CH557645A

CH557645A - Gamma-delta-unsatd carbonyl derivs - for perfumery, prepd esp from acrylates or propiolates and alkenyl cpds

Info

Publication number: CH557645A
Application number: CH230274A
Authority: CH
Original assignee: Firmenich & Cie
Priority date: 1971-04-29
Filing date: 1971-04-29
Publication date: 1975-01-15

Abstract

Cpds. for modifying, reinforcing or improving odour of perfumes or organoleptic cpds. and/or aromatising properties of food, animal fodder, beverages, pharmaceuticals and tobacco products of formula: R6R1C=CH2CR3nR5=== CHR4nCO(O)mR7 (where dotted line is a covalent or double bond in alpha-posn. (a), R1, R2, R3, R4, R5 and R6 are opt. linear, cyclic or acyclic, opt satd. monovalent hydrocarbyl or H, provided Ro and R5 have no multiple bonds in conjugation to alpha, beta-C-C bond, (b) R7 is same as (a), (c) m and n each are 0 or 1 and (d) R3, R4 or R5 may be bonded to R7 and may form a cycloaliphatic ring) are prepd. by reacting R3nR5C triple bond triple bond triple bond CR4n-CO(O)mR7 (where dotted line is a double or triple bond) with an organometallic cpd. R1R6C=CR2)-yMe- X+ (where Me is a transition metal esp. CuI, and X+ is a cation, esp. Li+ or (Mg-halogen) and y >= v + 1, where v is oxidn. state of Me). Pref. products are R6-CH=CH-(CH2)2C(O)OR2 and R6-CH=CH-CH=CH-C(O)-OR8 (where R8 is alkyl and R6 is esp. CH3-(CH2)p-CH=CH- where p is 0 to 12) esp. prepd. by reacting an alkyl acylate or an alkyl propiolate with organometallic cpd.

Description

  

  
 



   Le brevet principal   N"    544511 a pour objet l'utilisation comme agent aromatisant, pour la préparation d'arômes artificiels et pour l'aromatisation d'aliments, de boissons et du tabac, d'au moins un des composés carbonylés de formule
EMI1.1     
 possédant une double liaison de configuration cis- en position   y,i,    ainsi qu'une simple ou double liaison de configuration trans- en position   x,p,    et dans laquelle l'indice n vaut 1 ou 2, le symbole R représente un reste alkyle linéaire contenant 1, 2, 4, 6 ou 7 atomes de carbone et RI un reste méthyle ou éthyle.



   Il a été découvert que des composés homologues à ceux décrits précédemment, plus précisément les composés insaturés répondant à la formule ci-dessus et dans laquelle le symbole R représente un reste alkyle linéaire possédant 3, 8, 9, 10 ou 1 1 atomes de carbone possédaient également d'intéressantes propriétés organoleptiques et qu'ils pouvaient être de ce fait avantageusement utilisés dans l'industrie des arômes pour la préparation d'arômes artificiels variés et pour l'aromatisation d'aliments solides et liquides pour les hommes et les animaux, de boissons non nutritives et du tabac.



   La présente invention a par conséquent pour objet l'utilisation comme agent aromatisant, pour la préparation d'arômes artificiels et pour l'aromatisation d'aliments, de boissons et du tabac, d'au moins un des composés carbonylés de formule
EMI1.2     
 possédant une double liaison de configuration cis- en position   y,S,    ainsi qu'une simple ou double liaison de configuration trans- en position   x,ss,    et dans laquelle l'indice n vaut 1 ou 2, le symbole R représente un reste alkyle linéaire contenant 3, 8, 9, 10 ou
Il atomes de carbone et   Rl    un reste méthyle ou éthyle.



   Le terme aliment est utilisé ici dans son sens le plus large et sert également à désigner des aliments sans valeur nutritive intrinséque tels que thé ou café par exemple. En outre, les arômes artificiels résultant de l'utilisation d'au moins un des composés carbonylés de formule I, peuvent être employés pour l'aromatisation de préparation pharmaceutiques.



   Selon la nature des produits auxquels ils sont incorporés, lesdits composés ont la propriété de développer des notes gustatives fruitées originales, vertes ou grasses, rappelant selon les cas celles de la poire par exemple.



   Des effets aromatisants intéressants, tels que ceux décrits ci-dessus, peuvent être obtenus par l'utilisation de quantités de l'ordre de I à 10 ppm environ, par rapport au poids du produit à aromatiser. De telles proportions peuvent être cependant augmentées au-delà de 10 ppm, allant parfois jusqu'à 100, voire 1000 ppm, selon l'effet particulier recherché. Lorsque lesdits composés sont utilisés comme ingrédients pour la préparation d'arômes artificiels, on peut utiliser des quantités comprises entre 0,1 et 5% environ du poids total de la composition, des valeurs supérieures ou inférieures à celles-ci pouvant être également utilisées.



   Les composés carbonylés de formule I dont l'utilisation comme agents aromatisants constitue l'objet de la présente invention, sont des composés nouveaux. Ils peuvent être obtenus selon la méthode décrite ci-après: on traite un composé carbonylé de formule
EMI1.3     
 possédant une double ou triple liaison dans la position indiquée par les pointillés et dans laquelle l'indice m vaut 0 ou 1 et le symbole R2 représente un reste alkyle tel que méthyle ou éthyle par exemple, au moyen d'un dérivé organométallique contenant un métal de transition, un cation monovalent et un reste alcényle de formule
   R3-CH=CH-    (III) dans laquelle le symbole R3 représente un reste alkyle monovalent, linéaire ou ramifié.



   La méthode exposée ci-dessus permet en effet d'obtenir les composés de formule I avec de bons rendements et de maintenir en outre intacte la configuration de la double liaison du reste alcényle de formule III. Dans le cas précis, ladite double liaison
   posséde    une configuration cis-.



   Les dérivés organométalliques utilisés selon la méthode ci-dessus peuvent être représentés par la formule
EMI1.4     

Dans   celleci,    le symbole ME représente un métal de transition tel que le cuivre, le fer, le manganèse ou le cobalt par exemple, et   X    un cation monovalent tel que   Li ,      (Mg-halogène)    ou un groupement ammonium, substitué ou non, par exemple. Il faut cependant noter que la structure réelle d'un tel dérivé organométallique n'est pas encore connue avec précision. Comme métal de transition, on utilise de préférence le cuivre' et comme cation monovalent le   Li ,    tous deux associés à un reste alcényle de formule III.



   La méthode succinctement exposée ci-dessus est notamment l'objet du brevet suisse   N"    541530 au sein duquel elle est décrite de façon plus détaillée.



   REVENDICATION



   Utilisation comme agent aromatisant, pour la préparation d'arômes artificiels et pour l'aromatisation d'aliments, de boissons et du tabac, d'au moins un des composés carbonylés insaturés de form
EMI1.5     
 possédant une double liaison de configuration cis- en position   y,A,    ainsi qu'une simple ou double liaison, de configuration trans-, en position   x,p,    et dans laquelle l'indice n vaut   l    ou 2, le symbole R représente un reste alkyle linéaire contenant 3, 8, 9, 10 ou 1 1 atomes de carbone et   Rl    un reste méthyle ou éthyle.

 

   SOUS-REVENDICATIONS
 1. Utilisation selon la revendication d'au moins un des composés ci-après:
 2-trans-4-cis-octadiénoate de méthyle et
 2-trans-4-cis-octadiénoate d'éthyle
 2. Utilisation selon la revendication d'au moins un des composés ci-après:
 4-cis-tridécénoate de méthyle,
 4-cis-tridécénoate   d'éthyle.   



   2-trans-4-cis-tridécadiénoate de méthyle et
 2-trans-4-cis-tridécadiénoate d'éthyle.



   3. Utilisation selon la revendication d'au moins un des composés ci-après:
 4-cis-tétradécénoate de méthyle,
 4-cis-tétradécénoate d'éthyle,
 2-trans-4-cis-tétradécadiénoate de méthyle et
   2-trans-4 < is-tétradécadiénoate    d'éthyle. 

**ATTENTION** fin du champ DESC peut contenir debut de CLMS **.



   



  
 



   The main patent N "544511 relates to the use as a flavoring agent, for the preparation of artificial flavors and for the flavoring of foods, drinks and tobacco, of at least one of the carbonyl compounds of formula
EMI1.1
 possessing a double bond of cis- configuration in position y, i, as well as a single or double bond of trans- configuration in position x, p, and in which the index n is 1 or 2, the symbol R represents a residue linear alkyl containing 1, 2, 4, 6 or 7 carbon atoms and RI a methyl or ethyl residue.



   It has been discovered that compounds homologous to those described above, more precisely the unsaturated compounds corresponding to the above formula and in which the symbol R represents a linear alkyl residue having 3, 8, 9, 10 or 1 1 carbon atoms also possessed interesting organoleptic properties and that they could therefore be advantageously used in the flavoring industry for the preparation of various artificial flavors and for the flavoring of solid and liquid foods for humans and animals, non-nutritional drinks and tobacco.



   A subject of the present invention is therefore the use, as a flavoring agent, for the preparation of artificial flavors and for the flavoring of foods, drinks and tobacco, of at least one of the carbonyl compounds of formula
EMI1.2
 possessing a double bond of cis- configuration in position y, S, as well as a single or double bond of trans- configuration in position x, ss, and in which the index n is 1 or 2, the symbol R represents a residue linear alkyl containing 3, 8, 9, 10 or
There are carbon atoms and R1 is methyl or ethyl.



   The term food is used here in its broadest sense and is also used to designate foods with no intrinsic nutritional value such as tea or coffee for example. Furthermore, the artificial flavors resulting from the use of at least one of the carbonyl compounds of formula I can be used for the flavoring of pharmaceutical preparations.



   Depending on the nature of the products in which they are incorporated, said compounds have the property of developing original fruity taste notes, green or fatty, recalling, depending on the case, those of pear for example.



   Interesting flavoring effects, such as those described above, can be obtained by using amounts of the order of about 1 to 10 ppm, relative to the weight of the product to be flavored. Such proportions may however be increased beyond 10 ppm, sometimes going up to 100, or even 1000 ppm, depending on the particular effect sought. When said compounds are used as ingredients for the preparation of artificial flavors, it is possible to use amounts of between 0.1 and 5% approximately of the total weight of the composition, values higher or lower than these can also be used.



   The carbonyl compounds of formula I, the use of which as flavoring agents constitutes the object of the present invention, are new compounds. They can be obtained according to the method described below: treating a carbonyl compound of formula
EMI1.3
 having a double or triple bond in the position indicated by the dotted lines and in which the index m is 0 or 1 and the symbol R2 represents an alkyl residue such as methyl or ethyl for example, by means of an organometallic derivative containing a metal transition, a monovalent cation and an alkenyl residue of formula
   R3-CH = CH- (III) in which the symbol R3 represents a monovalent, linear or branched alkyl residue.



   The method described above in fact makes it possible to obtain the compounds of formula I in good yields and also to maintain intact the configuration of the double bond of the alkenyl residue of formula III. In the specific case, said double bond
   has a cis- configuration.



   The organometallic derivatives used according to the above method can be represented by the formula
EMI1.4

In it, the symbol ME represents a transition metal such as copper, iron, manganese or cobalt for example, and X a monovalent cation such as Li, (Mg-halogen) or an ammonium group, substituted or not, for example. It should however be noted that the actual structure of such an organometallic derivative is not yet known with precision. As the transition metal, copper is preferably used and Li as the monovalent cation, both associated with an alkenyl residue of formula III.



   The method briefly described above is in particular the subject of Swiss Patent No. 541530 in which it is described in more detail.



   CLAIM



   Use as a flavoring agent, for the preparation of artificial flavors and for the flavoring of foods, beverages and tobacco, of at least one of the unsaturated carbonyl compounds of form
EMI1.5
 possessing a double bond of cis- configuration in position y, A, as well as a single or double bond, of trans- configuration, in position x, p, and in which the index n is equal to 1 or 2, the symbol R represents a linear alkyl residue containing 3, 8, 9, 10 or 11 carbon atoms and Rl a methyl or ethyl residue.

 

   SUB-CLAIMS
 1. Use according to claim of at least one of the compounds below:
 Methyl 2-trans-4-cis-octadienoate and
 Ethyl 2-trans-4-cis-octadienoate
 2. Use according to claim of at least one of the compounds below:
 Methyl 4-cis-tridecenoate,
 Ethyl 4-cis-tridecenoate.



   Methyl 2-trans-4-cis-tridecadienoate and
 Ethyl 2-trans-4-cis-tridecadienoate.



   3. Use according to claim of at least one of the compounds below:
 Methyl 4-cis-tetradecenoate,
 Ethyl 4-cis-tetradecenoate,
 Methyl 2-trans-4-cis-tetradecadienoate and
   Ethyl 2-trans-4 <is-tetradecadienoate.

** ATTENTION ** end of DESC field can contain start of CLMS **.

Claims

** ATTENTION ** start of field CLMS can contain end of DESC **.

The main patent N "544511 relates to the use as a flavoring agent, for the preparation of artificial flavors and for the flavoring of foods, drinks and tobacco, of at least one of the carbonyl compounds of formula EMI1.1 possessing a double bond of cis- configuration in position y, i, as well as a single or double bond of trans- configuration in position x, p, and in which the index n is 1 or 2, the symbol R represents a residue linear alkyl containing 1, 2, 4, 6 or 7 carbon atoms and RI a methyl or ethyl residue.

It has been discovered that compounds homologous to those described above, more precisely the unsaturated compounds corresponding to the above formula and in which the symbol R represents a linear alkyl residue having 3, 8, 9, 10 or 1 1 carbon atoms also possessed interesting organoleptic properties and that they could therefore be advantageously used in the flavoring industry for the preparation of various artificial flavors and for the flavoring of solid and liquid foods for humans and animals, non-nutritional drinks and tobacco.

A subject of the present invention is therefore the use, as a flavoring agent, for the preparation of artificial flavors and for the flavoring of foods, drinks and tobacco, of at least one of the carbonyl compounds of formula EMI1.2 possessing a double bond of cis- configuration in position y, S, as well as a single or double bond of trans- configuration in position x, ss, and in which the index n is 1 or 2, the symbol R represents a residue linear alkyl containing 3, 8, 9, 10 or There are carbon atoms and R1 is methyl or ethyl.

The term food is used here in its broadest sense and is also used to designate foods with no intrinsic nutritional value such as tea or coffee for example. Furthermore, the artificial flavors resulting from the use of at least one of the carbonyl compounds of formula I can be used for the flavoring of pharmaceutical preparations.

Depending on the nature of the products in which they are incorporated, said compounds have the property of developing original fruity taste notes, green or fatty, recalling, depending on the case, those of pear for example.

Interesting flavoring effects, such as those described above, can be obtained by using amounts of the order of about 1 to 10 ppm, relative to the weight of the product to be flavored. Such proportions may however be increased beyond 10 ppm, sometimes going up to 100, or even 1000 ppm, depending on the particular effect sought. When said compounds are used as ingredients for the preparation of artificial flavors, it is possible to use amounts of between 0.1 and 5% approximately of the total weight of the composition, values higher or lower than these can also be used.

The carbonyl compounds of formula I, the use of which as flavoring agents constitutes the object of the present invention, are new compounds. They can be obtained according to the method described below: treating a carbonyl compound of formula EMI1.3 having a double or triple bond in the position indicated by the dotted lines and in which the index m is 0 or 1 and the symbol R2 represents an alkyl residue such as methyl or ethyl for example, by means of an organometallic derivative containing a metal transition, a monovalent cation and an alkenyl residue of formula R3-CH = CH- (III) in which the symbol R3 represents a monovalent, linear or branched alkyl residue.

The method described above in fact makes it possible to obtain the compounds of formula I in good yields and also to maintain intact the configuration of the double bond of the alkenyl residue of formula III. In the specific case, said double bond has a cis- configuration.

The organometallic derivatives used according to the above method can be represented by the formula EMI1.4 In it, the symbol ME represents a transition metal such as copper, iron, manganese or cobalt for example, and X a monovalent cation such as Li, (Mg-halogen) or an ammonium group, substituted or not, for example. It should however be noted that the actual structure of such an organometallic derivative is not yet known with precision. As the transition metal, copper is preferably used and Li as the monovalent cation, both associated with an alkenyl residue of formula III.

The method briefly described above is in particular the subject of Swiss Patent No. 541530 in which it is described in more detail.

CLAIM

Use as a flavoring agent, for the preparation of artificial flavors and for the flavoring of foods, beverages and tobacco, of at least one of the unsaturated carbonyl compounds of form EMI1.5 possessing a double bond of cis- configuration in position y, A, as well as a single or double bond, of trans- configuration, in position x, p, and in which the index n is equal to 1 or 2, the symbol R represents a linear alkyl residue containing 3, 8, 9, 10 or 11 carbon atoms and Rl a methyl or ethyl residue.

SUB-CLAIMS 1. Use according to claim of at least one of the compounds below: Methyl 2-trans-4-cis-octadienoate and Ethyl 2-trans-4-cis-octadienoate 2. Use according to claim of at least one of the compounds below: Methyl 4-cis-tridecenoate, Ethyl 4-cis-tridecenoate.

Methyl 2-trans-4-cis-tridecadienoate and Ethyl 2-trans-4-cis-tridecadienoate.

3. Use according to claim of at least one of the compounds below: Methyl 4-cis-tetradecenoate, Ethyl 4-cis-tetradecenoate, Methyl 2-trans-4-cis-tetradecadienoate and Ethyl 2-trans-4 <is-tetradecadienoate.

4. Use according to claim of at least one of the compounds below: Methyl 4cis-pentadecenoate, Ethyl 4-cis-pentadecenoate, Methyl 2-trans-4-cis-pentadecadienoate and Ethyl 2-trans-4-cis-pentadecadienoate.

5. Use according to claim of at least one of the compounds below: Methyl 4-cis-hexadecenoate, Ethyl 4-cis-hexadecenoate, Methyl 2-trans-4-cis-hexadecadienoate and Ethyl 2-trans-4-cis-hexadecadienoate.