EP0002743B1 - Bicyclo (2.2.1)-hept-5-enes (anes) (i), process for their preparation, their use as perfumes and perfume compositions containing the bicyclic compounds (i) - Google Patents

Bicyclo (2.2.1)-hept-5-enes (anes) (i), process for their preparation, their use as perfumes and perfume compositions containing the bicyclic compounds (i) Download PDF

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Publication number
EP0002743B1
EP0002743B1 EP78101703A EP78101703A EP0002743B1 EP 0002743 B1 EP0002743 B1 EP 0002743B1 EP 78101703 A EP78101703 A EP 78101703A EP 78101703 A EP78101703 A EP 78101703A EP 0002743 B1 EP0002743 B1 EP 0002743B1
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Prior art keywords
bicyclo
hept
enes
methyl
heptane
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French (fr)
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EP0002743A1 (en
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Gary W. Shaffer
Kenneth L. Purzycki
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Givaudan SA
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L Givaudan and Co SA
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    • 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
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings

Definitions

  • the invention relates to a new class of fragrances of the general formula wherein R 1 and R 2 are the same or different and denote hydrogen or methyl, and the dashed lines represent optional bonds.
  • the new compounds of the present invention have spicy, floral odor notes and are valuable components of fragrance compositions.
  • the compounds can be prepared as follows:
  • a stands for a Knoevenagel reaction and b for a hydrogenation.
  • the starting material 1 represents the Diels-Alder adduct between cyclopentadiene and a suitable dienophile, such as. As acrolein, crotonaldehyde, methyl vinyl ketone or 3-penten-2-one. 1 is then reacted with cyanoacetic acid according to Knoevenagel (see, for example, BG Jones, "The Knoevenagel Condensation” Organic Reactions, R. Adams et al., Eds., Volume 15, John Wiley and Sons Inc., New York, (1967) and HO House, "Modern Synthetic Reactions", WA Benjamin Inc., New York (1965), pages 225-229). Any of the known methods for producing ⁇ , y-unsaturated nitriles by means of the Knoevenagel reaction can be used in the present case.
  • the Knoevenagel reaction proceeds via the intermediates of the formula which can be isolated and then thermally decarboxylated. However, the above intermediates are preferably not isolated, but the crude reaction mixture is decarboxylated. During this last step, the olefinic double bond of the side chain is shifted into the ⁇ , y position and the compound of the formula II results.
  • Connection 3 can be established according to any of the routes shown in the diagram.
  • the Diels-Alder adduct 1 is preferably hydrogenated to the saturated compound 5. 5 is then reacted to 3 with cyanoacetic acid according to Knoevenagel.
  • Step 1 ⁇ 5 involves catalytic hydrogenation, but the conditions are not critical. For example, it is suitable to use a catalyst which is 5% palladium on carbon (dry) in a Parr bomb with shaking at 3.4 atm (50 psi) and at temperatures between approximately 20-50 ° C.
  • Compound 4 can be prepared by catalytic hydrogenation of 11 or also compound 3, the reaction being terminated after the required amount of hydrogen has been taken up. This type of reduction is familiar to the person skilled in the art. Any hydrogenation catalyst known to be suitable, such as palladium, Raney nickel or platinum oxide, can be used. As stated above, since the endocyclic olefinic double bond is reduced faster than the exocyclic olefinic bond, the reaction can be easily controlled, in other words, terminated after taking up a molecular equivalent of hydrogen.
  • the compounds of the present invention have spicy and floral scents and are valuable components of fragrance compositions.
  • Such compounds are suitable as components of a number of fragrance compositions, such as rose, jasmine, violet, carnation, galbanum, labdanum, tobacco, leather and cinnamon bark.
  • the new compounds of the formula I can be used in perfume formulations in a range from 0.1-30%.
  • concentration will of course depend on the type of composition. So it is quite understandable that even concentrations higher than 30%, for example even 80-90%, can be used successfully for special effects.
  • the compounds can be used, for example, in the preparation of fragrance compositions, which are used as fragrance bases for the production of perfumes and toilet water, by diluting these bases in the usual manner with alcohol or water.
  • perfumes approximately 15-20 percent by weight of the base can expediently be used, and in the case of toilet water, approximately 3-5 percent by weight of the base can be used.
  • the bases can also be used for perfuming soaps, detergents, cosmetics, etc.
  • a base concentration of about 0.5 to about 2 percent by weight is most suitable for these purposes.
  • the IR spectra were recorded using a Perkin-Elmer 457 Spectrophotometer recorded (substance as such (film)). The absorptions are given as cm ⁇ 1.
  • the NMR spectra were recorded using a Varian A-60A spectrophotometer as chloroform-D i solutions and reported as gamma units relative to TMS.
  • the compounds of the present invention can be used to either create or enhance spicy notes.
  • Compound A represents either the odorless diethyl phthalate or any compound of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)

Description

Die Erfindung betrifft eine neue Klasse von Riechstoffen der allgemeinen Formel

Figure imgb0001
worin R1 und R2 gleich ode verschieden sind und Wasserstoff oder Methyl bedeuten, und die gestrichelten Linien fakultative Bindungen darstelien.The invention relates to a new class of fragrances of the general formula
Figure imgb0001
 wherein R 1 and R 2 are the same or different and denote hydrogen or methyl, and the dashed lines represent optional bonds.

Die neuen Verbindungen der vorliegenden Erfindung weisen würzige, blumige Geruchsnoten auf und stellen wertvolle Komponenten von Riechstoffkompositionen dar. Die Verbindungen können wie folgt hergestellt werden:

Figure imgb0002
The new compounds of the present invention have spicy, floral odor notes and are valuable components of fragrance compositions. The compounds can be prepared as follows:
Figure imgb0002

Im obigen Schema steht ⓐ für eine Knoevenagelreaktion und ⓑ für eine Hydrierung.In the above scheme, ⓐ stands for a Knoevenagel reaction and ⓑ for a hydrogenation.

Das Verfahren zur Herstellung der Verbindungen der Formel ist also dadurch gekennzeichnet, daß man eine Verbindung der Formel

Figure imgb0003
worin R1, R2 und die gestrichelte Linien obige Bedeutung haben, durch Behandlung mit Cyanessigsäure und Decarboxylierung einer Knoevenagelreaktion unterwirft, und, gewünschtenfalls das primäre Reaktionsprodukt hydriert. Wie aus obigem Schema leicht ersichtlich ist, steht III für die Verbindungen 1 und 5.The process for the preparation of the compounds of the formula is thus characterized in that a compound of the formula
Figure imgb0003
 wherein R 1 , R 2 and the dashed lines have the above meaning, subjected to a Knoevenagel reaction by treatment with cyanoacetic acid and decarboxylation, and, if desired, hydrogenating the primary reaction product. As can easily be seen from the above diagram, III stands for compounds 1 and 5.

Das Ausgangsmaterial 1 stellt das Diels-Alder-Addukt zwischen Cyclopentadien und einem geeigneten Dienophilen dar, wie z. B. Acrolein, Crotonaldehyd, Methylvinylketon oder 3-Penten-2-on. 1 wird hierauf mit Cyanessigsäure nach Knoevenagel umgesetzt (siehe z. B. G. Jones, »The Knoevenagel Condensation« Organic Reactions, R. Adams et al., Eds., Band 15, John Wiley and Sons Inc., New York, (1967) und H. O. House, »Modern Synthetic Reactions«, W. A. Benjamin Inc., New York (1965), Seiten 225-229). Irgendeine der bekannten Methoden zur Herstellung ß, y-ungesättigter Nitrile mittels Knoevenagelreaktion kann im vorliegenden Fall benützt werden.The starting material 1 represents the Diels-Alder adduct between cyclopentadiene and a suitable dienophile, such as. As acrolein, crotonaldehyde, methyl vinyl ketone or 3-penten-2-one. 1 is then reacted with cyanoacetic acid according to Knoevenagel (see, for example, BG Jones, "The Knoevenagel Condensation" Organic Reactions, R. Adams et al., Eds., Volume 15, John Wiley and Sons Inc., New York, (1967) and HO House, "Modern Synthetic Reactions", WA Benjamin Inc., New York (1965), pages 225-229). Any of the known methods for producing β, y-unsaturated nitriles by means of the Knoevenagel reaction can be used in the present case.

Die Knoevenagel-Reaktion verläuft über die Zwischenprodukte der Formel

Figure imgb0004
welche isoliert und hierauf thermisch decarboxyliert werden können. Vorzugsweise werden jedoch obige Zwischenprodukte nicht isoliert, sondern das rohe Reaktionsgemisch decarboxyliert. Während dieses letzten Schrittes wird die olefinische Doppelbindung der Seitenkette in die ß, y-Position verschoben und die Verbindung der Formel Il resultiert.The Knoevenagel reaction proceeds via the intermediates of the formula
Figure imgb0004
 which can be isolated and then thermally decarboxylated. However, the above intermediates are preferably not isolated, but the crude reaction mixture is decarboxylated. During this last step, the olefinic double bond of the side chain is shifted into the β, y position and the compound of the formula II results.

Die Verbindung 3 kann nach jeder der im Schema dargestellten Routen hergestellt werden. Vorzugsweise wird jedoch das Diels-Alder-Addukt 1 zu der gesättigten Verbindung 5 hydriert. 5 wird hierauf mit Cyanessigsäure gemäß Knoevenagel zu 3 umgesetzt. Der Schritt 1 →5 beinhaltet eine katalytische Hydrierung, wobei die Bedingungen nicht kritisch sind. Geeignet ist beispielsweise die Verwendung eines Katalysators, der 5% Palladium auf Kohle (trocken) darstellt, in einer Parrbombe unter Schütteln bei 3,4 Atm (50 psi) und bei Temperaturen zwischen ungefähr 20-50° C.Connection 3 can be established according to any of the routes shown in the diagram. However, the Diels-Alder adduct 1 is preferably hydrogenated to the saturated compound 5. 5 is then reacted to 3 with cyanoacetic acid according to Knoevenagel. Step 1 → 5 involves catalytic hydrogenation, but the conditions are not critical. For example, it is suitable to use a catalyst which is 5% palladium on carbon (dry) in a Parr bomb with shaking at 3.4 atm (50 psi) and at temperatures between approximately 20-50 ° C.

Da andererseits bekannt ist, daß die endocyclische, olefinische Doppelbindung zuerst hydriert wird, kann ll mittels katalytischer Hydrierung zu 3 umgesetzt werden, wobei die Reaktion nach der Aufnahme eines Moläquivalents Wasserstoff abgebrochen wird.On the other hand, since it is known that the endocyclic, olefinic double bond is hydrogenated first, II can be converted to 3 by means of catalytic hydrogenation, the reaction being stopped after the absorption of one molar equivalent of hydrogen.

Die Verbindung 4 kann mittels katalytischer Hydrierung von 11 oder auch der Verbindung 3 hergestellt werden, wobei die Reaktion nach Aufnahme der benötigten Wasserstoffmenge abgebrochen wird. Diese Art Reduktion ist dem Fachmann geläufig. Irgendein bekannterweise dafür geeigneter Hydrierungskatalysator, wie Palladium, Raney-Nickel oder Platinoxid kann verwendet werden. Da wie oben gesagt, die endocyclische olefinische Doppelbindung rascher reduziert wird als die exocyclische olefinische Bindung, kann die Reaktion leicht kontrolliert werden, mit anderen Worten, nach Aufnahme eines molekularen Äquivalents Wasserstoff abgebrochen werden.Compound 4 can be prepared by catalytic hydrogenation of 11 or also compound 3, the reaction being terminated after the required amount of hydrogen has been taken up. This type of reduction is familiar to the person skilled in the art. Any hydrogenation catalyst known to be suitable, such as palladium, Raney nickel or platinum oxide, can be used. As stated above, since the endocyclic olefinic double bond is reduced faster than the exocyclic olefinic bond, the reaction can be easily controlled, in other words, terminated after taking up a molecular equivalent of hydrogen.

Die Verbindungen der vorliegenden Erfindung weisen würzige und blumige Geruchsnoten auf und sind wertvolle Komponenten von Riechstoffkompositionen. Solche Verbindungen sind als Komponenten einer Reihe von Riechstoffkompositionen, wie beispielsweise Rose, Jasmin, Veilchen, Nelke, Galbanum, Labdanum, Tabak, Leder, Zimtrinde geeignet.The compounds of the present invention have spicy and floral scents and are valuable components of fragrance compositions. Such compounds are suitable as components of a number of fragrance compositions, such as rose, jasmine, violet, carnation, galbanum, labdanum, tobacco, leather and cinnamon bark.

Es soll festgehalten werden, daß in den Fällen, in denen R, Methyl darstellt, während des Decarboxylierungsschrittes Dekonjugation in Richtung der Methylgruppe eintreten kann. Deshalb ist anzunehmen, daß die Verbindungen der Formel 3 und II, worin R, Methyl darstellt, auch einen Gehalt an Verbindungen der Formel

Figure imgb0005
aufweisen werden.It should be noted that in cases where R represents methyl, deconjugation towards the methyl group can occur during the decarboxylation step. Therefore it can be assumed that the compounds of the formula 3 and II, in which R represents methyl, also contain compounds of the formula
Figure imgb0005
 will have.

Weiter ist anzunehmen, daß unter den Bedingungen der Decarboxylierung, d. h. Anwesenheit einer Base und Hitzeeinwirkung, die ß, y-Doppelbindwng der Verbindungen II oder 3 zum Teil in Konjugation mit der Nitrilgruppe tritt. Daraus folgt, daß Verbindungen der Formel 11 oder 3 auch geringe Anteile an Verbindungen der Formel

Figure imgb0006
enthalten werden. Es wird also unterstellt, daß von den neuen Verbindungen der vorliegenden Erfindung diejenigen, die eine olefinische Doppelbindung in der Seitenkette aufweisen und durch die Formel
Figure imgb0007
dargestellt werden können, auch einen geringen Anteil an Isomeren 6 oder 7 aufweisen. Die Anwesenheit dieser Isomeren wird sich aber auf die oifaktorischen Eigenschaften der Riechstoffkompositionen nicht schädlich auswirken.It can also be assumed that under the conditions of decarboxylation, ie the presence of a base and exposure to heat, the β, y double bond of compounds II or 3 partly conjugates with the nitrile group. It follows that compounds of the formula 11 or 3 also have small proportions of compounds of the formula
Figure imgb0006
 be included. It is thus assumed that of the new compounds of the present invention, those which have an olefinic double bond in the side chain and by the formula
Figure imgb0007
 can also be represented, also have a small proportion of isomers 6 or 7. However, the presence of these isomers will not have a detrimental effect on the oifactor properties of the fragrance compositions.

Während alle der neuen Verbindungen nützliche Riechstoffe darstellen, sind die der allgemeinen Formel 11 speziell bevorzugt, dies darum, weil ihre Gerüche intensiver sind als diejenigen der entsprechenden semihydrierten und hydrierten Verbindungen.While all of the new compounds are useful fragrances, those of general formula 11 are especially preferred, because their smells are more intense than those of the corresponding semi-hydrated and hydrogenated compounds.

Für die meisten Zwecke können die neuen Verbindungen der Formel I in Parfümformulierungen in einem Bereich von 0,1-30% eingesetzt werden. Die geeignete Konzentration wird selbstverständlich vom Kompositionstyp abhängen. So ist es durchaus verständlich, daß auch höhere Konzentrationen als 30%, beispielsweise sogar 80-90%, für spezielle Effekte mit Erfolg eingesetzt werden können.For most purposes, the new compounds of the formula I can be used in perfume formulations in a range from 0.1-30%. The appropriate concentration will of course depend on the type of composition. So it is quite understandable that even concentrations higher than 30%, for example even 80-90%, can be used successfully for special effects.

Die Verbindungen können beispielsweise bei der Herstellung von Riechstoffkompositionen, die als Riechstoffbasen zur Herstellung von Parfums und Toilettenwasser verwendet werden, dienen, indem man diese Basen in üblicher Weise alkoholisch oder wäßrig verdünnt. Im Falle von Parfums können zweckmäßigerweise ungefähr 15-20 Gewichtsprozent der Base und im Falle von Toilettenwasser etwa 3-5 Gewichtsprozent der Base zum Einsatz gelangen.The compounds can be used, for example, in the preparation of fragrance compositions, which are used as fragrance bases for the production of perfumes and toilet water, by diluting these bases in the usual manner with alcohol or water. In the case of perfumes, approximately 15-20 percent by weight of the base can expediently be used, and in the case of toilet water, approximately 3-5 percent by weight of the base can be used.

Auf analoge Weise können die Basen auch zur Parfümierung von Seifen, Detergentien, Kosmetika etc. eingesetzt werden. Für diese Zwecke ist eine Basenkonzentration von ungefähr 0,5 bis ungefähr 2 Gewichtsprozent am ehesten geeignet.In an analogous manner, the bases can also be used for perfuming soaps, detergents, cosmetics, etc. A base concentration of about 0.5 to about 2 percent by weight is most suitable for these purposes.

Die folgenden Beispiele sollen illustrierend, nicht aber limitierend verstanden werden. Bei den Synthese-Beispielen handelt es sich um die Illustration der bevorzugten Aspekte der synthetischen Herstellung. Sowohl für diese Synthesebeispiele als auch für die Formulierungsbeispiele gilt, daß naheliegende Äquivalente oder naheliegende Ausdehnungen, die dem Fachmann bekannt sind, von der vorliegenden Erfindung ebenfalls umfaßt werden sollten.The following examples are to be understood as illustrative, but not as limiting. The synthesis examples illustrate the preferred aspects of synthetic production. For both these synthesis examples and for the formulation examples, obvious equivalents or obvious extensions, which are known to the person skilled in the art, should also be encompassed by the present invention.

Falls nicht anders angegeben, wurden die IR-Spektren mittels einem Perkin-Elmer 457 Spektrophotometer aufgenommen (Substanz als solche (Film)). Die Absorptionen sind als cm―1 angegeben. Die NMR-Spektren wurden unter Verwendung eines Varian A-60A Spektrophotometers als Chloroform-Di-Lösungen aufgenommen und als gamma-Einheiten relativ zu TMS angegeben. Die Molekulargewichte wurden mittels eines Perkin-Elmer 270 Massenspektrometers bestimmt. Die gaschromatographischen Bestimmungen wurden unter Verwendung einer 2%igen Carbowax® 20M Säule [18 Fuß x 1/8 Inch, wobei 1 Fuß = 30,48 cm und ein Inch = 2,54 cm ist] durchgeführt.Unless otherwise stated, the IR spectra were recorded using a Perkin-Elmer 457 Spectrophotometer recorded (substance as such (film)). The absorptions are given as cm ― 1. The NMR spectra were recorded using a Varian A-60A spectrophotometer as chloroform-D i solutions and reported as gamma units relative to TMS. The molecular weights were determined using a Perkin-Elmer 270 mass spectrometer. Gas chromatographic determinations were performed using a 2% Carbowax® 20M column [18 feet x 1/8 inch, where 1 foot = 30.48 cm and one inch = 2.54 cm].

Beispiel 1example 1 2-(2-Cyanoäthyliden)-3-methylbicyclo[2.2.1]hept-5-en2- (2-cyanoethylidene) -3-methylbicyclo [2.2.1] hept-5-ene

Eine Lösung von 136 g (1,0 Mol) von 2-Formyl-3-methylbicyclo[2.2.1]hept-5-en, 91 g (1,05 Mol) Cyanessigsäure, 3 g (0,05 Mol) Ammoniumhydroxid (58%ige Lösung), 132 ml Dimethylformamid und 170 ml Benzol wurden unter Rückflußtemperatur und Rühren gehalten und das gebildete Wasser mittels Dean-Stark-Falle abgetrennt. Das Gemisch wurde so lange erhitzt, bis die Kohlendioxidentwicklung aufhörte, was ca. 31 Stunden erforderte. Nach beendigter Reaktion wurde das Gemisch abgekühlt und das Lösungsmittel unter vermindertem Druck abdestilliert. Das zurückbleibende Öl wurde unter Vakuum destilliert, wobei 120 g (75,5% Ausbeute) 2(2-Cyanoäthyliden)-3-methyl-bicyclo[2.2.1]hept-5-en anfielen.

  • Sdp. 70―80°C/1,333 mbar;
  • Figure imgb0008
    ;
  • IR 3060, 2250,1460,1380, 760, 740, 726, 700;
  • NMR 1,15 (3H, d, J=7 Hz, Methyl), 4,9-5,5 (1 H, m, Vinyl, H), 5,7-6,1 (2H; m, Vinyl H);
  • MS 159.
    Figure imgb0009
A solution of 136 g (1.0 mol) of 2-formyl-3-methylbicyclo [2.2.1] hept-5-ene, 91 g (1.05 mol) cyanoacetic acid, 3 g (0.05 mol) ammonium hydroxide ( 58% solution), 132 ml of dimethylformamide and 170 ml of benzene were kept under reflux temperature and stirring and the water formed was separated off using a Dean-Stark trap. The mixture was heated until the evolution of carbon dioxide ceased, which took approximately 31 hours. After the reaction was completed, the mixture was cooled and the solvent was distilled off under reduced pressure. The remaining oil was distilled under vacuum, giving 120 g (75.5% yield) of 2 (2-cyanoethylidene) -3-methyl-bicyclo [2.2.1] hept-5-ene.
  • Bp 70-80 ° C / 1.333 mbar;
  • Figure imgb0008
    ;
  • IR 3060, 2250, 1460, 1380, 760, 740, 726, 700;
  • NMR 1.15 (3H, d, J = 7 Hz, methyl), 4.9-5.5 (1 H, m, vinyl, H), 5.7-6.1 (2H; m, vinyl H) ;
  • MS 159.
    Figure imgb0009

Beispiel 2Example 2 2-(2-Cyanoäthyliden)-bicyclo[2.2.1]hept-5-en2- (2-cyanoethylidene) bicyclo [2.2.1] hept-5-ene

Eine Lösung von 100 g (0,82 Mol) 2-Formyl-5-norbornen (Aldrich Chemical Co.), 65 g (0,76 Mol) Cyanessigsäure, 2 ml Ammoniumhydroxid (58%), 132 ml Dimethylformamid und 170 ml Benzol wurden unter Rühren bei Rückflußtemperatur gehalten, wobei das gebildete Wasser mittels Dean-Stark-Falle abdestilliert wurde. Das Gemisch wurde so lange erhitzt, bis die Entwicklung von Kohlenstoffdioxid aufhörte, was ca. 24 Stunden erforderte. Hierauf wurde das Reaktionsgemisch abgekühlt und das Lösungsmittel unter vermindertem Druck abdestilliert. Das zurückbleibende Öl wurde destilliert (Vakuum), wobei 79,6 g (68% Ausbeute) 2-(2-Cyanoäthyliden)-bicyclo[2.2.1]hept-5-en anfielen.

  • Sdp. 76-78° C/1,333 mbar;
  • 1 R 3060, 2260, 1420,1330, 915, 840, 755, 720;
  • NMR 1,3-2,5 (4H, m), 2,9-3,4 (4H, m), 5,0-5,5 (1 H, m), 5,9-6,2 (2H, m);
  • MS 145.
    Figure imgb0010
A solution of 100 g (0.82 mol) of 2-formyl-5-norbornene (Aldrich Chemical Co.), 65 g (0.76 mol) of cyanoacetic acid, 2 ml of ammonium hydroxide (58%), 132 ml of dimethylformamide and 170 ml of benzene were kept under stirring at the reflux temperature, the water formed being distilled off using a Dean-Stark trap. The mixture was heated until the evolution of carbon dioxide ceased, which took about 24 hours. The reaction mixture was then cooled and the solvent was distilled off under reduced pressure. The remaining oil was distilled (vacuum), whereby 79.6 g (68% yield) of 2- (2-cyanoethylidene) bicyclo [2.2.1] hept-5-ene were obtained.
  • Bp 76-78 ° C / 1.333 mbar;
  • 1 R 3060, 2260, 1420, 1330, 915, 840, 755, 720;
  • NMR 1.3-2.5 (4H, m), 2.9-3.4 (4H, m), 5.0-5.5 (1H, m), 5.9-6.2 (2H , m);
  • MS 145.
    Figure imgb0010

Beispiel 3Example 3 2-(2-Cyano-1-methyläthyliden)-bicyclo[2.2.1] ]hept-5-en2- (2-cyano-1-methylethylidene) bicyclo [2.2.1]] hept-5-ene

Eine Lösung von 100 g (0,72 Mol) 2-Acetyl-5-norbornen, (Aldrich Chemical Co.), 65 g (0,76 Mol) Cyanessigsäure, 2 ml Ammoniumhydroxid (58%), 132 ml Dimethylformamid und 170 ml Benzol wurden auf Rückflußtemperatur erhitzt und das Wasser mittels Dean-Stark-Falle abdestilliert. Es wurde so lange erhitzt, bis die Entwicklung von Kohlenstoffdioxid aufhörte, was ca. 24 Stunden erforderte. Nach beendigter Reaktion wurde das Gemisch gekühlt und das Lösungsmittel unter vermindertem Druck abdestilliert. Das zurückbleibende Öl wurde unter Vakuum destilliert, wobei 36g g (31%) 2-(2-Cyano-1-methyläthyliden)-bicyclo[2.2.1]hept-5-en vom Sdp. 73-84°C/1,333 mbar anfielen.

  • IR 3060,2255,2225, 1450, 1420, 1330, 905, 730, 715;
  • NMR 1,2-2,2 (m), 2,7-3,4 (m), 5,0-6,1 (m, Vinyl H);
  • MS 159.
    Figure imgb0011
A solution of 100 g (0.72 mol) of 2-acetyl-5-norbornene (Aldrich Chemical Co.), 65 g (0.76 mol) of cyanoacetic acid, 2 ml of ammonium hydroxide (58%), 132 ml of dimethylformamide and 170 ml Benzene was heated to the reflux temperature and the water was distilled off using a Dean-Stark trap. It was heated until the evolution of carbon dioxide stopped, which took about 24 hours. After the reaction was completed, the mixture was cooled and the solvent was distilled off under reduced pressure. The remaining oil was distilled under vacuum, 36g g (31%) of 2- (2-cyano-1-methylethylidene) bicyclo [2.2.1] hept-5-ene, bp 73-84 ° C./1.333 mbar, being obtained .
  • IR 3060,2255,2225, 1450, 1420, 1330, 905, 730, 715;
  • NMR 1.2-2.2 (m), 2.7-3.4 (m), 5.0-6.1 (m, vinyl H);
  • MS 159.
    Figure imgb0011

Beispiel 4Example 4 2-(2-Cyanoäthyliden)-3-methylbicyclo[2.2.1 ]heptan2- (2-cyanoethylidene) -3-methylbicyclo [2.2.1] heptane

Ein Gemisch von 97g g (0,7 Mol) 2-Formyl-3-methylbicyclo[2.2.1)heptan, 65g g (0,76 Mol) Cyanessigsäure, 2 ml Ammoniumhydroxid (58%), 132 ml Dimethylformamid und 170 ml Benzol wurden unter Rückflußtemperatur erhitzt, wobei das gebildete Wasser mittels Dean-Stark-Falle abgetrennt wurde. Es wurde so lange erhitzt, bis die Entwicklung von Kohlendioxidgas aufhörte, was ca. 24 Stunden erforderte. Nach Beendigung dieser Reaktion wurde gekühlt und das Lösungsmittel unter vermindertem Druck entfernt. Das zurückbleibende Öl wurde destilliert (Vakuum), wobei 87 g (77% Ausbeute) 2-(2-Cyanoäthyliden)-3-methylbicyclo[2.2.1]heptan anfielen:

  • Sdp. 72-85° C/1,333mbar;
  • IR 2940, 2870, 2220, 1610, 1450, 1380, 830, 740;
  • NMR 0,9-1,1 (3H, m), 1.2-2,8 (9H, m), 2,85-3,2 (2H, m), 4,8-5,4 (1H, m);
  • MS 161.
A mixture of 97 g (0.7 mole) of 2-formyl-3-methylbicyclo [2.2.1) heptane, 65 g (0.76 mole) of cyanoacetic acid, 2 ml of ammonium hydroxide (58%), 132 ml of dimethylformamide and 170 ml of benzene were heated under reflux temperature, the water formed was separated off using a Dean-Stark trap. It was heated until the evolution of carbon dioxide gas stopped, which took about 24 hours. After the completion of this reaction, the mixture was cooled and the solvent was removed under reduced pressure. The remaining oil was distilled (vacuum), 87 g (77% yield) of 2- (2-cyanoethylidene) -3-methylbicyclo [2.2.1] heptane being obtained:
  • Bp 72-85 ° C / 1 , 333mbar;
  • IR 2940, 2870, 2220, 1610, 1450, 1380, 830, 740;
  • NMR 0.9-1.1 (3H, m), 1.2-2.8 (9H, m), 2.85-3.2 (2H, m), 4.8-5.4 (1H, m) ;
  • MS 161.

Beispiel 5Example 5 2-(2-Cyanoäthyliden)bicyclo[2.2.1]heptan2- (2-cyanoethylidene) bicyclo [2.2.1] heptane

Eine Lösung von 95 g (0,77 Mol) 2-Formyl-bicyclo[2.2.1]heptan, 65 g (0,76 Mol) Cyanessigsäure, 2 ml Ammoniumhydroxid (58%), 132 ml Dimethylformamid und 170 ml Benzol wurden unter Rückflußtemperatur und Rühren erhitzt und das gebildete Wasser mittels Dean-Stark-Falle entfernt. Es wurde so lange erhitzt, bis die Entwicklung von Wasserstoffdioxid aufhörte, was nach ca. 24 Stunden der Fall war. Nach beendigter Reaktion wurde gekühlt und das Lösungsmittel unter vermindertem Druck entfernt. Das zurückbleibende Öl wurde unter Vakuum destilliert, wobei 88 g (79% Ausbeute) von 2-(2-Cyanoäthyliden)-bicyclo[2.2.1]heptan anfielen.

  • Sdp. 72―80°C/1,333 mbar;
  • IR 2960,2870,2260,1685,1450,1420,1305,920;
  • NMR 1,15-2,8 (10H, m), 2,96 (2H, m), 4,9-5,4 (1 H, m);
  • MS 147.
A solution of 95 g (0.77 mol) of 2-formyl-bicyclo [2.2.1] heptane, 65 g (0.76 mol) of cyanoacetic acid, 2 ml of ammonium hydroxide (58%), 132 ml of dimethylformamide and 170 ml of benzene were added The reflux temperature and stirring were heated and the water formed was removed using a Dean-Stark trap. It was heated until the evolution of hydrogen dioxide stopped, which was the case after about 24 hours. After the reaction was completed, the mixture was cooled and the solvent was removed under reduced pressure. The remaining oil was distilled in vacuo to give 88 g (79% yield) of 2- (2-cyanoethylidene) bicyclo [2.2.1] heptane.
  • Bp 72-80 ° C / 1.333 mbar;
  • IR 2960,2870,2260,1685,1450,1420,1305,920;
  • NMR 1.15-2.8 (10H, m), 2.96 (2H, m), 4.9-5.4 (1H, m);
  • MS 147.

Beispiel 6Example 6 2-(2-Cyanoäthyl)-3-methylbicyclo[2.2.1]heptan2- (2-cyanoethyl) -3-methylbicyclo [2.2.1] heptane

  • a) Ein Gemisch von 10 g (0,062 Mol) 2-(2-Cyanoäthyliden)-3-methylbicyclo[2.2.1]heptan, 10 ml Alkohol und 0,1 g Palladium, aufgebracht auf Aktivkohle (5%), wurde unter einem Wasserstoffdruck von 3,4 Atm (50 psi) solange hydriert, bis ein Äquivalent Wasserstoff absorbiert war. Das Gemisch wurde hierauf filtriert und unter vermindertem Druck konzentriert. Das zurückbleibende Öl wurde unter Vakuum destilliert, wobei 9,6 g (89% Ausbeute) 2-(2-Cyanoäthyl)-3-methylbicyclo[2.2.1]heptan anfielen.
    • Sdp. 55―57C0/0,666 mbar;
    • IR 2940, 2870, 2250, 1700, 1460, 1430, 1380;
    • NMR 0,95,1,1 (3H, 5),1,2-2,5 (14H, m);
    • MS 163.
    a) A mixture of 10 g (0.062 mol) of 2- (2-cyanoethylidene) -3-methylbicyclo [2.2.1] heptane, 10 ml of alcohol and 0.1 g of palladium, applied to activated carbon (5%), was added under a Hydrogen pressure of 3.4 atm (50 psi) was hydrogenated until one equivalent of hydrogen was absorbed. The mixture was then filtered and concentrated under reduced pressure. The remaining oil was distilled in vacuo to give 9.6 g (89% yield) of 2- (2-cyanoethyl) -3-methylbicyclo [2.2.1] heptane.
    • Bp 55-57C0 / 0.666 mbar;
    • IR 2940, 2870, 2250, 1700, 1460, 1430, 1380;
    • NMR 0.95.1.1 (3H, 5), 1.2-2.5 (14H, m);
    • MS 163.
  • b) Das 2-(2-Cyanoäthyliden)bicyclo[2.2.1]heptan (siehe Beispiel 5) kann auf analoge Weise zum 2-(2-Cyanoäthyl)bicyclo[2.2.1]heptan vom Sdp. 80―85c C/1,333 mbar reduziert werden.b) The 2- (2-cyanoethylidene) bicyclo [2.2.1] heptane (see Example 5) can be prepared in an analogous manner to the 2- (2-cyanoethyl) bicyclo [2.2.1] heptane of bp 80―85 c C / 1.333 mbar can be reduced.
Beispiel 7Example 7 Verwendung der Verbindungen I in ParfümbasenUse of the compounds I in perfume bases

Die Verbindungen der vorliegenden Erfindung können eingesetzt werden, um würzige Noten entweder zu erzeugen oder zu verstärken.

Figure imgb0012
The compounds of the present invention can be used to either create or enhance spicy notes.
Figure imgb0012

In obiger Formulierung steht Verbindung A entweder für das geruchlose Diäthylphthalat oder irgendeine Verbindung der vorliegenden Erfindung.In the above formulation, Compound A represents either the odorless diethyl phthalate or any compound of the present invention.

Bei Vergleich von Verbindung A, und zwar dem 2-(2-Cyanoäthyliden)-3-methylbicyclo[2.2.1]hept-5-en, mit Diäthylphthalat in obiger Formulierung wurde gefunden, daß die Anwesenheit von 2-(2-Cyanoäthyüden)-3-methylbicyclo(2.2.1]hept-5-en in dieser Komposition die würzige Note intensivierte, wobei die Kopfnote von fruchtig auf würzig wechselte, der geruchliche Gesamteindruck war stärker und gleichzeitig abgerundeter. Der allgemeine Eindruck war der einer natürlicheren Nelke. Alle anderen Verbindungen der vorliegenden Erfindung können auf analoge Weise eingesetzt werden. Es muß nochmals festgehalten werden, daß die Verbindungen der allgemeinen Formel 11 intensiver wirken und deshalb den Verbindungen der allgemeinen Formel 3 und 4 vorgezogen werden.

Figure imgb0013
Figure imgb0014
 When Compound A, namely 2- (2-cyanoethylidene) -3-methylbicyclo [2.2.1] hept-5-ene, was compared with diethyl phthalate in the above formulation, it was found that the presence of 2- (2-cyanoethylthene) -3-methylbicyclo (2.2.1] hept-5-en intensified the spicy note in this composition, whereby the top note changed from fruity to spicy, the overall smell impression was stronger and at the same time more rounded. The general impression was that of a more natural clove. All Other compounds of the present invention can be used in an analogous manner, it must be noted once again that the compounds of the general formula 11 have a more intensive effect and are therefore preferred to the compounds of the general formula 3 and 4.
Figure imgb0013
Figure imgb0014

Zugabe von 2-(2-Cyanoäthyliden)-3-methyl-bicyclo[2.2.1]hept-5-en wirkt sich auf das Gemisch der Aldehyde im vorliegenden Parfümöl vorteilhaft aus, die ganze Komposition wirkt einheitlicher, während dem die blumige Note beibehalten wird. Mengen von 0,1 bis 1 Gewichtsprozent können hinzu Verwendung finden, wobei 1,0% den optimalen Effekt ergibt. Für spezielle Zwecke können auch höhere Konzentrationen eingesetzt werden.Addition of 2- (2-cyanoethylidene) -3-methyl-bicyclo [2.2.1] hept-5-ene has an advantageous effect on the mixture of aldehydes in the perfume oil at hand, the whole composition appears more uniform, while maintaining the floral note becomes. Amounts of 0.1 to 1 percent by weight can be used, with 1.0% giving the optimal effect. Higher concentrations can also be used for special purposes.

Die anderen Verbindungen der vorliegenden Erfindung können auf analoge Weise eingesetzt werden.The other compounds of the present invention can be used in an analogous manner.

Claims (11)

1. Bicyclo[2.2.1]-heptanes and bicyclo[2.2.1]-hept-5-enes of the general formula
Figure imgb0022
wherein R1 and R2 are alike or different and stand for hydrogen or methyl and the dotted lines represent optinal bonds.
2. Bicyclo[2.2.1]-hept-5-enes of the general formula
Figure imgb0023
wherein R1 and R2 are alike or different and represent hydrogen or methyl.
3.2-(2-Cyanoethylidene)-bicyclo[2.2.1 ]hept-5-ene.
4.2-(2-Cyanoethylidene)-3-methylbicyclo[2.2.1 ]hept-5-ene.
5.2-(2-Cyano-1-methylethylidene)-bicyclo[2.2.1]hept-5-ene.
6. A compound selected from the group consisting of 2-(2-cyanoethylidene)-3-methylbicyc- lo[2.2.1]heptane and 2-(2-cyano-ethylidene)bicycio[2.2.1]heptane.
7. A compound selected from the group consisting of 2-(2-cyanoethyl)-3-methylbicyclo[2.2.1]heptane and 2-(2-cyanoethyl)bicyclo-[2.2.1 ]heptane.
8. Bicyclo[2.2.1 ]heptanes and bicyclo[2.2.1 ]-hept-5-enes of the general formula
Figure imgb0024
wherein R1 and R2 are alike or different and stand for hydrogen or methyl and the dotted lines represent optinal bonds, when used as odorants.
9. A fragrance composition, characterized in that it contains a bicyclo[2.2.1]heptane and/or a bicyclo [2.2.1 ]hept-5-ene of the general formula
Figure imgb0025
wherein R, and R2 are alike or different and stand for hydrogen or methyl and the dotted lines represent optional bonds.
10. Process for the manufacture of bicyclo[2.2.1]heptanes and bicyclo[2.2.1]-hept-5-enes of the formula
Figure imgb0026
wherein R1 and R2 are alike or different and stand for hydrogen or methyl and the dotted lines represent optional bonds, comprising subjecting a compound of formula
Figure imgb0027
wherein R1, R2 and the dotted line are as above, to a Knovenagel reaction by treatment with cyanoacetic acid and decarboxylation, and, if desired, hydrogenating the primary reaction product.
11. The use of the bicyclo[2.2.1 ]heptanes and bicyclo[2.2.1 ]-hept-5-enes of general formula
Figure imgb0028
wherein R1 and R2 are alike or different and stand for hydrogen or methyl and the dotted lines represent optinal bonds, as odorants.
EP78101703A 1977-12-15 1978-12-15 Bicyclo (2.2.1)-hept-5-enes (anes) (i), process for their preparation, their use as perfumes and perfume compositions containing the bicyclic compounds (i) Expired EP0002743B1 (en)

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US860660 1992-03-30

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CA1118450A (en) * 1978-03-20 1982-02-16 Willem Lenselink Menthane nitriles
US5011970A (en) * 1978-03-20 1991-04-30 Pfw(Nederland)B.V. Nitriles useful in perfume
NL8003068A (en) * 1980-05-28 1982-01-04 Naarden & Shell Aroma Chem PERFUME COMPOSITIONS AND PERFUMED MATERIALS AND ARTICLES CONTAINING ESTERS OF BICYCLIC MONOTERPEENIC ACIDS AS RAW MATERIAL.
DE3500057A1 (en) * 1985-01-03 1986-07-03 Basf Ag, 6700 Ludwigshafen NEW 2,3-DISUBSTITUTED BICYCLO (2.2.1) HEPTANES, THEIR PRODUCTION AND THEIR USE AS A FRAGRANCE
FR2621912B1 (en) * 1987-10-16 1990-03-02 Oreal NOVEL NORBORNANE DERIVATIVES, THEIR PREPARATION PROCESS AND COSMETIC AND MEDICINAL COMPOSITIONS CONTAINING THEM
DE3914391A1 (en) * 1989-04-29 1991-01-17 Basf Ag SS, (GAMMA) - UNSATURATED NITRILES, THEIR PRODUCTION AND USE AS A FRAGRANCE
US10723970B2 (en) 2018-07-16 2020-07-28 Promerus, Llc Fragrance compositions containing norbornene derivatives

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US3345419A (en) * 1963-09-25 1967-10-03 Union Carbide Corp Hydration of bicyclo-(2.2.1) heptenes and related nortricyclenes
US3335166A (en) * 1964-09-23 1967-08-08 Union Carbide Corp Exo-cyanobicyclo[2.2.1]heptanes and method of preparation
US3492330A (en) * 1965-12-09 1970-01-27 Union Carbide Corp Norbornane diisocyanates
BE756583A (en) * 1969-10-06 1971-03-24 Givaudan & Cie Sa NORBORNYL DERIVATIVES
CH566969A5 (en) * 1972-02-12 1975-09-30 Givaudan & Cie Sa
FR2191553A5 (en) * 1972-06-29 1974-02-01 Roure Bertrand Dupont Sa
DE2515485C2 (en) * 1975-04-09 1982-10-14 Bayer Ag, 5090 Leverkusen Bicycloaliphatic triisocyanates, process for their preparation and their use
GB1534132A (en) * 1975-12-11 1978-11-29 Polak Frutal Works Alpha beta-disubstituted conjugated nitriles for perfume use
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