CN101921177B - Preparation method of citronellol - Google Patents
Preparation method of citronellol Download PDFInfo
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- CN101921177B CN101921177B CN 201010287394 CN201010287394A CN101921177B CN 101921177 B CN101921177 B CN 101921177B CN 201010287394 CN201010287394 CN 201010287394 CN 201010287394 A CN201010287394 A CN 201010287394A CN 101921177 B CN101921177 B CN 101921177B
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Abstract
The invention provides a preparation method of citronellol, comprising the following steps of: putting a solvent, a reducing agent of borohydride, an antioxidant and an alkaline substance in a reduction pot for mixing, then pre-cooling to 0-40 DEG C and dripping citronellal in the reduction pot, wherein the temperature is controlled within 0-40 DEG C in the dripping process, and continuing the reaction for 2-5 hours at the temperature of 0-40 DEG C after the dripping; and reclaiming the solvent, washing via neutralized water to obtain the crude citronellol and performing vacuum distillation to obtain the citronellol. Under the alkaline condition and by adopting the method of utilizing the borohydride to perform reduction reaction to the citronellal to obtain the target product citronellol, the invention has the advantages of simple preparation technology, secure production process and low raw material cost as the special catalyst is not needed and all the raw materials can be bought on the industrial market.
Description
Technical field
The present invention relates to a kind of preparation method's of spices, particularly a kind of geraniol preparation method.
Background technology
At present, in perfume industry, geraniol is an extremely important class perfume material, and fragrance is pure and fresh, graceful like its rose and the spiceleaf, is a large amount of perfume materials that use in rose class, the lemongrass class essence.Through use for many years, the usage quantity of geraniol is still flourishing long time and increase year by year, its at present annual usage quantity surpassed 5000 tons, this product all receives in the world the concern of each big well-known essence and flavoring agent company all the time.
Favourablely on the traditional technology be used on the heterogeneous catalyst catalytic hydrogenation or pressurization hydrogenation and be the method for geraniol with geranial hydrogenation.In most cases, the heterogeneous catalyst catalytic hydrogenation uses fixed-bed reactor to carry out, to obtain the advantage of continuous processing operation.But this preparation method's shortcoming is: must produce and use the catalyzer of special preparation, and have catalyst failure, have to stop work and changed the risk of catalyzer with high one-tenth originally.This expensive and high risk preparation method is not that all enterprises can both be affordable.If in the city, use the operational path of pressurization hydrogenation then comparatively dangerous, also allow the use of this type of operational path have limitation simultaneously.
Summary of the invention
The objective of the invention is at above-mentioned existing problems and deficiency, a kind of hydrogenation pressurization, simple, operational safety of operational path of not needing is provided, nor need add special catalyzer, all raw materials all can have been bought at industrial market, the preparation method of the geraniol that raw materials cost is low, product purity is high.
Technical scheme of the present invention is achieved in that
The preparation method of geraniol of the present invention is characterized in may further comprise the steps:
(1), solvent, borane reducing agent hydride, oxidation inhibitor, alkaline matter put into reduction pot mixing after, carry out precooling treatment again, be chilled to 0 in advance
OC～40
ODuring C, geranial is added dropwise in the described reduction pot, the dropping process will be controlled temperature 0
OC～40
OC after dropwising, maintains 0
OC～40
OContinue reaction 2～5 hours under the temperature of C;
(2), reclaim solvent, again through neutralization wash the geraniol crude product, and then carry out rectification under vacuum and namely obtain geraniol.
The present invention is as follows to the reaction equation that geranial carries out reduction reaction:
Wherein above-mentioned solvent adopts methyl alcohol or ethanol.
Above-mentioned hydroborate is: KBH
4, NaBH
4, liBH
4
Above-mentioned alkaline matter is: KOH, NaOH, Na
2CO
3
In step (), before carrying out precooling treatment also need in the reduction pot adding oxidation inhibitor B.H.T(chemical name be: butylhydroxy toluene).The effect of oxidation inhibitor mainly is that the protection geranial is not oxidized in reaction process.
The method of the recovery solvent in step (two) is: make under the situation of reduction pot at normal pressure, open overhead condensation water and stirring; Begin slow heating then, require 120 ℃-122 ℃ of liquid temperature, 70 ℃-78 ℃ of top temperature, the 80%-90% that solvent accounts for the quantity of solvent of throwing is reclaimed in control, criticizes the usefulness that feeds intake to get ready.
In in step (two) with method for washing be: in the reduction pot, add clear water, stir, leave standstill then, slowly put sub-cloud water liquid, add the mixed solution of acetic acid and water again in the reduction pot, regulate pH value, control PH=7 leaves standstill, and slowly puts sub-cloud water liquid, add clear water washing more several times and after putting sub-cloud water liquid, the solution of staying in the reduction pot is the geraniol crude product.
The present invention is owing to adopt under alkaline condition, utilize hydroborate that geranial is carried out reduction reaction and obtain the method for our target product geraniol, utilized hydroborate to have the tetrahydro boron acid radical anion fully, when hydride ion is attacked the carbonyl carbon positive center, form covalent linkage, negative charge is transferred to Sauerstoffatom, be hydrolyzed into the principle of alcohol then, make the present invention not only preparation technology be simple, production process is than hydrogenation method safety, nor need add special catalyzer, all raw materials all can have been bought at industrial market, raw materials cost is low, product purity is high.
Embodiment
The preparation method of geraniol of the present invention is characterized in may further comprise the steps:
(1), solvent, borane reducing agent hydride, oxidation inhibitor, alkaline matter put into reduction pot mixing after, carry out precooling treatment again, be chilled to 0 in advance
OC～40
ODuring C, geranial is added dropwise in the described reduction pot, the dropping process will be controlled temperature 0
OC～40
OC after dropwising, maintains 0
OC～40
OContinue reaction 2～5 hours under the temperature of C;
(2), reclaim solvent, again through neutralization wash the geraniol crude product, and then carry out rectification under vacuum and namely obtain geraniol.
The present invention is as follows to the reaction equation that geranial carries out reduction reaction:
Wherein above-mentioned solvent adopts methyl alcohol or ethanol.
Above-mentioned hydroborate is: KBH
4, NaBH
4, liBH
4
Above-mentioned alkaline matter is: KOH, NaOH, Na
2CO
3
In step (), before carrying out precooling treatment also need in the reduction pot adding oxidation inhibitor B.H.T(chemical name be: butylhydroxy toluene).The effect of oxidation inhibitor mainly is that the protection geranial is not oxidized in reaction process.
In step of the present invention (), need the solution in the reduction pot is carried out adding geranial again after the precooling treatment, and the control temperature is 0
OC～40
OThe reason of reacting under the C is: because this reaction is thermopositive reaction, if a large amount of heat is just emitted in not precooling so in the reaction process, might produce side reaction, draw other undesired product, influence quality product.
The method of the recovery solvent in step (two) is: make under the situation of reduction pot at normal pressure, open overhead condensation water and stirring; Begin slow heating then, require 120 ℃-122 ℃ of liquid temperature, 70 ℃-78 ℃ of top temperature, the 80%-90% that solvent accounts for the quantity of solvent of throwing is reclaimed in control, criticizes the usefulness that feeds intake to get ready.
In in step (two) with method for washing be: in the reduction pot, add clear water, stir, leave standstill then, slowly put sub-cloud water liquid, add the mixed solution of acetic acid and water again in the reduction pot, regulate pH value, control PH=7 leaves standstill, and slowly puts sub-cloud water liquid, add clear water washing more several times and after putting sub-cloud water liquid, the solution of staying in the reduction pot is the geraniol crude product.
The product yield of rectification under vacuum gained geraniol: 65%～87%.Product purity: 96%～97%
Compare with traditional technology, it is simple that the present invention has technology, the advantage of process safety.Production process can significantly reduce cost, the product purity height.
The present invention will be further described below in conjunction with specific embodiment.
Embodiment 1:In methyl alcohol 100Kg, borane reducing agent potassium hydride KH 12Kg, oxidation inhibitor B.H.T 0.33Kg, the clean tasteless reduction pot of 50%～80% potassium hydroxide 0.1Kg suction, with geranial (more than the GC87%) the 100Kg suction header tank that is up to the standards.Start stirring, open freezingly, be chilled to 0 in advance
OC～40
OC at the uniform velocity drips geranial, and control dropwised at 4～5 hours, drips process temperature control 0
OC～40
OC.After dropwising, holding temperature 15
OC～40
OC continues reaction 2～5 hours, and reaction finishes.The logical atmosphere of affirmation equipment reduction pot is opened overhead condensation water and stirring; Begin slow heating then, reclaim methanol solvate, control is reclaimed methyl alcohol and is accounted for the quantity of methyl alcohol 80%-90% that throws, and criticizes the usefulness that feeds intake to get ready.For containing other unwanted material in the methanol solvate of avoiding reclaiming, as moisture or other materials, this is as the unwanted material of solvent that feeds intake next time, thus when reclaiming solvent, require the liquid temperature at 120 ℃-122 ℃, 65 ℃-70 ℃ of top temperature.And then under agitation add process water 100Kg, and continue to stir 15 minutes, left standstill 30 minutes, slowly put sub-cloud water liquid.Under agitation add process water 100Kg again, about acetic acid 0.18Kg, stirred 15 minutes, pH value is surveyed in sampling, and control PH=7(is because influencing the quality of product under the condition of soda acid), left standstill 30 minutes, slowly put sub-cloud water liquid from the reduction pot bottom.Stir adding process water 100Kg down, continue to stir 15 minutes, pH value is surveyed in sampling, control PH=7 left standstill 30 minutes, slowly put sub-cloud water liquid again, after washing with water several times and put sub-cloud water liquid by same operation, the solution of staying in the reduction pot is the geraniol crude product.Carry out rectification under vacuum at last again and get the geraniol product.Yield: 84%～87%.Product content 96%～97%.
Embodiment 2:In methyl alcohol 70Kg, water 30Kg, borane reducing agent potassium hydride KH 12Kg, oxidation inhibitor B.H.T 0.33Kg, the clean tasteless reduction pot of 50%～80% potassium hydroxide 0.1Kg suction, with geranial (more than the GC87%) the 100Kg suction header tank that is up to the standards.Start stirring, open freezingly, be chilled to 0 in advance
OC～40
OC at the uniform velocity drips geranial, and control dropwised at 4～5 hours, drips process temperature control 0
OC～40
OC.After dropwising, holding temperature 15
OC～40
OC continues reaction 2～5 hours, and reaction finishes.The logical atmosphere of affirmation equipment reduction pot (just making the reduction pot under the situation of normal pressure) is opened overhead condensation water and stirring; Beginning is heating slowly, requires 120-122 ℃ of liquid temperature, 70 ℃ of top temperature.Control is reclaimed methyl alcohol and is accounted for the quantity of methyl alcohol 80%-90% that throws, and criticizes the usefulness that feeds intake to get ready.Stir adding process water 100Kg down, continue to stir 15 minutes, left standstill 30 minutes, slowly put sub-cloud water liquid.Stir adding process water 100Kg down, about acetic acid 0.18Kg, stirred 15 minutes, pH value is surveyed in sampling, and control PH=7 left standstill 30 minutes, slowly put sub-cloud water liquid.Stir and to add process water 100Kg down, continue to stir 15 minutes, pH value is surveyed in sampling, leaves standstill 30 minutes, slowly puts sub-cloud water liquid, and several times and after putting sub-cloud water liquid, the solution of staying in the reduction pot is the geraniol crude product by same operated wash.Carry out rectification under vacuum at last and get geraniol.Yield: 71%～75%.Product content 96%～97%.
Embodiment 3:In ethanol 100Kg, borane reducing agent sodium hydride 8.5Kg, oxidation inhibitor B.H.T 0.33Kg, the clean tasteless reduction pot of 50%～80% sodium hydroxide 0.1Kg suction, with geranial (more than the GC87%) the 100Kg suction header tank that is up to the standards.Start stirring, open freezingly, be chilled to 0 in advance
OC～40
OC at the uniform velocity drips geranial, and control dropwised at 4～5 hours, drips process temperature control 0
OC～40
OC.After dropwising, holding temperature 15
OC～40
OC continues reaction 2～5 hours, and reaction finishes.The logical atmosphere of affirmation equipment reduction pot is opened overhead condensation water and stirring; Beginning is heating slowly, requires 120-122 ℃ of liquid temperature, pushes up warm 70-78 ℃.Control is reclaimed ethanol and is accounted for the amount of alcohol 80%-90% that throws, and criticizes the usefulness that feeds intake to get ready.Stir adding process water 100Kg down, continue to stir 15 minutes, left standstill 30 minutes, slowly put sub-cloud water liquid.Stir adding process water 100Kg down, about acetic acid 0.18Kg, stirred 15 minutes, pH value is surveyed in sampling, and control PH=7 left standstill 30 minutes, slowly put sub-cloud water liquid.Stir and to add process water 100Kg down, continue to stir 15 minutes, pH value is surveyed in sampling, leaves standstill 30 minutes, slowly puts sub-cloud water liquid, by same operated wash, sampling, control PH=7, put sub-cloud water liquid after, the solution of staying in the reduction pot is the geraniol crude product.Carry out rectification under vacuum at last and get geraniol.Yield: 82%～85%.Product content 96%～97%.
Embodiment 4:In water 100Kg, borane reducing agent lithium hydride 6Kg, oxidation inhibitor B.H.T 0.33Kg, the clean tasteless reduction pot of 50%～80% soda ash 0.5Kg suction, with geranial (more than the GC87%) the 100Kg suction header tank that is up to the standards.Start stirring, open freezingly, be chilled to 2 in advance
OC～40
OC at the uniform velocity drips geranial, and control dropwised at 4～5 hours, drips process temperature control 2
OC～40
OC.After dropwising, holding temperature 2
OC～40
OC continues reaction 2～5 hours, and reaction finishes.Stir adding process water 100Kg down, continue to stir 15 minutes, left standstill 30 minutes, slowly put sub-cloud water liquid.Stir adding process water 100Kg down, about acetic acid 0.18Kg, stirred 15 minutes, pH value is surveyed in sampling, and control PH=7 left standstill 30 minutes, slowly put sub-cloud water liquid.Stir and to add process water 100Kg down, continue to stir 15 minutes, pH value is surveyed in sampling, leaves standstill 30 minutes, slowly puts sub-cloud water liquid, by same operated wash, sampling, control PH=7, put sub-cloud water liquid after, the solution of staying in the reduction pot is the geraniol crude product.Carry out rectification under vacuum at last and get geraniol.Yield: 68%～72%.Product content 96%～97%.
Although the present invention describes with reference to specific embodiment, this description and not meaning that is construed as limiting the present invention.With reference to description of the invention, other of the disclosed embodiments change, and all can expect for those skilled in the art, and this variation should belong in the affiliated claim institute restricted portion.
Claims (7)
1. the preparation method of a geraniol is characterized in that may further comprise the steps:
(1), solvent, borane reducing agent hydride, alkaline matter put into reduction pot mixing after, carry out precooling treatment, be chilled to 0 in advance
OC～40
ODuring C, geranial is added dropwise in the described reduction pot, the dropping process will be controlled temperature 0
OC～40
OC after dropwising, maintains 0
OC～40
OContinue reaction 2～5 hours under the temperature of C, wherein solvent is: methyl alcohol or ethanol;
(2), reclaim solvent, obtain the geraniol crude product through the neutralization washing again, and then the geraniol crude product is carried out rectification under vacuum namely obtain geraniol.
2. according to the preparation method of the described geraniol of claim 1, it is characterized in that the hydroborate in step () is: KBH
4, NaBH
4, LiBH
4
3. according to the preparation method of the described geraniol of claim 1, it is characterized in that the alkaline matter in step () is: KOH, NaOH, Na
2CO
3
4. according to the preparation method of the described geraniol of claim 1, it is characterized in that in step (), before carrying out precooling treatment, also need in the reduction pot, to add oxidation inhibitor B.H.T.
5. according to the preparation method of the described geraniol of claim 1, it is characterized in that in step () that above-mentioned geranial at the uniform velocity splashes in the reduction pot from header tank.
6. according to the preparation method of the described geraniol of claim 1, it is characterized in that the method for the recovery solvent in step (two) is: make under the situation of reduction pot at normal pressure, open overhead condensation water and stirring; Begin slow heating then, require 120 ℃-122 ℃ of liquid temperature, 70 ℃-78 ℃ of top temperature, the 80%-90% that solvent accounts for the quantity of solvent of throwing is reclaimed in control, criticizes the usefulness that feeds intake to get ready.
7. according to the preparation method of the described geraniol of claim 1, it is characterized in that in step (two) in and method for washing be: add clear water in reduction pot, stirring is left standstill then, slowly put sub-cloud water liquid, add the mixed solution of acetic acid and water again in the reduction pot, regulate pH value, control pH=7, leave standstill, slowly put sub-cloud water liquid, after adding clear water washing more several times and putting sub-cloud water liquid, the solution of staying in the reduction pot is the geraniol crude product.
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| CN 201010287394 CN101921177B (en) | 2010-09-20 | 2010-09-20 | Preparation method of citronellol |
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|---|---|---|---|
| CN 201010287394 CN101921177B (en) | 2010-09-20 | 2010-09-20 | Preparation method of citronellol |
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| CN106397113A (en) * | 2016-08-31 | 2017-02-15 | 防城港市绿华源农林科技有限公司 | Preparation method of citronellol by three-step method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434014A (en) * | 2003-02-21 | 2003-08-06 | 中国科学院广州化学研究所 | Improved process for synthesizing citronellol from dihydromyrcene |
| CN101012154A (en) * | 2007-02-01 | 2007-08-08 | 厦门中坤化学有限公司 | Method of preparing citronellol |
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2010
- 2010-09-20 CN CN 201010287394 patent/CN101921177B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434014A (en) * | 2003-02-21 | 2003-08-06 | 中国科学院广州化学研究所 | Improved process for synthesizing citronellol from dihydromyrcene |
| CN101012154A (en) * | 2007-02-01 | 2007-08-08 | 厦门中坤化学有限公司 | Method of preparing citronellol |
Non-Patent Citations (2)
| Title |
|---|
| Ganapati D.Yadav et al..Novelties of kinetics of chemoselective reduction of citronellal to citronellol by sodium borohydride under liquid-liquid phase transfer catalysis.《Journal of Molecular Catalysis A: Chemical》.2006,第247卷253-259. |
| Novelties of kinetics of chemoselective reduction of citronellal to citronellol by sodium borohydride under liquid-liquid phase transfer catalysis;Ganapati D.Yadav et al.;《Journal of Molecular Catalysis A: Chemical》;20060109;第247卷;253-259 * |
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