CN1660737A - Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol - Google Patents
Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol Download PDFInfo
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- CN1660737A CN1660737A CN 200410093265 CN200410093265A CN1660737A CN 1660737 A CN1660737 A CN 1660737A CN 200410093265 CN200410093265 CN 200410093265 CN 200410093265 A CN200410093265 A CN 200410093265A CN 1660737 A CN1660737 A CN 1660737A
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- borneol
- butyraldehyde
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Abstract
A process for preparing 2-bornylenylidene butanol from bornylene aldehyde includes mixing methanol with solid catalyst A, heating while stirring for dissolving catalyst, dropping bornylene aldehyde and butanal, reaction water wash, rectifying to obtain 2-bornylenylidene butanal, mixing it with alcohol, dropping the mixture of water, solid alkali and catalyst B, reaction, water washing and rectifying.
Description
Technical field:
The present invention relates to a kind of chemical synthesis process, mainly is a kind of method of synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol.
Background technology:
Campholenic aldehyde is widely used in sandenol class series spices.With the campholenic aldehyde is that raw material synthetic spices mainly contains: Switzerland GIV company is with campholenic aldehyde and butanone condensation, hydrogenation obtains 3-sub-borneol alkene base-2-butanols again, be commonly called as santal 210, Japanese KAO company is with campholenic aldehyde and propionic aldehyde condensation, and hydrogenation obtains 2-sub-borneol alkene base propyl alcohol again.Campholenic aldehyde and butyraldehyde condensation obtain 2-sub-borneol alkene base butyraldehyde, restore to make 2-sub-borneol alkene base butanols, are commonly called as santal 208.Be a kind ofly cost an arm and a leg, fragrance spices preferably.Can be used for the allotment of all kinds of perfume.
2-sub-borneol alkene base butanols is to be the raw material synthetic with the campholenic aldehyde, in synthetic method in the past (as GB68936, US4619781, US4666629), what reduction was adopted is to use hydrogen reducing, needs hydrogen and reaction under high pressure, react dangerous, dangerous property, the yield of 2-sub-borneol alkene base butanols is not high, and fragrance is bad.
Summary of the invention:
The present invention will solve above-mentioned described deficiency, provides a kind of technology simply, not need under the severe condition, and the yield height is the method for the synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol of economical and efficient again.
The technical solution adopted in the present invention can also be further perfect.This method with synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol is that campholenic aldehyde makes 2-sub-borneol alkene base butanols by two-step reaction.
The first step reaction is to drop into methyl alcohol, solid catalyst I, stirring heating for dissolving catalyst I down, and drip campholenic aldehyde and butyraldehyde, wherein campholenic aldehyde when temperature rises to 50～60 ℃ in treating: the mass ratio of butyraldehyde is 1: 1.0～2.0; Butyraldehyde: the mass ratio of catalyst I is 1: 0.03～0.05; Butyraldehyde: the mass ratio of methyl alcohol is 1: 1.5～3; In 1～3 hour reaction times, after dropwising, the continuation stirring reaction is 1～3 hour between 50～60 ℃ of temperature, and the washing crude product gets 2-sub-borneol alkene base butyraldehyde to neutral after product washing, the rectifying.
The reaction of second step is 2-sub-borneol alkene base butyraldehyde, ethanol to be mixed the back drip in entry, solid alkali, the miscible mixed solution that is made into of catalyst I I; 2-sub-borneol alkene base butyraldehyde wherein: the alcoholic acid mass ratio is 1: 0.5～2; The mass ratio of water: solid alkali: catalyst I I is 1: 0.03～0.05: 0.2～1.0; Drip mixed solution between 10-40 ℃, 2-6 hour dropwise reaction time, crude product promptly gets 2-sub-borneol alkene base butanols through washing, rectifying.
Described catalyst I is selected KOH or NaOH etc. for use, and described catalyst I I selects sodium borohydride or POTASSIUM BOROHYDRIDE etc. for use; Described solid alkali is selected KOH or NaOH for use.
The present invention has the following advantages: the present invention adopts campholenic aldehyde to prepare 2-sub-borneol alkene base butanols, is commonly called as santal 208, advantage such as the gentleness that responds, operational safety, the santal that obtains are 208 colourless, fragrance is good.Santal 208 is a kind of expensive spices, is used to allocate all kinds of perfume fragrances.
Embodiment:
The invention will be described further below in conjunction with embodiment:
Embodiment 1:
The first step: add 72ml methyl alcohol, 1.5gKOH in the 250ml four-hole boiling flask (stirring, dropping funnel, thermometer, reflux exchanger are housed), stir heating for dissolving down, continue the mixed solution that heating begins to drip 40.6g campholenic aldehyde and 45g butyraldehyde in treating during temperature rise to 50 ℃, 2～3 hours dropping time.Control reaction temperature is at 50 ℃-60 ℃, after all dropwising, continues with this understanding stirring reaction 2～3 hours.React to such an extent that thick profit is washed till neutrality, 90～120 ℃/2.5mmHg is collected in underpressure distillation, and cut is a 2-sub-borneol alkene base butyraldehyde certified products, content 90%, yield 90.5%.
Second step: add 36.7g2-sub-borneol alkene base butyraldehyde and 18ml ethanol in the 250ml four-hole boiling flask (stirring, dropping funnel, thermometer, reflux exchanger are housed), stir.Then 25ml water, 0.2gKOH, 3.1g sodium borohydride are mixed into solution,, dropwised in about 0.5～2 hour dripping below 30 ℃.Continuing reaction 2～4 hours below 30 ℃ then.Reaction solution is washed to neutrality, and first normal pressure fractionates out etoh solvent, and fractionation obtains product 2-sub-borneol alkene base butanols under 118～122 ℃/2.5～3mmHg then.Content 90%, yield 92%.Product has graceful sandalwood aroma.
Embodiment 2:
The first step: add 58ml methyl alcohol, 2.0gNaOH in the 250ml four-hole boiling flask (stirring, dropping funnel, thermometer, reflux exchanger are housed), stir heating for dissolving down, continue the mixed solution that heating begins to drip 38g campholenic aldehyde and 47g butyraldehyde in treating during temperature rise to 50 ℃, 2～3 hours dropping time.Control reaction temperature is at 50 ℃-60 ℃, after all dropwising, continues with this understanding stirring reaction 2～3 hours.Mixture by the method processing reaction of example 1 obtains 2-sub-borneol alkene base butyraldehyde certified products, content 90%, yield 89.6%.
Second step: add 42g 2-sub-borneol alkene base butyraldehyde and 25ml ethanol in the 250ml four-hole boiling flask (stirring, dropping funnel, thermometer, reflux exchanger are housed), stir.Then 25ml water, 0.3gNaOH, 3.5g POTASSIUM BOROHYDRIDE are mixed into solution,, dropwised in about 0.5～2 hour dripping below 30 ℃.Then in continuing reaction 2～4 hours below 30 ℃.Mixture by the method processing reaction of example 5 obtains 2-sub-borneol alkene base butanols.Content 90%, yield 91%.Product has graceful sandalwood aroma.
Embodiment 3:
With embodiment 1 different being: add 132m1 methyl alcohol, 4.0gKOH in the 500ml four-hole boiling flask (stirring, dropping funnel, thermometer, reflux exchanger are housed), stir heating for dissolving down, continue the mixed solution that heating begins to drip 68g campholenic aldehyde and 90g butyraldehyde in treating during temperature rise to 50 ℃, 1～2 hour dropping time.Control reaction temperature is at 50 ℃-60 ℃, after all dropwising, continues with this understanding stirring reaction 2～3 hours.Mixture by the method processing reaction of example 1 obtains 2-sub-borneol alkene base butyraldehyde certified products, content 90%, yield 92%.
Embodiment 4:
With embodiment 1 different being: add 66ml methyl alcohol, 2.0gNaOH in the 250ml four-hole boiling flask (stirring, dropping funnel, thermometer, reflux exchanger are housed), stir heating for dissolving down, continue the mixed solution that heating begins to drip 36g campholenic aldehyde and 49g butyraldehyde in treating during temperature rise to 50 ℃, 1～2 hour dropping time.Control reaction temperature is at 50 ℃-60 ℃, after all dropwising, continues with this understanding stirring reaction 2～3 hours.Mixture by the method processing reaction of example 1 obtains 2-sub-borneol alkene base butyraldehyde certified products, content 90%, yield 91%.
Table 1: reaction conditions, productive rate, purity summary sheet
| Reaction conditions | The principal reaction condition | Productive rate | Purity |
| Embodiment 1 | Catalyzer KOH, dropping temperature 50-60 ℃, time 2-3h, afterreaction time 2-3h | ?90.5％ | 90％ |
| Embodiment 2 | Catalyst n aOH, dropping temperature 50-60 ℃, time 2-3h, afterreaction time 2-3h | ?89.6％ | 90％ |
| Embodiment 3 | Catalyzer KOH, dropping temperature 50-60 ℃, time 1-2h, afterreaction time 2-3h | ?92％ | 90％ |
| Embodiment 4 | Catalyst n aOH, dropping temperature 50-60 ℃, time 1-2h, afterreaction time 2-3h | ?91％ | 90％ |
Table 2: reaction conditions, productive rate, purity, aroma characteristic summary sheet
| Reaction conditions | The principal reaction condition | Productive rate | Purity | Fragrance |
| Embodiment 1 | The catalyzer sodium borohydride, solid alkali is selected KOH for use, | 92％ | 90％ | Graceful sandalwood aroma |
| Embodiment 2 | The catalyzer sodium borohydride, solid alkali is selected NaOH for use, | 91％ | 90％ | Graceful sandalwood aroma |
Claims (5)
1, a kind of method with synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol is characterized in that: be that campholenic aldehyde makes 2-sub-borneol alkene base butanols by two-step reaction; The first step reaction is that campholenic aldehyde and butyraldehyde are mixed in the methanol solution that adds catalyst I, wherein campholenic aldehyde: the mass ratio of butyraldehyde is 1: 1.0～2.0; Butyraldehyde: the mass ratio of catalyst I is 1: 0.03～0.05; Butyraldehyde: the mass ratio of methyl alcohol is 1: 1.5～3; 50～60 ℃ of temperature of reaction, 2～6 hours reaction times; Get 2-sub-borneol alkene base butyraldehyde after product washing, the rectifying; The reaction of second step is 2-sub-borneol alkene base butyraldehyde, ethanol to be mixed the back drip in entry, solid alkali, the miscible mixed solution that is made into of catalyst I I; 2-sub-borneol alkene base butyraldehyde wherein: the alcoholic acid mass ratio is 1: 0.5～2; The mass ratio of water: solid alkali: catalyst I I is 1: 0.03～0.05: 0.2～1.0; Drip mixed solution between 10-40 ℃, 2-6 hour dropwise reaction time, crude product promptly gets 2-sub-borneol alkene base butanols through washing, rectifying.
2, the method with synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol according to claim 1, it is characterized in that: described the first step reaction is to drop into methyl alcohol, solid catalyst I, stirring heating for dissolving catalyst I down, drip campholenic aldehyde and butyraldehyde, 1～3 hour reaction times when temperature rises to 50～60 ℃ in treating; After dropwising, the continuation stirring reaction is 1～3 hour between 50～60 ℃, and the washing crude product gets 2-sub-borneol alkene base butyraldehyde to neutral after product washing, the rectifying.
3, the method with synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol according to claim 1, it is characterized in that: described catalyst I is selected KOH or NaOH for use.
4, the method with synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol according to claim 1, it is characterized in that: described catalyst I I selects sodium borohydride or POTASSIUM BOROHYDRIDE for use.
5, the method with synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol according to claim 1, it is characterized in that: described solid alkali is selected KOH or NaOH for use.
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| CN 200410093265 CN1660737A (en) | 2004-12-21 | 2004-12-21 | Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol |
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| CN 200410093265 CN1660737A (en) | 2004-12-21 | 2004-12-21 | Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798259A (en) * | 2010-02-08 | 2010-08-11 | 浙江新化化工股份有限公司 | Method for synthesizing 2-campholenic propyl alcohol by campholenic aldehyde |
| CN101492347B (en) * | 2009-01-06 | 2011-11-02 | 格林生物科技股份有限公司 | Method for synthesis of 2-sub-borneol alkene butanol with organic base |
| CN101723816B (en) * | 2009-11-26 | 2013-06-05 | 杭州友邦香料香精有限公司 | Method for preparing 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal |
| CN103449988A (en) * | 2013-08-30 | 2013-12-18 | 广州百花香料股份有限公司 | Production method of 2-campholenic propyl aldehyde |
-
2004
- 2004-12-21 CN CN 200410093265 patent/CN1660737A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492347B (en) * | 2009-01-06 | 2011-11-02 | 格林生物科技股份有限公司 | Method for synthesis of 2-sub-borneol alkene butanol with organic base |
| CN101723816B (en) * | 2009-11-26 | 2013-06-05 | 杭州友邦香料香精有限公司 | Method for preparing 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal |
| CN101798259A (en) * | 2010-02-08 | 2010-08-11 | 浙江新化化工股份有限公司 | Method for synthesizing 2-campholenic propyl alcohol by campholenic aldehyde |
| CN103449988A (en) * | 2013-08-30 | 2013-12-18 | 广州百花香料股份有限公司 | Production method of 2-campholenic propyl aldehyde |
| CN103449988B (en) * | 2013-08-30 | 2015-11-18 | 广州百花香料股份有限公司 | A kind of production method of 2-sub-borneol alkene base propionic aldehyde |
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