CN103449993A - Production method of 3-campholenyl-2-butanone - Google Patents
Production method of 3-campholenyl-2-butanone Download PDFInfo
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- CN103449993A CN103449993A CN2013103691416A CN201310369141A CN103449993A CN 103449993 A CN103449993 A CN 103449993A CN 2013103691416 A CN2013103691416 A CN 2013103691416A CN 201310369141 A CN201310369141 A CN 201310369141A CN 103449993 A CN103449993 A CN 103449993A
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Abstract
The invention discloses a production method of 3-campholenyl-2-butanone. The production method comprises the following steps: adding campholenic aldehyde, butanone, water, a catalyst and an alkaline substance into a pressure kettle; reacting under the hydrogen pressure of 0.5-4.0 MPa at the temperature of 20-90 DEG C until the reaction is finished; filtering the catalyst, separating the alkaline solution and purifying to obtain the 3-campholenyl-2-butanone product. According to the production method, a one-pot reaction technology is adopted, so that two reactions, i.e., aldol condensation and catalytic hydrogenation, are simultaneously finished in one reaction pot, the operation is greatly simplified, the production period is shortened, and the labor intensity is reduced.
Description
Technical field
The invention belongs to the fine chemical technology field, specifically refer to the production method of 3-borneol alkenyl-2-butanone.
Background technology
3-borneol alkenyl-2-butanone can be used as the raw material of synthesis of artificial santalol (Sandalore), is the important middle product of synthetic perfume 3-borneol alkenyl-2-butanols, has strong banksia rose fragrance, and fragrance exactly likes natural sandalwood.Be widely used in the daily chemical essence formulas such as perfumed soap, shampoo, makeup.The preparation method of U.S. Pat 4052341 and document CN101125798A report 3-borneol alkenyl-2-butanone is that to utilize campholenic aldehyde and butanone be raw material, and methyl alcohol is that solvent is synthesized by aldol condensation, shortening two-step reaction.This traditional industry production method is all by two step synthesis 3-borneol alkenyl-2-butanone.Be specially: the first step campholenic aldehyde and butanone be aldol reaction under methanol solvate, liquid caustic soda condition, and reaction finishes, and needs to obtain 3-sub-borneol alkene base-2-butanone finished product through operations such as neutralization, washing, solvent recuperation, rectifying.Second step: 3-sub-borneol alkene base-2-butanone catalytic reaction hydrogenation under hydrogen, catalyzer, alkali lye, solvent condition obtains 3-borneol alkenyl-2-butanone crude product, through operations such as filtration, washing, solvent recuperation, rectifying, obtains 3-borneol alkenyl-2-butanone finished product.
In above-mentioned document, two step synthesis 3-borneol alkenyl-2-butanone reaction principle is as follows:
The first step: campholenic aldehyde and methyl ethyl ketone condensation reaction obtain 3-sub-borneol alkene base-2-butanone (1),
Second step: 3-sub-borneol alkene base-2-butanone and hydrogen are under catalyzer, liquid caustic soda, solvent condition, and catalytic hydrogenation reaction, make 3-borneol alkenyl-2-butanone (2)
This two step synthesis techniques, operation is numerous and diverse, and the production cycle is long, and labour intensity is large.Plant factor is not high, and solvent loss is large, and cost is high, and the wastewater treatment expense is high, contaminate environment.
Summary of the invention
Purpose of the present invention is just in order to overcome above-mentioned the deficiencies in the prior art, and what provide is a kind of simple to operation, high yield, the production method of the 3-borneol alkenyl-2-butanone of environmental protection.
Reaction principle of the present invention following (2):
The present invention is achieved by the following technical programs:
The production method of 3-borneol alkenyl-2-butanone of the present invention comprises the following steps:
Add campholenic aldehyde, butanone, catalyzer and alkaline matter, water in an autoclave pressure, then in hydrogen pressure 0.5 MPa-4.0MPa, temperature, under 20 ℃-90 ℃, react, reaction finishes to obtain 3-borneol alkenyl-2-butanone crude product, again by crude product after filtration catalyzer, separate basic solution, remove butanone, and, after rectification under vacuum is purified, obtain 3-borneol alkenyl-2-butanone product.
Wherein the weight ratio of campholenic aldehyde and butanone, catalyzer and alkaline matter is: campholenic aldehyde: butanone=: 1:70%-400%, campholenic aldehyde: catalyzer=1:0.05%-5%, campholenic aldehyde: alkaline matter=1:0.1%-5%.
Preferred version is: above-mentioned campholenic aldehyde: butanone=1:100%-180%.
Above-mentioned campholenic aldehyde: catalyzer=1:2%-5%.
Above-mentioned campholenic aldehyde: alkaline matter=1:0.5%-2%.
Described catalyzer can adopt 5% palladium charcoal, ruthenium carbon, ruthenium aluminium or Raney's nickel etc., is preferably 5% palladium charcoal, Raney's nickel.Above-mentioned alkaline matter is the series materials such as sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or diethylamine, and the consumption of above-mentioned water is to form the basic solution that concentration is 0.10%-5% after alkaline matter is dissolved.
The time that above-mentioned reaction finishes accounts for the weight percent of W-response material<1% for show intermediate 3-sub-borneol alkene base in raw material campholenic aldehyde or reaction process-2-butanone content by gas-chromatography.
The present invention is owing to adopting the raw material campholenic aldehyde, butanone, catalyzer and alkaline matter, water is put into the one pot reaction technology of same reactor (also being reactor) reaction, thereby two reactions of aldol condensation and shortening are all directly completed in a reactor simultaneously, the 3-sub-borneol alkene base generated between the reaction period like this-2-butanone intermediate separates without process, refining step, directly in this reactor, at hydrogen, complete catalytic hydrogenation reaction under the catalyzer condition, generate 3-borneol alkenyl-2-butanone target product, therefore greatly simplified operation sequence, shortened the production cycle, reduced labour intensity.And product yield of the present invention is up to more than 90%, product purity, more than 95%, greatly reduces production cost.And due to noxious solvents such as methyl alcohol in water replacement traditional technology of the present invention; Catalyzer with can be recycled after basic solution separates, without the waste water output, whole process environmental protection, efficiently solve existing 3-borneol alkenyl-2-butanone and need two step synthesis techniques, and operation is numerous and diverse, production cycle is long, it is not high that labour intensity reaches greatly plant factor, and solvent loss is large, and cost is high, the wastewater treatment expense is high, the problems such as contaminate environment.
Embodiment
The production method of 3-borneol alkenyl-2-butanone of the present invention comprises the following steps:
Add campholenic aldehyde, butanone, catalyzer and alkaline matter, water in an autoclave pressure, then in hydrogen pressure 0.5 MPa-4.0MPa, temperature, under 20 ℃-90 ℃, react, reaction finishes to obtain 3-borneol alkenyl-2-butanone crude product, again by crude product after filtration catalyzer, separate basic solution, remove butanone, and, after rectification under vacuum is purified, obtain 3-borneol alkenyl-2-butanone product.
The weight ratio of wherein said campholenic aldehyde and butanone, catalyzer and alkaline matter is: campholenic aldehyde: butanone=: 1:70%-400%, campholenic aldehyde: catalyzer=1:0.05%-5%, campholenic aldehyde: alkaline matter=1:0.1%-5%.
Preferred version is: above-mentioned campholenic aldehyde: butanone=1:100%-180%.Above-mentioned campholenic aldehyde: catalyzer=1:2%-5%.Above-mentioned campholenic aldehyde: alkaline matter=1:0.5%-2%.
Described catalyzer can be 5% palladium charcoal, ruthenium carbon, ruthenium aluminium or Raney's nickel.Be preferably 5% palladium charcoal, Raney's nickel.Described alkaline matter is the series materials such as sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or diethylamine.The consumption of above-mentioned water is to form the basic solution that concentration is 0.10%-5% after alkaline matter is dissolved.
The preferred version of above-mentioned reaction conditions is: above-mentioned hydrogen pressure 1 MPa-3MPa, temperature are at 30 ℃-70 ℃.
Above-mentioned logical hydrogen until the time that reaction finishes for by gas-chromatography, to show that raw material campholenic aldehyde or reaction intermediate 3-sub-borneol alkene base-2-butanone content account for the weight percent of W-response material<1%.
Production method provided by the invention has following beneficial effect:
1, adopt the one pot reaction technology, two reactions of aldol condensation and shortening are completed in a reactor simultaneously.So-called one pot reaction technology is: the 3-sub-borneol alkene base generated between the reaction period-2-butanone intermediate without through separating, refining step, directly in this reactor, complete catalytic hydrogenation reaction under hydrogen, catalyzer condition, generate 3-borneol alkenyl-2-butanone target product.
2, this invention technology has been simplified operation greatly, has shortened the production cycle, has reduced labour intensity.
3, product yield is up to more than 90%, and product purity, more than 95%, greatly reduces production cost.
4. water replaces in traditional technology the noxious solvents such as methyl alcohol; Catalyzer with can be recycled after basic solution separates, without the waste water output, whole process environmental protection.
below in conjunction with specific embodiment, the present invention is described in further detail:
embodiment 1
In the hydrogenation still of 2 liters, add 300g campholenic aldehyde (90%, 1.7740 mole of GC content), 300g butanone, 500g water, 10g 5% palladium carbon catalyst and 5g potassium hydroxide.Get rid of still Air three times with nitrogen, room temperature, logical hydrogen is to pressure 1MPa, and hydrogenation reaction to campholenic aldehyde content is less than 1.0%.Reaction finishes, and leaches catalyzer, separates basic solution, after purifying, obtains 3-borneol alkenyl-2-butanone product 350g, content 95.04%, yield 90.00%.(theoretical finished product 369.6 g that obtain)
embodiment 2
In the hydrogenation still of 2 liters, add 300g campholenic aldehyde (1.7740 moles), 400g butanone, 500g water, 6g 5% palladium carbon catalyst and 2.5g sodium hydroxide.Get rid of still Air three times with nitrogen, be heated to 65 ℃, logical hydrogen is to pressure 2MPa, and hydrogenation reaction to campholenic aldehyde content is less than 1.0%.Reaction finishes, and leaches catalyzer, separates basic solution, after purifying, obtains 3-borneol alkenyl-2-butanone product 358.2g, content 95.50%, yield 92.55%.
embodiment 3
In the hydrogenation still of 2 liters, add 300g campholenic aldehyde (1.7740 moles), 450g butanone, 500g water, 6g 5% palladium carbon catalyst and 2.5g potassium hydroxide.Get rid of still Air three times with nitrogen, be heated to 45 ℃, logical hydrogen is to pressure 3MPa, and hydrogenation reaction to campholenic aldehyde content is less than 1.0%.Reaction finishes, and leaches catalyzer, separates basic solution, after purifying, obtains 3-borneol alkenyl-2-butanone product 362.7g, content 96.10%, yield 94.31%.
embodiment 4
In the hydrogenation still of 2 liters, add 300g campholenic aldehyde (1.7740 moles), 300g butanone, 500g water, 15g Raney's nickel and 2.5g potassium hydroxide.Get rid of still Air three times with nitrogen, be heated to 60 ℃, logical hydrogen is to pressure 2MPa, and hydrogenation reaction to campholenic aldehyde content is less than 1.0%.Reaction finishes, and leaches catalyzer, separates basic solution, after purifying, obtains 3-borneol alkenyl-2-butanone product 352.8g, content 96.75%, yield 92.35%.
embodiment 5
In the hydrogenation still of 2 liters, other is with example 4, and 90 ℃ of temperature of reaction, lead to hydrogen to pressure 2MPa, and hydrogenation reaction to campholenic aldehyde content is less than 1.0%.Reaction finishes, and leaches catalyzer, separates basic solution, after purifying, obtains 3-borneol alkenyl-2-butanone product 346.5g, content 90.4%, yield 84.75 %.Comparative Examples 4, because temperature of reaction improves, cause the hydrogenation reaction elective reduction, part by-product alcohols material, and yield descends,
embodiment 6
In the hydrogenation still of 2 liters, add 15g potassium hydroxide.Other obtains 3-borneol alkenyl-2-butanone product 328.5g, content 94.2%, yield 83.72 % with example 4 after purifying.Comparative Examples 4, because alkalescence strengthens, cause raffinate to increase, and yield descends.
embodiment 7
In the hydrogenation still of 2 liters, add the 210g butanone.Other obtains 3-borneol alkenyl-2-butanone product 343.8g, content 94.6%, yield 88.00 % with example 4 after purifying.Comparative Examples 4, yield descends, and because the butanone consumption reduces, causes the campholenic aldehyde side reaction to increase.
Certainly; the present invention can also have other various embodiments; in the situation that do not deviate from spirit of the present invention and essence; those of ordinary skill in the art are when making according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (7)
1. the production method of a 3-borneol alkenyl-2-butanone is characterized in that comprising the following steps:
Add campholenic aldehyde, butanone, catalyzer, alkaline matter and water in an autoclave pressure, then in hydrogen pressure 0.5 MPa-4.0MPa, temperature, under 20 ℃-90 ℃, react, reaction finishes to obtain 3-borneol alkenyl-2-butanone crude product, again by crude product after filtration catalyzer, separate basic solution, remove butanone, and, after rectification under vacuum is purified, obtain 3-borneol alkenyl-2-butanone product;
The weight ratio of wherein said campholenic aldehyde and butanone, catalyzer and alkaline matter is: campholenic aldehyde: butanone=: 1:70%-400%, campholenic aldehyde: catalyzer=1:0.05%-5%, campholenic aldehyde: alkaline matter=1:0.1%-5%, described catalyzer is 5% palladium charcoal, ruthenium carbon, ruthenium aluminium or Raney's nickel.
2. the production method of 3-borneol alkenyl-2-butanone according to claim 1, is characterized in that above-mentioned campholenic aldehyde: butanone=1:100%-180%.
3. the production method of 3-borneol alkenyl-2-butanone according to claim 1, is characterized in that above-mentioned campholenic aldehyde: catalyzer=1:2%-5%.
4. the production method of 3-borneol alkenyl-2-butanone according to claim 1, is characterized in that above-mentioned campholenic aldehyde: alkaline matter=1:0.5%-2%.
5. the production method of 3-borneol alkenyl-2-butanone according to claim 1, it is characterized in that above-mentioned reaction conditions is: above-mentioned hydrogen pressure 1 MPa-3MPa, temperature are at 30 ℃-70 ℃.
6. the production method of 3-borneol alkenyl-2-butanone according to claim 1, it is characterized in that above-mentioned alkaline matter is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or diethylamine, the consumption of above-mentioned water is to form the basic solution that concentration is 0.10%-5% after alkaline matter is dissolved.
7. the production method of 3-borneol alkenyl-2-butanone according to claim 1, is characterized in that time that above-mentioned reaction finishes accounts for the weight percent of W-response material<1% for show intermediate 3-sub-borneol alkene base in raw material campholenic aldehyde or reaction process-2-butanone content by gas-chromatography.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4149020A (en) * | 1978-04-05 | 1979-04-10 | International Flavors & Fragrances Inc. | Intermediate for preparation of 2,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol |
| CN101125798A (en) * | 2007-09-14 | 2008-02-20 | 杭州格林香料化学有限公司 | Method for preparing 3- bornylene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4149020A (en) * | 1978-04-05 | 1979-04-10 | International Flavors & Fragrances Inc. | Intermediate for preparation of 2,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol |
| CN101125798A (en) * | 2007-09-14 | 2008-02-20 | 杭州格林香料化学有限公司 | Method for preparing 3- bornylene |
Non-Patent Citations (1)
| Title |
|---|
| 刘德臣 等: "以龙脑烯醛为原料合成香料的研究情况简介", 《山东化工》 * |
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