CN101209965A - Method for preparing dehydrolinalyl acetate from dehydrolinalool - Google Patents
Method for preparing dehydrolinalyl acetate from dehydrolinalool Download PDFInfo
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- CN101209965A CN101209965A CNA2006101481748A CN200610148174A CN101209965A CN 101209965 A CN101209965 A CN 101209965A CN A2006101481748 A CNA2006101481748 A CN A2006101481748A CN 200610148174 A CN200610148174 A CN 200610148174A CN 101209965 A CN101209965 A CN 101209965A
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- dehydrolinalool
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Abstract
The invention relates to a method for preparing dehydrolinalyl acetate from dehydrolinalool. The method comprises esterification between dehydrolinalool and acetic anhydride is carried out in the presence of catalyst so as to obtain dehydrolinalyl acetate. Molar ratio of raw material provided of dehydrolinalool to acetic anhydride is 1: (1-5); reaction temperature is 25-70 DEG C; reaction pressure is normal pressure; reaction time is 20-150min; the catalyst is sulfosalicylic acid, dosage of which is 0.05-5wt percentage of total amount of the raw material provided. Compared with the prior art, the invention has the advantages that reaction activity of the adopted esterification catalyst is high, which is reflected by moderate reaction temperature and short reaction time, raw material conversion and product selectivity, etc. are ideal and removal of the catalyst from the product is convenient.
Description
Technical field
The present invention relates to a kind of preparation method who contains sour fragrant camphor tree ester, particularly dehydrolinalool carries out the preparation method that esterification generates acetate dehydrogenation virtue camphor tree ester in the presence of an acidic catalyst.
Background technology
Acetate dehydrogenation virtue camphor tree ester is a kind of important fine-chemical intermediate for preparing spices, can be used for producing fine chemical products such as citral, jononeionone.Acetate dehydrogenation virtue camphor tree ester also can obtain phanteine by hydrogenation reaction, phanteine is one of lavandula angustifolia main body of oil, the fragrance elegance, approximate Oils, bergamot peel and Oleum lavandula angustifolia are the important source material of the high-grade perfume of preparation and multiple senior spices or essence.Phanteine adopts phantol and diacetyl oxide to make through esterification more in the prior art, because phantol can be made by the product separation isoprene of the C5 fraction of petroleum cracking system ethylene by-product, raw material sources are abundant and price is comparatively cheap, introduced two kinds of methods of using different catalyzer phantol and diacetyl oxide to be prepared phanteine by esterification respectively as Chinese patent ZL03129192.9 and ZL03129214.3.But, react simultaneously with multiple by product generation such as neryl acetate, meraneine because phantol is the relative higher reversible reaction of a kind of opposite direction reaction velocity constant with the esterification of diacetyl oxide.The general difficult higher reaction conversion ratio that obtains, when transformation efficiency is higher than 90%, selectivity will obviously descend, and generally can only reach about 60%.
In fact, preparing phantol by isoprene is to make dehydrolinalool earlier, obtains phantol through hydrogenation then.And dehydrolinalool and suitable acylating agent also can carry out esterification, and as obtaining acetate dehydrogenation virtue camphor tree ester with acetic anhydride, reaction formula is:
Acetate dehydrogenation virtue camphor tree ester can obtain phanteine equally through hydrogenation again.
According to experience in the past, though the esterification of dehydrolinalool and diacetyl oxide also belongs to a kind of reversible reaction, side reactions such as isomery, cyclisation also may take place in the esterification process generate by products such as ring-type pyrans and cyclic ester.But the reciprocal reaction velocity constant of this esterification is relatively low, and therefore, dehydrolinalool is carried out esterification and then obtains phanteine through hydrogenation with diacetyl oxide earlier should be a kind of even more ideal operational path.Moreover acetate dehydrogenation virtue camphor tree ester itself is again a kind of important fine-chemical intermediate, can be used as the raw materials for production of multiple fine chemical product, has stronger industrial applicibility by the fragrant camphor tree ester of dehydrolinalool esterification system acetate dehydrogenation.In one's early years really once the someone to propose with the dehydrolinalool be raw material, first esterification generates acetate dehydrogenation virtue camphor tree ester, obtains the method for phanteine then through hydrogenation, it is catalyzer that esterification process adopts phosphoric acid, as U.S. Pat 2,797,235 are introduced.But the catalyst activity that esterification process uses is very low, and the reaction times reaches tens hours, and catalyzer separating process from product is also comparatively complicated, lacks industrial applications and is worth.
Summary of the invention
The invention provides and a kind ofly prepare the method for acetate dehydrogenation virtue camphor tree ester by dehydrolinalool, it has used a kind of ideal esterifying catalyst, and is not only active higher, and transformation efficiency and selectivity are all very desirable, have solved the technical problem that prior art exists effectively.
Below be the detailed technical scheme of the present invention:
A kind ofly prepare the method for acetate dehydrogenation virtue camphor tree ester by dehydrolinalool, this method comprises that dehydrolinalool and diacetyl oxide are carried out esterification in the presence of catalyzer obtain the fragrant camphor tree ester of acetate dehydrogenation.The raw material molar ratio of dehydrolinalool and diacetyl oxide is 1: (1～5), temperature of reaction are 25～70 ℃, and reaction pressure is a normal pressure, and the reaction times is 20～150min, and catalyzer is a sulphosalicylic acid, and its consumption is feed intake 0.05～5wt% of total amount of raw material.
The raw material molar ratio of above-mentioned dehydrolinalool and diacetyl oxide is best 1: (1.2～3); Temperature of reaction is preferably 35～60 ℃; Reaction times is preferably 30～120min; Catalyst levels is preferably feed intake 0.1～1.0wt% of total amount of raw material.
The product that esterification obtains is washed, be neutral, promptly obtain acetate dehydrogenation virtue camphor tree ester product to oil phase material.
Key of the present invention is the selection of esterifying catalyst, the contriver screens multiple esterifying catalyst through a large amount of experiments, find that sulphosalicylic acid is used for this esterification and has very ideal catalytic performance, activity is higher, reaction conditions is gentle, be reflected under the normal pressure and under 25～70 ℃ the temperature and can both carry out well, usually can adopt the reaction conditions of normal temperature and pressure, be very beneficial for industrial applications.Generally react just can obtain the ideal transformation efficiency more than 20min, reaction is very complete when carrying out 90min.Another characteristics of this catalyzer are that product selectivity is very high, and the side reaction that dehydrolinalool is converted into other compound does not exist substantially.Reaction product can be finished the refining of product through being washed to neutrality, because carry out of this type of esterification in order more to help reacting usually, diacetyl oxide is excessive feeding intake, and the acetate of excessive acetic anhydride via, unreacted raw material dehydrolinalool and esterification by-product etc. generally all adopt washing, static layering sepn process to be removed, and sulphosalicylic acid can be soluble in the aqueous phase well, catalyzer can be removed simultaneously in the process of removing excessive acetic acid acid anhydride and by-product acetic acid.So the removal of catalyzer does not need extra technological process in the reaction product, the conversion of dehydrolinalool is very complete in addition, and does not have the by product generation except that acetate, so product purification is very easy.
Compared with prior art, the invention has the advantages that the esterifying catalyst reactive behavior height of employing, show that reaction conditions gentleness and reaction times are shorter, and conversion of raw material and product selectivity etc. are also very desirable, and catalyzer from product, remove also very convenient.
Below will the invention will be further described by specific embodiment, transformation efficiency and optionally being defined as in an embodiment:
Embodiment
[embodiment 1～11]
One there-necked flask that has the 500ml of whipping appts is placed water-bath, add the 152g dehydrolinalool, nitrogen purging 20min, impose to stir and be warming up to temperature of reaction, drop into diacetyl oxide by required molar ratio, and the catalyzer sulphosalicylic acid that adds aequum begins reaction, keeps the required reaction times to finish reaction.The product cooling, washing, static layering separating oil water are neutral until oil phase material, get oil phase material and get acetate dehydrogenation virtue camphor tree ester product.
The concrete reaction conditions of each embodiment sees Table 1, and reaction result sees Table 2.
Table 1.
| Temperature of reaction (℃) | Reaction times (min) | Catalyst levels (wt%) | The raw material molar ratio | |
| Embodiment 1 | 25 | 120 | 0.05 | 1∶5.0 |
| Embodiment 2 | 35 | 90 | 0.2 | 1∶1.2 |
| Embodiment 3 | 50 | 30 | 5.0 | 1∶1.2 |
| Embodiment 4 | 70 | 20 | 0.2 | 1∶1.2 |
| Embodiment 5 | 35 | 150 | 0.1 | 1∶1.2 |
| Embodiment 6 | 60 | 90 | 0.2 | 1∶1.2 |
| Embodiment 7 | 35 | 60 | 1.0 | 1∶1.0 |
| Embodiment 8 | 50 | 75 | 0.2 | 1∶1.2 |
| Embodiment 9 | 40 | 60 | 0.2 | 1∶1.2 |
| Embodiment 10 | 30 | 80 | 0.2 | 1∶2.0 |
| Embodiment 11 | 35 | 60 | 0.2 | 1∶3.0 |
Annotate: 1) catalyst levels is the feed intake weight percent of total amount of raw material;
2) the raw material molar ratio is dehydrolinalool/diacetyl oxide.
Table 2.
| Transformation efficiency (%) | Selectivity (%) | Yield (%) | |
| Embodiment 1 | 89.2 | 100 | 89.2 |
| Embodiment 2 | 99.8 | 100 | 99.8 |
| Embodiment 3 | 96.8 | 95.8 | 92.7 |
| Embodiment 4 | 91.8 | 89.4 | 82.1 |
| Embodiment 5 | 89.7 | 100 | 89.7 |
| Embodiment 6 | 100 | 100 | 100 |
| Embodiment 7 | 100 | 97.9 | 97.9 |
| Embodiment 8 | 100 | 100 | 100 |
| Embodiment 9 | 99.8 | 100 | 99.8 |
| Embodiment 10 | 95.2 | 100 | 95.2 |
| Embodiment 11 | 99.3 | 100 | 99.3 |
Claims (6)
1. method for preparing acetate dehydrogenation virtue camphor tree ester by dehydrolinalool, this method comprises that dehydrolinalool and diacetyl oxide are carried out esterification in the presence of catalyzer obtain acetate dehydrogenation virtue camphor tree ester, the raw material molar ratio of dehydrolinalool and diacetyl oxide is 1: (1～5), temperature of reaction is 25～70 ℃, reaction pressure is a normal pressure, reaction times is 20～150min, and catalyzer is a sulphosalicylic acid, and its consumption is feed intake 0.05～5wt% of total amount of raw material.
2. the method for preparing acetate dehydrogenation virtue camphor tree ester according to claim 1, the raw material molar ratio that it is characterized in that described dehydrolinalool and diacetyl oxide is 1: (1.2～3).
3. the method for preparing acetate dehydrogenation virtue camphor tree ester according to claim 1 is characterized in that described temperature of reaction is 35～60 ℃.
4. the method for preparing acetate dehydrogenation virtue camphor tree ester according to claim 1 is characterized in that the described reaction times is 30～120min.
5. the method for preparing acetate dehydrogenation virtue camphor tree ester according to claim 1 is characterized in that described catalyst levels is feed intake 0.1～1.0wt% of total amount of raw material.
6. the method for preparing acetate dehydrogenation virtue camphor tree ester according to claim 1 is characterized in that the product that esterification obtains washes, and is neutral to oil phase material, obtains acetate dehydrogenation virtue camphor tree ester product.
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| CNA2006101481748A CN101209965A (en) | 2006-12-28 | 2006-12-28 | Method for preparing dehydrolinalyl acetate from dehydrolinalool |
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| CNA2006101481748A CN101209965A (en) | 2006-12-28 | 2006-12-28 | Method for preparing dehydrolinalyl acetate from dehydrolinalool |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014180915A1 (en) * | 2013-05-08 | 2014-11-13 | Dsm Ip Assets B. V. | Process of production of dehydrolinalyl acetate (i) |
| CN104292087A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Method for preparing citral through rearrangement reaction of dehydrolinalool |
| CN105209422A (en) * | 2013-05-08 | 2015-12-30 | 帝斯曼知识产权资产管理有限公司 | Process of production of dehydrolinalyl acetate (II) |
| CN115073287A (en) * | 2021-03-11 | 2022-09-20 | 万华化学(四川)有限公司 | High-quality linalyl acetate and preparation method thereof |
-
2006
- 2006-12-28 CN CNA2006101481748A patent/CN101209965A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014180915A1 (en) * | 2013-05-08 | 2014-11-13 | Dsm Ip Assets B. V. | Process of production of dehydrolinalyl acetate (i) |
| CN105189442A (en) * | 2013-05-08 | 2015-12-23 | 帝斯曼知识产权资产管理有限公司 | Process of production of dehydrolinalyl acetate (I) |
| CN105209422A (en) * | 2013-05-08 | 2015-12-30 | 帝斯曼知识产权资产管理有限公司 | Process of production of dehydrolinalyl acetate (II) |
| JP2016520584A (en) * | 2013-05-08 | 2016-07-14 | ディーエスエム アイピー アセッツ ビー．ブイ． | Method for producing dehydrolinalyl acetate (I) |
| US9505699B2 (en) | 2013-05-08 | 2016-11-29 | Dsm Ip Assets B.V. | Process of production of dehydrolinalyl acetate (I) |
| EA027812B1 (en) * | 2013-05-08 | 2017-09-29 | ДСМ АйПи АССЕТС Б.В. | Process of production of dehydrolinalyl acetate (i) |
| CN104292087A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Method for preparing citral through rearrangement reaction of dehydrolinalool |
| CN115073287A (en) * | 2021-03-11 | 2022-09-20 | 万华化学(四川)有限公司 | High-quality linalyl acetate and preparation method thereof |
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