EP0100822B1 - Verfahren zur Herstellung von Cyclopentadec-4-Inone und seines Homologes 3-Methyl - Google Patents
Verfahren zur Herstellung von Cyclopentadec-4-Inone und seines Homologes 3-Methyl Download PDFInfo
- Publication number
- EP0100822B1 EP0100822B1 EP83104893A EP83104893A EP0100822B1 EP 0100822 B1 EP0100822 B1 EP 0100822B1 EP 83104893 A EP83104893 A EP 83104893A EP 83104893 A EP83104893 A EP 83104893A EP 0100822 B1 EP0100822 B1 EP 0100822B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- effected
- formula
- process according
- radical
- 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
Links
- 0 C*(CC[N+](CN)[O-])CN Chemical compound C*(CC[N+](CN)[O-])CN 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Definitions
- Acetylenic ketone compounds of formula in which the symbol R is used to denote a hydrogen atom or a methyl radical, are used as starting materials for the preparation of muscone and Exaltone @ , two of the macrocyclic compounds with musky odor particularly prized in perfume industry.
- the present invention provides a new method for obtaining said compounds, which method is based on an anodic oxidation reaction of a hydrazone of formula in which R is used to define a hydrogen atom or a methyl radical and A represents a hydrogen atom or a sulfonyl radical of formula R 1 -S ° 2- ' in which R 1 represents an aryl radical, substituted or unsubstituted.
- R 1 can represent in particular a phenyl or o-, m- and p-tolyl radical.
- the method of the invention characterized by a simple operating mode, offers several advantages over known methods. It turned out that the course of the reaction is easily controllable, the yields observed are excellent and the operation is perfectly reproducible, even under variable conditions of temperature, current density or concentration of the reactants. It follows that its application to preparations on an industrial scale is greatly facilitated.
- the electrolysis is carried out in a bath comprising, in addition to the starting hydrazone, an aliphatic alcohol, preferably lower, or an araliphatic alcohol and an inert organic solvent chosen from aliphatic or aromatic nitriles and ethers.
- lower aliphatic alcohol it is possible, for example, to use methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, tert-butanol or also a glycol.
- the presence of alcohol is a critical parameter.
- araliphatic alcohol phenylethyl alcohol is preferably used.
- solvent is of course a function of the solubility of the compound subjected to electrolysis. Good results have been obtained by carrying out the anodic oxidation in the presence of a mixture consisting of an alcohol, an ether, such as tetrahydrofuran, and a nitrile, preferably acetonitrile. The proportions of these different solvents are about 1: 2: 2, respectively.
- a compound selected from salts such as perchlorate, tetrafluoroborate, p-toluenesulfonate or tetralkylammonium hexafluorophosphate is used.
- salts such as perchlorate, tetrafluoroborate, p-toluenesulfonate or tetralkylammonium hexafluorophosphate
- tetramethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate and tetrabutylammonium perchlorate are used.
- Other salts the use of which is common in electrochemistry, can also be used, the selection criteria being their stability and their solubility in the reaction medium.
- the concentration of the support electrolyte in the electrolytic solution can vary within a fairly wide range, preferably it is however of the order of about 0.1 molar.
- concentration of the starting material in the electrolytic solution is not particularly critical. Too low concentrations have been shown to be uneconomical, while with too high concentrations, the formation of side products, for example polymers, has been observed. Preferred concentrations are between about 1 and 5% by weight.
- the electrodes which can be used in the process of the invention, they can consist of graphite plates or platinum sheets as regards the anode and platinum sheets or plates of titanium, stainless steel, Monel @ (nickel and copper alloy), nickel for the cathode. Their nature is not critical, just like their form.
- the current densities used were of the order of 3 to 40 mAlcm 2 .
- the reaction temperature can be between 10 and 60 ° C, without however being limited to these absolute values.
- the process according to the invention can be carried out in the presence of air, but preferably under an atmosphere of an inert gas, nitrogen or argon for example.
- the process can be carried out in a single-tank electrolyser or a separate-tank electrolyser, although the latter method does not provide any particular advantages.
- the process of the invention can very well lend itself to continuous implementation.
- the solution is stirred magnetically at room temperature for the duration of the electrolysis at a current density of 7 mA / cm 2 and a voltage across the cell of 2.7-3.2 V. After passing 4 F / mole, the current is cut and the mixture is concentrated by evaporation of the solvents. The residue is then treated with 30 ml of ethyl ether and the insoluble tetrabutylammonium perchlorate is recovered practically quantitatively by filtration. The filtrate is again concentrated and the yellowish residue is distilled under a pressure of 13.3 Pa.
- a mixture consisting mainly of 2 isomers is obtained, namely muscynone and methylbicyclenone of formula and respectively, in the ratio 56: 44, and which can be separated by chromatography on a column of silica (hexane / diethyl ether).
- the theoretical yield of the isolated products is 80%.
- the reaction was carried out with electrodes constituted by a graphite plate (anode) and a platinum plate (cathode) whose dimensions were 20 x 20 x 2 mm and 20 x 20 x 0.1 mm respectively.
- reaction was also carried out by replacing tetrabutylammonium perchlorate by tetrafluoroborate and by tetraethylammonium hexachlorophosphate without a noticeable change in yield being perceptible.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH407882 | 1982-07-05 | ||
CH4078/82 | 1982-07-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0100822A1 EP0100822A1 (de) | 1984-02-22 |
EP0100822B1 true EP0100822B1 (de) | 1986-03-05 |
Family
ID=4269412
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83104893A Expired EP0100822B1 (de) | 1982-07-05 | 1983-05-18 | Verfahren zur Herstellung von Cyclopentadec-4-Inone und seines Homologes 3-Methyl |
Country Status (4)
Country | Link |
---|---|
US (1) | US4448650A (de) |
EP (1) | EP0100822B1 (de) |
JP (1) | JPS5937349B2 (de) |
DE (1) | DE3362401D1 (de) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4277318A (en) * | 1980-04-15 | 1981-07-07 | Union Carbide Corporation | Electrochemical benzylic oxidations |
-
1983
- 1983-05-18 DE DE8383104893T patent/DE3362401D1/de not_active Expired
- 1983-05-18 EP EP83104893A patent/EP0100822B1/de not_active Expired
- 1983-05-25 US US06/498,050 patent/US4448650A/en not_active Expired - Fee Related
- 1983-06-21 JP JP58110281A patent/JPS5937349B2/ja not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE3362401D1 (en) | 1986-04-10 |
EP0100822A1 (de) | 1984-02-22 |
JPS599183A (ja) | 1984-01-18 |
JPS5937349B2 (ja) | 1984-09-08 |
US4448650A (en) | 1984-05-15 |
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