhydrous MgSO of organic layer of gained4It is dry
Dry, next day is filtered with filter paper, the filtrate of gained evaporated with Rotary Evaporators, concentrate after obtain furan type linalool oxide crude product
0.61g, is detected through gas chromatographic analysis, and its purity is 97.80%, yield 72.91%, wherein both cis and trans mass ratioes
For 1：1；
(3), the furan type linalool oxide crude product purified by silica gel post separation for obtaining step (2), with petroleum ether and acetic acid
Ethyl ester is petroleum ether by volume：Ethyl acetate is 9：The mixed solvent of 1 ratio composition makees eluent elution, until without product
Untill outflow, then steaming petroleum ether and ethyl acetate mixed solvent, finally give 0.44g colourless substance.Through gas-chromatography
Analysis, its purity is 98.00%, and yield is 72.28%.Its both cis and trans mass ratio is 1：1.
The ir data of the colourless substance of above-mentioned gained is as follows：
IR(ν/cm-1, liquid film)：3455(ν-OH),3090(νC=CH2),1637(νC=C),1465(νCH2),1375(νCH3),
1121(νC-O-C)。
The nuclear magnetic resonance modal data of the colourless substance of above-mentioned gained is as follows：
Trans furan type linalool oxide：1HNMR(500MHZ,CDCl3)δ：1.14(s,3H,CH3),1.23(s,3H,
CH3),1.32(s,3H,CH3),1.70-1.95(m,4H,H-3,H-4),2.18(s,1H,OH),3.80(m,1H,H-5),5.00
(dd, J=1.6,10.6Hz, 1H ,=CH2), 5.16 (dd, J=1.6,17.3Hz, 1H ,=CH2), 5.88 (dd, J=10.6,
17.3Hz, 1H ,=CH-)；
Cis furan type linalool oxide：1HNMR(500MHZ,CDCl3)δ:1.13(s,3H,CH3),1.23(s,3H,
CH3),1.32(s,3H,CH3),1.70-1.95(m,4H,H-3,H-4),2.18(s,1H,OH),3.87(m,1H,H-5),5.01
(dd, J=1.2,10.7Hz, 1H ,=CH2), 5.20 (dd, J=1.2,17.4Hz, 1H ,=CH2), 5.98 (dd, J=10.7,
17.4Hz, 1H ,=CH-).
Ir data, nuclear magnetic resonance modal data and the mass spectrometric data of colourless substance as obtained by above-mentioned are divided
Analysis, as a result shows, the colourless substance of above-mentioned gained is furan type linalool oxide.
Embodiment 2
A kind of preparation method of furan type linalool oxide, comprises the following steps：
(1), at room temperature, by 1.21 grams of (98.90%, 6.37mmol) 4H-5- (1- hydroxyl -1- Methylethyls) -2- first
Base -2- furans
The mixed solution A for the ethanol, 2.43 grams of (12.76mmol) paratoluensulfonyl chlorides and 7mL anhydrous pyridines composition of muttering, stirring
React after 24h, the reaction solution of gained is washed with mass percent concentration for 10% HCl/water solution, pH is to neutrality for washing, uses second
Acetoacetic ester extractive reaction liquid, the anhydrous MgSO of organic layer of gained4Dry, next day is filtered with filter paper, the filtrate rotation of gained
Intermediate sulfonic acid ester crude product I is obtained after evaporimeter evaporation, concentration.In this crude product, 1.43 grams are further added
(12.77mmol) potassium tert-butoxide, the 25.00mL tert-butyl alcohols, obtain solution B, rise to 70~80 DEG C of reflux temperature, continue to be stirred at reflux
6h is reacted, the HCl/water solution that cooling adds 10% washs pH to neutrality；
(2), step (1) pH is washed to neutral reaction solution extracted by ether, the anhydrous MgSO of organic layer of gained4It is dry
Dry, next day is filtered with filter paper, the filtrate of gained evaporated with Rotary Evaporators, concentrate after obtain furan type linalool oxide crude product
0.80g, is detected through gas chromatographic analysis, and its purity is 97.63%, and yield is 79.70%, wherein both cis and trans quality
Than for 1：1；
(3), the furan type linalool oxide crude product purified by silica gel post separation for obtaining step (2), with petroleum ether and acetic acid
Ethyl ester is petroleum ether by volume：Ethyl acetate is 9：The mixed solvent of 1 ratio composition makees eluent elution, until without product
Untill outflow, then steaming petroleum ether and ethyl acetate solvent, the colourless furan type linalool oxide for finally giving 0.56g are pure
Product, through gas chromatographic analysis, its purity 98.00%, yield is 70.27%, wherein cis is 1 with both trans mass ratioes：1.
Embodiment 3
A kind of preparation method of furan type linalool oxide, comprises the following steps：
(1), at room temperature, by 1.11 grams of (98.90%, 5.84mmol) 4H-5- (1- hydroxyl -1- Methylethyls) -2- first
The mixed solution A of base -2- furans ethanol, 3.34 grams of (17.53mmol) paratoluensulfonyl chlorides and 8mL anhydrous pyridines composition, stirring
React after 24h, the reaction solution of gained is washed with mass percent concentration for 10% HCl/water solution, pH is to neutrality for washing, uses second
Acetoacetic ester extractive reaction liquid, the anhydrous MgSO of organic layer of gained4Dry, next day is filtered with filter paper, the filtrate rotation of gained
Intermediate sulfonic acid ester crude product I is obtained after evaporimeter evaporation, concentration.In this crude product, 1.96 grams are further added
(17.50mmol) potassium tert-butoxide, the 30.00mL tert-butyl alcohols, obtain solution B, rise to 70~80 DEG C of reflux temperature, continue to be stirred at reflux
6h is reacted, the HCl/water solution that cooling adds 10% washs pH to neutrality；
(2) step (1), is washed into pH to neutral reaction solution extracted by ether, the anhydrous MgSO of organic layer of gained4It is dry
Dry, next day is filtered with filter paper, the filtrate of gained evaporated with Rotary Evaporators, concentrate after obtain furan type linalool oxide crude product
0.77g, through gas chromatographic detection, its purity is 96.18%, and yield is 82.38%, wherein cis be with both trans mass ratioes
1：1；
(3), the furan type linalool oxide crude product purified by silica gel post separation for obtaining step (2), with petroleum ether and acetic acid
Ethyl ester is petroleum ether by volume：Ethyl acetate is 9：The mixed solvent of 1 ratio composition makees eluent elution, until without product
Untill outflow, then steaming petroleum ether and ethyl acetate solvent, the colourless furan type linalool oxide for finally giving 0.53g are pure
Product, through gas chromatographic analysis, its purity is more than 98.00%, and yield is 70.13%, wherein cis is 1 with both trans mass ratioes：
1。
Embodiment 4
A kind of preparation method of furan type linalool oxide, comprises the following steps：
(1), at room temperature, by 1.32 grams of (98.90%, 6.94mmol) 4H-5- (1- hydroxyl -1- Methylethyls) -2- first
The mixed solution A of base -2- furans ethanol, 3.96 grams of (20.75mmol) paratoluensulfonyl chlorides and 8mL anhydrous pyridines composition, stirring
React after 24h, the reaction solution of gained is washed with mass percent concentration for 10% HCl/water solution, pH is to neutrality for washing, uses second
Acetoacetic ester extractive reaction liquid, the anhydrous MgSO of organic layer of gained4Dry, next day is filtered with filter paper, the filtrate rotation of gained
Intermediate sulfonic acid ester crude product I is obtained after evaporimeter evaporation, concentration.In this crude product, 2.32 grams are further added
(20.71mmol) potassium tert-butoxide, the 40.00mL tert-butyl alcohols, obtain solution B, rise to 70~80 DEG C of reflux temperature, continue to be stirred at reflux
6h is reacted, the HCl/water solution that cooling adds 10% washs pH to neutrality；
(2) step (1), is washed into pH to neutral reaction solution extracted by ether, the anhydrous MgSO of organic layer of gained4It is dry
Dry, next day is filtered with filter paper, the filtrate of gained evaporated with Rotary Evaporators, concentrate after obtain furan type linalool oxide crude product
0.88g, through gas chromatographic analysis, its purity is 96.27%, and yield is 79.18%, wherein cis be with both trans mass ratioes
1：1；
(3), the furan type linalool oxide crude product purified by silica gel post separation for obtaining step (2), with petroleum ether and acetic acid
Ethyl ester is petroleum ether by volume：Ethyl acetate is 9：The mixed solvent of 1 ratio composition makees eluent elution, until without product
Untill outflow, then steaming petroleum ether and ethyl acetate mixed solvent, finally give the 0.62g colourless fragrant camphor tree of furan type oxidation
Alcohol, through gas chromatographic analysis, its purity is more than 98.00%, and yield is 71.71%, wherein cis be with both trans mass ratioes
1：1.
Above example is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, reading this hair
After the content of bright instruction, those skilled in the art can make various changes or modifications to the present invention, and these equivalent form of values are same
Fall within the application appended claims limited range.
Claims (6)
1. a kind of preparation method of furan type linalool oxide, it is characterised in that comprise the following steps that：
(1) after 4H-5- (1- hydroxyl -1- Methylethyls) -2- methyl -2- furans ethanol, paratoluensulfonyl chloride and alkali being mixed, room
Lower 20~the 25h of stirring reaction of temperature, after reaction terminates, with the pH of sour regulation system to neutrality, then is extracted, organic phase is dried, concentration
Obtain sulphonic acid ester；
(2) sulphonic acid ester and potassium tert-butoxide are dissolved in the tert-butyl alcohol, reacted 5~7 hours at a temperature of 70~80 DEG C, reaction knot
Shu Hou, with the pH of sour regulation system to neutrality, then is extracted, organic phase is dried, is concentrated to give crude product；Crude product is carried out at purifying again
Reason obtains furan type linalool oxide.
2. preparation method according to claim 1, it is characterised in that in step (1), 4H-5- (1- hydroxyl -1- methyl second
Base) mol ratio of -2- methyl -2- furans ethanol and paratoluensulfonyl chloride is 1:1.0~1：3.0.
3. preparation method according to claim 1, it is characterised in that in step (1), alkali is pyridine or sodium hydroxide.
4. preparation method according to claim 1, it is characterised in that in step (1) and step (2), acid is hydrochloric acid.
5. preparation method according to claim 1, it is characterised in that in step (2), sulphonic acid ester, potassium tert-butoxide and tertiary fourth
The rate of charge of alcohol is 1mol:(1.0~3.0) mol：(2.00~4.00) L.
6. preparation method according to claim 1, it is characterised in that in step (2), is carried out at purifying using column chromatography
Reason.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002293775A (en) * | 2001-03-29 | 2002-10-09 | Kuraray Co Ltd | Method for producing linalool oxide |
| CN1396262A (en) * | 2000-11-07 | 2003-02-12 | 哈尔曼及赖默股份有限公司 | Preparation method of epoxyinalool or mixture containing epoxy inalool |
| CN101041647A (en) * | 2006-03-24 | 2007-09-26 | 杭州格林香料化学有限公司 | Novel production technique for linalool oxide |
| WO2016183150A1 (en) * | 2015-05-12 | 2016-11-17 | Temple University-Of The Commonwealth System Of Higher Education | Novel sigma-2 receptor binders and their method of use |
-
2017
- 2017-04-27 CN CN201710287134.XA patent/CN107129475B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396262A (en) * | 2000-11-07 | 2003-02-12 | 哈尔曼及赖默股份有限公司 | Preparation method of epoxyinalool or mixture containing epoxy inalool |
| JP2002293775A (en) * | 2001-03-29 | 2002-10-09 | Kuraray Co Ltd | Method for producing linalool oxide |
| CN101041647A (en) * | 2006-03-24 | 2007-09-26 | 杭州格林香料化学有限公司 | Novel production technique for linalool oxide |
| WO2016183150A1 (en) * | 2015-05-12 | 2016-11-17 | Temple University-Of The Commonwealth System Of Higher Education | Novel sigma-2 receptor binders and their method of use |
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| Title |
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| PARTHA GHOSAL ET AL: "Diastereoselective one-pot Wittig olefination–Michael addition and olefin cross metathesis strategy for total synthesis of cytotoxic natural product (+)-varitriol and its higher analogues", 《ORG. BIOMOL. CHEM》 * |
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