CN1194974C - Method for preparing epoxy pinane using sodium percarbonate as reagent - Google Patents
Method for preparing epoxy pinane using sodium percarbonate as reagent Download PDFInfo
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- CN1194974C CN1194974C CNB021509018A CN02150901A CN1194974C CN 1194974 C CN1194974 C CN 1194974C CN B021509018 A CNB021509018 A CN B021509018A CN 02150901 A CN02150901 A CN 02150901A CN 1194974 C CN1194974 C CN 1194974C
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Abstract
The present invention relates to a method for preparing alpha pinene oxide from pinene by suing sodium percarbonate as a reagent. Because the pinene is sensitive to acid, the open loop recomposition of the pinene can be easily caused in the prior art; thus, the alpha pinene oxide has the disadvantages of low yield, low purity, etc. The method takes the sodium percarbonate as the reagent, acetic anhydride is added to the sodium percarbonate in a reaction, and a phase transfer catalyst is added to the sodium percarbonate if necessary; thereby, under the condition that the reaction is controlled under the temperature of 60 DEGC for 1 to 24 hours, the alpha pinene oxide can be obtained. The method is used for oxidizing alkene loops under neutral conditions, so that the method effectively avoids side reactions, such as the open loop recomposition of the pinene, etc., improves the purity of the alpha pinene oxide, and has the characteristics of stable reaction, high yield, low cost, etc. Thereby, the method has certain application prospects.
Description
Technical field
The present invention be a kind of be the method for reagent preparation epoxypinane with the SPC-D.
Background technology
Firpene is terebinthine important component, and there are abundant natural resource in China.Because the difference of position of double bond in the molecule, the branch of α-Pai Xi and beta-pinene is arranged again.Because the chemical property of firpene is quite active, is a kind of important material in the perfume industry, can produce a series of spices that are widely used.Wherein α-Pai Xi is a kind of useful as intermediates in spices and the medicine industry through the epoxypinane that epoxidation reaction generates.As α-Huan Yangpaiwan at ZnCl
2Effect down open loop is reset and is obtained campholytic aldehyde, and it and multiple carbonyl compound condensation can generate serial santal series products (US4052341, CH629461,629462 etc.), and they are widely used in fragrance industry.The open-loop products of α-Huan Yangpaiwan under the acid effect is the medicine of the respiratory stimulant of a kind of commodity " Sobrerol " by name.
Epoxypinane is prepared through epoxidation reaction by firpene.With the α-Huan Yangpaiwan is example: the most frequently used epoxidation reagent is that (as EP 55387, USSR 456806, and ES 548516 for Peracetic Acid, JP 04264079 etc.), Peracetic Acid has instability, decomposes easily, be difficult for weakness such as storage, and its acidity causes the open loop rearrangement of α-Pai Xi easily.Therefore, Peracetic Acid is not a very good epoxidation reagent to the epoxidation of acid sensitive compound.Hydrogen peroxide also can make α-Pai Xi epoxidation (as JP 5976077, EP 68564 etc.) under metal-organic catalysis.Use O
2Making reagent, also is the epoxidised a kind of process useful of α-Pai Xi (as Fr 1505337, US 4345984 etc.) through catalyzed oxidation.In addition, also useful other organic peroxy compound is that reagent carries out the epoxidised patent of α-Pai Xi (as GB 2330358), and thinks a kind of quite effectively epoxidizing method.Aforesaid method respectively has its strong point and deficiency, wherein most methods, and the productive rate of product epoxypinane is on the low side and purity is not high.As intermediate, further producing spices and medicine is a unfavorable factor to it for this.
Summary of the invention
The objective of the invention is to obtain a kind of reacting balance, operational safety, productive rate is good, product purity the is high and with low cost method for preparing epoxypinane.
The present invention is a kind of method of firpene being carried out epoxidation reaction under neutrallty condition, uses present method not only can avoid the open loop of firpene to reset effectively, but also has improved the purity of the productive rate and the product epoxypinane of epoxidation reaction.
Epoxidation reagent used in the present invention is a SPC-D, and it is a kind of Industrial products, in the washing composition of being everlasting as additive.Cheap, stable in properties is convenient to store and transportation.Though other inorganic peroxy compounds, as Sodium peroxoborate, pertungstic acid sodium etc. also can be as the epoxidation reagent of firpene, and it is good that effect all is not so good as SPC-D.SPC-D is a kind of mineral compound, and white solid, the content of its " available oxygen " are 12～13%, but it does not dissolve in organic solvent, therefore participates in organic reaction hardly.
Key of the present invention is by adding the indirect method of diacetyl oxide, makes SPC-D discharge " available oxygen " in its molecule effectively.After adding diacetyl oxide, it at first reacts with SPC-D, generate the organic peroxy compound intermediate, be converted into the organic peroxy compound with a kind of like this inorganic peroxy compounds of the SPC-D of olefine reaction, generate epoxy compounds with olefine reaction subsequently being difficult to originally.In reaction, once be separated to a kind of organic peroxy compound, determined after identifying that it was Peracetic Acid acid anhydride (CH
3CO-O-O-COCH
3).This is the epoxidation reagent that really works.The essence of present method is by SPC-D and diacetyl oxide effect, epoxidation reagents such as in-situ preparing Peracetic Acid acid anhydride, and their limits in reaction process produce, limit and olefine reaction, thus organic peroxy compound instability avoided, easy weakness of decomposing, reacting balance, operational safety.
Another characteristics of the present invention are that a large amount of solid sodium carbonates are arranged in the reaction system, can in and the acidic substance in the system, make reaction remain under the neutrallty condition and carry out.Therefore, be particularly suitable for the epoxidation of the alkene of those acid labile.
With SPC-D-diacetyl oxide is that reagent carries out as follows to the epoxidation reaction of firpene: after firpene, SPC-D and suitable solvent, stir down and adds diacetyl oxide gradually, and by adding the speed control temperature of reaction of diacetyl oxide.Reaction finishes back elimination inorganics, eliminates remaining peralcohol, and rectifying obtains epoxypinane.
Be reagent to the epoxidation reaction of firpene with SPC-D-diacetyl oxide be solid-liquid two phase reaction, in order to ensure reacting completely, it is excessive that SPC-D needs.Before reaction, can analyze the content of its " available oxygen " earlier, calculate the charging capacity of SPC-D according to analytical results.Common 1.1～3.0 times of SPC-D being controlled at the firpene mole dosage.
The effect of diacetyl oxide is to form the Peracetic Acid acid anhydride with the SPC-D reaction, and the latter and firpene reaction have also generated epoxypinane, and the Peracetic Acid acid anhydride originally is reduced to diacetyl oxide after having shifted Sauerstoffatom to firpene.According to this process, diacetyl oxide can recycle.Except generating the Peracetic Acid acid anhydride with the SPC-D effect, in reaction it some be hydrolyzed, no longer participate in circulation.Therefore, for fast reaction speed, during actually operating, diacetyl oxide to the mol ratio of SPC-D with 0.5～2.0: 1 is advisable.
React used solvent, except that the multi-halogenated compounds that methylene dichloride, chloroform, ethylene dichloride etc. are used always in epoxidation reaction of olefines, organic solvents such as sherwood oil, benzene,toluene,xylene, ethyl acetate all can use.Can select only solvent according to the particular case of producing.Temperature of reaction is controlled at room temperature to 60 and ℃ is advisable, and the reaction times is as the criterion to react completely, and needs 1～24 hour usually.
The reaction of carrying out with SPC-D is solid-liquid two phase reaction, so the reaction times is longer.The present invention adopts the method for adding phase-transfer catalyst to promote reaction.Used phase-transfer catalyst has two classes: a class is a quaternary ammonium salt, and two kinds of triethyl benzyl ammonia chloride and palmityl trimethyl ammonium chlorides are arranged; Another kind of is polyoxyethylene glycol (PEG) class, because of change of molecular weight, three kinds of PEG-200, PEG-400 and PEG-600 is arranged.This two classes phase-transfer catalyst is all effective, and catalyzer feeds intake by 3～5mol% of firpene consumption, under same reaction conditions, adds quaternary ammonium salt-type phase transfer catalyst and can make the reaction times shorten 1/4～1/5.But added after the quaternary ammonium salt, the aftertreatment of reacting has been had disadvantageous effect.Mainly be after the operation that washes and remove residual peralcohol with water, the layering of organic phase and water is had any problem, and tangible emulsion is arranged sometimes.For layering was wanted polyvoltine two, three hours, the shortening reaction times just becomes has not had too big meaning.
Compare with quaternary ammonium salt, the better effects if of polyoxyethylene glycol is a little, can shorten for about 1/4 reaction times usually, separates and also is not difficult.
Three kinds of used PEG effect basically identicals, because reaction is that mol% by the firpene consumption feeds intake, therefore from cost consideration, in these three kinds of PEG, the PEG-200 that molecular weight is little is more suitable.
Fast reaction speed, shortening the most effective way of reaction times is that ultrasonic radiation is implemented in reaction.Method is to insert ultrasonic probe in reaction system, or reaction vessel is immersed in the ultrasonic cleaner together with reactant, makes to be reflected under the ultrasonic radiation and carries out.Reaction can finish in 1～4 hour usually.When under being reflected at ultrasonic radiation, carrying out, want the attentive response temperature especially.Because cavitation effect of ultrasonic waves can make reaction medium heat up gradually.In the reaction of carrying out with ultrasonic probe, need use the water-bath control reaction temperature in case of necessity.During as ultrasonic generator, can use recirculated water with ultrasonic cleaner in the rinse bath to keep temperature of reaction.In addition, select toluene as far as possible, boiling points such as dimethylbenzene are than higher solvent.The disadvantage of ultrasonic radiation is that reacting weight is limited, and when reaction vessel surpassed 500mL, reaction was just very difficult.
The present invention is applicable to α-Pai Xi, beta-pinene.
The present invention uses cheap, and the SPC-D of stable in properties is the reagent preparation epoxypinane, and advantages such as gentleness, operational safety respond.And react and under neutrallty condition, carry out, avoided the side reactions such as open loop rearrangement of firpene effectively, improved degree of purity of production.Very favourable with the epoxypinane that present method obtains to further preparation spice product.
Embodiment
Embodiment 1
Add 136g (1mole) α-Pai Xi in the 2000mL three-necked bottle, 250g (available oxygen content is 12%) SPC-D and 1000mL methylene dichloride.Add the 200mL diacetyl oxide under the high degree of agitation, keep reaction under refluxad to carry out.At room temperature continue after adding to stir, and follow the tracks of reaction, finish, need 20～24 hours usually until the α-Pai Xi reaction with GC.Remove by filter inoganic solids, reaction mixture eliminates remaining peralcohol with ordinary method.Rectifying behind the recovery solvent, the cut of 102-5 ℃/7Kpa of collection.The α-Huan Yangpaiwan productive rate is 85～90%, and purity＞95% has refrigerant fragrance.
Embodiment 2
Add 34g beta-pinene, 50g SPC-D, 150mL benzene and 3g triethyl benzyl ammonia chloride (TEBA) in the 500mL three-necked bottle.Add the 45mL diacetyl oxide under the high degree of agitation, temperature of reaction is controlled at below 40 ℃ carries out.Continue stirring reaction at room temperature after adding, follow the tracks of, finish, need 18～20 hours usually until the beta-pinene reaction with GC.Method reaction mixture by embodiment 1 obtains the beta epoxide pinane, and productive rate is 80～90%, purity＞95%.
Embodiment 3
Add 34g α-Pai Xi, 50g SPC-D, 150mL toluene and 2.5g PEG-200 (consumption of PEG-400 is 5g, and PEG-600 is 7.5g) in the 500mL three-necked bottle.Add the 40mL diacetyl oxide under the high degree of agitation, temperature of reaction is controlled at below 60 ℃ carries out.Add the back and continue at room temperature to stir, follow the tracks of reaction, finish, need 15～20 hours usually until the α-Pai Xi reaction with GC.Press the method reaction mixture of embodiment 1, the productive rate of α-Huan Yangpaiwan is 85～90%, purity＞95%.
Embodiment 4
Add 10g α-Pai Xi, 20g SPC-D and 100mL dimethylbenzene in the 250mL three-necked bottle.Reaction flask is placed ultrasonic cleaner, and reaction flask bottom is aimed at the loud speaker in the rinse bath as far as possible, and reaction flask is fixed on position apart from about the about 1cm in loud speaker top.Effect was better when water level in the ultrasonic cleaner and the liquid level in the reaction flask remained basically stable.Open ultrasonic generator, and add the 15mL diacetyl oxide gradually, temperature of reaction is controlled at about 40 ℃ carries out.Add the back and continue ultrasonic radiation, temperature of reaction is controlled at below 60 ℃.Afterreaction finished substantially in about 1～2 hour.The concrete reaction times is determined by the result that GC follows the tracks of, and finishing with the α-Pai Xi reaction is as the criterion.Reaction finishes the method reaction mixture that embodiment 1 is pressed in the back, obtains α-Huan Yangpaiwan, and productive rate is 85～95%, purity＞95%.
Claims (5)
1, a kind of is the method for reagent preparation epoxypinane with the SPC-D, it is characterized in that after firpene, SPC-D and the solvent, stir and add diacetyl oxide down gradually, wherein the add-on mol ratio is a firpene: SPC-D=1: (1.1-3.0), SPC-D: diacetyl oxide=1: (0.5-2.0), temperature of reaction: room temperature-65 ℃, reaction times 1-24 hour.
2, according to claim 1 is the method for reagent preparation epoxypinane with the SPC-D, it is characterized in that adding phase-transfer catalyst quaternary ammonium salt or polyethylene glycols in the reaction, and add-on is the 3-5mol% of firpene amount.
3, according to claim 2 is the method for reagent preparation epoxypinane with the SPC-D, it is characterized in that the phase-transfer catalyst that adds is a polyethylene glycols.
4, according to claim 3 is the method for reagent preparation epoxypinane with the SPC-D, it is characterized in that the phase-transfer catalyst that adds is a polyoxyethylene glycol-200.
5, according to claim 1 is the method for reagent preparation epoxypinane with the SPC-D, it is characterized in that implementing in the reaction process ultrasonic radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021509018A CN1194974C (en) | 2002-11-28 | 2002-11-28 | Method for preparing epoxy pinane using sodium percarbonate as reagent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021509018A CN1194974C (en) | 2002-11-28 | 2002-11-28 | Method for preparing epoxy pinane using sodium percarbonate as reagent |
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|---|---|
| CN1422853A CN1422853A (en) | 2003-06-11 |
| CN1194974C true CN1194974C (en) | 2005-03-30 |
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| CNB021509018A Expired - Lifetime CN1194974C (en) | 2002-11-28 | 2002-11-28 | Method for preparing epoxy pinane using sodium percarbonate as reagent |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5357038B2 (en) * | 2007-09-26 | 2013-12-04 | 株式会社Ａｄｅｋａ | Process for epoxidation of olefins |
| CN101973838B (en) * | 2010-10-28 | 2013-04-24 | 岳阳昌德化工实业有限公司 | Method for purifying beta-pinene and preparing alpha-epoxy pinane from turpentine oil |
| CN103833690B (en) * | 2014-02-19 | 2016-05-04 | 西南林业大学 | Utilize australene to prepare the method for 2,3-epoxypinane |
| CN106588819B (en) * | 2016-11-02 | 2018-10-23 | 昆明理工大学 | A kind of preparation method of highly selective epoxypinane |
| CN111548250B (en) * | 2020-04-30 | 2023-10-20 | 厦门中坤化学有限公司 | Method for preparing 3-carenol from 3-carene |
| 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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2002
- 2002-11-28 CN CNB021509018A patent/CN1194974C/en not_active Expired - Lifetime
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Address after: 000000 No. 220, Handan Road, Shanghai Co-patentee after: HANGZHOU GRASCENT CO.,LTD. Patentee after: FUDAN University Address before: 000000 No. 220, Handan Road, Shanghai Co-patentee before: Hangzhou Aroma Chemical Co. Patentee before: Fudan University |
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Granted publication date: 20050330 |
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