CN103449993B - Production method of 3-campholenyl-2-butanone - Google Patents
Production method of 3-campholenyl-2-butanone Download PDFInfo
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- CN103449993B CN103449993B CN201310369141.6A CN201310369141A CN103449993B CN 103449993 B CN103449993 B CN 103449993B CN 201310369141 A CN201310369141 A CN 201310369141A CN 103449993 B CN103449993 B CN 103449993B
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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 technical field of fine, 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), and be the important middle product of synthetic perfume 3-borneol alkenyl-2-butanols, have strong banksia rose fragrance, fragrance exactly likes natural sandalwood.Be widely used in the daily chemical essence formulas such as perfumed soap, shampoo, makeup.The preparation method that US Patent No. 4052341 and document CN101125798A report 3-borneol alkenyl-2-butanone utilizes campholenic aldehyde and butanone to 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 aldol reaction under methanol solvate, liquid caustic soda condition, reaction terminates, and need 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, obtains 3-borneol alkenyl-2-butanone finished product through operations such as filtration, washing, solvent recuperation, rectifying.
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, obtains 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, wastewater treatment costly, contaminate environment.
Summary of the invention
Object of the present invention is just in order to overcome above-mentioned the deficiencies in the prior art, and the one provided is 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:
Campholenic aldehyde, butanone, catalyzer and alkaline matter, water is added in an autoclave pressure, then react at 20 DEG C-90 DEG C in hydrogen pressure 0.5 MPa-4.0MPa, temperature, reaction terminates to obtain 3-borneol alkenyl-2-butanone crude product, again by crude product catalyzer, separation basic solution, removal butanone after filtration, and after rectification under vacuum is purified, namely 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 that after alkaline matter is dissolved, formation concentration is the basic solution of 0.10%-5%.
The time that above-mentioned reaction terminates is the weight percent < 1% being accounted for W-response material by the intermediate 3-sub-borneol alkene base-2-butanone content in gas-chromatography display raw material campholenic aldehyde or reaction process.
The present invention is owing to adopting raw material campholenic aldehyde, butanone, catalyzer and alkaline matter, water puts into the one pot reaction technology of same reactor (being also reactor) reaction, thus aldol condensation and shortening two reaction are all directly completed in a reactor simultaneously, the 3-sub-borneol alkene base-2-butanone intermediate generated between such reaction period is separated without the need to passing through, refining step, directly in this reactor, at hydrogen, catalytic hydrogenation reaction is completed under catalysts conditions, generate 3-borneol alkenyl-2-butanone target product, therefore enormously simplify operation sequence, shorten the production cycle, reduce 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 can be recycled after being separated with basic solution, without waste water output, whole process environmental protection, efficiently solve existing 3-borneol alkenyl-2-butanone and need two step synthesis techniques, operation is numerous and diverse, production cycle is long, labour intensity is large and plant factor is not high, and solvent loss is large, and cost is high, wastewater treatment costly, the problems such as contaminate environment.
Embodiment
The production method of 3-borneol alkenyl-2-butanone of the present invention, comprises the following steps:
Campholenic aldehyde, butanone, catalyzer and alkaline matter, water is added in an autoclave pressure, then react at 20 DEG C-90 DEG C in hydrogen pressure 0.5 MPa-4.0MPa, temperature, reaction terminates to obtain 3-borneol alkenyl-2-butanone crude product, again by crude product catalyzer, separation basic solution, removal butanone after filtration, and after rectification under vacuum is purified, namely 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 that after alkaline matter is dissolved, formation concentration is the basic solution of 0.10%-5%.
The preferred version of above-mentioned reaction conditions is: above-mentioned hydrogen pressure 1 MPa-3MPa, temperature are at 30 DEG C-70 DEG C.
Above-mentioned logical hydrogen is until the time that reaction terminates is the weight percent < 1% being accounted for W-response material by gas-chromatography display raw material campholenic aldehyde or reaction intermediate 3-sub-borneol alkene base-2-butanone content.
Production method provided by the invention, has following beneficial effect:
1, adopt one pot reaction technology, aldol condensation and shortening two reaction are completed in a reactor simultaneously.So-called one pot reaction technology is namely: the 3-sub-borneol alkene base-2-butanone intermediate generated between the reaction period without the need to through being separated, refining step, directly in this reactor, under hydrogen, catalysts conditions, complete catalytic hydrogenation reaction, generate 3-borneol alkenyl-2-butanone target product.
2, this invention technology enormously simplify operation, shortens the production cycle, reduces labour intensity.
3, product yield is up to more than 90%, and product purity more than 95%, greatly reduces production cost.
4. water to replace in traditional technology the noxious solvents such as methyl alcohol; Catalyzer can be recycled after being separated with basic solution, without waste water output, and 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 (GC content 90%, 1.7740 moles), 300g butanone, 500g water, 10g 5% palladium carbon catalyst and 5g potassium hydroxide.To get rid of in still air three times with nitrogen, room temperature, logical hydrogen is to pressure 1MPa, and hydrogenation reaction is less than 1.0% to campholenic aldehyde content.Reaction terminates, and leaches catalyzer, is separated basic solution, after purifying, obtain 3-borneol alkenyl-2-butanone product 350g, content 95.04%, yield 90.00%.(theoretical finished product 369.6 g)
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.To get rid of in still air three times with nitrogen, be heated to 65 DEG C, logical hydrogen is to pressure 2MPa, and hydrogenation reaction is less than 1.0% to campholenic aldehyde content.Reaction terminates, and leaches catalyzer, is separated basic solution, after purifying, obtain 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.To get rid of in still air three times with nitrogen, be heated to 45 DEG C, logical hydrogen is to pressure 3MPa, and hydrogenation reaction is less than 1.0% to campholenic aldehyde content.Reaction terminates, and leaches catalyzer, is separated basic solution, after purifying, obtain 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.To get rid of in still air three times with nitrogen, be heated to 60 DEG C, logical hydrogen is to pressure 2MPa, and hydrogenation reaction is less than 1.0% to campholenic aldehyde content.Reaction terminates, and leaches catalyzer, is separated basic solution, after purifying, obtain 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, temperature of reaction 90 DEG C, and logical hydrogen is to pressure 2MPa, and hydrogenation reaction is less than 1.0% to campholenic aldehyde content.Reaction terminates, and leaches catalyzer, is separated basic solution, after purifying, obtain 3-borneol alkenyl-2-butanone product 346.5g, content 90.4%, yield 84.75 %.Comparative example 4, because temperature of reaction improves, causes hydrogenation reaction selectivity to reduce, part by-product alcohols material, and yield declines,
embodiment 6
In the hydrogenation still of 2 liters, add 15g potassium hydroxide.Other is with example 4, after purifying, obtain 3-borneol alkenyl-2-butanone product 328.5g, content 94.2%, yield 83.72 %.Comparative example 4, because alkalescence strengthens, causes raffinate to increase, and yield declines.
embodiment 7
In the hydrogenation still of 2 liters, add 210g butanone.Other is with example 4, after purifying, obtain 3-borneol alkenyl-2-butanone product 343.8g, content 94.6%, yield 88.00 %.Comparative example 4, yield declines, and because butanone consumption reduces, causes campholenic aldehyde side reaction to increase.
Certainly; the present invention can also have other various embodiments; when not deviating from the present invention's spirit and essence; those of ordinary skill in the art are when making various corresponding change and distortion according to the present invention, but these change accordingly and are out of shape the protection domain that all should belong to the claim appended by the present invention.
Claims (7)
1. a production method for 3-borneol alkenyl-2-butanone, is characterized in that comprising the following steps:
Campholenic aldehyde, butanone, catalyzer, alkaline matter and water is added in an autoclave pressure, then react at 20 DEG C-90 DEG C in hydrogen pressure 0.5 MPa-4.0MPa, temperature, reaction terminates to obtain 3-borneol alkenyl-2-butanone crude product, again by crude product catalyzer, separation basic solution, removal butanone after filtration, and after rectification under vacuum is purified, namely 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, is characterized in that above-mentioned reaction conditions is: above-mentioned hydrogen pressure 1 MPa-3MPa, temperature are at 30 DEG C-70 DEG C.
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 that after alkaline matter is dissolved, formation concentration is the basic solution of 0.10%-5%.
7. the production method of 3-borneol alkenyl-2-butanone according to claim 1, is characterized in that the time that above-mentioned reaction terminates is the weight percent < 1% being accounted for W-response material by the intermediate 3-sub-borneol alkene base-2-butanone content in gas-chromatography display raw material campholenic aldehyde or reaction process.
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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 |
|---|
| 以龙脑烯醛为原料合成香料的研究情况简介;刘德臣 等;《山东化工》;19981231(第6期);第29-32页 * |
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