CN1438222A

CN1438222A - Epoxidizing method of alpha-pinene

Info

Publication number: CN1438222A
Application number: CN 03113924
Authority: CN
Inventors: 江焕峰; 欧阳小月; 陈伟强; 邹钢; 黄宇平; 许琳; 李国平; 赵妍
Original assignee: Guangzhou Institute of Chemistry of CAS
Current assignee: Guangzhou Chemical Co Ltd of CAS; Guangzhou Institute of Chemistry of CAS
Priority date: 2003-03-17
Filing date: 2003-03-17
Publication date: 2003-08-27
Anticipated expiration: 2023-03-17
Also published as: CN1176082C

Abstract

The invention refers to an epoxidizing method of alpha-pinene, including the steps: accoridng to mol shares, mixing alpha-pinene, 100, ethylic nitrile 400-500, tert-butanol 1100-1400, hydrogen carbonate, 50-70, and hydrogen peroxide, 600-800, using the metal salt of subgroup B in cycle, 4, 1.0-1.4, as catalyzer, blending to react for 45-55h at normal temperature, filtering deposit, extracting organic matter, and by washing and drying, getting rid of solvent to collect the product.

Description

The epoxidizing method of α-Pai Xi

Technical field

The present invention relates to the epoxidizing method of α-Pai Xi.

Technical background

With the α-Pai Xi is raw material, can synthesize the famous and precious spices of a big class---sandalwood type spices.And be the only way which must be passed to the epoxidation of α-Pai Xi, also be in several committed steps.Produce in the epoxidation process in this field existing still generally popular " high density hydrogen peroxide---Peracetic Acid " this dangerous production method at sandalwood type spices.Why say dangerous be because: 1.30% hydrogen peroxide (H ₂O ₂) need be concentrated into more than 70%, and this process is very dangerous, and the danger of blast is arranged, especially in large-scale industrial production.2. come further production Peracetic Acid with this high dense hydrogen peroxide.The Peracetic Acid that obtains thus also is explosive.Therefore, how under safety condition to the epoxidation of α-Pai Xi, and further seek a kind of safe epoxidation systems and come epoxidation to comprise the various alkene of α-Pai Xi, be one of problem of exploring of chemist always.

As far back as 1909, Prileschajew (Ber 424814 (1909)) just made epoxidizing agent with peroxybenzoic acid, has made 2 first, the 3-epoxypinane.The people is arranged successively with single o-benzoic acid (Arbuzor B.A.et al. that crosses later on again, J.Prak.Chem., 1930,1272), cross oxydisuccinic acid (Lombard R.et al., Bull Soc.Chim.France, 1963,2800), Peracetic Acid (Cocker W.et al., J.Chem.Soc., Perkin Trans I, 1972,1971) etc. multiple organic peroxide acid is studied this reaction.The eighties, Japan, Spain and Germany have the patent introduction to make the method for epoxypinane in succession, and (Japan's special permission discloses clear 61-72774 (1986), Japan's special permission discloses clear 62-201878 (1987), Spain patent ES548,516 (1985), German Patent Ger.Offen2,835,940 (1980) German patent DE 3049,434 (1982)).But significantly deficiency is, or catalyzer makes trouble, and cost is higher, or is difficult to repetition.As by Spain's patent, not only difficult the repetition, even and if by its result that writes, separation yield also only 60%.

Came so far in 90 years, and all had many documents that the epoxidation of α-Pai Xi is had report both at home and abroad.But integrate, following two characteristics are arranged: 1. the diversity of oxygenant kind.Useful oxygen, useful hydrogen peroxide, useful clorox, useful SPC-D, useful oxone (oxone) or the like.And formation oxidation system separately.2. this oxidation system still can not be fully up to expectations.Though some system has in the following Column Properties one or more: safety, convenient, economy, practicality.But situation nearly all is or safe ready, reagent catalyzer are expensive (as will be with the quaternary amine of some ad hoc structure with clorox, to use methyl trioxy-rhenium with SPC-D, to use baroque fluoride-catalyzed with lower concentration 30% hydrogen peroxide, these catalyzer are all very expensive), or economical and practical, security is relatively poor (as using the higher concentration hydrogen peroxide).Therefore at present still lack a kind of more satisfactory to the α-Pai Xi process for epoxidation.

Summary of the invention

The epoxidizing method that the purpose of this invention is to provide a kind of α-Pai Xi, this method have safe, economic, practical characteristics.

The epoxidizing method of α-Pai Xi provided by the invention, comprise the steps: by the mole umber, 100 parts of α-Pai Xis are mixed with 400～500 parts of acetonitriles, 1100～1400 parts of trimethyl carbinols, 50～70 parts of supercarbonates, 600～800 parts of hydrogen peroxide, period 4 subgroup metal-salt with 1.0～1.4 parts is made catalyzer, stirring at normal temperature reaction 45～55 hours, elimination precipitation, extraction organism, through washing, drying, remove the solvent collection reaction product.

Wherein hydrogen peroxide not only can adopt the hydrogen peroxide of high density, also can adopt the hydrogen peroxide of lower concentration, and especially can adopt commercially available concentration is the hydrogen peroxide of 30wt%.

α-Pai Xi and acetonitrile, the trimethyl carbinol, supercarbonate, hydrogen peroxide mole proportion optimization are 100: 400～450: 1200～1300: 50～60: 700～800.

Period 4 subgroup metal-salt comprises zinc salt, molysite, cobalt salt, manganese salt etc., and preferred manganese salt especially can be manganous sulfate.Preferred 1.0～1.2 parts of its consumption.

Reaction is carried out at normal temperatures, 20～30 ℃ of preferred temperature.

Preferred 45～52 hours of reaction times.

Under 60mmHg, collect about 110 ℃ colourless liquid, with standard nuclear-magnetism spectrum and the contrast of picture library mass spectrum, prove required product.

Method provided by the invention can adopt the hydrogen peroxide of the 30wt% of commercially available low concentration, and is safe in utilization and inexpensive.Used catalyzer is easy to get very much, and is cheap and consumption is small.This method synthetic yield height (75～80%), used condition is very gentle, simultaneously compliance with environmental protection requirements.This method safety, economic, practical is suitable for suitability for industrialized production.If be used for large-scale industrial production, expectation will produce huge economic benefit.

Preferred forms

Umber in following examples is molfraction.

Embodiment 1

With 100 parts of α-Pai Xis, with 400 parts acetonitrile, 1200 parts of trimethyl carbinols, 50 parts of supercarbonates, 700 parts of 30wt%H ₂O ₂, 1 part of zinc chloride catalyst mix, soon and begin reaction, temperature rises slowly under stirring at normal temperature.The white before this mist-like bleary of reaction solution, after become pale yellow.Keeping reaction stopped after 50 hours.Filtration, extraction, saturated common salt water washing, anhydrous sodium sulfate drying, distillating recovering solvent gets light yellow liquid.GC analyzes: contain raw material 10.8%, contain epoxypinane 78%.

Embodiment 2

With 100 parts of α-Pai Xis, with 420 parts of acetonitriles, 1230 parts of trimethyl carbinols, 52 parts of supercarbonates, 730 parts of 30wt%H ₂O ₂, 1.1 parts of cobalt-chloride catalysts mix, external application water-bath cooling makes temperature be no more than 30 ℃, stirred 48 hours, filtration, extraction, saturated common salt water washing, anhydrous sodium sulfate drying, distillating recovering solvent must light yellow liquid.GC analyzes: contain raw material 4.1%%, contain epoxypinane 76.7%.

Embodiment 3

With 100 parts of α-Pai Xis, with 440 parts of acetonitriles, 1270 parts of trimethyl carbinols, 60 parts of supercarbonates, 760 parts of 30wt%H ₂O ₂, 1.2 parts of manganous sulfate catalyst mix, external application water-bath cooling makes temperature be no more than 30 ℃, stirred 52 hours, filtration, extraction, saturated common salt water washing, anhydrous sodium sulfate drying, distillating recovering solvent must light yellow liquid.GC analyzes: contain raw material 1.1%%, contain epoxypinane 94.6%.With the underpressure distillation of gained light yellow liquid, collect the 108-110/60mmHg colourless liquid, net weight 34.38 grams.Calculate if press α-Pai Xi purity 95%, separating yield is 78.8%.

Claims

1, a kind of epoxidizing method of α-Pai Xi, comprise the steps: by the mole umber, 100 parts of α-Pai Xis are mixed with 400～500 parts of acetonitriles, 1100～1400 parts of trimethyl carbinols, 50～70 parts of supercarbonates, 600～800 parts of hydrogen peroxide, period 4 subgroup metal-salt with 1.0～1.4 parts is made catalyzer, stirring at normal temperature reaction 45～55 hours, elimination precipitation, extraction organism, through washing, drying, remove the solvent collection reaction product.

2, the process of claim 1 wherein that hydrogen peroxide adopts the hydrogen peroxide of lower concentration.

3, claim 1 or 2 method, wherein to adopt commercially available concentration be the hydrogen peroxide of 30wt% to hydrogen peroxide.

4, claim 1 or 2 method, wherein α-Pai Xi and acetonitrile, the trimethyl carbinol, supercarbonate, hydrogen peroxide mole proportioning are 100: 400～450: 1200～1300: 50～60: 700～800.

5, claim 1 or 2 method, wherein period 4 subgroup metal-salt is selected from zinc salt, molysite, cobalt salt, manganese salt.

6, the method for claim 5, wherein period 4 subgroup metal-salt is a manganese salt.

7, the method for claim 6, wherein manganese salt is manganous sulfate.

8, claim 1 or 2 method, wherein period 4 subgroup amount of metal salts is 1.0～1.2 parts.

9, claim 1 or 2 method, wherein temperature of reaction is 20～30 ℃.

10, claim 1 or 2 method, wherein the reaction times is 45～52 hours.