EP0100822A1 - Process for producing cyclopentadec-4-ynone and its homologous 3-methyl - Google Patents

Process for producing cyclopentadec-4-ynone and its homologous 3-methyl Download PDF

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EP0100822A1
EP0100822A1 EP83104893A EP83104893A EP0100822A1 EP 0100822 A1 EP0100822 A1 EP 0100822A1 EP 83104893 A EP83104893 A EP 83104893A EP 83104893 A EP83104893 A EP 83104893A EP 0100822 A1 EP0100822 A1 EP 0100822A1
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Prior art keywords
formula
reaction
carried out
radical
hydrogen atom
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EP0100822B1 (en
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François Dr. Delay
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Firmenich SA
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    • 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 wherein 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 Facaltone ®, both of macrocyclic compounds musky smell particularly popular in the 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 SO 2 -, in which R represents an aryl radical, substituted or unsubstituted.
  • R 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 the group consisting of aliphatic or aromatic nitriles and ethers.
  • the lower aliphatic alcohol it is possible, for example, to use methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, tert-butanol or alternatively a glycol.
  • the presence of alcohol is a critical parameter.
  • 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 the group formed by the salts such as perchlorate, tetrafluoroborate, p-toluenesulfonate or tetralkylammonium hexafluorophosphate is used.
  • the salts such as perchlorate, tetrafluoroborate, p-toluenesulfonate or tetralkylammonium hexafluorophosphate.
  • tetramethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate and tetrabutylammonium perchlorate are used.
  • Other salts, including use 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 mA / cm 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.
  • a mixture consisting mainly of 2 isomers is obtained, namely muscynone and methylbicyclenone of formula respectively, in the ratio 56: 44, and which can be separated by chromatography on a silica column (hexahe / 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 20x20x2 mm and 20x20x0.1 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.

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  • Organic Chemistry (AREA)
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Abstract

La cétone acétylénique de formule <IMAGE> dans laquelle le symbole R sert à désigner un atome d'hydrogène ou un radical méthyle, est préparée par une réaction d'oxydation anodique d'une hydrazone de formule <IMAGE> dans laquelle le symbole R a le sens défini ci-dessus et A représente un atome d'hydrogène ou un radical sulfonyle de formule R¹-SO2-, dans laquelle R¹ représente un radical aryle, substitué ou non. Les composés de formule (I) sont des composés intermédiaires utiles à la préparation d'Exaltone® et muscone, deux ingrédients musques employés dans l'industrie de la parfumerie.The acetylene ketone of formula <IMAGE> in which the symbol R is used to denote a hydrogen atom or a methyl radical, is prepared by an anodic oxidation reaction of a hydrazone of formula <IMAGE> in which the symbol R a the meaning defined above and A represents a hydrogen atom or a sulfonyl radical of formula R¹-SO2-, in which R¹ represents an aryl radical, substituted or not. The compounds of formula (I) are intermediate compounds useful in the preparation of Exaltone® and muscone, two musk ingredients used in the perfume industry.

Description

Les composés cétoniques acétyléniques de formule

Figure imgb0001
dans laquelle le symbole R sert à désigner un atome d'hydrogène ou un radical méthyle, sont utilisés à titre de produits de départ pour la préparation de muscone et d'Facaltone®, deux parmi les composés macrocycliques à odeur musquée particulièrement prisés dans l'industrie de la parfumerie.Acetylenic ketone compounds of formula
Figure imgb0001
 wherein 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 Facaltone ®, both of macrocyclic compounds musky smell particularly popular in the perfume industry.

La demande de brevet européen no. 13995, publiée le 6.8.80, décrit un procédé pour leur préparation, lequel procédé est caractérisé en ce que a) on traite une hydrazone de formule

Figure imgb0002
dans laquelle R désigne un atome d'hydrogène ou un radical méthyle et le symbole A sert à désigner un radical sulfonyle de formule R1-SO2-, dans laquelle R représente un radical aryle, au moyen d'un réactif halogénant choisi parmi les composés suivants :

  • - brome
  • à chlore
  • - iode
  • -1,3-dibromo-5,5-diméthyl-hydantoine
  • - N-bromosuccinimide
  • - N-iodosuccinimide et
  • - N-chlorosuccinimide,

en présence d'un alcool aliphatique inférieur et à une température comprise entre environ -25 et +23°C;
  • b) on réduit l'excès de réactif halogénant et
  • c) on chauffe enfin le produit de réaction en milieu aqueux, à une température comprise entre 20 et 60°C.
European patent application no. 13995, published 6.8.80, describes a process for their preparation, which process is characterized in that a) a hydrazone of formula is treated
Figure imgb0002
 in which R denotes a hydrogen atom or a methyl radical and the symbol A is used to denote a sulfonyl radical of formula R 1 - SO 2 -, in which R represents an aryl radical, by means of a halogenating reagent chosen from following compounds:
  • - bromine
  • chlorine
  • - iodine
  • -1,3-dibromo-5,5-dimethyl-hydantoine
  • - N-bromosuccinimide
  • - N-iodosuccinimide and
  • - N-chlorosuccinimide,

in the presence of a lower aliphatic alcohol and at a temperature between about -25 and + 23 ° C;
  • b) reducing the excess of halogenating reagent and
  • c) finally heating the reaction product in an aqueous medium, to a temperature between 20 and 60 ° C.

L'art antérieur fait également état du procédé illustré par le schéma que voici :

Figure imgb0003
[référence: Helv. Chim. Acta, 50, 708 (1967)].The prior art also describes the process illustrated by the diagram below:
Figure imgb0003
 [reference: Helv. Chim. Acta, 50, 708 (1967)].

La présente invention propose une nouvelle méthode d'obtention desdits composés, laquelle méthode est basée sur une réaction d'oxydation anodique d'une hydrazone de formule

Figure imgb0004
dans laquelle R sert à définir un atome d'hydrogène ou un radical méthyle et A représente un atome d'hydrogène ou un radical sulfonyle de formule R1-SO2-, dans laquelle R représente un radical aryle, substitué ou non. C'est ainsi que R peut représenter en particulier un radical phényle ou o-, m- et p-tolyle.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
Figure imgb0004
 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 SO 2 -, in which R represents an aryl radical, substituted or unsubstituted. Thus, R can represent in particular a phenyl or o-, m- and p-tolyl radical.

L'invention est définie comme indiqué dans les revendications.The invention is defined as indicated in the claims.

Le procédé de l'invention, caractérisé par un mode opératoire simple, offre plusieurs avantages par rapport aux procédés connus. Il s'est révélé que le déroulement de la réaction est facilement contrôlable, les rendements observés sont excellents et l'opération est parfaitement reproductible, même dans des conditions variables de température, densité de courant ou concentration des réactifs. Il s'en suit que son application à des préparations à l'échelle industrielle s'en trouve grandement facilitée.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.

L'oxydation anodique qui caractérise le procédé de la présente invention s'effectue en présence d'un électrolyte support et d'un solvant constitué par un alcool et un cosolvant et elle conduit essentiellement à la formation d'une quantité prépondérante de la cétone acétylénique désirée accompagnée de la cétone bicyclique correspondante de formuleThe anodic oxidation which characterizes the process of the present invention is carried out in the presence of a support electrolyte and of a solvent constituted by an alcohol and a cosolvent and it essentially leads to the formation of a preponderant amount of the acetylene ketone desired accompanied by the corresponding bicyclic ketone of formula

Figure imgb0005
Figure imgb0005

L'électrolyse est effectuée dans un bain comprenant, outre l'hydrazone de départ, un alcool aliphatique, de préférence inférieur, ou un alcool araliphatique et un solvant organique inerte choisi dans le groupe constitué par les nitriles aliphatiques ou aromatiques et les éthers.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 the group consisting of aliphatic or aromatic nitriles and ethers.

Comme alcool aliphatique inférieur, on peut utiliser par exemple le méthanol, l'éthanol, le propanol, l'isopropanol, le butanol, le 2-butanol, le tert- butanol ou encore un glycol. La présence de l'alcool représente un paramètre critique. Comme alcool araliphatique, on utilise de préférence l'alcool phényléthy- lique.As the lower aliphatic alcohol, it is possible, for example, to use methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, tert-butanol or alternatively a glycol. The presence of alcohol is a critical parameter. As the araliphatic alcohol, phenylethyl alcohol is preferably used.

Le choix particulier du solvant est fonction bien entendu de la solubilité du composé soumis à électrolyse. Des bons résultats ont été obtenus en effectuant l'oxydation anodique en présence d'un mélange constitué par un alcool, un éther, tel le tétrahydrofuranne, et un nitrile, de préférence l'acétonitrile. Les proportions de ces différents solvants se situent à environ 1 : 2 : 2, respectivement.The particular choice of 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.

Comme électrolyte support, on utilise un composé sélectionné dans le groupe formé par les sels tels le perchlorate, le tétrafluoroborate, le p-toluènesulfonate ou l'hexafluorophosphate de tétralkylammonium. De préférence on utilise le tétrafluoroborate de tétraméthylammonium, le p-toluènesulfonate de tétraéthylammonium et le perchlorate de tétrabutylammonium. D'autres sels, dont l'utilisation est courante en électrochimie, peuvent également être employés, les critères de sélection étant leur stabilité et leur solubilité dans le milieu réactionnel.As support electrolyte, a compound selected from the group formed by the salts such as perchlorate, tetrafluoroborate, p-toluenesulfonate or tetralkylammonium hexafluorophosphate is used. Preferably, tetramethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate and tetrabutylammonium perchlorate are used. Other salts, including use is common in electrochemistry, can also be used, the selection criteria being their stability and their solubility in the reaction medium.

La concentration de l'électrolyte support dans la solution électrolytique peut varier dans une gamme assez large, de préférence elle est cependant de l'ordre d'environ 0,1 molaire.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.

La concentration du produit de départ dans la solution électrolytique n'est pas particulièrement critique. Des concentrations trop faibles se sont révélées ne pas être économiques, tandis qu'avec des concentrations trop élevées, on a pu observer la formation de produits secondaires, des polymères par exemple. Des concentrations préférentielles sont comprises entre environ 1 et 5% en poids.The 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.

Quant aux électrodes qui peuvent être utilisées dans le procédé de l'invention, elles peuvent consister en plaquettes de graphite ou en feuilles de platine pour ce qui est de l'anode et en feuilles de platine ou en plaquettes de titane, d'inox, de Monel@ (alliage de nickel et cuivre), de nickel pour ce qui est de la cathode. Leur nature ne revêt aucun caractère critique, tout comme d'ailleurs leur forme.As for 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.

- Les densités de courant utilisées étaient de l'ordre de 3 à 40 mA/cm2.- The current densities used were of the order of 3 to 40 mA / cm 2 .

La température de la réaction peut être comprise entre 10 et 60°C, sans pour autant être limitée à ces valeurs absolues.The reaction temperature can be between 10 and 60 ° C, without however being limited to these absolute values.

Le procédé selon l'invention peut être conduit en présence d'air, mais de préférence sous atmosphère d'un gaz inerte, l'azote ou l'argon par exemple.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.

Le procédé peut être conduit dans un électrolyseur à cuve unique ou à cuve séparée, quoique cette dernière façon d'opérer n'apporte pas d'avantages particuliers. Bien entendu, le procédé de l'invention peut fort bien se prêter à une mise en oeuvre continue.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. Of course, the process of the invention can very well lend itself to continuous implementation.

L'invention est illustrée de manière plus détaillée par l'exemple suivant dans lequel les températures sont indiquées en degrés centigrades et les abréviations ont le sens usuel dans l'art.The invention is illustrated in more detail by the following example in which the temperatures are indicated in degrees centigrade and the abbreviations have the usual meaning in the art.

ExempleExample

1 g (2,5 mmoles) de 14-méthyl-bicyclo[10.3.0]pentadéc-[1(12)]-ène-13-one p-toluènesulfonyl-hydrazone et 1,7 g (5 mmoles) de perchlorate de tétrabutylammonium sont dissous dans un mélange de tétrahydrofuranne (20 ml), d'acéto- nitrile (20 ml) et d'alcool méthylique (10 ml). La solution est placée dans un récipient cylindrique du type bécher de 100 ml muni d'un couvercle en téflon faisant office de support aux 2 électrodes distant de 1 cm, à un thermomètre ainsi qu'à une entrée et une sortie pour la circulation d'argon. La solution est agitée magné- tiquement à température ambiante pendant la durée de l'électrolyse à une densité de courant de 7 mA/cm2 et une tension aux bornes de la cellule de 2,7-3,2 V. Après le passage de 4 F/mole, le courant est coupé et le mélange est concentré par évaporation des solvants. Le résidu est alors traité avec 30 ml d'éther éthylique et le perchlorate de tétrabutylammonium insoluble est récupéré pratiquement quantitativement par filtration. Le filtrat est à nouveau concentré et le résidu jaunâtre est distillé sous une pression de 13,3 Pa. On obtient un mélange constitué principalement de 2 isomères, à savoir la muscynone et la méthylbicyclénone de formule

Figure imgb0006
respectivement, dans le rapport 56 : 44, et qui peuvent être séparés par chromatographie sur une colonne de silice (hexahe/éther diéthylique).1 g (2.5 mmol) of 14-methyl-bicyclo [10.3.0] pentadec- [1 (12)] - ene-13-one p-toluenesulfonyl-hydrazone and 1.7 g (5 mmol) of perchlorate tetrabutylammonium are dissolved in a mixture of tetrahydrofuran (20 ml), acetonitrile (20 ml) and methyl alcohol (10 ml). The solution is placed in a 100 ml beaker-type cylindrical container fitted with a Teflon cover serving as a support for the 2 electrodes 1 cm apart, a thermometer and an inlet and outlet for circulation of argon. 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 at the terminals of 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
Figure imgb0006
 respectively, in the ratio 56: 44, and which can be separated by chromatography on a silica column (hexahe / diethyl ether).

Le rendement théorique des produits isolés est de 80%. La réaction a été effectuée avec des électrodes constituées par une plaquette de graphite (anode) et une plaquette de platine (cathode) dont les dimensions étaient respectivement 20x20x2 mm et 20x20x0,1 mm.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 20x20x2 mm and 20x20x0.1 mm respectively.

Des résultats analogues ont été obtenus en utilisant comme électrodes, les combinaisons suivantes :

Figure imgb0007
Similar results have been obtained using the following combinations as electrodes:
Figure imgb0007

1) graphite1) graphite

La réaction a également été conduite en remplaçant le perchlorate de tétrabutylammonium par le tétrafluoroborate et par l'hexachlorophosphate de tétraéthylammonium sans qu'un changement notable de rendement soit perceptible.The reaction was also carried out by replacing tetrabutylammonium perchlorate by tetrafluoroborate and by tetraethylammonium hexachlorophosphate without a noticeable change in yield being perceptible.

Les essais effectués ont également montré que le rendement global n'était pas affecté par l'utilisation de quantités d'électricité supérieures à 4 F/mole. Celui-ci par contre diminuait sensiblement à des quantités inférieures.The tests carried out also showed that the overall yield was not affected by the use of quantities of electricity greater than 4 F / mole. This on the other hand decreased appreciably to lower quantities.

Enfin la réaction a été effectuée à des températures de 10, 27, 45 et 60°. Là non plus le rendement global n'était pas affecté.Finally the reaction was carried out at temperatures of 10, 27, 45 and 60 °. Again, overall performance was not affected.

En remplaçant le 14-méthyl-bicyclo[10.3.0]pentadéc-[1(12)]-ène-13-one p-toluène-sulfonyl-hydrazone par son homologue inférieur, le composé déméthylé correspondant, on a obtenu avec un rendement théorique de 90% un mélange contenant de l'exaltynone et de bicyclénone de formule

Figure imgb0008
respectivement, dans le rapport d'environ 56 : 44, composés qui peuvent être séparés par chromatographie sur une colonne de silice (hexane/éther diéthylique).By replacing 14-methyl-bicyclo [10.3.0] pentadec- [1 (12)] - ene-13-one p-toluene-sulfonyl-hydrazone with its lower homologue, the corresponding demethylated compound, there was obtained with a yield theoretical of 90% a mixture containing exaltynone and bicyclenone of formula
Figure imgb0008
 respectively, in the ratio of about 56: 44, compounds which can be separated by chromatography on a silica column (hexane / diethyl ether).

Claims (5)

1. Procédé pour la préparation d'une cétone acétylénique de formule
Figure imgb0009
dans laquelle le symbole R sert à désigner un atome d'hydrogène ou un radical méthyle, caractérisé en ce qu'on soumet à une oxydation anodique, en présence d'un alcool aliphatique ou araliphatique ou un glycol, une hydrazone de formule
Figure imgb0010
dans laquelle le symbole R a le sens défini ci-dessus et A représente un atome d'hydrogène ou un radical sulfonyle de formule R1-S02-, dans laquelle R1 représente un radical aryle, substitué ou non.1. Process for the preparation of an acetylene ketone of formula
Figure imgb0009
 in which the symbol R is used to denote a hydrogen atom or a methyl radical, characterized in that it is subjected to an anodic oxidation, in the presence of an aliphatic or araliphatic alcohol or a glycol, a hydrazone of formula
Figure imgb0010
 in which the symbol R has the meaning defined above and A represents a hydrogen atom or a sulfonyl radical of formula R 1- SO 2 -, in which R 1 represents an aryl radical, substituted or unsubstituted. 2. Procédé suivant la revendication 1, caractérisé en ce que la réaction s'effectue en présence d'un électrolyte support constitué par un composé sélectionné dans le groupe formé par le tétrafluoroborate de tétraméthylammonium, l'hexachlorophosphate de tétraéthylammonium et le perchlorate de tétrabutylammonium.2. Method according to claim 1, characterized in that the reaction is carried out in the presence of a support electrolyte consisting of a compound selected from the group formed by tetramethylammonium tetrafluoroborate, tetraethylammonium hexachlorophosphate and tetrabutylammonium perchlorate. 3. Procédé suivant la revendication 2, caractérisé en ce que la réaction s'effectue à une température comprise entre 10 et 60°C.3. Method according to claim 2, characterized in that the reaction is carried out at a temperature between 10 and 60 ° C. 4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la réaction s'effectue sur une anode en platine ou en graphite.4. Method according to any one of claims 1 to 3, characterized in that the reaction is carried out on a platinum or graphite anode. 5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la réaction s'effectue dans un bain d'électrolyte comprenant, outre l'hydrazone de départ et l'alcool aliphatique ou araliphatique, un solvant organique inerte choisi dans le groupe constitué par les nitriles aliphatiques ou aromatiques et les éthers.5. Method according to any one of claims 1 to 4, characterized in that the reaction is carried out in an electrolyte bath comprising, in addition to the starting hydrazone and the aliphatic or araliphatic alcohol, an inert organic solvent chosen in the group consisting of aliphatic or aromatic nitriles and ethers.
EP83104893A 1982-07-05 1983-05-18 Process for producing cyclopentadec-4-ynone and its homologous 3-methyl Expired EP0100822B1 (en)

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* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 89, no. 13, 25 septembre 1978, page 817, no. 108366a, Columbus, Ohio, USA & JP-A-53 034 750 (UBE INDUSTRIES, LTD.) 31-03-1978 *
EXTENDED ABSTRACTS, vol. 80-1, 11-16 mai 1980, pages 1100-1101, abrégé no. 448, Spring Meeting, Princeton, New Jersey, USA *

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EP0100822B1 (en) 1986-03-05
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US4448650A (en) 1984-05-15
JPS599183A (en) 1984-01-18

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