CN101723816A - 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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- CN101723816A CN101723816A CN 200910153924 CN200910153924A CN101723816A CN 101723816 A CN101723816 A CN 101723816A CN 200910153924 CN200910153924 CN 200910153924 CN 200910153924 A CN200910153924 A CN 200910153924A CN 101723816 A CN101723816 A CN 101723816A
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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, mainly is a kind of preparation method of 2-sub-borneol alkene base butyraldehyde.
Background technology
2-sub-borneol alkene base butyraldehyde is the important middle product of the inferior bornyl butanols of synthetic perfume 2-, and the inferior bornyl butanols of 2-China is called santal 208.Have the intensive 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 prescriptions 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, is used for synthetic 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 being that main raw material synthesizes with campholenic aldehyde and butyraldehyde-n, 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 catalyst I are heated to 65～90 ℃, and wherein the mass ratio of campholenic aldehyde and catalyst I is 1: 0.1～0.2;
Step 2, add butyraldehyde-n and catalyst I I in order respectively in the mixed solution of campholenic aldehyde and catalyst 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 I I is 1: 0.1～0.4;
75～100 ℃ of step 3, temperature controls 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.
Catalyst I of the present invention is secondary amine type organics such as morpholine or piperidines, and catalyst I I is an acetate.
As preferably, butyraldehyde-n and catalyst I I feeding method and temperature controlling range are as follows:
Feed intake for the first time: 65～90 ℃ of temperature controls drip 10% of butyraldehyde-n total amount; After butyraldehyde-n feeds intake and finishes, drop into 33% of catalyst I I total amount, 80～95 ℃ of temperature controls;
Feed intake for the second time: 70～95 ℃ of temperature controls, drip 27.5% of butyraldehyde-n total amount, after butyraldehyde-n feeds intake and finishes, drop into 32% of catalyst I I total amount;
Feed intake for the third time: 70～95 ℃ of temperature controls, drip 27.5% of butyraldehyde-n total amount, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount;
Feed intake for the 4th time: 70～95 ℃ of temperature controls, drip 10% of butyraldehyde-n total amount, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount;
Feed intake for the 5th time: 70～95 ℃ of temperature controls, drip 10% of butyraldehyde-n total amount, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount;
Feed intake for the 6th time: 70～95 ℃ of temperature controls, drip 7.5% of butyraldehyde-n total amount, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount;
Feed intake for the 7th time: 70～95 ℃ of temperature controls drip 7.5% of butyraldehyde-n total amount;
The invention has the advantages that: it is main raw material Synthetic 2-sub-borneol alkene base butyraldehyde product that the present invention adopts campholenic aldehyde and butyraldehyde-n, reaction conditions Wen Li, easy-to-operate, product yield, product quality are greatly improved, are used for synthetic santal product fragrance and handle simple.
Embodiment
Below in conjunction with embodiment the present invention is further described, but should understand these embodiment limits the scope of the invention, under the situation of 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 225g in the 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, acetate 45g adds butyraldehyde-n and acetate then in order respectively: drip for the first time butyraldehyde-n 25g (butyraldehyde-n total amount 10%), 65～90 ℃ of temperature controls, drop into acetate 14.85g (acetate total amount 33%) then, 70～95 ℃ of temperature controls; For the second time all control 70～95 ℃, drip 27.5% of butyraldehyde-n total amount for the second time, drop into 32% of acetate total amount then to the temperature that drips butyraldehyde-n the 7th time and add acetate; Drip 27.5% of butyraldehyde-n total amount for the third time, drop into 8.75% of acetate total amount then; Drip 10% of butyraldehyde-n total amount, drop into 8.75% of acetate total amount then for the 4th time; Drip 10% of butyraldehyde-n total amount, drop into 8.75% of acetate total amount then for the 5th time; Drip 7.5% of butyraldehyde-n total amount, drop into 8.75% of acetate total amount then for the 6th time; Drip 7.5% of butyraldehyde-n total amount the 7th time; After the reinforced end of butyraldehyde-n and acetate, 75～100 ℃ of controlled 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 a 2-sub-borneol alkene base butyraldehyde finished product, content 94%, yield 92.5%.
Add 250g in the 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, acetate 65g adds butyraldehyde-n and acetate then in order respectively: drip for the first time butyraldehyde-n 28g (butyraldehyde-n total amount 10%), 65～90 ℃ of temperature controls, drop into acetate 21.45g (acetate total amount 33%) then, 70～95 ℃ of temperature controls; For the second time all control 70～95 ℃, drip 27.5% of butyraldehyde-n total amount for the second time, drop into 32% of acetate total amount then to the temperature that drips butyraldehyde-n the 7th time and add acetate; Drip 27.5% of butyraldehyde-n total amount for the third time, drop into 8.75% of acetate total amount then; Drip 10% of butyraldehyde-n total amount, drop into 8.75% of acetate total amount then for the 4th time; Drip 10% of butyraldehyde-n total amount, drop into 8.75% of acetate total amount then for the 5th time; Drip 7.5% of butyraldehyde-n total amount, drop into 8.75% of acetate total amount then for the 6th time; Drip 7.5% of butyraldehyde-n total amount the 7th time; After the reinforced end of butyraldehyde-n and acetate, 75～100 ℃ of controlled temperature continue reaction 2～3 hours.Method according to example 1 is handled crude product oil, obtains 2-sub-borneol alkene base butyraldehyde finished product, content 94%, yield 92%.
Embodiment 3: difference from Example 1 is: catalyst 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: catalyst I is used piperidines instead by morpholine, obtains 2-sub-borneol alkene base butyraldehyde finished product, content 94%, yield 91.5%.
Claims (4)
1. the preparation method of a 2-sub-borneol alkene base butyraldehyde, it is characterized in that: this method steps is as follows: with campholenic aldehyde and butyraldehyde-n is raw material Synthetic 2-sub-borneol alkene base butyraldehyde, campholenic aldehyde and catalyst I are dropped in the reactor, be heated to 65～90 ℃, wherein the mass ratio of campholenic aldehyde and catalyst I is 1: 0.1～0.2; Add butyraldehyde-n and catalyst I I in the mixed solution of campholenic aldehyde and catalyst I in order respectively, wherein the mass ratio of campholenic aldehyde and butyraldehyde-n is 1: 1.0～1.5; The mass ratio of campholenic aldehyde and catalyst I I is 1: 0.1～0.4; Behind reinforced the end, 75～100 ℃ of temperature controls 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.
2. the preparation method of 2-sub-borneol alkene base butyraldehyde according to claim 1, it is characterized in that: in the mixed solution of campholenic aldehyde and catalyst I, add butyraldehyde-n and catalyst I I in order respectively, butyraldehyde-n and catalyst I I feeding method and temperature controlling range are: drip 10% of butyraldehyde-n total amount for the first time, 65～90 ℃ of temperature controls, after butyraldehyde-n feeds intake and finishes, drop into 33% of catalyst I I total amount, 70～95 ℃ of temperature controls; For the second time all control 70～95 ℃ to the temperature that drips butyraldehyde-n the 7th time and add catalyst I I; Drip for the second time 27.5% of butyraldehyde-n total amount, after butyraldehyde-n feeds intake and finishes, drop into 32% of catalyst I I total amount; Drip 27.5% of butyraldehyde-n total amount for the third time, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount; Throw for the 4th time and drip 10% of butyraldehyde-n total amount, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount; Drip 10% of butyraldehyde-n total amount the 5th time, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount; Drip 7.5% of butyraldehyde-n total amount the 6th time, after butyraldehyde-n feeds intake and finishes, drop into 8.75% of catalyst I I total amount; Drip 7.5% of butyraldehyde-n total amount the 7th time.
3. the preparation method of 2-sub-borneol alkene base butyraldehyde according to claim 1, it is characterized in that: catalyst I is selected morpholine or piperidines for use.
4. the preparation method of 2-sub-borneol alkene base butyraldehyde according to claim 1 and 2, it is characterized in that: catalyst I I selects acetate for use.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 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 |
| EP1930317A1 (en) * | 2006-12-08 | 2008-06-11 | V. Mane Fils | Use of campholenic derivatives as fragrant ingredients in perfumery and flavouring |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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