CN101492347B - Method for synthesis of 2-sub-borneol alkene butanol with organic base - Google Patents
Method for synthesis of 2-sub-borneol alkene butanol with organic base Download PDFInfo
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- CN101492347B CN101492347B CN200910095311XA CN200910095311A CN101492347B CN 101492347 B CN101492347 B CN 101492347B CN 200910095311X A CN200910095311X A CN 200910095311XA CN 200910095311 A CN200910095311 A CN 200910095311A CN 101492347 B CN101492347 B CN 101492347B
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Abstract
The invention discloses a method for catalyzing and synthesizing 2-ethide-4-(2, 2, 3-trimethyl-3-cyclopentene)-2-butylene-1-alcohol by organic base. In the method, 2, 2, 3-trimethyl-1-oxoethyl-3-cyclopentene is mixed with the organic base, butanal and glacial acetic acid are dripped to react and manufacture the 2-ethide-4-(2, 2, 3-trimethyl-3-cyclopentene)-2-butylene-1-alcohol, and a product is obtained after the post treatment. The invention has the advantages that the side reaction caused by the self condensation and the transitional condensation of the material are less; and the product has high content, pure fragrance, high yield, and low cost, etc. The invention has wide application at the flavor industry.
Description
Technical field
The invention belongs to the synthetic field of organic chemical industry, specifically be meant a kind of method with organic base catalytic Synthetic 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol.
Technical background
2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol is a kind ofly to have dense sandalwood fragrance, and has the spices of faint Rose Essentielle, and molecular formula is C
14H
24O.Its fragrance is pure, is widely used in all kinds of essence.
Its synthetic method is generally with 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes is a raw material, under the catalysis of alkali, with n butyraldehyde aldolization and dehydration, obtain intermediate 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-aldehyde, again aldehyde is reduced to alcohol and promptly obtains 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol.
Condensation catalyst in the existing production technique adopts mineral alkali more, and as (as US4052341) such as sodium hydroxide, potassium hydroxide, catalytic efficiency is low, side reactions such as material self condensation and transition condensation are serious, cause product content low, and fragrance is bad, and productive rate is low, the cost height.
Summary of the invention
At deficiency of the prior art, the present invention proposes the production method of a kind of effective minimizing side reaction, raising productive rate.
The present invention is achieved by following technical proposals:
Introduce a kind of organic bases in the present invention and substitute traditional mineral alkali, organic bases has gentle alkalescence and suitable polarity, is used for the condensation reaction of catalysis aldehyde aldehyde, and it is few to have a transition condensation reaction, the selectivity advantages of higher.
With the method for organic bases Synthetic 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol, it is characterized in that being undertaken by following step:
(1) with raw material 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and organic bases are that 1: 0.05～2.0 proportioning is mixed according to mol ratio, stir;
(2) controlled temperature 30-100 ℃, stir down and drip butyraldehyde-n and glacial acetic acid, raw material 2,2, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes, butyraldehyde-n and glacial acetic acid is 1: 0.5～6.0: 0.05-3.0;
(3) dropwise, mixture continues more than 1 hour, to be cooled to room temperature at 30-100 ℃ of following stirring reaction then;
(4) add water washing, oil reservoir is intermediate 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-aldehyde;
(5) intermediate obtains 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol with the reductive agent reduction.
In the present invention, organic bases is a nitrogenous class alkaline organic, comprises pyridine, picoline, pyrroles, methylpyrrole, Pyrrolidine, morpholine, piperidines etc., and wherein, pyridine, morpholine, pyrroles are preferred.
As preferably, 2,2 in the above-mentioned synthetic method, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and organic bases is 1: 0.1～1.5; As more preferably selecting, described 2,2, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and organic bases is 1: 0.1～1.0.
As preferably, 2,2 in the above-mentioned synthetic method, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and butyraldehyde-n is 1: 0.6～5.0; As more preferably selecting, described 2,2, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and butyraldehyde-n is 1: 1.2～3.0.
As preferably, 2,2 in the above-mentioned synthetic method, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and glacial acetic acid is 1: 0.1～1.5; As more preferably selecting, described 2,2, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and glacial acetic acid is 1: 0.5～1.2.
Butyraldehyde-n and glacial acetic acid can drip simultaneously, separately drip or the dropping of branch minor tick.
As preferably, the temperature of reaction described in the above-mentioned synthetic method is 60～100 ℃, and the reaction times is 1～12 hour.When temperature of reaction is too low, speed of response is slow.Temperature is too high, and then by product is many, and yield is low.
Beneficial effect: mineral alkalis such as the sodium hydroxide that the present invention replaces using in the existing production technique with organic bases, potassium hydroxide are as catalyzer, it is few to have side reactions such as material self condensation and transition condensation, the product content height, and fragrance is pure, the productive rate height, low cost and other advantages.
Embodiment
Embodiment 1:
In the there-necked flask that agitator, addition funnel, thermometer are housed, add 268g (1.5mol) 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes (content 85%) and 53g (0.75mol) Pyrrolidine stir, and adjust 65 ℃-70 ℃ of temperature, in 3 hours, drip butyraldehyde-n 324g (4.5mol) and glacial acetic acid 45g (0.75mol), dropwise, reaction mixture is cooled to 25 ℃ behind 70 ℃ of reaction 8h.Add water 150g, stirred 15 minutes, pour into and leave standstill 30 minutes in the separating funnel.Separatory, oil reservoir are intermediate 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-aldehyde crude product, GC content: 2,2, and 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes 0.2%, intermediate 84.5%.Obtain intermediate finished product 293g (1.3mol) through rectifying, content 91.2%, yield 86.7% (to 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes).
Embodiment 2:
In the there-necked flask that agitator, addition funnel, thermometer are housed, add 268g (1.5mol) 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes (content 85%) and 24g (0.30mol) pyridine, stir, adjust 70 ℃-75 ℃ of temperature, in 3 hours, drip butyraldehyde-n 324g (4.5mol), in 1 hour, drip glacial acetic acid 30g (0.5mol) again.Dropwise, reaction mixture is cooled to 25 ℃ behind 100 ℃ of reaction 3h.Add water 150g, stirred 15 minutes, pour into and leave standstill 30 minutes in the separating funnel.Separatory, oil reservoir are the intermediate crude product, GC content: 2,2, and 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes 0.4%, intermediate 82.6%.Obtain intermediate finished product 302g (1.35mol) through rectifying, content 91.8%, yield 89.7% (to 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes).
Embodiment 3:
In the there-necked flask that agitator, addition funnel, thermometer are housed, add 268g (1.5mol) 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes (content 85%) and 39g (0.45mol) morpholine, stir, adjust 80 ℃-85 ℃ of temperature, in 2 hours, drip butyraldehyde-n 216g (3.0mol), in 1 hour, drip glacial acetic acid 45g (0.75mol) again.Dropwise, reaction mixture is cooled to 25 ℃ behind 85 ℃ of reaction 5h.Add water 150g, stirred 15 minutes, pour into and leave standstill 30 minutes in the separating funnel.Separatory, oil reservoir are the intermediate crude product, GC content: 2,2, and 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes 0.5%, intermediate 82.8%.Obtain intermediate finished product 295g (1.3mol) through rectifying, content 90.7%, yield 86.6% (to 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes).
Embodiment 4:
In the there-necked flask that agitator, addition funnel, thermometer are housed, add 268g (1.5mol) 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes (content 85%) and 30g (0.30mol) pyrroles, stir, adjust 85 ℃-90 ℃ of temperature, in 2 hours, drip butyraldehyde-n 216g (3.0mol) and glacial acetic acid 30g (0.5mol).Dropwise, reaction mixture is cooled to 25 ℃ behind 60 ℃ of reaction 8h.Add water 150g, stirred 15 minutes, pour into and leave standstill 30 minutes in the separating funnel.Separatory, oil reservoir are the intermediate crude product, GC content: 2,2, and 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes 0.3%, intermediate 83.7%.Obtain intermediate finished product 305g (1.34mol) through rectifying, content 90.5%, yield 89.3% (to 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes).
Embodiment 5:
In the there-necked flask that agitator, addition funnel, thermometer are housed, add the 500mL dehydrated alcohol, stir and add 18.9g (0.5mol) sodium borohydride down, be cooled to 0～10 ℃, in 1 hour, drip 227g (1mol) intermediate finished product (content 90.8%), dropwise, stirred 3 hours down at 0～10 ℃.
The reaction solution air distillation is reclaimed ethanol, up to 80 ℃ of temperature.Debris to neutral, obtains target product 2-ethyl-4-(2,2 with dilute sulfuric acid dip, 3-trimethylammonium-3-cyclopentenes)-and the crude product of 2-butylene-1-alcohol, GC analyzes, 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-and the content of 2-butylene-1-alcohol is 89.2%, the residual quantity of intermediate is 0.02%.
The crude product high vacuum rectification, the cut of 95～97 ℃/5mmHg of collection gets compound 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol 212.6g, content 92.6%, yield 94.6%.
Claims (11)
1. with the method for organic bases Synthetic 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol, it is characterized in that comprising the steps carrying out:
(1) with raw material 2,2,3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and organic bases are that 1: 0.05～2.0 proportioning is mixed according to mol ratio, stir;
(2) controlled temperature 30-100 ℃, stir down and drip butyraldehyde-n and glacial acetic acid, raw material 2,2, the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes, butyraldehyde-n and glacial acetic acid is 1: 0.5～6.0: 0.05-3.0;
(3) dropwise, mixture continues more than 1 hour, to be cooled to room temperature at 30-100 ℃ of following stirring reaction then;
(4) add water washing, oil reservoir is intermediate 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-aldehyde;
(5) intermediate obtains 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes)-2-butylene-1-alcohol with the reductive agent reduction.
2. synthetic method according to claim 1 is characterized in that described organic bases is nitrogenous alkaline organic.
3. synthetic method according to claim 2 is characterized in that described organic bases is pyridine, picoline, pyrroles, methylpyrrole, Pyrrolidine, morpholine, piperidines.
4. synthetic method according to claim 3 is characterized in that described organic bases is pyridine, morpholine, pyrroles.
5. synthetic method according to claim 1 is characterized in that describedly 2,2, and the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and organic bases is 1: 0.1～1.5.
6. synthetic method according to claim 5 is characterized in that describedly 2,2, and the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and organic bases is 1: 0.1～1.0.
7. synthetic method according to claim 1 is characterized in that describedly 2,2, and the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and butyraldehyde-n is 1: 0.6～5.0.
8. synthetic method according to claim 7 is characterized in that describedly 2,2, and the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and butyraldehyde-n is 1: 1.2～3.0.
9. synthetic method according to claim 1 is characterized in that 2,2 in the described synthetic method, and the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and glacial acetic acid is 1: 0.1～1.5.
10. synthetic method according to claim 9 is characterized in that describedly 2,2, and the mol ratio of 3-trimethylammonium-1-aldehyde-base-3-cyclopentenes and glacial acetic acid is 1: 0.5～1.2.
11. synthetic method according to claim 1 is characterized in that described temperature of reaction is 60～100 ℃, the reaction times is 1～12 hour.
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| CN110590500A (en) * | 2019-09-29 | 2019-12-20 | 格林生物科技股份有限公司 | Preparation of 3-methyl-5- (2,2, 3-trimethyl-3-cyclopenten-1-yl) pent-4-en-2-ol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4052341A (en) * | 1976-04-29 | 1977-10-04 | Givaudan Corporation | 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol compound and perfume compositions |
| 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 |
-
2009
- 2009-01-06 CN CN200910095311XA patent/CN101492347B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4052341A (en) * | 1976-04-29 | 1977-10-04 | Givaudan Corporation | 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol compound and perfume compositions |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 李春丽.以龙脑烯醛为原料合成檀香类化合物的研究.《香料香精化妆品》.2007,(第1期),19-23. * |
| 浙江大学.羰羰缩合.《化学工艺学》.高等教育出版社,2001,615. * |
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