CN1438222A - Epoxidizing method of alpha-pinene - Google Patents
Epoxidizing method of alpha-pinene Download PDFInfo
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- CN1438222A CN1438222A CN 03113924 CN03113924A CN1438222A CN 1438222 A CN1438222 A CN 1438222A CN 03113924 CN03113924 CN 03113924 CN 03113924 A CN03113924 A CN 03113924A CN 1438222 A CN1438222 A CN 1438222A
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- parts
- hydrogen peroxide
- salt
- pai
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- 238000000034 method Methods 0.000 title claims abstract description 24
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 title abstract 6
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 title abstract 3
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 title abstract 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 37
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- -1 50-70 Chemical compound 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 2
- 239000002184 metal Substances 0.000 claims abstract 2
- 150000003839 salts Chemical class 0.000 claims abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 238000006735 epoxidation reaction Methods 0.000 description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- TYOAYLVUTSWKHK-UHFFFAOYSA-M COOO[Re] Chemical compound COOO[Re] TYOAYLVUTSWKHK-UHFFFAOYSA-M 0.000 description 1
- 241000221035 Santalaceae Species 0.000 description 1
- 235000008632 Santalum album Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KEUKAQNPUBYCIC-UHFFFAOYSA-N ethaneperoxoic acid;hydrogen peroxide Chemical compound OO.CC(=O)OO KEUKAQNPUBYCIC-UHFFFAOYSA-N 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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 (10)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031139248A CN1176082C (en) | 2003-03-17 | 2003-03-17 | Epoxidizing method of alpha-pinene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031139248A CN1176082C (en) | 2003-03-17 | 2003-03-17 | Epoxidizing method of alpha-pinene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1438222A true CN1438222A (en) | 2003-08-27 |
| CN1176082C CN1176082C (en) | 2004-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031139248A Expired - Fee Related CN1176082C (en) | 2003-03-17 | 2003-03-17 | Epoxidizing method of alpha-pinene |
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| Country | Link |
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| CN (1) | CN1176082C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973838A (en) * | 2010-10-28 | 2011-02-16 | 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 |
| CN103626821A (en) * | 2013-11-07 | 2014-03-12 | 浙江大学 | Synthetic method of 25-hydroxycholesterol |
| EP2518061A4 (en) * | 2009-12-24 | 2014-04-02 | Showa Denko Kk | PROCESS FOR PRODUCING EPOXY COMPOUND |
| CN106588819A (en) * | 2016-11-02 | 2017-04-26 | 昆明理工大学 | High-selectivity epoxy pinane preparation method |
| CN107570208A (en) * | 2017-08-31 | 2018-01-12 | 昆明理工大学 | A kind of preparation method and application of epoxidation catalysts |
-
2003
- 2003-03-17 CN CNB031139248A patent/CN1176082C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2518061A4 (en) * | 2009-12-24 | 2014-04-02 | Showa Denko Kk | PROCESS FOR PRODUCING EPOXY COMPOUND |
| US8993791B2 (en) | 2009-12-24 | 2015-03-31 | Showa Denko K.K. | Process for producing epoxy compounds |
| CN101973838A (en) * | 2010-10-28 | 2011-02-16 | 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 |
| 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 |
| CN103626821A (en) * | 2013-11-07 | 2014-03-12 | 浙江大学 | Synthetic method of 25-hydroxycholesterol |
| CN106588819A (en) * | 2016-11-02 | 2017-04-26 | 昆明理工大学 | High-selectivity epoxy pinane preparation method |
| CN106588819B (en) * | 2016-11-02 | 2018-10-23 | 昆明理工大学 | A kind of preparation method of highly selective epoxypinane |
| CN107570208A (en) * | 2017-08-31 | 2018-01-12 | 昆明理工大学 | A kind of preparation method and application of epoxidation catalysts |
| CN107570208B (en) * | 2017-08-31 | 2020-08-25 | 昆明理工大学 | Preparation method and application of epoxidation reaction catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1176082C (en) | 2004-11-17 |
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