CN101723816B - Method for preparing 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal - Google Patents
Method for preparing 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal Download PDFInfo
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- CN101723816B CN101723816B CN 200910153924 CN200910153924A CN101723816B CN 101723816 B CN101723816 B CN 101723816B CN 200910153924 CN200910153924 CN 200910153924 CN 200910153924 A CN200910153924 A CN 200910153924A CN 101723816 B CN101723816 B CN 101723816B
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Abstract
The invention relates to a method for preparing 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal, which comprises the following steps: synthesizing the 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal by campholenic aldehyde and n-butanal which are taken as raw materials, putting the campholenic aldehyde and a catalyst I into a reaction kettle, and heating to the temperature of between 65 and 90 DEG C, wherein the mass ratio of the campholenic aldehyde to the catalyst I is 1:0.1-0.2; orderly adding the n-butanal and a catalyst II into the mixed solution of the campholenic aldehyde and the catalyst I respectively, wherein the mass ratio of the campholenic aldehyde to the n-butanal is 1:1.0-1.5, and the mass ratio of the campholenic aldehyde to the catalyst II is 1:0.1-0.4; and after addition of the materials, controlling the temperature to between 75 and 100 DEG C, continuously reacting for 2 to 3 hours, washing crude product oil with water to neutrality, and distilling the crude product oil under reduced pressure to obtain the 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal. The method has the advantages that: the campholenic aldehyde and n-butanal are adopted as main raw materials to synthesize the 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal product, the reaction conditions are mild, the operation is safe and convenient, the yield and quality of the product are greatly improved, and the aroma of sandalwood products synthesized is simple to treat.
Description
Technical field
The present invention relates to a kind of chemical synthesis process of field of perfumery, is mainly a kind of preparation method of 2-sub-borneol alkene base butyraldehyde.
Background technology
2-sub-borneol alkene base butyraldehyde be the inferior bornyl butanols of synthetic perfume 2-important in the middle of product, the inferior bornyl butanols of 2-China is called santal 208.Have strong sandalwood aroma, and have faint Rose Essentielle aromatic, the more natural santal oil of fragrance remaining time is short.Be widely used in the daily chemical essence formulas such as perfumed soap, makeup, shampoo.The preparation method of 2-sub-borneol alkene base butyraldehyde utilizes campholenic aldehyde and butyraldehyde-n to be raw material, sodium hydroxide or potassium hydroxide are catalyzer, methyl alcohol synthesizes as solvent, but such synthetic method plant factor is not high, transformation efficiency is not high, side reaction is many, for the synthesis of santal product fragrance difficult treatment.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned deficiency, and a kind of preparation method who improves the 2-sub-borneol alkene base butyraldehyde of transformation efficiency is provided.
The present invention solves the technical scheme that its technical problem adopts: the present invention is for synthesizing take campholenic aldehyde and butyraldehyde-n as main raw material, the synthetic 2-sub-borneol alkene base butyraldehyde crude product oil that obtains, and the rectification under vacuum of crude product oil process obtains 2-sub-borneol alkene base butyraldehyde finished product.
The preparation method of this 2-sub-borneol alkene base butyraldehyde of the present invention, concrete steps are as follows:
Step 1, input campholenic aldehyde and catalyzer I are heated to 65～90 ℃, and wherein the mass ratio of campholenic aldehyde and catalyzer I is 1: 0.1～0.2;
Step 2, add respectively in order butyraldehyde-n and catalyst II in the mixed solution of campholenic aldehyde and catalyzer I, wherein the mass ratio of campholenic aldehyde and butyraldehyde-n is 1: 1.0～1.5; The mass ratio of campholenic aldehyde and catalyst II is 1: 0.1～0.4;
Step 3, temperature are controlled 75～100 ℃, continue reaction 2～3 hours, and washing crude product oil is to neutral, and crude product oil obtains 2-sub-borneol alkene base butyraldehyde through rectification under vacuum.
Catalyzer I of the present invention is the secondary amine type organics such as morpholine or piperidines, and catalyst II is acetic acid.
As preferably, butyraldehyde-n and catalyst II feeding method and temperature controlling range are as follows:
Feed intake for the first time: temperature is controlled 65～90 ℃, drips 10% of butyraldehyde-n total amount; Butyraldehyde-n drops into 33% of catalyst II total amount after feeding intake and finishing, and temperature is controlled 70～95 ℃;
Feed intake for the second time: temperature is controlled 70～95 ℃, drips 27.5% of butyraldehyde-n total amount, and butyraldehyde-n drops into 32% of catalyst II total amount after feeding intake and finishing;
Feed intake for the third time: temperature is controlled 70～95 ℃, drips 27.5% of butyraldehyde-n total amount, and butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing;
Feed intake for the 4th time: temperature is controlled 70～95 ℃, drips 10% of butyraldehyde-n total amount, and butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing;
Feed intake for the 5th time: temperature is controlled 70～95 ℃, drips 10% of butyraldehyde-n total amount, and butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing;
Feed intake for the 6th time: temperature is controlled 70～95 ℃, drips 7.5% of butyraldehyde-n total amount, and butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing;
Feed intake for the 7th time: temperature is controlled 70～95 ℃, drips 7.5% of butyraldehyde-n total amount;
The invention has the advantages that: it is the synthetic 2-sub-borneol alkene base butyraldehyde product of main raw material that the present invention adopts campholenic aldehyde and butyraldehyde-n, reaction conditions is gentle, easy-to-operate, product yield, product quality are greatly improved, for the synthesis of santal product fragrance process simple.
Embodiment
The invention will be further described below in conjunction with embodiment, but should understand these embodiment limits the scope of the invention, in the situation that without prejudice to the spirit and scope of the present invention, those skilled in the art can make changes and improvements so that it is fit to different service conditions, condition and embodiment to the present invention.
Add campholenic aldehyde 225g in embodiment 1:1000ml four-hole boiling flask (stirring, thermometer, reflux condensing tube, addition funnel are housed), morpholine 26g, stirring is warming up to 65～90 ℃, prepare butyraldehyde-n 250g, then acetic acid 45g adds respectively butyraldehyde-n and acetic acid in order: drip for the first time butyraldehyde-n 25g(butyraldehyde-n total amount 10%), temperature is controlled 65～90 ℃, then drop into acetic acid 14.85g(acetic acid total amount 33%), temperature is controlled 70～95 ℃; The temperature that for the second time to the seven times drips butyraldehyde-ns and add acetic acid is all controlled 70～95 ℃, drips for the second time 27.5% of butyraldehyde-n total amount, then drops into 32% of acetic acid total amount; Drip for the third time 27.5% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount; Drip 10% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount for the 4th time; Drip 10% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount for the 5th time; Drip 7.5% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount for the 6th time; Drip 7.5% of butyraldehyde-n total amount the 7th time; After the reinforced end of butyraldehyde-n and acetic acid, control 75～100 ℃ of temperature, continue reaction 2～3 hours.The crude product profit that reaction obtains is washed till neutrality, and 85～100 ℃/1.5mmHg is collected in rectification under vacuum, and cut is 2-sub-borneol alkene base butyraldehyde finished product, content 94%, yield 92.5%.
Add campholenic aldehyde 250g in embodiment 2:1000ml four-hole boiling flask (stirring, thermometer, reflux condensing tube, addition funnel are housed), morpholine 35g, stirring is warming up to 65～90 ℃, prepare butyraldehyde-n 280g, then acetic acid 65g adds respectively butyraldehyde-n and acetic acid in order: drip for the first time butyraldehyde-n 28g(butyraldehyde-n total amount 10%), temperature is controlled 65～90 ℃, then drop into acetic acid 21.45g(acetic acid total amount 33%), temperature is controlled 70～95 ℃; The temperature that for the second time to the seven times drips butyraldehyde-ns and add acetic acid is all controlled 70～95 ℃, drips for the second time 27.5% of butyraldehyde-n total amount, then drops into 32% of acetic acid total amount; Drip for the third time 27.5% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount; Drip 10% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount for the 4th time; Drip 10% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount for the 5th time; Drip 7.5% of butyraldehyde-n total amount, then drop into 8.75% of acetic acid total amount for the 6th time; Drip 7.5% of butyraldehyde-n total amount the 7th time; After the reinforced end of butyraldehyde-n and acetic acid, control 75～100 ℃ of temperature, continue reaction 2～3 hours.Process crude product oil according to the method for example 1, obtain 2-sub-borneol alkene base butyraldehyde finished product, content 94%, yield 92%.
Embodiment 3: difference from Example 1 is: the catalyzer I is used piperidines instead by morpholine, obtains 2-sub-borneol alkene base butyraldehyde finished product, content 94%, yield 91.8%.
Embodiment 4: difference from Example 2 is: the catalyzer I is used piperidines instead by morpholine, obtains 2-sub-borneol alkene base butyraldehyde finished product, content 94%, yield 91.5%.
Claims (2)
1. the preparation method of a 2-sub-borneol alkene base butyraldehyde, it is characterized in that: the method step is as follows: the synthetic 2-sub-borneol alkene base butyraldehyde take campholenic aldehyde and butyraldehyde-n as raw material, campholenic aldehyde and catalyzer I are dropped in reactor, be heated to 65～90 ℃, wherein the mass ratio of campholenic aldehyde and catalyzer I is 1: 0.1～0.2; Add respectively in order butyraldehyde-n and catalyst II in the mixed solution of campholenic aldehyde and catalyzer I, wherein the mass ratio of campholenic aldehyde and butyraldehyde-n is 1: 1.0～1.5; The mass ratio of campholenic aldehyde and catalyst II is 1: 0.1～0.4; After reinforced the end, temperature is controlled 75～100 ℃, continues reaction 2～3 hours, and washing crude product oil is to neutral, and crude product oil obtains 2-sub-borneol alkene base butyraldehyde through rectification under vacuum; The catalyzer I is selected morpholine or piperidines, and catalyst II is selected acetic acid.
2. the preparation method of 2-sub-borneol alkene base butyraldehyde according to claim 1, it is characterized in that: add respectively in order butyraldehyde-n and catalyst II in the mixed solution of campholenic aldehyde and catalyzer I, butyraldehyde-n and catalyst II feeding method and temperature controlling range are: drip for the first time 10% of butyraldehyde-n total amount, temperature is controlled 65～90 ℃, after butyraldehyde-n feeds intake and finishes, drop into 33% of catalyst II total amount, temperature is controlled 70～95 ℃; The temperature that for the second time to the seven times drips butyraldehyde-ns and add catalyst II is all controlled 70～95 ℃; Drip for the second time 27.5% of butyraldehyde-n total amount, butyraldehyde-n drops into 32% of catalyst II total amount after feeding intake and finishing; Drip for the third time 27.5% of butyraldehyde-n total amount, butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing; Drip 10% of butyraldehyde-n total amount the 4th time, butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing; Drip 10% of butyraldehyde-n total amount the 5th time, butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing; Drip 7.5% of butyraldehyde-n total amount the 6th time, butyraldehyde-n drops into 8.75% of catalyst II total amount after feeding intake and finishing; Drip 7.5% of butyraldehyde-n total amount the 7th time.
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| CN 200910153924 CN101723816B (en) | 2009-11-26 | 2009-11-26 | Method for preparing 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal |
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| CN 200910153924 CN101723816B (en) | 2009-11-26 | 2009-11-26 | Method for preparing 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-yl)-but-2-enal |
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| CN101723816B true CN101723816B (en) | 2013-06-05 |
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660737A (en) * | 2004-12-21 | 2005-08-31 | 建德市新化化工有限责任公司 | Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol |
| CN101589021A (en) * | 2006-12-08 | 2009-11-25 | 玛奈·菲尔萨公司 | Use of campholenic derivatives as fragrant ingredients in perfumery and flavouring |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660737A (en) * | 2004-12-21 | 2005-08-31 | 建德市新化化工有限责任公司 | Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol |
| CN101589021A (en) * | 2006-12-08 | 2009-11-25 | 玛奈·菲尔萨公司 | Use of campholenic derivatives as fragrant ingredients in perfumery and flavouring |
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