CN103012097A - Method for preparing fenchone - Google Patents
Method for preparing fenchone Download PDFInfo
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- CN103012097A CN103012097A CN2012104413803A CN201210441380A CN103012097A CN 103012097 A CN103012097 A CN 103012097A CN 2012104413803 A CN2012104413803 A CN 2012104413803A CN 201210441380 A CN201210441380 A CN 201210441380A CN 103012097 A CN103012097 A CN 103012097A
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- fenchone
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Abstract
The invention provides a method for preparing fenchone through catalytic dehydrogenation of fenchol. According to the method, fenchol with purity being more than 95% is used as raw material, dimethylbenzene is used as a solvent, and a self-prepared catalyst is used as a dehydrogenation catalyst to perform catalytic dehydrogenation on the fenchol to obtain finished product, wherein the formula contains the following components: 75% of fenchol, 3% of self-prepared dehydrogenation catalyst, 16% of dimethylbenzene, 4% of acetic anhydride and 3% of sulfuric acid; and the fenchone is prepared through the steps of material dehydration, catalytic dehydrogenation, continuous esterification, fractional distillation and refining, and the like. According to the method, fenchone conversion rate is high, the solvent is recyclable, the environment is protected, and the cost is saved; the prepared fenchone has cool fragrance, camphor fragrance, mint fragrance, and the like, has a local stimulation effect similar to the effect of camphor, has antimicrobial, sterilizing and insecticidal activities, can be used for synthesizing chiral drugs and used as an intermediate for pesticide formulation, and a good solvent or a balance solvent for industrial paint, vinylite, acrylate-based resin.
Description
Technical field
The present invention is applicable to the compound preparation field, relates in particular to a kind of preparation method of fenchone.
Background technology
Fenchone (fenchone) chemical name is (1R, 4S)-1,3, and 3-trimethylammonium-two ring [2,2,1] heptane-2-ketone claims again fenchone, fenchone, 1,3,3-trimethylammonium-2-norborneol ketone.English name is 1,3,3-trimethylbicyclo[2.2.1] heptan-2-one, Fenchone; Cas No.:1195-79-5, EINECSNo.:214-804-6, molecular formula: C
10H
16O; Molecular weight: 152.23; Fusing point: 5～6 ℃ of@101.325kPa; Boiling point: 193～194 ℃ of@101.325kPa; Flash-point (TCC): 60 ℃; Refractive index: 20 ℃ of 1.460～1.463@; Density: 25 ℃ of 0.938～0.948@.Fenchone is colourless to the pale yellow oily liquid body, is dissolved in ethanol and nonvolatile oil, is insoluble in propylene glycol, and the utmost point is insoluble in water (solubleness is 25 ℃ of 744mg/L@in the water).
Natural product are present in sweet fennel, the arbor-vitae etc.
Fenchone has icy, camphor, peppermint fragrance, has antibiotic, sterilization and insecticidal activity, is widely used in the food flavour, daily essence, sterilant, sanitising agent, washing agent of allotment mint aroma, icy type, spicy etc.Typical amounts is soap 0.02%, sanitising agent, washing agent 0.002%, and washing lotion 0.005%, perfume 0.05%, candy, bakery 0.25ppm, soft drink 0.13～80ppm contains pure soft drink 5.0ppm.Also be the raw material of synthesis of chiral medicine, agricultural chemicals simultaneously.Fenchone is fine solvent and the balance solvent of vinyl, acrylic varnish and vinyl, acrylic based resin and industrial finish, the characteristics such as have smell fragrance, safety non-toxic, evaporation rate is moderate, solubility property is good are widely used in the industrial circles such as silk screen printing, circuit card printing, printing ink.
Fenchone usually by Spain's anise-oil (Fennel oil) single from and get, it is restricted that Spain's anise-oil is originated, cost of material is high, production process comprises stage trapping, the repetition fractionation is extracted, and step is many, complex process, and energy consumption is high, product purity is low, and production cost is high, and the market competitiveness is not strong.Fenchone also can adopt the preparation of fenchol oxidizing process, and general common oxygenant has chlorine bleach liquor, potassium permanganate, potassium bichromate etc.Existing research is used and shown: clorox has higher transformation efficiency, preserve but clorox is easy to rotten being difficult for, and chlorine bleach liquor's consumption is large in actually operating, causes plant factor very low; The potassium permanganate reaction conversion ratio is not high; Potassium bichromate is made catalyzer also can obtain preferably transformation efficiency, but reaction solution is deeply blackish green, and oil reservoir and water layer are differentiated very difficult, be unfavorable for production operation, and wastewater flow rate are large, easily cause environmental pollution.Preparation content 99% fenchone is delivered there are no mature technology at present.
Summary of the invention
For above fenchone preparation technology's deficiency, the invention provides a kind of method of more desirable synthetic fenchone.Product of the present invention is made solvent take fenchol as raw material with p-Xylol, prepares fenchone by steps such as catalytic dehydrogenation, continuous esterification, fractionation are refining.It is characterized in that: before (1) catalytic dehydrogenating reaction, supplementary material fenchol, p-Xylol need dehydrate; (2) the further esterification of dehydrogenation reaction thing makes not that the dehydrogenation fenchol is converted into acetic acid turnip ester, and the fractionation of being convenient to the product fenchone is refining; (3) the self-control dehydrogenation catalyst has that transformation efficiency is high, selectivity good, the characteristics such as reaction process gentleness; (4) solvent p-Xylol reusable edible.
This method has that transformation efficiency is high, finished product purity is high, technique is simple and easy, draws materials cheap, the characteristics such as solvent is recyclable.
The present invention adopts following technical scheme to realize its purpose:
1. making flow process of the present invention as shown in Figure 1.
2. proportioning raw materials of the present invention:
The preparation method of described fenchone, the best proportioning of its catalytic dehydrogenating reaction is: fenchol 1: self-control dehydrogenation catalyst 0.05: p-Xylol 0.2.
The preparation method of described fenchone, the optimal proportion of its esterification is: dehydrogenation reaction liquid (not containing p-Xylol) 1: aceticanhydride 0.06: esterifying catalyst 0.03.
3. the present invention makes efficient dehydrogenation catalyst by oneself and is: copper-bath and sodium carbonate solution (mol ratio 1: 1.2) are at the resultants of 60～80 ℃ of lower reactions.
4. esterifying catalyst of the present invention is the sulfuric acid of content 98%.
5. the physico-chemical property of the main raw and auxiliary material of product of the present invention:
(1) fenchol
English name: Fenchyl alcohol;
Chemical name: 1,3,3-trimethylammonium dicyclo-[2,2,1]-enanthol-2;
Molecular formula: C
10H
18O;
Molecular weight: 154.25;
Fusing point: 35-41 ℃ is that white is to light yellow crystal at normal temperatures;
Purposes: be mainly used in preparing fresh, the food flavour (chewing gum, toothpaste etc.) of mint flavor and the daily chemical essence of various uses.
(2) dehydrogenation catalyst: the resultant of reaction of copper-bath and sodium carbonate solution.
Outward appearance: grass green is to bottle-green meal;
Density: 3.85g/cm
3
Characteristic: unstable, easily decompose during heating; Energy and hydrochloric acid reaction;
Solvability: be insoluble to water and alcohol below 35 ℃, be dissolved in acid, ammoniacal liquor and ammonium salt.
(3) p-Xylol
P-Xylol claims again Isosorbide-5-Nitrae-dimethylbenzene, and English name is p-Xylene, Isosorbide-5-Nitrae-Xylene, Isosorbide-5-Nitrae-DIMETHYLBENZENE, chemical formula: C
8H
10Molecular weight: 106.17.
Proterties: colourless transparent liquid, at low temperatures crystallization.The special odor that aromatic hydrocarbon is arranged.Can be miscible, water insoluble with ethanol, ether, benzene, acetone.
Fusing point: 12～13 ℃;
Boiling point: 138 ℃;
Density: 0.861g/mL (20 ℃);
Vapour density: 3.7 (to air);
Vapour pressure: 9mmHg (20 ℃);
Specific refractory power: 1.495 (20 ℃);
Flash-point: 25 ℃;
Purposes: solvent.For the production of terephthalic acid, and then produce the vibrin such as ethylene glycol terephthalate, butanediol ester.
(4) diacetyl oxide
Diacetyl oxide claims again acetic anhydride, aceticanhydride, and Glacial acetic acid, acetic anhydride, English name are Acetic anhydride, Acetyl oxide, Acetyl acetate.Be colourless transparent liquid.Strong acetic acid smell is arranged.Flavor acid.Water absorbability is arranged.Be corrosive.Be dissolved in chloroform and ether, lentamente water-soluble formation acetic acid.Form ethyl acetate with the ethanol effect.
Molecular formula: C
4H
6O
3
Molecular weight: 102.09;
Fusing point :-73.1 ℃;
Boiling point: 140 ℃;
Density: 1.087 (20 ℃);
Vapour density: 3.5 (to air);
Vapour pressure: 10mmHg (36 ℃);
Specific refractory power: 1.390 (20 ℃);
Flash-point: 54 ℃;
Spontaneous ignition temperature: 400 ℃, inflammable;
Purposes: be important acetylation reagent, in perfume industry for the production of tonka bean camphor; Bornyl acetate; Musk ambrette; Cedryl acetate; The acetic acid rosin ester; Phenylethyl ethanoate; Meraneine etc.; By the acetyl peroxide that acetic anhydride is made, be initiator and the SYNTHETIC OPTICAL WHITNER of polyreaction.
Esterifying catalyst: it is esterifying catalyst that the present invention takes 98% sulfuric acid.
Chinese: sulfuric acid;
English name: Sulphuric acid;
Chemical formula: H
2SO
4
Molecular weight: 98.08;
Fusing point: 10 ℃;
Boiling point :～290 ℃;
Density: 1.840g/mL (25 ℃);
Vapour density:＜0.3 (25 ℃, to air);
Vapour pressure: 1mmHg (146 ℃);
Flash-point: 11 ℃;
Character: be a kind of colorless and odorless oily liquids, be the strong acid of the difficult volatilization of a kind of high boiling point, soluble in water, can be miscible with water with any ratio;
Purposes: sulfuric acid is one of staple product in the basic chemical industry.It is not only as the raw material of many Chemicals, but also is widely used in other sector of the national economy.Sulfuric acid is chemistry six large inorganic acid [sulfuric acid, nitric acid (HNO
3), hydrochloric acid (HCl), Hydrogen bromide (HBr), hydroiodic acid HI (HI), perchloric acid (HClO
4One of)], also be one of modal strong acid in all acid, the present invention is mainly used in the esterification agent.
Preparation process of the present invention is:
(1) material dewatering: by proportioning with fenchol and p-Xylol in there-necked flask, load onto thermometer, agitator, water trap and spherical return line, heating removes a small amount of moisture in the material.
(2) catalytic dehydrogenation: after the feed back dehydration, add the proportioning dehydrogenation catalyst and carry out dehydrogenation reaction.
(3) solvent p-Xylol, recycle are reclaimed in distillation (I).
(4) esterification: add required aceticanhydride and the esterifying catalyst of esterification by proportioning, esterification refluxes.
(5) distillation (II) recovery of acetic acid and unreacted aceticanhydride after the esterification.
(6) after distillation (II) is finished, the separating dehydrogenated catalyzer of suction filtration, with saturated aqueous common salt that the filtrate washing is extremely neutral.
(7) fractionation is refining: will wash to neutral reaction product vacuum fractionation, and collect the fenchone of content＞99.0%.
Description of drawings
Fig. 1 represents the realization flow figure of the preparation fenchone that the embodiment of the invention provides.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Fig. 1 shows the realization flow of the preparation fenchone that the embodiment of the invention provides, and details are as follows:
(1) material dewatering: fenchol and the p-Xylol proportioning with 1: 0.2 is added in the there-necked flask that thermometer, agitator, water trap and spherical return line are housed, and reflux is 30min approximately, sloughs a small amount of moisture in the material.
(2) catalytic dehydrogenation: after the feed back dehydration, the proportioning by 0.05 adds the dehydrogenation catalyst dehydrogenation reaction (170～190 ℃) that refluxes, and the reaction times is 6～9h, is preferably 8h.
(3) the dehydrogenation reaction formula is:
(4) after the dehydrogenation reaction, solvent p-Xylol, recycle are reclaimed in distillation (I).
(5) esterification: by weight being dehydrogenation reaction liquid (not containing p-Xylol) 1: aceticanhydride 0.06: esterifying catalyst 0.03 adds aceticanhydride and esterifying catalyst, stirs lower backflow esterification, and the reaction times is 3～5h, is preferably 4.5h.
(6) the esterification equation is:
(7) after esterification is finished, distillation (II) recovery of acetic acid and unreacted aceticanhydride.
(8) behind distillation (II) recovery of acetic acid and the unreacted aceticanhydride, filtering to isolate dehydrogenation catalyst, be filtrate by volume: the ratio of saturated aqueous common salt=1: 1 adds saturated aqueous common salt, with filtrate washing 3 times, until filtrate is neutrality, gets the fenchone crude product.
(9) fractionation is refining: will get the fenchone crude product and add in the fractionation still, be under 90～91kPa in vacuum tightness, carries out vacuum fractionation, collects 112 ℃～118 ℃ section cuts, gets the fenchone finished product of content＞99.0%.
Subordinate list 1:98% fenchol catalytic dehydrogenation experimental record
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. the preparation method of a fenchone is characterized in that, this product is formed by following each proportioning raw materials:
Fenchol (concentration 95% and 98%) 75%, self-control dehydrogenation catalyst 3%, dimethylbenzene 16%, aceticanhydride 4% and sulfuric acid 3%.
2. the preparation method of a fenchone is characterized in that: take fenchol as raw material, take p-Xylol as solvent, through behind the material dewatering, catalytic dehydrogenation under the self-control catalyst action, then prepare fenchone through operations such as continuous esterification, fractionation are refining.
3. method as claimed in claim 2, it is characterized in that, the process of described material dewatering is: take by weighing a certain amount of fenchol and dimethylbenzene in there-necked flask, load onto thermometer, agitator, water trap and spherical return line, stir lower oil bath and be heated to feed back, remove a small amount of moisture in the material.
4. method as claimed in claim 2, it is characterized in that, the process of described catalytic dehydrogenation is: after the feed back dehydration, stop oil bath heating, treat that still temperature (oil temperature) is down to below 170 ℃, stop stirring, add again a certain amount of from controlling catalyst, open stirring, reacting by heating liquid carries out dehydrogenation reaction to reflux temperature, and the reaction times is 5-7 hour.
5. method as claimed in claim 2 is characterized in that, described method also comprises:
Make water trap and return line into water distilling apparatus, the distilling off solvent p-Xylol.
6. method as claimed in claim 2, it is characterized in that, the process of described continuous esterification is: add required aceticanhydride and the esterifying catalyst sulfuric acid of esterification, make water distilling apparatus into reflux again, open stirring, oil bath is heated to feed back, carries out esterification, and reaction time of esterification is 3-5 hour.
7. method as claimed in claim 2 is characterized in that, the refining process of described fractionation is: will wash to neutral reaction product adding fractionation still, in vacuum tightness greater than carrying out fractionation under the 680mmHg.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012104413803A CN103012097A (en) | 2012-11-08 | 2012-11-08 | Method for preparing fenchone |
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|---|---|---|---|
| CN2012104413803A CN103012097A (en) | 2012-11-08 | 2012-11-08 | Method for preparing fenchone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892378A (en) * | 2015-05-12 | 2015-09-09 | 郑照 | Preparation method of fenchone |
| CN105152885A (en) * | 2015-09-15 | 2015-12-16 | 南宁辰康生物科技有限公司 | Preparation method of fenchone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059711A (en) * | 1990-09-10 | 1992-03-25 | 中国科学院广州化学研究所 | The synthetic method of optically active camphor |
| CN1059710A (en) * | 1990-09-10 | 1992-03-25 | 中国科学院广州化学研究所 | Preparation of camphor with isoborneol by gas phase dehydrogenation |
| CN1065451A (en) * | 1991-03-22 | 1992-10-21 | 中国科学院广州化学研究所 | The method of preparation of high purity camphor from dehydrogenated and impuritier removal iso-borneo camphor |
| JPH0791554B2 (en) * | 1989-06-21 | 1995-10-04 | 高砂香料工業株式会社 | Fragrance composition |
| AU2003256741A1 (en) * | 2002-08-02 | 2004-02-23 | Aromagen Corporation | Ketocampholenic acid derivatives and their use in fragrance and flavour applications |
-
2012
- 2012-11-08 CN CN2012104413803A patent/CN103012097A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791554B2 (en) * | 1989-06-21 | 1995-10-04 | 高砂香料工業株式会社 | Fragrance composition |
| CN1059711A (en) * | 1990-09-10 | 1992-03-25 | 中国科学院广州化学研究所 | The synthetic method of optically active camphor |
| CN1059710A (en) * | 1990-09-10 | 1992-03-25 | 中国科学院广州化学研究所 | Preparation of camphor with isoborneol by gas phase dehydrogenation |
| CN1065451A (en) * | 1991-03-22 | 1992-10-21 | 中国科学院广州化学研究所 | The method of preparation of high purity camphor from dehydrogenated and impuritier removal iso-borneo camphor |
| AU2003256741A1 (en) * | 2002-08-02 | 2004-02-23 | Aromagen Corporation | Ketocampholenic acid derivatives and their use in fragrance and flavour applications |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892378A (en) * | 2015-05-12 | 2015-09-09 | 郑照 | Preparation method of fenchone |
| CN105152885A (en) * | 2015-09-15 | 2015-12-16 | 南宁辰康生物科技有限公司 | Preparation method of fenchone |
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Application publication date: 20130403 |