CN101209969A - Method for preparing linalyl acetate from dehydrolinalool - Google Patents
Method for preparing linalyl acetate from dehydrolinalool Download PDFInfo
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- CN101209969A CN101209969A CNA2006101481771A CN200610148177A CN101209969A CN 101209969 A CN101209969 A CN 101209969A CN A2006101481771 A CNA2006101481771 A CN A2006101481771A CN 200610148177 A CN200610148177 A CN 200610148177A CN 101209969 A CN101209969 A CN 101209969A
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Abstract
The invention relates to a method for preparing linalyl acetate from dehydrolinalool. The method comprises esterification between dehydrolinalool and acetic anhydride is carried out in the presence of catalyst. The catalyst is macroporous sulfonic acidic cation exchange resin, dosage of which is 2-20wt percent of total amount of the raw material provided. Product of the esterification, after being removed of the catalyst, is washed till oil phase material is neutral, and the dehydrolinalyl acetate is obtained. The dehydrolinalyl acetate undertakes hydrogenation reaction with hydrogen in the presence of catalyst ; the catalyst adopts calcium carbonate as a carrier; active components loaded contain Pd, Pb and A ingredient, A is either Bi or Zn or mixture of Bi and Zn, total content of Pd and Pb is 0.1-4.0wt percent, mass ratio of Pd and Pb is (5-1):1, content of A is 0.5-3.0wt percent and dosage of the catalyst accounting for 0.01-5.0wt percent of reaction liquid. The catalyst is removed from the product of the hydrogenation reaction through solid and liquid separation, and linalyl acetate is obtained by rectifying and refining. The invention has the advantages that the catalyst of esterification and hydrogenation reaction has relatively high activity, and conversion and selectivity are higher.
Description
Technical field
The present invention relates to a kind of preparation method who contains sour fragrant camphor tree ester, particularly dehydrolinalool carries out esterification and generates acetate dehydrogenation virtue camphor tree ester in the presence of an acidic catalyst, again through the method for hydrogenation preparing phanteine.
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, and reaction formula is:
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.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, as U.S. Pat 2,797,235 are introduced.The catalyst activity that its esterification process of the method that this patent is introduced uses is very low, and the reaction times reaches tens hours, and catalyzer separating process from product is also comparatively complicated, therefore lacks industrial applications and is worth.
In the prior art, Lindlar catalyzer (promptly be carrier with lime carbonate, active constituent is Pd, or also further contains the loaded catalyst that helps catalyst component Pb) is can promote the acetylene bond selection hydrogenation in hydro carbons and other compound efficiently and to be widely used.But its shortcoming is that the selectivity of reaction is relatively low, in order to remedy this defective, introduces compounds such as pyridine, quinoline usually in reaction system or support of the catalyst.Though these organism can improve reaction preference effectively, make the reaction mixture variable color easily and bring peculiar smell, and compound such as pyridine, quinoline is difficult to be separated from hydrocarbon compound.Because the purposes of phanteine is mainly the manufacturing raw material of spice product, general Lindlar catalyzer is used for acetate dehydrogenation virtue camphor tree ester through hydrogenation prepares phanteine, then the form and aspect of product and flavouring essence quality obviously can be seriously influenced.Above-mentioned U.S. Pat 2,797,235 its hydrogenation processes of the method for being introduced have promptly adopted a kind of hydrogenation catalyst of similar Lindlar catalyzer, it not only will add quinoline as catalytic promoter, and hydrogenation reaction to add a large amount of cyclohexane gives be solvent, so this method is except that the esterification required time is very long, making with extra care of hydrogenation products is also very difficult, is difficult to reach the requirement of making high-grade spices.
Summary of the invention
The invention provides a kind of method for preparing phanteine by dehydrolinalool, the catalyzer that its esterification process and hydrogenation process adopt all has higher activity, ideal transformation efficiency and selectivity, and hydrogenation process need not to use compounds such as pyridine, quinoline as catalytic promoter, do not use any solvent yet, can solve 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 phanteine by dehydrolinalool, this method may further comprise the steps:
1) dehydrolinalool and diacetyl oxide are carried out esterification in the presence of catalyzer, the raw material molar ratio of dehydrolinalool and diacetyl oxide is 1: (1～5), temperature of reaction are 40～80 ℃, and reaction pressure is a normal pressure, and the reaction times is 60～240min.Catalyzer is a macropore sulfonic acid Zeo-karb, and its exchange capacity is 4.8～5.0mmol/g, and degree of crosslinking is 16～18%, and the aperture is 15～20nm, and catalyst levels is feed intake 2～20wt% of total amount of raw material;
2) esterification reaction product is washed after solid-liquid separation removes catalyzer, is neutral to oil phase material, gets acetate dehydrogenation virtue camphor tree ester;
3) acetate dehydrogenation virtue camphor tree ester carries out hydrogenation reaction with hydrogen in the presence of catalyzer, and temperature of reaction is 20～150 ℃, and hydrogen pressure is 1.0～10.0Mpa, and the reaction times is 30～240min.Catalyzer is a loaded catalyst, and it is carrier with lime carbonate, contains Pd, Pb and component A in the active constituent of load, and A is a kind of among Bi or the Zn or both mixtures.The total content of Pd and Pb is 0.1～4.0wt% in the catalyzer, and the mass ratio of Pd and Pb is (5～1): 1, and the content of component A is 0.5～3.0wt% in the catalyzer.Catalyst consumption is 0.01～5.0wt% that catalyzer accounts for reaction solution;
4) hydrogenation products removes catalyzer through solid-liquid separation, by the rectified purified phanteine product that gets.
The raw material molar ratio of above-mentioned steps 1 described dehydrolinalool and diacetyl oxide is preferably 1: (1.2～3); Described temperature of reaction is preferably 50～70 ℃; The described reaction times is preferably 90～150min; Described catalyst levels is preferably feed intake 5～10wt% of total amount of raw material.
Above-mentioned steps 3 described hydrogenation reaction temperature are preferably 30～80 ℃; Hydrogen pressure is preferably 1.5～3.5Mpa; The hydrogenation reaction time is preferably 60～120min.
The total content of active constituent Pd and Pb is preferably 0.5～1.5wt% in the above-mentioned steps 3 described catalyzer; The mass ratio of Pd and Pb is preferably (3～1): 1; The content of A is preferably 0.5～1.5wt%.
Above-mentioned steps 3 described catalyst consumption are preferably 0.1～1.0wt% that catalyzer accounts for reaction solution.
As the preparation of loaded catalyst, above-mentioned hydrogenation catalyst also can adopt the known pickling process in present technique field to prepare, and following preparation process is what the present invention recommended:
The starting material of each active ingredient is selected certain density metal salt solution for use, can adopt palladium nitrate solution as Pd, and Pb can adopt lead nitrate solution, and the Bi among the component A can adopt bismuth nitrate solution, and Zn can adopt zinc nitrate solution.Earlier each starting material is mixed with steeping fluid by required proportioning, then calcium carbonate carrier is placed the steeping fluid dipping to obtain catalyst precursor, the dipping liquid measure is 95～110% of a carrier hygroscopicity value; In addition roasting after the catalyst precursor oven dry; Catalyst precursor after the roasting reduces processing, and reductive agent generally can adopt formaldehyde, hydrazine hydrate or hydrogen etc., and then promptly gets the catalyzer finished product after washing, oven dry.
One of key of the present invention is the esterification process selection of catalysts, the contriver screens multiple esterifying catalyst through a large amount of experiments, find that above-mentioned macropore sulfonic acid Zeo-karb is used for this esterification and has very ideal catalytic performance, activity is higher, reaction conditions is gentle, is very beneficial for industrial applications.The selectivity that its another advantage is an esterification products is very high, 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, and catalyzer can come out from product separation by precipitation after esterification finishes easily, and can be repeatedly used.There is not corrodibility substantially in catalyzer, and environment is not produced any influence yet.
Two of key of the present invention is that hydrogenation catalyst is improved, its essence is and adopt suitable base metal (being component A) that general Lindlar catalyzer is carried out modification, the contriver finds by a large amount of experiments, this improvement makes catalyzer outside characteristic such as guarantee active height, hydrogenation technique mild condition that general Lindlar catalyzer had, can be repeatedly used, also improved the performance of catalyzer from many aspects, it shows as: need not to use compounds such as pyridine, quinoline as catalytic promoter; Hydrogenation process is not used solvent, has reduced reaction volume, thereby has reduced energy consumption and material consumption; Catalyzer can avoid Pd to be poisoned by oxy radical impurity in hydrogenation process; Have higher selectivity of product under the prerequisite of high conversion, when transformation efficiency was 99%, selectivity of product also can reach about 99%.Except that a small amount of unreacted raw material, do not have other impurity substantially in the hydrogenation products, can obtain highly purified purified product through simple rectifying.
It is that the consumption of precious metals pd significantly reduces in the hydrogenation catalyst that this improvement brings another benefit, the Pd content of general Lindlar catalyzer is generally about 5wt%, and the hydrogenation catalyst that the present invention adopts just has extraordinary activity when Pd content is 1wt%.
The solid-liquid separating method of available routine was more easily separated catalyzer after hydrogenation reaction finished from hydrogenation products, catalyzer is reusable, reuse generally speaking and still show goodish activity more than 10 times, and decaying catalyst can be regenerated with the method that present technique field those skilled in the art know.
In sum, the invention has the advantages that compared with prior art the catalyzer that esterification process and hydrogenation process adopt all has higher activity, ideal transformation efficiency and selectivity, and hydrogenation process need not to use compounds such as pyridine, quinoline as catalytic promoter, does not also use any solvent.No matter be esterification products and hydrogenation products, the removal of catalyzer is all very convenient, and making with extra care of product is also all very easy, and the product that finally obtains has higher quality.
Below will the invention will be further described by specific embodiment, transformation efficiency and optionally being defined as in an embodiment:
One, esterification process:
Two, hydrogenation process:
Embodiment
One, esterification process:
[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 that adds aequum begins reaction, keeps the required reaction times to finish reaction.After the product cooling that esterification is obtained, the precipitate and separate catalyzer.Liquid phase washing, static layering separating oil water are neutral until oil phase material, get oil phase material and get esterification products acetate dehydrogenation virtue camphor tree ester.
Above-mentioned catalyzer is a macropore sulfonic acid Zeo-karb, and its exchange capacity is 4.8～5.0mmol/g, and degree of crosslinking is 16～18%, and the aperture is 15～20nm.
Embodiment 1～11 concrete esterification condition sees Table 1, and esterification the results are shown in Table 2.
Table 1.
| Temperature of reaction (℃) | Reaction times (min) | Catalyst levels (wt%) | The raw material molar ratio | |
| Embodiment 1 | 40 | 240 | 2.0 | 1∶5.0 |
| Embodiment 2 | 55 | 200 | 5.0 | 1∶1.2 |
| Embodiment 3 | 70 | 60 | 5.0 | 1∶1.2 |
| Embodiment 4 | 80 | 120 | 5.0 | 1∶1.2 |
| Embodiment 5 | 55 | 150 | 10.0 | 1∶1.2 |
| Embodiment 6 | 50 | 120 | 5.0 | 1∶1.2 |
| Embodiment 7 | 55 | 90 | 20.0 | 1∶1.0 |
| Embodiment 8 | 70 | 150 | 10.0 | 1∶1.2 |
| Embodiment 9 | 60 | 120 | 8.0 | 1∶1.2 |
| Embodiment 10 | 70 | 90 | 8.0 | 1∶2.0 |
| Embodiment 11 | 45 | 160 | 8.0 | 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 | 76.3 | 98.1 | 74.8 |
| Embodiment 2 | 96.3 | 92.9 | 89.5 |
| Embodiment 3 | 86.2 | 97.2 | 83.8 |
| Embodiment 4 | 89.9 | 92.2 | 82.9 |
| Embodiment 5 | 90.4 | 91.3 | 82.5 |
| Embodiment 6 | 89.2 | 96.4 | 86.0 |
| Embodiment 7 | 90.2 | 85.7 | 77.3 |
| Embodiment 8 | 99.8 | 91.5 | 91.3 |
| Embodiment 9 | 99.8 | 96.1 | 95.9 |
| Embodiment 10 | 99.8 | 93.8 | 93.6 |
| Embodiment 11 | 96.8 | 94.6 | 91.6 |
Two, hydrogenation process:
[embodiment 12～23]
The preparation of hydrogenation catalyst:
The starting material of each active ingredient is: Pd adopts palladium nitrate solution; Pb adopts lead nitrate solution; Bi among the component A adopts bismuth nitrate solution, and Zn adopts zinc nitrate solution.
Above-mentioned each starting material is made steeping fluid in required ratio; Place the steeping fluid dipping to obtain catalyst precursor a certain amount of calcium carbonate carrier, the dipping liquid measure is 95～110% of a carrier hygroscopicity value, floods respectively 1 hour at normal temperatures with under 70 ℃ of temperature; Catalyst precursor oven dry back was 280 ℃ of roasting temperatures 5 hours; Catalyst precursor after the roasting reduces processing with hydrazine hydrate; Near neutral through washed several times with water pH value to the washing lotion again, under 75 ℃ of temperature, dry at last, it is standby to obtain the catalyzer finished product.
Embodiment 12～23 employed hydrogenation catalysts, its active ingredient and content see Table 3.
The esterification products acetate dehydrogenation virtue camphor tree ester that embodiment 9 is obtained carries out hydrogenation reaction by following reaction conditions:
Pour 194g dehydroacetic acid (DHA) virtue camphor tree ester in being connected with the 500ml autoclave of water coolant, adding the hydrogenation catalyst of above preparation, catalyzer accounts for the 0.2wt% of reaction solution.After the hydrogen exchange three times, feed hydrogen under temperature of reaction, control reaction temperature is 50 ℃, and hydrogen pressure is 2.5Mpa, begins reaction.Reaction 60min and 120min measure the hydrogenation reaction result respectively, and data see Table 4.
Hydrogenation products removes catalyzer through solid-liquid separation, by the rectified purified phanteine product that gets.
Table 3.
| (Pd+Pb) content (wt%) | Pd/Pb (mass ratio) | Component A | A content (wt%) | |
| Embodiment 12 | 2.0 | 3/1 | Bi | 1.0 |
| Embodiment 13 | 4.0 | 3/1 | Bi | 0.5 |
| Embodiment 14 | 0.5 | 2/1 | Bi | 1.5 |
| Embodiment 15 | 2.0 | 3/1 | Zn | 1.0 |
| Embodiment 16 | 0.1 | 3/1 | Zn | 3.0 |
| Embodiment 17 | 2.0 | 2/1 | Zn | 1.0 |
| Embodiment 18 | 1.5 | 3/1 | Bi+Zn | 0.5 |
| Embodiment 19 | 1.5 | 2/1 | Bi+Zn | 2.0 |
| Embodiment 20 | 0.5 | 2.5/1 | Bi+Zn | 2.0 |
| Embodiment 21 | 4.0 | 1/1 | Bi+Zn | 1.0 |
| Embodiment 22 | 1.5 | 3/1 | Bi+Zn | 1.0 |
| Embodiment 23 | 2.0 | 5/1 | Bi+Zn | 1.0 |
Table 4.
[embodiment 24～31]
Use the hydrogenation catalyst of embodiment 19, change hydrogenation conditions, the reaction conditions of change sees Table 5, and all the other the results are shown in Table 6 with embodiment 12～23.
Table 5.
| Temperature of reaction (℃) | Hydrogen pressure (Mpa) | Reaction times (min) | Catalyzer accounts for reaction solution (wt%) | |
| Embodiment 24 | 30 | 1.5 | 100 | 1.0 |
| Embodiment 25 | 20 | 3.0 | 240 | 0.2 |
| Embodiment 26 | 50 | 2.5 | 110 | 0.2 |
| Embodiment 27 | 80 | 2.5 | 60 | 5.0 |
| Embodiment 28 | 50 | 3.5 | 120 | 0.01 |
| Embodiment 29 | 90 | 5.5 | 90 | 2.0 |
| Embodiment 30 | 65 | 2.0 | 180 | 0.5 |
| Embodiment 31 | 150 | 10 | 80 | 0.1 |
Table 6.
| Transformation efficiency (%) | Selectivity (%) | Yield (%) | |
| Embodiment 24 | 86.8 | 99.6 | 86.5 |
| Embodiment 25 | 97.0 | 99.2 | 96.2 |
| Embodiment 26 | 99.0 | 99.1 | 98.1 |
| Embodiment 27 | 99.5 | 95.8 | 95.3 |
| Embodiment 28 | 88.0 | 99.0 | 87.1 |
| Embodiment 29 | 99.4 | 96.2 | 95.6 |
| Embodiment 30 | 99.3 | 97.7 | 97.0 |
| Embodiment 31 | 99.2 | 72.3 | 71.7 |
Claims (8)
1. one kind prepares the method for phanteine by dehydrolinalool, and this method may further comprise the steps:
1) dehydrolinalool and diacetyl oxide are carried out esterification in the presence of catalyzer, the raw material molar ratio of dehydrolinalool and diacetyl oxide is 1: (1～5), temperature of reaction is 40～80 ℃, reaction pressure is a normal pressure, and the reaction times is 60～240min, and catalyzer is a macropore sulfonic acid Zeo-karb, its exchange capacity is 4.8～5.0mmol/g, degree of crosslinking is 16～18%, and the aperture is 15～20nm, and catalyst levels is feed intake 2～20wt% of total amount of raw material;
2) esterification reaction product is washed after solid-liquid separation removes catalyzer, is neutral to oil phase material, gets acetate dehydrogenation virtue camphor tree ester;
3) acetate dehydrogenation virtue camphor tree ester carries out hydrogenation reaction with hydrogen in the presence of catalyzer, temperature of reaction is 20～150 ℃, hydrogen pressure is 1.0～10.0Mpa, reaction times is 30～240min, catalyzer is a loaded catalyst, it is carrier with lime carbonate, contain Pd in the active constituent of load, Pb and component A, A is a kind of among Bi or the Zn or both mixtures, the total content of Pd and Pb is 0.1～4.0wt% in the catalyzer, the mass ratio of Pd and Pb is (5～1): 1, and the content of component A is 0.5～3.0wt% in the catalyzer, catalyst consumption is 0.01～5.0wt% that catalyzer accounts for reaction solution;
4) hydrogenation products removes catalyzer through solid-liquid separation, by the rectified purified phanteine product that gets.
2. the method for preparing phanteine according to claim 1, the raw material molar ratio that it is characterized in that described dehydrolinalool of step 1 and diacetyl oxide is 1: (1.2～3); Described temperature of reaction is 50～70 ℃; The described reaction times is 90～150min.
3. the method for preparing acetate dehydrogenation virtue camphor tree ester according to claim 1 and 2 is characterized in that the described catalyst levels of step 1 is feed intake 5～10wt% of total amount of raw material.
4. the method for preparing acetate dehydrogenation virtue camphor tree ester according to claim 1 is characterized in that the described temperature of reaction of step 3 is 30～80 ℃; Hydrogen pressure is 1.5～3.5Mpa; Reaction times is 60～120min.
5. according to claim 1 or the 4 described methods that prepare acetate dehydrogenation virtue camphor tree ester, it is characterized in that the total content of active constituent Pd and Pb is 0.5～1.5wt% in the described catalyzer of step 3.
6. according to claim 1 or the 4 described methods that prepare acetate dehydrogenation virtue camphor tree ester, it is characterized in that the mass ratio of active constituent Pd and Pb is (3～1) in the described catalyzer of step 3: 1.
7. according to claim 1 or the 4 described methods that prepare acetate dehydrogenation virtue camphor tree ester, the content that it is characterized in that active constituent A in the described catalyzer of step 3 is 0.5～1.5wt%.
8. according to claim 1 or the 4 described methods that prepare acetate dehydrogenation virtue camphor tree ester, it is characterized in that the described catalyst consumption of step 3 is 0.1～1.0wt% that catalyzer accounts for reaction solution.
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