CN101723807B - Preparation method of borneol - Google Patents
Preparation method of borneol Download PDFInfo
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- CN101723807B CN101723807B CN200910201021A CN200910201021A CN101723807B CN 101723807 B CN101723807 B CN 101723807B CN 200910201021 A CN200910201021 A CN 200910201021A CN 200910201021 A CN200910201021 A CN 200910201021A CN 101723807 B CN101723807 B CN 101723807B
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Abstract
The invention discloses a preparation method of borneol, which comprises the following steps: A, adding lithium aluminium hydride in an anhydrous solvent in a nitrogen atmosphere, then adding 3,3-epoxy pinane, heating and stirring to perform reaction at 40 to 90 DEG C for 1 to 20 hours and tracing the extent of the reaction with a gas chromatogram; and B, after reaction raw materials runs out, adding water to decompose superfluous aluminium hydride, extracting the reaction liquid with a diethyl or an ethylacetate, washing the reaction liquid with saturated salt solution, taking an oil layer on the upper layer, drying the oil layer with an anhydrous sodium sulphate, concentrating the organic layer, performing column chromatographic separation on the organic layer to purify the organic layer to obtain a white crystal product. The preparation method of the invention has the advantages of high selectivity and simple and convenient operation.
Description
Technical field
The present invention relates to a kind of preparation method of borneol, relate to a kind ofly with 2 in particular, the 3-epoxypinane is the method for feedstock production borneol.
Background technology
Borneolum Syntheticum is claimed 2-camphor tree alcohol again, is a kind of medicine commonly used and spices, is widely used in medicine and perfume industry.Borneol is the crystallization of sexangle sheet, is present in the certain plants volatile oil, and nature has the left and right body that revolves, and synthetics is a racemic modification.Borneol has effects such as sweating, antispastic, pain relieving, is the composition of jintan, BINGPENG SAN.Except itself being used for medicine and spices, borneol still is the main raw material of SYNTHETIC CAMPHOR DAB 6.Therefore, seek effectively preparation method of borneol receives people's very big concern in the organic synthesis field.The compound method of existing borneol mainly contains: (1) esterification-saponification method: be about to α-Pai Xi at high temperature or special catalyst have down that isomery turns to amphene, amphene carries out esterification, generates Bornyl acetate, carries out saponification reaction again and obtains borneol.Method is similar therewith, also has with solid super-strong acid SO
2 -4/ Al
2O
3The esterification of catalysis α-Pai Xi and anhydrous oxalic acid, preparation earlier generates oxalic acid two borneol acetates, again through saponification reaction, also can borneolum syntheticum.The major technique deficiency of these class methods is that reaction scheme is longer, need use special catalyzer during isomerizing, like titanium oxide hydrate or ion exchange resin etc.(2) hydration method: be about to α-Pai Xi at high temperature or special catalyst have down that isomery turns to amphene, amphene directly carries out hydration reaction and obtains borneol without esterification.The major technique characteristics of this method are to have reduced by a step chemical reaction; The Technology comparative maturity; Obtain the higher pharmaceutical grade SYNTHETIC CAMPHOR DAB 6 product of rank than being easier to, but raw material consumption is higher, also exists throughput simultaneously and be difficult for enlarging, need to increase deficiencies such as some accessory aftertreatment technologys.
Summary of the invention
Technical problem to be solved by this invention provides a kind of with 2, and the 3-epoxypinane is the method for feedstock production borneol.
Technical scheme of the present invention, a kind of preparation method of borneol comprises the following steps:
A, under nitrogen atmosphere, in anhydrous solvent, add lithium aluminum hydride, add 2 more subsequently, the 3-epoxypinane at 40-90 ℃ of heated and stirred reaction 1～20h, is followed the tracks of extent of reaction with gc;
After B, question response raw material consumption are intact, drip water excessive lithium aluminum hydride is decomposed, reaction solution is used anhydrous sodium sulfate drying with ether or ethyl acetate extraction, again with the saturated common salt water washing, get the upper strata oil reservoir at last.Organic layer concentrates after column chromatography for separation is purified, and obtains the white crystal product.
Solvent and lithium aluminum hydride, 2 in the steps A, the preferred proportion of 3-epoxypinane are 10～30mL: 26.7～80mmol: 13mmol.
The beneficial effect of the invention, the contriver is attempting with 2, and the 3-epoxypinane is raw material and lithium aluminum hydride when carrying out ring-opening reaction research, has found following conversion:
When 2, when 3-epoxypinane and lithium aluminum hydride reaction, open loop, rearrangement and hydrolysis reaction carry out simultaneously, have obtained borneol once going on foot.This reaction preference is high, and is easy and simple to handle.
The present invention is with α-Pai Xi epoxidation product 2, and the 3-epoxypinane is a raw material, through lithium aluminum hydride open loop, rearrangement and hydrolysis reaction, can prepare borneol easily.Raw material 2, the transformation efficiency of 3-epoxypinane are near 100%, and the borneol selectivity is greater than 70% in the product.
Description of drawings
Fig. 1 is the nmr spectrum of the borneol of embodiment 1;
Fig. 2 is the mass spectrum of the borneol of embodiment 1;
Fig. 3 is the infrared spectrogram of the borneol of embodiment 1.
Embodiment
Through embodiment the present invention is described in further detail below, a kind of preparation method of borneol comprises the following steps:
A, under nitrogen atmosphere, in anhydrous solvent, add lithium aluminum hydride, add 2 more subsequently, the 3-epoxypinane at 40-90 ℃ of heated and stirred reaction 1～20h, is followed the tracks of extent of reaction with gc;
After B, question response raw material consumption are intact, drip water excessive lithium aluminum hydride is decomposed, reaction solution is used anhydrous sodium sulfate drying with ether or ethyl acetate extraction, again with the saturated common salt water washing, get the upper strata oil reservoir at last.Organic layer concentrates after column chromatography for separation is purified, and obtains the white crystal product.Also can be through the method purified product of sherwood oil recrystallization.
Solvent and lithium aluminum hydride, 2 in the steps A, the preferred proportion of 3-epoxypinane are anhydrous solvent 10～30mL: lithium aluminum hydride 26.7～80mmol: 2, and 3-epoxypinane 13mmol.
A. the normal hexane of under nitrogen atmosphere, the 20mL drying treatment being crossed joins in the there-necked flask, adds 3.0g lithium aluminum hydride (80mmol), adds 2.0g 2 subsequently again, 3-epoxypinane (13mmol), 65 ℃ of heated and stirred 12h.Follow the tracks of reaction with gc.
B. after treating that raw material consumption is intact, slowly add suitable quantity of water and decompose excessive lithium aluminum hydride.The reaction solution that obtains is used saturated aqueous common salt 3 times again with ether (or ETHYLE ACETATE) extraction 3 times, gets the upper strata oil reservoir, uses anhydrous sodium sulfate drying.
C. organic layer concentrates after column chromatography for separation is purified, and obtains 1.26 white crystals, is title product borneol.2, the transformation efficiency of 3-epoxypinane reaches 100%, and the productive rate of borneol is 64.5%.
As shown in Figure 1, NMR (300MHz, CDCl
3): δ: 0.85, s, 9H; 0.86-0.95 (m, 1H), 1.2-1.3 (m, 2H), 1.4 (s, 1H), 1.6-1.9 (m, 3H), 2.2-2.3 (m, 1H), 4.0 (d, 1H);
As shown in Figure 2, Ms (m/z): 154,137 (base peaks), 107,95,81
As shown in Figure 3, and IR (film/CCl4, cm-1): 3354,2951,1455,1386,1368,1108,1054,791,763
A. the normal hexane of under nitrogen atmosphere, the 20mL drying treatment being crossed joins in the there-necked flask, adds 1.5g lithium aluminum hydride (40mmol), adds 2.0g 2 subsequently again, 3-epoxypinane (13mmol), 65 ℃ of heated and stirred 12h.Follow the tracks of reaction with gc.
B. after treating that raw material consumption is intact, slowly add suitable quantity of water and decompose excessive lithium aluminum hydride.The reaction solution that obtains is used saturated aqueous common salt 3 times again with ether (or ETHYLE ACETATE) extraction 3 times, gets the upper strata oil reservoir, uses anhydrous sodium sulfate drying.
C. organic layer concentrates after column chromatography for separation is purified, and obtains 1.21 white crystals, is title product borneol.2, the transformation efficiency of 3-epoxypinane reaches 97%, and the productive rate of borneol is 60.5%.
The embodiment content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. a preparation method of borneol comprises the following steps:
A, under nitrogen atmosphere, in normal hexane, add lithium aluminum hydride, add 2 more subsequently, the 3-epoxypinane at 40-90 ℃ of heated and stirred reaction 1～20h, is followed the tracks of extent of reaction with gc;
After B, question response raw material consumption are finished; Drip water excessive lithium aluminum hydride is decomposed, reaction solution is used anhydrous sodium sulfate drying with ether or ethyl acetate extraction, again with the saturated common salt water washing, get the upper strata oil reservoir at last; Organic layer concentrates after column chromatography for separation is purified, and obtains the white crystal product.
2. preparation method of borneol according to claim 1 is characterized in that: solvent and lithium aluminum hydride, 2 in the steps A, the ratio of 3-epoxypinane are 10～30mL: 26.7～80mmol: 13mmol.
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| CN200910201021A CN101723807B (en) | 2009-12-14 | 2009-12-14 | Preparation method of borneol |
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| CN200910201021A CN101723807B (en) | 2009-12-14 | 2009-12-14 | Preparation method of borneol |
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| CN101723807B true CN101723807B (en) | 2012-10-24 |
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| CN104447225B (en) * | 2014-12-31 | 2017-01-11 | 格林生物科技股份有限公司 | Costustoot-ambergris spice and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049842A (en) * | 1990-06-05 | 1991-03-13 | 中国科学院广州化学所 | Method for preparing isoborneol by catalyzing camphene hydration with resin |
| CN101318880A (en) * | 2008-07-23 | 2008-12-10 | 嘉兴学院 | Green synthesis process for bornyl alcohol |
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2009
- 2009-12-14 CN CN200910201021A patent/CN101723807B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049842A (en) * | 1990-06-05 | 1991-03-13 | 中国科学院广州化学所 | Method for preparing isoborneol by catalyzing camphene hydration with resin |
| CN101318880A (en) * | 2008-07-23 | 2008-12-10 | 嘉兴学院 | Green synthesis process for bornyl alcohol |
Non-Patent Citations (2)
| Title |
|---|
| 尹延柏等.环氧蒎烷异构生成龙脑烯醛研究进展.《现代化工》.2007,第27卷(第7期),23－27. * |
| 李春丽等.以龙脑烯醛为原料合成檀香类化合物的研究.《香料香精化妆品》.2007,(第1期), * |
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