CH473753A - Process for the preparation of unsaturated aldehydes - Google Patents

Process for the preparation of unsaturated aldehydes

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Publication number
CH473753A
CH473753A CH751167A CH751167A CH473753A CH 473753 A CH473753 A CH 473753A CH 751167 A CH751167 A CH 751167A CH 751167 A CH751167 A CH 751167A CH 473753 A CH473753 A CH 473753A
Authority
CH
Switzerland
Prior art keywords
condenses
methylbutadienyl
general formula
sinensal
subclaims
Prior art date
Application number
CH751167A
Other languages
French (fr)
Inventor
Francis Dr Thomas Alan
Original Assignee
Firmenich & Cie
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Firmenich & Cie filed Critical Firmenich & Cie
Priority to CH751167A priority Critical patent/CH473753A/en
Priority to CH1365267A priority patent/CH479515A/en
Priority to CH697268A priority patent/CH510602A/en
Priority to US731277A priority patent/US3654309A/en
Priority to GB1233222D priority patent/GB1233222A/en
Priority to GB1233221D priority patent/GB1233221A/en
Priority to NL6807345A priority patent/NL6807345A/xx
Priority to DE19681768552 priority patent/DE1768552A1/en
Priority to FR1582515D priority patent/FR1582515A/fr
Publication of CH473753A publication Critical patent/CH473753A/en

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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/201—Compounds of unspecified constitution characterised by the chemical reaction for their preparation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/202—Aliphatic compounds
    • A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/09—Geometrical isomers

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

  



  Procédé pour la préparation d'aldéhydes non saturés
 La présente invention a pour objet un procédé de préparation d'aldehydes non saturés dont certains repré sentants peuvent être utilisés avantageusement dans des compositions de parfums ou d'arômes.



   On a découvert que les aldéhydes sesquiterpéniques représentés par les formules I et II, appelés respective ment a - et   B    - sinensals sont doués de propriétés
EMI1.1     
   L'a ;-sinensal    I, le B-sinensal   II    et leurs confomères n'avaient, jusqu'à présent, pas été préparés par synthèse.



  Or on a maintenant découvert que des aldéhydes non saturés répondant à la formule générale V comprenant au moins 10 et au plus 22 atomes de carbone (laquelle organoleptiques et sont utilisables comme condiments d'aliments et de boissons. Ces composés ont été trouvés dans la nature et isolés à partir de l'huile d'orange de
Chine (Citrus Sinensis) (K. L. Stevens, R.E. Lundin, R.



  Teranishi, J. Org. Chem.   30    1690 (1965); R.A. Fath,
R.E. Lundin, R. Teranishi, Tetrahedron letters 295, (1966)).
EMI1.2     
 englobe les   a - et      p - sinensals)    peuvent tre préparés par la condensation, en présence d'un catalyseur, d'un alcool allylique répondant à la formule générale III avec un éther vinylique répondant à la formule générale IV, selon le schéma suivant:

  
EMI1.3     
 
 Dans les formules III, IV et V, les groupes R1, R2,
R3, R4, R5, R6, R7 et   R6    représentent l'hydrogène ou des restes aromatiques, hétérocycliques ou aliphatiques linéaires ou ramifiés, libres ou reliés entre-eux de façon à former des cycles, saturés ou non saturés, substitués ou non par des restes aromatiques ou hétérocycliques, tandis
 que R) représente un reste aliphatique, alicyclique,
 aromatique ou hétérocyclique pouvant être aisément
 scindé, par exemple méthyle, benzyle, phenyle ou furanyle.   I1    est à noter que R), étant éliminé lors de la réaction, n'a pas d'influence sur la structure du produit final et l'importance de sa nature est d'ordre secondaire.



   Conformément à un mode d'exécution du procédé de l'invention on chauffe, en présence d'un catalyseur de condensation, l'alcool allylique substitué III avec l'éther vinylique substitué IV, à des températures comprises entre 40 et 160  mais de préférence au voisinage de
 100  pendant une période dépendant de la réactivité des matières de départ, laquelle est généralement liée à la nature des substituants Ri à   R6    selon le mode approximatif suivant: la réactivité est généralement en raison directe du pouvoir électronique répulsif des groupes   3k,   
R3 et R4 et du pouvoir électronique attracteur des groupes   R5,    R7, R8, ces pouvoirs étant évalués selon les règles usuelles.



   Comme catalyseur, on peut utiliser des sels de métaux ayant la propriété de former des complexes d'addition avec les oléfines tels, par exemple, de métaux appartenant à la 4e, 50 ou 6e période des éléments comme le cobalt, l'argent ou le mercure.



   Suivant des modes d'exécution du procédé de l'invention on emploie comme produit de départ, par exemple   éther      méthylbutadiényl éthylique    (IV, R1
CH3, R2 = R3 = R4 = H et R) = (C2H5) et comme alcool allylique III le trans-2-méthyl-6-vinylheptadièn (2,6)-ol-(1) III, R5 = R7 = H, R6 = CH3, R8 =
 On obtient dans ce cas   l'α-sinensal.    Si, pour l'alcool
III on prend le trans-3,7-diméthyloctatrièn-(1, 3, 6)-ol (8), on obtient alors le ss-sinenseal. On peut aussi utiliser des alcools comme par exemple le géraniol ou le nérol et on obtient alors des aldéhydes non saturés d'odeur intéressante.



   Les exemples qui suivent illustrent la mise en oeuvre de l'invention.



   Exemple I
 Préparation de   ra-et    du   ss-sinensal   
 Sous protection d'azote, on chauffe pendant 18 heures à 980, un mélange de 10 g de 2-méthyl-6  vinylheptadièn-(2, 6)-ol-( 1),    25 g d'éther méthylbutadiényl éthylique,   6,6 g    d'acétate mercurique et 2,7 g d'acétate de soude pulvérisés. Après refroidissement, on filtre les matières solides et neutralise la phase liquide par agitation avec du carbonate de potasse anhydre. On distille ensuite sous vide pussé et recueille la fraction passant à 80  / 0,001 Torr.

   Cette fraction est constituée par   l'α-sinensal    dont la pureté est supérieure à 90 % selon l'analyse par chromatographie en phase gazeuse
 (rendement 43   O/o).    En RMN, le groupe méthyle se
 trouvant dans la partie du champ dont l'intensité est la
 plus élevée montre une résonance à   a    = 1,60 ppm (valeur corrigée). Les spectres de masse et IR sont en
 accord avec ceux de   l'a -sinensal    naturel (voir J. Org.



   Chem. 30, 1690 (1965) et, la dinitrophényl-hydrazone
 de   l'α-sinensal    synthétique (F (80-81 ) le montre pas
 de dépression du F. en mélange avec la dinitrophénylhydrazone de   l'α-sinensal    naturel.



   En utilisant la même méthode et les memes quanti
 tés de réactifs mais en remplaçant le venylheptadiénol
 ci-dessus par son isomère, le 3,7-diméthyloctatrièn-(1, 3,
 6)-ol-(8) on obtient avec un rendement comparable le ss 
 sinensal dont la Dinitrophénylhydrazone fond à    96-980.   



   Exemple 2
 Préparation des-trans-et-cis- 2,7,11-triméthyl-dodécatrièn-(2,6,10)-al-(1).



   Sous protection d'azote, on chauffe pendant 18 heures à 980, un mélange de 10 g de géraniol, 25 g d'éther méthylbutadiényl éthylique,   6,6    g d'acétate mercurique et 2,7 g d'acétate de soude. Après refroidissement, on neutralise et sépare la phase liquide comme indiqué dans l'Exemple 1, puis la distille sous vide poussé. On obtient 9,3 g de distillant qui est purifié par chromatographie sur colonne de silice. l'échantillon analytique de-trans-2,7,11-triméthyl-dodécatrién-(2, 6,
 10)-al-(1) ainsi obtenu est encore redistillé et transformé
 en dinitrophénylhydrazone, F.   83-840.   



   Analyse:
Calc. pr. C21H28O4N4 % C 62,98, % H 7,05, % N 14,0
 Trouvé: C 62,47, H 7,29, N 14,5
 En remplaçant dans le mélange ci-dessus le géraniol par le nérol et en procédant exactement dans les mêmes conditions on obtient 11,5 g de - cis   -2,7,1 1-triméthyl-      dodécatrièn-(2,6,10)-al-(1)    brut dont la dinitrophényldrazone fond à 102-104   ".   




  



  Process for the preparation of unsaturated aldehydes
 The present invention relates to a process for the preparation of unsaturated aldehydes, certain representatives of which can be used advantageously in perfume or flavoring compositions.



   It has been found that the sesquiterpene aldehydes represented by the formulas I and II, called respectively a - and B - sinensals are endowed with properties
EMI1.1
   Α; -sinensal I, β-sinensal II and their confomers had not heretofore been synthetically prepared.



  However, it has now been discovered that unsaturated aldehydes corresponding to the general formula V comprising at least 10 and at most 22 carbon atoms (which are organoleptic and can be used as condiments for food and drink. These compounds have been found in nature. and isolated from orange oil from
China (Citrus Sinensis) (K. L. Stevens, R.E. Lundin, R.



  Teranishi, J. Org. Chem. 1690 (1965); R.A. Fath,
R.E. Lundin, R. Teranishi, Tetrahedron letters 295, (1966)).
EMI1.2
 includes a - and p - sinensals) can be prepared by the condensation, in the presence of a catalyst, of an allylic alcohol corresponding to general formula III with a vinyl ether corresponding to general formula IV, according to the following scheme:

  
EMI1.3
 
 In formulas III, IV and V, the groups R1, R2,
R3, R4, R5, R6, R7 and R6 represent hydrogen or linear or branched aromatic, heterocyclic or aliphatic residues, free or linked together so as to form rings, saturated or unsaturated, substituted or not by aromatic or heterocyclic residues, while
 that R) represents an aliphatic or alicyclic residue,
 aromatic or heterocyclic which can easily be
 cleaved, for example methyl, benzyl, phenyl or furanyl. It should be noted that R), being eliminated during the reaction, has no influence on the structure of the final product and the importance of its nature is secondary.



   In accordance with one embodiment of the process of the invention, in the presence of a condensation catalyst, the substituted allylic alcohol III with the substituted vinyl ether IV is heated to temperatures of between 40 and 160 but preferably at the neighborhood of
 100 for a period depending on the reactivity of the starting materials, which is generally linked to the nature of the substituents R 1 to R 6 according to the following approximate mode: the reactivity is generally a direct result of the repulsive electronic power of the 3k groups,
R3 and R4 and the electronic attracting power of the groups R5, R7, R8, these powers being evaluated according to the usual rules.



   As catalyst, it is possible to use salts of metals having the property of forming addition complexes with olefins such, for example, of metals belonging to the 4th, 50 or 6th period of elements such as cobalt, silver or mercury.



   According to embodiments of the process of the invention, as starting material, for example methylbutadienyl ethyl ether (IV, R1
CH3, R2 = R3 = R4 = H and R) = (C2H5) and as allyl alcohol III trans-2-methyl-6-vinylheptadien (2,6) -ol- (1) III, R5 = R7 = H, R6 = CH3, R8 =
 In this case, we obtain α -sinensal. If, for alcohol
III we take trans-3,7-dimethyloctatrièn- (1, 3, 6) -ol (8), we then obtain ss-sinenseal. It is also possible to use alcohols such as, for example, geraniol or nerol, and unsaturated aldehydes with an interesting odor are then obtained.



   The examples which follow illustrate the implementation of the invention.



   Example I
 Preparation of ra-and ss-sinensal
 Under nitrogen protection, heated for 18 hours at 980, a mixture of 10 g of 2-methyl-6 vinylheptadien- (2, 6) -ol- (1), 25 g of methylbutadienyl ethyl ether, 6.6 g of mercuric acetate and 2.7 g of pulverized sodium acetate. After cooling, the solids are filtered off and the liquid phase is neutralized by stirring with anhydrous potassium carbonate. It is then distilled under high vacuum and the fraction passing through 80 / 0.001 Torr is collected.

   This fraction consists of α -sinensal, the purity of which is greater than 90% according to analysis by gas chromatography.
 (yield 43 O / o). In NMR, the methyl group is
 found in the part of the field whose intensity is the
 higher shows resonance at a = 1.60 ppm (corrected value). The mass spectra and IR are in
 accord with those of natural a -sinensal (see J. Org.



   Chem. 30, 1690 (1965) and, dinitrophenyl-hydrazone
 synthetic α -sinensal (F (80-81) does not show it
 depression of F. mixed with dinitrophenylhydrazone of natural α; -sinensal.



   Using the same method and the same amounts
 t of reagents but replacing venylheptadienol
 above by its isomer, 3,7-dimethyloctatrien- (1, 3,
 6) -ol- (8) one obtains with a comparable yield the ss
 sinensal whose Dinitrophenylhydrazone melts at 96-980.



   Example 2
 Preparation of-trans-and-cis-2,7,11-trimethyl-dodecatrien- (2,6,10) -al- (1).



   Under nitrogen protection, a mixture of 10 g of geraniol, 25 g of methylbutadienyl ethyl ether, 6.6 g of mercuric acetate and 2.7 g of sodium acetate is heated for 18 hours at 980. After cooling, the liquid phase is neutralized and separated as indicated in Example 1, then it is distilled off under high vacuum. 9.3 g of distilling agent are obtained which is purified by chromatography on a silica column. the analytical sample of-trans-2,7,11-trimethyl-dodecatrien- (2, 6,
 10) -al- (1) thus obtained is further redistilled and transformed
 in dinitrophenylhydrazone, F. 83-840.



   Analysis:
Calc. pr. C21H28O4N4% C 62.98,% H 7.05,% N 14.0
 Found: C 62.47, H 7.29, N 14.5
 By replacing in the above mixture the geraniol by nerol and proceeding exactly under the same conditions, 11.5 g of - cis -2.7.1 1-trimethyl- dodecatrièn- (2,6,10) - are obtained. crude al- (1) in which dinitrophenyldrazone melts at 102-104 ".

Claims (1)

Analyse: Calc. pr. C21H28O4N4 % C 62,98, % H 7,05, % N 14,0 Trouvé: C 63,6 , H 7,23, N, 14,8 REVENDICATION Procédé pour la préparation d'aldéhydes non saturés comprenant au moins 10 et au plus 22 atomes de carbone de formule générale V suivante EMI2.1 dans laquelle les groupes Rr, R2, R3, R4, R5, R6, R7, R8 représentent l'hydrogène ou des restes aromatiques, hétérocycliques ou aliphatiques linéaires ou ramifiés, libres ou reliés entre-eux de façon à former des cycles saturés ou non saturés, substitués ou non par des restes aromatiques ou hétérocycliques, caractérisé en ce qu'on condense, en présence d'un catalyseur de condensation, Analysis: Calc. pr. C21H28O4N4% C 62.98,% H 7.05,% N 14.0 Found: C 63.6, H 7.23, N, 14.8 CLAIM Process for the preparation of unsaturated aldehydes comprising at least 10 and at most 22 carbon atoms of the following general formula V EMI2.1 in which the groups Rr, R2, R3, R4, R5, R6, R7, R8 represent hydrogen or linear or branched aromatic, heterocyclic or aliphatic residues, free or linked together so as to form saturated or unsaturated rings, substituted or not by aromatic or heterocyclic residues, characterized in that condenses, in the presence of a condensation catalyst, un alcool allylique substitué de formule générale III suivante EMI3.1 avec un éther vinylique substitué de formule générale IV suivante EMI3.2 dans lesquelles les groupes R, à R3 ont la signification définie ci-dessus et R) est un groupe aliphatique, alicyclique, aromatique ou hétérocyclique aisément scindé ou cours de la réaction. a substituted allylic alcohol of the following general formula III EMI3.1 with a substituted vinyl ether of the following general formula IV EMI3.2 in which the groups R 1 to R 3 have the meaning defined above and R) is an aliphatic, alicyclic, aromatic or heterocyclic group which is easily split or during the reaction. SOUS-REVENDICATIONS 1. Procédé suivant la revendication caractérisé en ce qu on emploie comme catalyseur de condensation un sel d'un métal faisant partie des 4e, 5e, et 6e période des éléments. SUB-CLAIMS 1. Process according to claim characterized in that a salt of a metal forming part of the 4th, 5th and 6th element periods is used as the condensation catalyst. 2. Procédé suivant la revendication et la sousrevendication 1 caractérisé en ce qu'on emploie un sel de cobalt, d'argent ou de mercure et qu'on opère à une température comprise entre 40 et 1600 mais de préférence voisine de 1000. 2. Method according to claim and subclaim 1 characterized in that a salt of cobalt, silver or mercury is used and that the operation is carried out at a temperature between 40 and 1600 but preferably close to 1000. 3. Procédé suivant la revendication et les sousrevendications 1 et 2 caractérisé en ce qu'on condense l'éther méthylbutadiényl éthylique avec le trans-2-mé thyl-6-vinylheptadièn-(2, 6)-ol-(1), cette réaction produisant de l'a -sinensal. 3. A method according to claim and subclaims 1 and 2 characterized in that condenses methylbutadienyl ethyl ether with trans-2-methyl-6-vinylheptadien- (2, 6) -ol- (1), this reaction producing α -sinensal. 4. Procédé suivant la revendication et les sousrevendications 1 et 2 caractérisé en ce qu'on condense l'éther méthylbutadiényl éthylique avec le 3,7 -dimé thyloctatrièn-(l, 3, 6)-ol-(8), cette réaction produisant du p -sinensal. 4. A method according to claim and subclaims 1 and 2 characterized in that condenses methylbutadienyl ethyl ether with 3,7 -dime thyloctatrièn- (l, 3, 6) -ol- (8), this reaction producing p -sinensal. 5. Procédé suivant la revendication et les sousrevendications 1 et 2 caractérisé en ce qu'on condense l'éther méthylbutadiényl éthylique avec le géraniol (respectivement le nérol), cette réaction produisant l'isomère-trans-du 2, 7, il -triméthyl-dodecatrièn-(2, 6, 10)-al-(1) (respectivement l'isomère-cis-). 5. Method according to claim and subclaims 1 and 2 characterized in that the methylbutadienyl ethyl ether condenses with geraniol (respectively nerol), this reaction producing the trans-isomer of 2, 7, il -trimethyl -dodecatrien- (2, 6, 10) -al- (1) (respectively the cis-isomer).
CH751167A 1967-05-26 1967-05-26 Process for the preparation of unsaturated aldehydes CH473753A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
CH751167A CH473753A (en) 1967-05-26 1967-05-26 Process for the preparation of unsaturated aldehydes
CH1365267A CH479515A (en) 1967-05-26 1967-09-29 Process for the preparation of unsaturated aldehydes
CH697268A CH510602A (en) 1967-05-26 1968-05-10 Process for the preparation of carbonyl compounds
US731277A US3654309A (en) 1967-05-26 1968-05-22 Process for the preparation of unsaturated aldehydes
GB1233222D GB1233222A (en) 1967-05-26 1968-05-23
GB1233221D GB1233221A (en) 1967-05-26 1968-05-23
NL6807345A NL6807345A (en) 1967-05-26 1968-05-24
DE19681768552 DE1768552A1 (en) 1967-05-26 1968-05-25 Process for the preparation of unsaturated carbonyl compounds
FR1582515D FR1582515A (en) 1967-05-26 1968-05-27

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CH751167A CH473753A (en) 1967-05-26 1967-05-26 Process for the preparation of unsaturated aldehydes

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CH473753A true CH473753A (en) 1969-06-15

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