CN101985415B - Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature - Google Patents
Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature Download PDFInfo
- Publication number
- CN101985415B CN101985415B CN 201010539291 CN201010539291A CN101985415B CN 101985415 B CN101985415 B CN 101985415B CN 201010539291 CN201010539291 CN 201010539291 CN 201010539291 A CN201010539291 A CN 201010539291A CN 101985415 B CN101985415 B CN 101985415B
- Authority
- CN
- China
- Prior art keywords
- promotor
- verbenone
- verbenol
- catalyzer
- firpene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of verbenol and verbenone through the air oxidation of a-pinene at room temperature, belonging to the technical field of the preparation of the verbenol and the verbenone. In the method disclosed by the invention, a catalyst, a co-catalyst 1 and a co-catalyst 2 are added in the a-pinene as a raw material to prepare the verbenol and the verbenone through the catalytic oxidation at the room temperature in the presence of the air. The preparation method of the verbenol and the verbenone has moderate reaction condition and short reaction time and is simple to operate, catalysts are cheap and available, and the prepared verbenol and verbenone are high in yield and have the characteristic of higher industrial production value.
Description
Technical field
Atmospheric oxidation under a kind of normal temperature
A-Firpene prepares the method for verbenol and verbenone, belongs to verbenol and verbenone preparing technical field.
Background technology
Verbenol (4,6,6-trimethylammonium dicyclo [3.1.1]-3-heptene-2-alcohol), verbenone (4,6,6-trimethylammonium dicyclo [3.1.1]-3-hepten-2-one) are the containing oxygen derivatives of monoterpene, and important application is arranged in the middle of organic synthesis and chemical industry.Verbenol and verbenone have vervain sample fragrance, can be used for foodstuff additive, makeup, essence and flavoring agent aspect.Verbenol and verbenone are the natural constituents of plant, also are the pheromone of insect simultaneously.It has important effect aspect dried insect of post---pine is little stupid---of control serious harm Pinus seeds.The method of chemosynthesis verbenol and verbenone is not a lot of at present, and productive rate is not high.For example:
(1) use cobalt chloride to make catalyzer, Journal of Molecular Catalysis A:Chemical 201 (2003) 71 – 77, the productive rate of verbenol is about 10%, and the productive rate of verbenone is about 10%, and the shortcoming productive rate is too low.
(2) use and to contain cobalt complex and make catalyzer, Journal of Molecular Catalysis A:Chemical 198 (2003) 223 – 229, the shortcoming productive rate is low, and the productive rate of verbenol and verbenone is less than 20%, need to use dioxygen oxidation, the reaction times is about 7h.
(3) use silicon-dioxide and titanium dioxide associating catalysis, Catalysis Letters 67 (2000) 203 – 206, the shortcoming productive rate is low, and the verbenol productive rate is less than 12%, and the verbenone productive rate is less than 20%.
(4) use iron nitrate to make catalyzer, Green Chemistry, 2002,4,495 – 497, the verbenone productive rate is about 24%, and the flaw response condition is harsh, oxygen pressure 3.4bar, nitrogen pressure 10.3bar.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method that verbenol and the verbenone of higher industrial using value are arranged.
Technical scheme of the present invention: a kind of
A-Firpene prepares the method for verbenol and verbenone, adopts the normal temperature air oxidation, will in reaction vessel
A-Firpene is dissolved in the organic solvent, adds successively catalyzer, promotor 1 and promotor 2, molar ratio
A-Firpene: catalyzer: promotor 1: promotor 2 is 10:0.5-3:0.5-3:10-40, magnetic agitation, control temperature of reaction and time, temperature of reaction is 15-60 ℃, reacts 0.5-4 hour, and reaction finishes, remove catalyzer, promotor 1 and promotor 2, use anhydrous sodium sulfate drying, decompression steams solvent, obtains verbenol and verbenone;
Reaction formula is:
Described organic solvent is selected acetonitrile, methylene dichloride, dioxane or acetic acid;
Described catalyzer is selected a kind of in ferrous chloride, iron trichloride, tindichloride, cuprous chloride or the dichloride copper;
Described promotor 1 selects 2,2 '-dipyridyl, 1, a kind of in 10-phenanthroline, Tetramethyl Ethylene Diamine or the quadrol;
Described promotor 2 is selected a kind of in potassium hydrogen peroxymonosulfate, Peracetic Acid, tertbutyl peroxide, sodium carbonate peroxide or the hydrogen peroxide.
The authentication method of verbenol and verbenone adopts nucleus magnetic resonance.
Beneficial effect of the present invention: it is gentle that the present invention prepares the method reaction conditions of verbenol and verbenone, the reaction times weak point, and simple to operate, catalyzer cheaply is easy to get, and productive rate is high, has higher suitability for industrialized production to be worth.
Embodiment
Embodiment 1:
With 0.994g(7.3mmol)
A-Firpene joins in the 10 mL acetonitrile solvents, adds 0.185g(1.46mmol) the catalyzer ferrous chloride, add 0.263g(1.46mmol) 1, the 10-phenanthroline adds the 22mmol hydrogen peroxide again, 15 ℃ of lower stirrings, stopped reaction behind the 2h.Centrifugal or remove by filter catalyzer, use anhydrous sodium sulfate drying, rotary evaporation is removed acetonitrile and hydrogen peroxide.Take sherwood oil: the ethyl acetate volume ratio as the mixed solvent of 5:1 as eluent, remove promotor 1(1 through column chromatography, the 10-phenanthroline) and by product, obtain 0.078g verbenol (productive rate is 7%), 0.941g verbenone (productive rate is 85.9%).
Verbenol: CDCl
3,
δ(ppm); NMR
1H:0.85 (3H, s, CH
3, 8-H); 1.31 (3H, s, CH
3, 10-H); 1.71 (t,
J=1.59 Hz, CH
3, 9-H); (2.00 m, 1H, 4-H); (2.17 m, 1H, 5-H); (2.26 m, 1H, 6-H); (4.43 m, 1H, 1-H); (5.32 m, 1H, 2-H).
Verbenone: CDCl
3,
δ(ppm); NMR
1H:0.98 (3H, s, CH
3, 8-H); 1.47 (3H, s, CH
3, 10-H); 1.98 (d,
J=1.65 Hz, CH
3, 9-H); 2.39 (td, 1H,
J 1=6.36 Hz,
J 2=1.59 Hz, 4-H); 2.63 (td, 1H,
J 1=6.67 Hz,
J 2=1.27 Hz, 6-H); 2.78 (dt, 1H,
J 1=8.9 Hz,
J 2=5.4 Hz, 5-H); (5.70 m, 1H, 2-CH).
Embodiment 2:
With 0.994g(7.3mmol)
A-Firpene joins in the 10 mL dichloromethane solvents, adds 0.277g(1.46mmol) tindichloride, add 0.263g(1.46mmol) 1, the 10-phenanthroline adds the 29.2mmol Peracetic Acid again, 25 ℃ of lower stirrings, stopped reaction behind the 3h.Centrifugal or remove by filter catalyzer, use anhydrous sodium sulfate drying, rotary evaporation is removed methylene dichloride and Peracetic Acid.Take sherwood oil: the ethyl acetate volume ratio as the mixed solvent of 5:1 as eluent, remove promotor 1(1 through column chromatography, the 10-phenanthroline) and by product, obtain 0.973g verbenol (productive rate is 87.6%), 0.035g verbenone (productive rate is 3.2%).
Embodiment 3:
With 0.994g(7.3mmol)
A-Firpene joins in the 10mL acetic acid solvent, adds 0.098 g(0.73mmol) dichloride copper, add 0.114g(0.73mmol) 2,2 '-dipyridyl adds the 14.6mmol tertbutyl peroxide again, 40 ℃ of lower stirrings, stopped reaction behind the 1h.Centrifugal and remove by filter catalyzer, use anhydrous sodium sulfate drying, rotary evaporation is removed acetic acid and tertbutyl peroxide.Take sherwood oil: the ethyl acetate volume ratio as the mixed solvent of 5:1 as eluent, remove 2 through column chromatography, 2 '-dipyridyl and by product separate obtaining 0.087g verbenol (productive rate is 7.8%), 0.902g verbenone (productive rate is 82.3%).
Embodiment 4:
With 0.994 g(7.3mmol)
A-Firpene joins in the 10mL acetonitrile solvent, adds 1.184g(0.73mmol) cuprous chloride, add 0.085 g(0.73mmol) Tetramethyl Ethylene Diamine, add again the 22mmol tertbutyl peroxide, 30 ℃ of lower stirrings, stopped reaction behind the 1h.Centrifugal and remove by filter catalyzer, use anhydrous sodium sulfate drying, rotary evaporation is removed Tetramethyl Ethylene Diamine, acetonitrile and tertbutyl peroxide.Take sherwood oil: the mixed solvent of ethyl acetate volume ratio 5:1 obtains 0.047g verbenol (productive rate is 4.2%) as eluent through column chromatography for separation, 0.968g verbenone (productive rate is 88.3%).
Embodiment 5:
With 0.994 g(7.3mmol)
A-Firpene joins in the 10mL dichloromethane solvent, adds 0.355g(2.19mmol) iron trichloride, add 0.342 g(2.19mmol) 2,2 '-dipyridyl adds the 7.3mmol potassium hydrogen peroxymonosulfate again, 45 ℃ of lower stirrings, stopped reaction behind the 0.5h.Centrifugal and remove by filter catalyzer and potassium hydrogen peroxymonosulfate, use anhydrous sodium sulfate drying, rotary evaporation is removed methylene dichloride.Take sherwood oil: the ethyl acetate volume ratio as the mixed solvent of 5:1 as eluent, remove 2 through column chromatography, 2 '-dipyridyl and by product obtain 0. 100g verbenol (productive rate is 9%), 0.881g verbenone (productive rate is 80.4%).
Claims (1)
1. one kind
A-Firpene prepares the method for verbenol and verbenone, it is characterized in that adopting the normal temperature air oxidation, will in reaction vessel
A-Firpene is dissolved in the organic solvent, adds successively catalyzer, promotor 1 and promotor 2, molar ratio
A-Firpene: catalyzer: promotor 1: promotor 2 is 10:0.5-3:0.5-3:10-40, magnetic agitation, control temperature of reaction and time, temperature of reaction is 15-60 ℃, reacts 0.5-4 hour, and reaction finishes, remove catalyzer, promotor 1 and promotor 2, use anhydrous sodium sulfate drying, decompression steams solvent, obtains verbenol and verbenone;
Described organic solvent is selected a kind of in acetonitrile, methylene dichloride, Isosorbide-5-Nitrae-dioxane or the acetic acid;
Described catalyzer is selected a kind of in ferrous chloride, iron trichloride, tindichloride, cuprous chloride or the dichloride copper;
Described promotor 1 selects 2,2 '-dipyridyl, 1, a kind of in 10-phenanthroline, Tetramethyl Ethylene Diamine or the quadrol;
Described promotor 2 is selected a kind of in potassium hydrogen peroxymonosulfate, Peracetic Acid, sodium carbonate peroxide or the hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010539291 CN101985415B (en) | 2010-11-11 | 2010-11-11 | Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010539291 CN101985415B (en) | 2010-11-11 | 2010-11-11 | Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101985415A CN101985415A (en) | 2011-03-16 |
| CN101985415B true CN101985415B (en) | 2013-01-02 |
Family
ID=43709817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010539291 Expired - Fee Related CN101985415B (en) | 2010-11-11 | 2010-11-11 | Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101985415B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788336B (en) * | 2014-04-10 | 2016-11-30 | 申俊 | The synthetic method of imide analog compounds |
| CN104725266B (en) * | 2014-04-10 | 2016-08-10 | 申俊 | The synthetic method of imide analog compounds |
| CN104725267B (en) * | 2014-04-10 | 2016-08-24 | 申俊 | The synthetic method of imide analog compounds |
| CN105566061A (en) * | 2016-01-12 | 2016-05-11 | 中国林业科学研究院林产化学工业研究所 | Beta-pinene selective hydroxylation oxidation method and product thereof |
| CN110156566B (en) * | 2019-06-18 | 2021-11-19 | 中国林业科学研究院森林生态环境与保护研究所 | Green and simple preparation method for synthesizing (-) -trans-verbenol and enantiomer (+) -trans-verbenol thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821195A (en) * | 2006-03-24 | 2006-08-23 | 云南大学 | Method for synthesizing verbenol and verbenone with alpha-pinene |
-
2010
- 2010-11-11 CN CN 201010539291 patent/CN101985415B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821195A (en) * | 2006-03-24 | 2006-08-23 | 云南大学 | Method for synthesizing verbenol and verbenone with alpha-pinene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101985415A (en) | 2011-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101985415B (en) | Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature | |
| Suggs et al. | Synthesis of a chiral rhodium alkyl via metal insertion into an unstrained CC bond and use of the rate of racemization at carbon to obtain rhodium-carbon bond dissociation energy | |
| Xiong et al. | Palladium-catalyzed allylic C–H amination of alkenes with N-fluorodibenzenesulfonimide: water plays an important role | |
| Romanowski et al. | Oxidovanadium (V) complexes with chiral tridentate Schiff bases derived from R (−)-phenylglycinol: Synthesis, spectroscopic characterization and catalytic activity in the oxidation of sulfides and styrene | |
| Alcaide et al. | Metal‐Catalyzed Cycloetherification Reactions of β, γ‐and γ, δ‐Allendiols: Chemo‐, Regio‐, and Stereocontrol in the Synthesis of Oxacycles | |
| CN101786948A (en) | Method for preparing 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone | |
| Rubtsov et al. | Recent Advances in the Synthesis of 2, 2′-Bipyridines and Their Derivatives | |
| Toubi et al. | Synthesis, characterization and catecholase activity of copper (II) complexes with bispyrazole tri-podal ligands | |
| Rezaeifard et al. | Cytochrome P-450 model reactions: Efficient and highly selective oxidation of alcohols with tetrabutylammonium peroxymonosulfate catalyzed by Mn-porphyrins | |
| CN106946823B (en) | Method for asymmetric synthesis of (R) -natural jasminolide | |
| CN102241624B (en) | Preparation method of pyridine-2-formaldehyde | |
| CN105037189B (en) | A kind of method that 1,8 Meng's alkane diacetayl amides are prepared by turpentine oil | |
| CN108047185A (en) | A kind of benzodihydropyrone analog derivative and preparation method thereof | |
| CN102617453A (en) | Method for preparing pyridine-4-formaldehyde | |
| CN108503548B (en) | Pyruvic acid menthyl ester cooling agent and preparation method thereof | |
| CN102206146B (en) | Preparation method of vanillin | |
| CN107353288B (en) | 4- ethamine (2- carboxyl) -9H- pyrimido [4,5-b] indoles and preparation method thereof | |
| CN107973768A (en) | The method of one-step synthesis coumarin kind compound | |
| CN102584760B (en) | Enantiomorphous-kaurene diterpene and derivative and preparation method thereof | |
| CN105418691A (en) | Method for preparing bis-ferrocenyl pyridine derivative in supercritical carbon dioxide | |
| Borah et al. | New vanadium mediated one-pot in situ (L)-histidine based ligand cyclization and aerobic dehydrogenative aromatization | |
| Wei et al. | Synthesis, oxygenation and catalytic epoxidation performance of Salen and Salophen transition-metal complexes with aza-crown or morpholino pendants | |
| Nadali et al. | Efficient reductive Claisen rearrangement of prop-2'-enyloxyanthraquinones and 2'-chloroprop-2'-enyloxyanthraquinones with iron powder in ionic liquids | |
| Basu et al. | Ruthenium‐Promoted Ring‐Closing Metathesis of Ene‐Dienes. Competitive Intramolecular Regioselection as a Function of Chain Length | |
| CN112138663B (en) | Catalyst for preparing chloropyridine, preparation method thereof and method for preparing chloropyridine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130102 Termination date: 20131111 |