CN105001061A - Methoxy elgenol derivative and preparation method thereof - Google Patents
Methoxy elgenol derivative and preparation method thereof Download PDFInfo
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- CN105001061A CN105001061A CN201510307830.3A CN201510307830A CN105001061A CN 105001061 A CN105001061 A CN 105001061A CN 201510307830 A CN201510307830 A CN 201510307830A CN 105001061 A CN105001061 A CN 105001061A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
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Abstract
The invention provides a methoxy elgenol derivative. The methoxy elgenol derivative is characterized in that the general formula of the methoxy elgenol derivative is shown (please see the formula in the instruction), wherein R is methyl or ethyl or propyl or butyl or isobutyl. The invention further provides a preparation method of the methoxy elgenol derivative. Dihydromyrcenol is taken as a raw material, and after etherification and epoxidation, the obtained product is subjected to hydrogenation reduction to obtain the methoxy elgenol similar derivative. According to the methoxy elgenol derivative and the preparation method thereof, the raw material is low in price and easy to obtain, simple and safe effects are achieved, the environmentally friendly effect is achieved, the range of application is wide, post processing is simple, the yield is high, the method for synthesizing the methoxy elgenol derivative is fast and efficient, and the methoxy elgenol derivative has strong and favorable sandalwood odor and cool and refreshing flowery fragrance.
Description
Technical field
The invention belongs to organic learning areas, particularly relate to a kind of sandaler derivative and preparation method thereof.
Background technology
Due to current natural santal resource scarcity, tooling cost is large, and on market, the price of santal class spices soars, and this just makes its application be restricted in many aspects, supply falls short of demand for current natural sandalwood oil, and this becomes increasingly active with regard to impelling the exploitation of sandenol.And sandenol has very high chemical stability and very little volatility, also be good fixative, can improve persistence and the stability of essence, sandenol also can be coordinated with the fragrance of floral type with illusion type component well mutually, is thus used to preparation perfume fragrance and soap compound.But China is developing in santal series products, and kind is few, and product quality and external product also have a certain distance, competitive power is in the international market also strong, and the market share shared is in the international market not high yet.Therefore, exploitation sandenol compounds, optimizes its production technique, and improving the purity that it sends out component fragrant, is the focus of domestic and international spices worker research.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of sandaler derivative and preparation method thereof, described this sandaler derivative and preparation method thereof solves natural santal resource scarcity in prior art, technical problem that natural sandalwood oil use cost is high.
The invention provides a kind of sandaler derivative, its general formula is as follows:
Wherein, R is methyl, ethyl, propyl group, butyl or isobutyl-.
Present invention also offers the preparation method of above-mentioned a kind of sandaler derivative, comprise the steps:
The step of (1) preparation formula (1) compound, the structural formula of described formula (1) compound describes as follows,
at room temperature, in the first organic solvent, add dihydromyrcenol and sodium hydrogen, the mol ratio of sodium hydrogen and dihydromyrcenol is 1.2 ~ 2.5:1, then refluxes 2 ~ 8 hours, drip halogenated alkane, continue reaction, TLC detection reaction terminates, and uses frozen water cancellation, separate organic layer, carry out underpressure distillation and obtain formula 1 compound;
The step of (2) preparation formula (2) compounds, the structural formula of described formula (2) compound describes as follows,
take hydrogen peroxide as oxygen source, add formula (1) compound in a second organic solvent, under phospho heteropoly tungstate catalyst action, back flow reaction, TLC detection reaction terminates, filtering recovering catalyst, organic layer concentrates underpressure distillation and obtains formula (2) compound, wherein, and mass ratio 1:0.08 ~ 0.1 of formula (1) compound and catalyzer; The mol ratio of formula (1) compound and hydrogen peroxide is 1:3 ~ 7;
(3) formula (2) compound is dissolved in the 3rd organic solvent, under reflux conditions, add POTASSIUM BOROHYDRIDE or sodium borohydride in batches, continue back flow reaction, after reaction terminates, add frozen water cancellation, extraction, organic layer concentrates underpressure distillation and obtains sandaler derivative, wherein, and mol ratio 1:1 ~ 2 of formula (2) compound and POTASSIUM BOROHYDRIDE or sodium borohydride.
Further, in step (1), the rate of addition of halogenated alkane is 0.1 ~ 0.8ml/s.
Further, the first described organic solvent is toluene.Concrete, the add-on of the first organic solvent is exceed the amount of dissolving dihydromyrcenol and sodium hydrogen.
Further, the second described organic solvent is methylene dichloride.Concrete, the add-on of the second organic solvent is for exceeding the amount of dissolution type (1) compound.
Further, the 3rd described organic solvent is ethanol.Concrete, the add-on of the 3rd organic solvent is for exceeding the amount of dissolution type (2) compound, POTASSIUM BOROHYDRIDE or sodium borohydride.
Further, in step (3), extraction into ethyl acetate is adopted.
The synthetic route of above-mentioned preparation method is as follows:
Wherein, X is halogen, and R is the alkyl groups such as methyl, ethyl, propyl group, butyl, isobutyl-.
The present invention is by being raw material with dihydromyrcenol, and first through etherificate, epoxidation, eventually passes hydro-reduction and obtain a kind of sandaler derivative.
The present invention compares with prior art, and its technical progress is significant.Cheaper starting materials of the present invention is easy to get, simple and safe, environmentally friendly, applied widely, aftertreatment is simple, productive rate is high, it is a kind of method of rapidly and efficiently sandenol ether derivant, and derivative of the present invention not only has strong and favorable santal, and there is refrigerant and refreshing fragrance of a flower fragrance.
Embodiment
Below in conjunction with the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
(1) 3,7-dimethyl-7-butoxy octene is synthesized
Under room temperature, toluene 400ml is joined in the there-necked flask of 1000ml, myrcenol (156.1g is added successively under stirring, 1mol) add 60% sodium hydride (48g in batches, 1.2mol), be warming up to 110 degree, be incubated 2 hours, drip 1-chlorobutane (92.6g, 1mol) and continue stirring reaction 6 hours, be cooled to room temperature, shrend on the rocks is gone out reaction, separates organic layer, organic layer rectification under vacuum, reclaim raw material myrcenol 41.2g, collect product frac 142.4g(gas phase content 95.8) productive rate 67.2%.
(2) 3,7-dimethyl-7-butoxy-1,2-octylene oxide is synthesized
The catalyzer of epoxidation reaction is open in CN00123339. 4, and its preparation process is shown in CN00123339. 4.
80 g (2. 32mol) 30% hydrogen peroxide is added in 500 mL, tri-mouthfuls of round-bottomed flasks, 98.4 g (0. 464 mol) 3, 7-dimethyl-7-butoxy-1, 2-octylene oxide, 9.8 g catalyzer 250 mL methylene dichloride, after back flow reaction 22 h, gas chromatographic analysis 3, 7-dimethyl-7-methoxyl group-1, the selectivity of 2-octylene oxide is 86. 4%, cooling, the hydrogen peroxide do not run out of is removed with sodium bisulfite, suction filtration, filter cake is washed, reclaim catalyzer (reusable), filtrate extraction obtains organic layer, carry out normal pressure recycling design, raw material 3 is reclaimed in underpressure distillation, 7-dimethyl-7-methoxyl group octene 13.6 g, collecting ring oxidation products 3, 7-dimethyl-7-butoxy-1, 2-octylene oxide 82.7g (gas phase content 97. 21%), productive rate 78.2%.
(3) sandenol ether derivant 3,7-dimethyl-7-butoxy-sec-n-octyl alcohol
3 are added in 250 mL, tri-mouthfuls of round-bottomed flasks, 7-dimethyl-7-butoxy-1, 2-octylene oxide (34.2 g, 0. 15mol) and 220mL ethanol, under reflux conditions, 3 times (adding once every 10 min) are divided to add in reactor 7. 4 g (0. 2 mol) POTASSIUM BOROHYDRIDE, after back flow reaction 5 h, the selectivity of gas chromatographic analysis sandaler is 98. 85%, cooling, be washed to neutrality, be extracted with ethyl acetate and obtain organic layer, first normal pressure steams solvent, underpressure distillation obtains product 3 again, 7-dimethyl-7-butoxy-sec-n-octyl alcohol 26.7 g (gas phase content is 98. 84%), productive rate 77.9%.
Embodiment 2
(1) 3,7-dimethyl-7-pentyloxy octene is synthesized
Under room temperature, toluene 400ml is joined in the there-necked flask of 1000ml, myrcenol (156.1g is added successively under stirring, 1mol) add 60% sodium hydride (60g in batches, 1.5mol), be warming up to 110 degree, be incubated 2 hours, drip 1-chloropentane (106.6g, 1mol) and continue stirring reaction 6 hours, be cooled to room temperature, shrend on the rocks is gone out reaction, separates organic layer, organic layer rectification under vacuum, reclaim raw material myrcenol 36g, collect product frac 239.2g(gas phase content 96.3) productive rate 75.1%.
(2) 3,7-dimethyl-7-butoxy-1,2-octylene oxide is synthesized
The catalyzer of epoxidation reaction is open in CN00123339. 4, and its preparation process is shown in CN00123339. 4.
80 g (2. 32mol) 30% hydrogen peroxide is added in 500 mL, tri-mouthfuls of round-bottomed flasks, 147.6g (0. 464 mol) 3, 7-dimethyl-7-pentyloxy-1, 2-octylene oxide, 15 g catalyzer 300 mL methylene dichloride, after back flow reaction 22 h, gas chromatographic analysis 3, 7-dimethyl-7-methoxyl group-1, the selectivity of 2-octylene oxide is 88. 4%, cooling, the hydrogen peroxide do not run out of is removed with sodium bisulfite, suction filtration, filter cake is washed, reclaim catalyzer (reusable), filtrate extraction obtains organic layer, carry out normal pressure recycling design, raw material 3 is reclaimed in underpressure distillation, 7-dimethyl-7-methoxyl group octene 22.1 g, collecting ring oxidation products 3, 7-dimethyl-7-butoxy-1, 2-octylene oxide 116.9g (gas phase content 98. 56%), productive rate 79.7%.
(3) sandenol ether derivant 3,7-dimethyl-7-butoxy-sec-n-octyl alcohol
3 are added in 250 mL, tri-mouthfuls of round-bottomed flasks, 7-dimethyl-7-pentyloxy-1, 2-octylene oxide (36.3 g, 0. 15mol) and 250mL ethanol, under reflux conditions, 3 times (adding once every 10 min) are divided to add in reactor 7. 4 g (0. 2 mol) POTASSIUM BOROHYDRIDE, after back flow reaction 5 h, the selectivity of gas chromatographic analysis sandaler is 98.92%, cooling, be washed to neutrality, be extracted with ethyl acetate and obtain organic layer, first normal pressure steams solvent, underpressure distillation obtains product 3 again, 7-dimethyl-7-butoxy-sec-n-octyl alcohol 29.54 g (gas phase content is 98. 32%), productive rate 81.3%.
Upper embodiment shows, according to preparation method provided by the invention, can obtain a series of sandaler derivative that has use value, operation is simple for whole implementation process, can meet Technological Economy requirement, environmentally friendly.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all belong to protection scope of the present invention.
Claims (7)
1. a sandaler derivative, is characterized in that: its general formula is as follows,
, wherein, R is methyl, ethyl, propyl group, butyl or isobutyl-.
2. the preparation method of a kind of sandaler derivative according to claim 1, is characterized in that comprising the steps:
The step of (1) preparation formula (1) compound, the structural formula of described formula (1) compound describes as follows,
at room temperature, in the first organic solvent, add dihydromyrcenol and sodium hydrogen, the mol ratio of sodium hydrogen and dihydromyrcenol is 1.2 ~ 2.5:1, then refluxes 2 ~ 8 hours, drip halogenated alkane, continue reaction, TLC detection reaction terminates, and uses frozen water cancellation, separate organic layer, carry out underpressure distillation and obtain formula 1 compound;
The step of (2) preparation formula (2) compounds, the structural formula of described formula (2) compound describes as follows,
take hydrogen peroxide as oxygen source, add formula (1) compound in a second organic solvent, under phospho heteropoly tungstate catalyst action, back flow reaction, TLC detection reaction terminates, filtering recovering catalyst, organic layer concentrates underpressure distillation and obtains formula (2) compound, wherein, and mass ratio 1:0.08 ~ 0.1 of formula (1) compound and catalyzer; The mol ratio of formula (1) compound and hydrogen peroxide is 1:3 ~ 7;
(3) formula (2) compound is dissolved in the 3rd organic solvent, under reflux conditions, add POTASSIUM BOROHYDRIDE or sodium borohydride in batches, continue back flow reaction, after reaction terminates, add frozen water cancellation, extraction, organic layer concentrates underpressure distillation and obtains sandaler derivative, wherein, and mol ratio 1:1 ~ 2 of formula (2) compound and POTASSIUM BOROHYDRIDE or sodium borohydride.
3. the preparation method of a kind of sandaler derivative according to claim 2, is characterized in that: in step (1), the rate of addition of halogenated alkane is 0.1 ~ 0.8ml/s.
4. the preparation method of a kind of sandaler derivative according to claim 2, is characterized in that: the first described organic solvent is toluene.
5. the preparation method of a kind of sandaler derivative according to claim 2, is characterized in that: the second described organic solvent is methylene dichloride.
6. the preparation method of a kind of sandaler derivative according to claim 2, is characterized in that: the 3rd described organic solvent is ethanol.
7. the preparation method of a kind of sandaler derivative according to claim 2, is characterized in that: in step (3), adopts extraction into ethyl acetate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002970A (en) * | 2019-04-29 | 2019-07-12 | 宁夏万香源生物科技有限公司 | The production method and production system of sandaler |
| CN111675606A (en) * | 2020-04-22 | 2020-09-18 | 南平青华科技有限公司 | Preparation method of sandalwood ether |
| CN112898159A (en) * | 2021-01-29 | 2021-06-04 | 东莞波顿香料有限公司 | Ester compound and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906024A (en) * | 2010-07-29 | 2010-12-08 | 上海应用技术学院 | Method for preparing sandaler |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906024A (en) * | 2010-07-29 | 2010-12-08 | 上海应用技术学院 | Method for preparing sandaler |
Non-Patent Citations (2)
| Title |
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| -: "RN 87605-58-1 REGISTRY", 《STN REGISTRY》 * |
| A. LEE MILLER II ET AL.: "Site-Isolation and Recycling of PdCl2 using PDMS Thimbles", 《J. ORG. CHEM.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002970A (en) * | 2019-04-29 | 2019-07-12 | 宁夏万香源生物科技有限公司 | The production method and production system of sandaler |
| CN110002970B (en) * | 2019-04-29 | 2021-12-10 | 宁夏万香源生物科技有限公司 | Production method and production system of sandalwood ether |
| CN111675606A (en) * | 2020-04-22 | 2020-09-18 | 南平青华科技有限公司 | Preparation method of sandalwood ether |
| CN111675606B (en) * | 2020-04-22 | 2023-01-31 | 南平青华科技有限公司 | Preparation method of sandalwood ether |
| CN112898159A (en) * | 2021-01-29 | 2021-06-04 | 东莞波顿香料有限公司 | Ester compound and preparation method and application thereof |
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Application publication date: 20151028 |