WO1999012880A9 - Process for the preparation of carvone - Google Patents
Process for the preparation of carvoneInfo
- Publication number
- WO1999012880A9 WO1999012880A9 PCT/NL1998/000505 NL9800505W WO9912880A9 WO 1999012880 A9 WO1999012880 A9 WO 1999012880A9 NL 9800505 W NL9800505 W NL 9800505W WO 9912880 A9 WO9912880 A9 WO 9912880A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- carvone
- acid
- oxidation
- salt
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
Definitions
- the invention relates to a process for the preparation of carvone by catalytic oxidation of limonene with a palladiun (II) salt and a re-oxidising agent.
- D-Carvone (2-methyl-5-isopro ⁇ enyl-2-cyclohexenone) can be used as an anti- sprouting agent for potatoes and as a fungicide. It is a natural substance which occurs in dill and caraway seeds. However, these natural sources are inadequate for economically justifiable production of carvone.
- D-limonene (l-methyl-4-isopropenyl-cyclohexene) is available in larger quantities from natural sources and can be oxidised by a biochemical or chemical route to produce carvone.
- the known methods for the oxidation of olefins such as limonene to give the corresponding ⁇ , ⁇ -unsaturated ketones give a low yield of ketone, which, moreover, is impure.
- Wacker oxidation products such as, for example, 2,3-dihydrocarvone or p-menth-l-en-9-one (8,9-dihydrolimonene-9-aldehyde), are not formed at all.
- the selectivity for carvone formation is higher than
- the starting concentration of limonene used in the oxidation reaction can be 0.1-2 mol/1.
- the oxygen to be used can be present in the form of air, an adequate concentration of oxygen in the reaction mixture being ensured by stirring, shaking or blowing in.
- enriched oxygen or even pure oxygen is used, preferably under a pressure of 0.5-10 bar.
- the presence of water is also important according to the invention.
- the quantity of water in the reaction mixture is in general 0.01-50 % V/V, preferably 2-40 and in particular 4-20 % V/V.
- the primary oxidation takes place with palladium or a divalent salt thereof.
- Suitable palladium salts are, for example, the chloride, acetate or other carboxylate, haloacetate or other halocarboxylate, sulphate, nitrate, tetraborate, acetylacetonate or other beta-dike tonate. Only a catalytic amount of the palladium is needed, i.e. in general 0.001-0.2 equivalent with respect to the olefin to be oxidised, in particular 0.01-0.1 equivalent.
- the oxidation can be carried out at room temperature or elevated temperature, preferably at 25-120 °C, in particular at 40-80 °C.
- the palladium or salt thereof used is oxidised in situ by a re-oxidising agent.
- Suitable re-oxidising agents are, for example, salts and oxides of copper, iron(III), manganese(IV), lead(IV), tantalum(III) and other transition metals. It is also possible to use other re-oxidising agents that are known as such, including heteropolyacids and corresponding anions, such as phosphomolybdovanadic, phosphotungstomolybdic and phosphotungstovanadic acids and organic oxidising agents such as unsubstituted or substituted quinones and benzoquinones. A less than equivalent amount of the reoxidising agent as well can suffice. In general, 0.005-2.0 equivalent based on the olefin, and in particular 0.2-0.6 equivalent, is used. Copper salts such as copper(I) chloride and copper(II) chloride, especially copper(II) salts, are preferred.
- the organic solvent is in general a polar solvent that is able to withstand the oxidation conditions.
- Suitable solvents are, in particular, liquid carboxylic acids, such as formic acid, acetic acid, chloroacetic acid, propionic acid, butyric acid and isobutyric acid.
- liquid carboxylic acids such as formic acid, acetic acid, chloroacetic acid, propionic acid, butyric acid and isobutyric acid.
- up to 75 % V V but preferably no more than 50 % V/V, other polar or apolar solvents may be present.
- Examples of these are water, aromatic compounds (benzene, toluene, xylene), esters (ethyl acetate, butyl acetate), ethers (THF, dioxane, dimethoxyethane), acetonitrile, DMSO and amides (DMF, DMA, NMP) and mixtures thereof.
- Acetic acid and propionic acid are most preferred. It has been found that the yield of the oxidation can be further increased if a strong acid is incorporated in the reaction medium.
- Examples are phosphoric acid, sulphuric acid, hydrochloric acid, unsubstituted or substituted alkanesulphonic and arenesulphonic acids (for example trifluoromethanesulphonic acid or p-toluenesulphonic acid) and in particular ⁇ -halo- alkanoic acids, such as dichloro-, trichloro- and trifluoro-acetic acid and dichloro- propionic acid. Trichloroacetic acid and in particular trifluoroacetic acid are most preferred.
- the quantity to be used is preferably 0.01-20 % V/V based on the total solvent, in particular 0.1-2 % V/V.
- the pH is preferably below 3 and preferentially between 1 and 2.
- the salt of a non-transition metal used can be, for example, a salt of an alkali metal, alkaline earth metal or rare earth metal, and preferably a hydroxide or a salt of a carboxylic acid, in particular an alkali metal hydroxide, acetate or propionate.
- the reagents, such as the re-oxidising agent (copper salt) or the non-transition metal salt can be added beforehand or can be added gradually during the oxidation.
- the limonene conversion was 99.5 % and the selectivity for carvone was 61 %.
- Carveol and carveyl acetate were formed as by-products. It was found that no significant oxidation of carveol to carvone takes place under the reaction conditions (see also comparative example D).
- Example 1 was repeated except that no trifluoroacetic acid was added.
- the limonene conversion was 98.5 %.
- the selectivity for carvone was 44 %.
- Example 1 was repeated except that propionic acid was used instead of acetic acid.
- the limonene conversion was 98.5 % and the selectivity for carvone was 68 %.
- Example 4 Example 1 was repeated except that the reaction was carried out under 1.1 bar air instead of oxygen.
- the limonene conversion was 99 % and the selectivity for carvone was 38 %.
- Example 1 was repeated except that no palladium(II) chloride was added.
- the limonene conversion was 18 %.
- the selectivity for carvone was less than 1 %.
- Example 1 was repeated except that no water was added.
- the limonene conversion was 99 % and the selectivity for carvone was 6 %.
- Example 1 Comparative Example D Example 1 was repeated except that carveol was used instead of limonene.
- the carvone yield was 5 %.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU90075/98A AU9007598A (en) | 1997-09-05 | 1998-09-04 | Process for the preparation of carvone |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1006959A NL1006959C2 (en) | 1997-09-05 | 1997-09-05 | Process for the preparation of carvone. |
NL1006959 | 1997-09-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1999012880A1 WO1999012880A1 (en) | 1999-03-18 |
WO1999012880A9 true WO1999012880A9 (en) | 2002-11-21 |
Family
ID=19765625
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1998/000505 WO1999012880A1 (en) | 1997-09-05 | 1998-09-04 | Process for the preparation of carvone |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU9007598A (en) |
NL (1) | NL1006959C2 (en) |
WO (1) | WO1999012880A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009040285A1 (en) * | 2007-09-21 | 2009-04-02 | Basf Se | Method for dehydrogenating cyclical terpene derivatives having exocyclic double bonds |
US8586794B2 (en) | 2008-07-25 | 2013-11-19 | Basf Se | 5-isopropyl-3-aminomethyl-2-methyl-1-amino-cyclohexane (carvone diamine), and method for the production thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50149648A (en) * | 1974-05-20 | 1975-11-29 |
-
1997
- 1997-09-05 NL NL1006959A patent/NL1006959C2/en not_active IP Right Cessation
-
1998
- 1998-09-04 AU AU90075/98A patent/AU9007598A/en not_active Abandoned
- 1998-09-04 WO PCT/NL1998/000505 patent/WO1999012880A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
WO1999012880A1 (en) | 1999-03-18 |
NL1006959C2 (en) | 1999-03-08 |
AU9007598A (en) | 1999-03-29 |
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