CN100478335C - Method for preparing epoxy myrcene - Google Patents
Method for preparing epoxy myrcene Download PDFInfo
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- CN100478335C CN100478335C CNB2006101189139A CN200610118913A CN100478335C CN 100478335 C CN100478335 C CN 100478335C CN B2006101189139 A CNB2006101189139 A CN B2006101189139A CN 200610118913 A CN200610118913 A CN 200610118913A CN 100478335 C CN100478335 C CN 100478335C
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Abstract
This invention discloses a method for preparing epoxymyrcene. The method comprises: utilizing industrial myrcene as the raw material, reacting with SO2 to form myrcenesulfone, and epoxidizing with sodium percarbonate/acetic anhydride system to obtain epoxymyrcene. The method has such advantages as stable reactions, mild conditions, safe operation, and high product quality.
Description
Technical field
The invention belongs to chemical technology field, is a kind of preparation method of epoxy myrcene.
Background technology
Epoxy myrcene (myrcene epoxide) has the fragrance of moon sweet osmanthus, is a kind of spices in fine chemistry industry, also is a kind of reodorant.It with its fragrance of osmanthus and low fragrance threshold property and being applied in spices and essence industry pleasant the moon.And it still is a kind of useful as intermediates, can be converted into a series of useful derivatives (Synth.Commun., 1999,29,3673, Tetrahedron, 2001,57,1235) through reaction.
Epoxy myrcene is made through epoxidation reaction by myrcene.Contain a plurality of pairs of keys in the myrcene molecule, multiple epoxidation product might occur during epoxidation.But as long as reaction conditions control is proper, can obtain single 6,7-position epoxy compounds.
Organic peracid is the effective epoxidation reagent of a class in the myrcene epoxidation reaction, as Peracetic Acid (US2838524, US2692876) etc.Wherein use (J.Org.Chem., 1975,40,2259, Synthesis, 2001,13,2035) the most always with metachloroperbenzoic acid (m-CPBA), it is quite desirable to the effect of myrcene epoxidation reaction.The shortcoming of m-CPBA is that price is more expensive, also has certain danger.Also useful hydrogen peroxide carry out the report (Chem.Lett., 1991,1937, J.Org.Chem., 1991,56,496) of epoxidation reaction under organometallics catalysis, but reaction yield is not fully up to expectations as epoxidation reagent in the document.
How the raw material myrcene makes by rectifying separation or by the beta-pinene cracking with some natural essential oil.The content of industrial goods myrcene has a lot of impurity about 75%.Prepare epoxy myrcene if such raw material is carried out epoxidation, be bound to bring many difficulties to the separation and purification of product with aforesaid method.
Summary of the invention
The object of the present invention is to provide a kind of cheap, reaction temperature and, the preparation method of the epoxy myrcene of operational safety.
The epoxy myrcene preparation method that the present invention proposes is to be raw material with the industrial goods myrcene, is that the epoxidation reaction reagent preparation gets epoxy myrcene with SPC-D-diacetyl oxide.Concrete steps are as follows:
(1) myrcene sulfone preparation: industrial goods myrcene, sulfurous gas and stopper are added in the autoclave pressure, the mol ratio that feeds intake of sulfurous gas and myrcene is 2-3: 1 (actual content of pressing myrcene in the raw material calculates), and the stopper consumption is the 0.5-1mol% of myrcene consumption; Control reaction temperature is between room temperature-100 ℃; Along with reaction is carried out, the autoclave pressure internal pressure can descend gradually, and when no longer changing (being that pressure is steady) when pressure drops to certain numerical value, the expression reaction draws to an end, continues reaction 1-3 hour again; Reaction finishes, and residue sulfurous gas carries out underpressure distillation with the gained reactant in the emptying reactor, removes unreacted impurity, gets myrcene sulfone crude product;
(2) epoxy myrcene preparation: back is made myrcene sulfone, SPC-D and solvent add in the reaction flask, room temperature, stirring slowly add diacetyl oxide down; Reaction is under refluxad carried out; Wherein, the molar ratio of SPC-D and alkene is controlled at 1.5-3: 1, the mol ratio of diacetyl oxide and SPC-D is controlled at 1.5-2: 1, reaction times 12-24 hour, the epoxidation product of myrcene sulfone.
In this step, solvent can adopt methylene dichloride, also can adopt multi-halogenated compounds such as chloroform, ethylene dichloride, also can adopt sherwood oil, benzene,toluene,xylene or ethyl acetate etc.
The epoxidation product of myrcene sulfone is heated to 120-150 ℃, makes it to decompose; Separate on the branch limit, the limit underpressure distillation, collect epoxy myrcene.
The present invention at first at having this feature structure of conjugated double bond in the myrcene molecule, generates corresponding sulfone by it and sulfurous gas reaction, thereby changes the character of myrcene, can easily it be separated with impurities in raw materials.
Epoxidation reaction adopts the method for SPC-D-diacetyl oxide agent combination.SPC-D is a kind of inorganic peroxy compounds, and is cheap, stable in properties, reaction conditions gentleness, operational safety.In addition, under neutrallty condition, carry out, be particularly suitable for the epoxidation of the alkene of acid labile with the epoxidation reaction that this agent combination is implemented.
The myrcene sulfone is easy to be decomposed into epoxy myrcene after the product heating that epoxidation obtains.
The reaction of myrcene and sulfurous gas is carried out in autoclave pressure.Because sulfurous gas at room temperature is gas, so the time action of feeding intake needs rapidly, and keep suitable excessive, react completely guaranteeing.The molar ratio that it and myrcene feed intake should be controlled at 2～3: 1 (actual content of pressing myrcene in the raw material calculates).Consider the easy polymerization of myrcene, except above-mentioned two kinds of reagent, also need add the stopper (for example 2,6 di tert butyl 4 methyl phenol etc.) of some amount, its consumption is 0.5～1mol% of myrcene consumption.Be reflected between room temperature～100 ℃ and carry out.The difference of reaction times because of temperature of reaction changes to some extent, and along with the carrying out of reaction, the pressure in the reactor can descend gradually, and when pressure dropped to certain numerical value and no longer changes, the expression reaction drew to an end, and continues reaction 1～3 hour, promptly accuses and finishes.
Reactant adopts the method for underpressure distillation, the impurity that does not participate in reacting is eliminated as far as possible.Owing to be easy to decompose after the heating of product myrcene sulfone, therefore in still-process, should note strict control Heating temperature, can not surpass 120 ℃, be advisable with 75～90 ℃.
Adopt SPC-D be the epoxidation reaction of reagent earlier with myrcene sulfone, SPC-D and solvent, slowly add diacetyl oxide after, stirring at room is until reacting completely.
SPC-D is a kind of inorganic peroxide that has 1.5 molecular crystal hydrogen peroxide, with it and diacetyl oxide as the essence of agent combination be in reaction diacetyl oxide earlier with SPC-D effect, " original position " preparation Peracetic Acid acid anhydride (CH
3CO-O-O-COCH
3), and carry out epoxidation reaction with alkene thereupon, obtain into corresponding epoxidation product.
Since SPC-D-diacetyl oxide be the epoxidation reaction of reagent solid-liquid two alternate carrying out, react completely in order to make, it is excessive that SPC-D needs.Measure the feed ratio that calculates reaction on the basis of crossing oxygen level in the SPC-D in advance.Usually the mol ratio with SPC-D and alkene is controlled at 1.5～3: 1, and the mol ratio of diacetyl oxide and SPC-D is with 1.5～2: 1 is advisable.
Methylene dichloride is a kind of quite suitable solvent, and it also has the function of control reaction temperature except playing solvent action.When diacetyl oxide adds reaction mixture, have an exothermic process.Therefore can reach the purpose of control feed rate and temperature of reaction by the method for control methylene chloride reflux speed.Except methylene dichloride, multi-halogenated compounds such as chloroform, ethylene dichloride, and sherwood oil, benzene,toluene,xylene and ethyl acetate etc. also can be as the solvents of epoxidation reaction.But when making solvent, note temperature of reaction with these compounds, comparatively suitable to be controlled at 40～60 ℃.
Reaction times finished in 12～24 hours usually with the standard that reacts completely.Can follow the tracks of reaction with TLC during actually operating, and determine the suitable reaction times.
The epoxidation product of myrcene sulfone begins when being heated to 120～150 ℃ to decompose.Can adopt the limit to decompose, the method for limit underpressure distillation is collected epoxy myrcene.
The present invention is a raw material with industrial pale blue osmanthus alkene, the method that generates sulfone by the reaction of it and sulfurous gas realize with raw material in separate impurities.Adopting SPC-D-diacetyl oxide is that reagent carries out epoxidation, the mild condition that responds, characteristics such as operational safety and cost are low.The sulfone thermal degradation can obtain required product epoxy myrcene easily.And product property is good.
Embodiment
Embodiment 1
The preparation of myrcene sulfone: add in the autoclave pressure 200g myrcene (industrial goods, content is about 75%, 1.1mol), 2g (9mmol) 2,6 di tert butyl 4 methyl phenol and 200g (3.1mol) sulfurous gas.Heated and stirred, temperature are controlled at 65～75 ℃.Question response still internal pressure continues reaction 2 hours after steadily and no longer descending.Reaction finishes, and with remaining sulfurous gas emptying in the reactor, emptying gas absorbs with buck.
The reactant of gained is carried out underpressure distillation, and the cut before the 85 ℃/5mmHg is the impurity that has neither part nor lot in reaction in the raw material, as far as possible with they Ex-alls.Residue is the crude product of myrcene sulfone, purity about 90～95%.The actual content of pressing myrcene in the raw material calculates, and productive rate is near 95%.Crude product need not be further purified the epoxidation reaction that promptly can be used for next step.
The preparation of epoxy myrcene: add 100g (0.5mol) myrcene sulfone in the three-necked bottle, 500mL methylene dichloride and 120g SPC-D (cross oxygen level and be about 12%) slowly add the 100mL diacetyl oxide under the high degree of agitation, make reaction keep under refluxad carrying out.Add the back and continue reaction at room temperature, and follow the tracks of until reacting completely, need 18～24 hours approximately with TLC.The solids removed by filtration inorganics, filtrate eliminates residual peralcohol with ordinary method.Obtain the crude product of myrcene sulfone epoxidation product behind the recovery solvent.
The crude product of gained is placed vacuum distillation apparatus.Be heated to 120 ℃, sulfone begins to decompose.Decompose on the limit, the limit underpressure distillation, and the cut of 75～80 ℃/10mmHg of collection is until decomposing fully.Get 62～65g colourless liquid, productive rate 85～90%.
1H?NMR：δ6.31(dd，1H，J＝10.2，17.5Hz)，5.25(d，1H，J＝17.5Hz)，5.10(d，1H，J＝10.3Hz)，5.05(s，1H)，5.02(s，1H)，2.76(m，1H，J＝6.2Hz)，2.39(m，2H)，1.65(m，2H)，1.31(s，1H)，1.22(s，1H)ppm。
Embodiment 2
Add 100g (0.5mol) myrcene sulfone in the three-necked bottle by embodiment 1 preparation, 500mL dimethylbenzene and 120g SPC-D slowly add the 100mL diacetyl oxide under the high degree of agitation, exothermic heat of reaction is obvious, the rate of addition of control diacetyl oxide makes temperature of reaction maintain 40～60 ℃.Add the back room temperature reaction and spend the night, remove inoganic solids.Filtrate eliminates residual peralcohol with ordinary method, obtains the crude product of myrcene sulfone epoxidation product behind the decompression and solvent recovery.The heating of crude product limit, decompose on the limit, the limit underpressure distillation, the cut of 75～80 ℃/10mmHg of collection is until decomposing fully.Get the 56g colourless liquid, productive rate 78%.
In described various components of the inventive method and condition and range, change relevant experiment condition data, according to the preparation process of embodiment 1, all can obtain result similar to Example 1, can obtain the epoxy myrcene of high yield, do not enumerate one by one at this.
Claims (3)
1, a kind of preparation method of epoxy myrcene is characterized in that concrete steps are as follows:
(1) myrcene sulfone preparation: industrial myrcene, sulfurous gas and stopper are added in the autoclave pressure, and the mol ratio that feeds intake of sulfurous gas and myrcene is 2-3: 1, and the stopper consumption is the 0.5-1mol% of myrcene consumption; Control reaction temperature is between room temperature-100 ℃; Along with reaction is carried out, the autoclave pressure internal pressure can descend gradually, and when pressure dropped to certain numerical value and no longer changes, the expression reaction drew to an end, continued reaction 1-3 hour again; Reaction finishes, and residue sulfurous gas carries out underpressure distillation with the gained reactant in the emptying reactor, removes unreacted impurity, gets myrcene sulfone crude product; Here stopper is a 2,6 di tert butyl 4 methyl phenol;
(2) epoxy myrcene preparation: back is made myrcene sulfone, SPC-D and solvent add in the reaction flask, room temperature, stirring slowly add diacetyl oxide down; Reaction is under refluxad carried out; Wherein, the molar ratio of SPC-D and alkene is controlled at 1.5-3: 1, the mol ratio of diacetyl oxide and SPC-D is controlled at 1.5-2: 1, reaction times 12-24 hour, the epoxidation product of myrcene sulfone; This epoxidation product is heated to 120-150 ℃, makes it to decompose, decompose on the limit, the limit underpressure distillation, collect epoxy myrcene.
2, the preparation method of epoxy myrcene according to claim 1 is characterized in that temperature of reaction is 75-90 ℃ in the step (1).
3, the preparation method of epoxy myrcene according to claim 1 is characterized in that solvent is methylene dichloride, chloroform or ethylene dichloride described in the step (2), perhaps is sherwood oil, benzene,toluene,xylene or ethyl acetate.
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| CNB2006101189139A CN100478335C (en) | 2006-11-30 | 2006-11-30 | Method for preparing epoxy myrcene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190055521A (en) * | 2017-11-15 | 2019-05-23 | 주식회사 엘지화학 | Method for preparing myrcene derived compound |
| KR20190055522A (en) * | 2017-11-15 | 2019-05-23 | 주식회사 엘지화학 | Myrcene derived compound and method for preparing the same |
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| KR101459811B1 (en) | 2007-09-26 | 2014-11-07 | 가부시키가이샤 아데카 | Oxidizing agent composition for epoxidation and oxidation method thereof |
| BRPI1013223A2 (en) * | 2009-03-04 | 2017-09-26 | Regenera Pharma Ltd | therapeutic uses of mastic gum fractions |
| EP2831139A4 (en) * | 2012-03-27 | 2015-10-28 | Stepan Co | Surfactants and solvents containing diels-alder adducts |
| CN112159372A (en) * | 2020-10-22 | 2021-01-01 | 怀化宝华生物科技有限公司 | Preparation method of bicalutamide |
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2006
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190055521A (en) * | 2017-11-15 | 2019-05-23 | 주식회사 엘지화학 | Method for preparing myrcene derived compound |
| KR20190055522A (en) * | 2017-11-15 | 2019-05-23 | 주식회사 엘지화학 | Myrcene derived compound and method for preparing the same |
| KR102425715B1 (en) | 2017-11-15 | 2022-07-28 | 주식회사 엘지화학 | Method for preparing myrcene derived compound |
| KR102425716B1 (en) | 2017-11-15 | 2022-07-28 | 주식회사 엘지화학 | Myrcene derived compound and method for preparing the same |
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| CN101003522A (en) | 2007-07-25 |
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