| JPH02270835 | DIPHENYLHETEROALKYL DERIVATIVE |
| WO/2002/017866 | PRIMARY INTERMEDIATES FOR OXIDATIVE COLORATION OF HAIR |
| WO/2000/000164 | LEAVE-ON HAIR COMPOSITIONS WHICH CONTAIN A DIOL |
GAUDIN JEAN-MARC (FR)
| WO1996018604A1 | 1996-06-20 | |||
| WO2008117254A1 | 2008-10-02 |
| US4146507A | 1979-03-27 |
| Claims 1. Use as perfuming ingredient of a compound of formula (I) in the form of any one of its stereoisomers or a mixture thereof, and wherein n represents 0 or 1 , and R represents a C3_7 linear, branched or cyclic alkyl or alkenyl group optionally comprising an oxygen atom. 2. Use according to claim 1, characterized in that R represents a C4_6 branched or cyclic alkyl or alkenyl group. 3. Use according to claim 1, characterized in that n is 1 and R represents a C4_6 branched or cyclic alkyl or alkenyl group. 4. Use according to claim 1, characterized in that said compound is cis 4-isobutylcyclohexanecarbonitrile, trans 4-isobutylcyclohexanecarbonitrile, or 4-isobutyl- cyclohexanecarbonitrile in the form of a mixture of isomers cis/trans = 30/70. 5. A compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein n is 0 or 1 and R represents a C4_6 branched or cyclic alkyl or alkenyl group, provided that 4-isopropylcyclohexanecarbonitrile, 4-bicyclohexyl-carbonitrile and 4-terbutyl- cyclohexanecarbonitrile are excluded. 6. As a compound of claim 5, cis 4-isobutylcyclohexanecarbonitrile, trans 4- isobutylcyclohexanecarbonitrile, or 4-isobutylcyclohexanecarbonitrile in the form of a mixture of isomers cis/trans = 30/70. 7. A perfuming ingredient in the form of a composition comprising i) at least one compound of formula (I), as defined in claim 1; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant. 8. A perfumed article comprising: i) as perfuming ingredient, at least one invention's compound, as defined above; and ii) a perfumery base. 9. A perfumed article according to claim 8, characterized in that the perfumery base is a perfume, a fabric care product, a body-care product, an air care product or a home care product. 10. A perfumed article according to claim 8, characterized in that the perfumery base is a fine perfume, a cologne, an after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a shampoo, a coloring preparation, a hair spray, a vanishing cream, a deodorant or antiperspirant, a perfumed soap, shower or bath mousse, oil or gel, a hygiene product, an air freshener, a "ready to use" powdered air freshener, a wipe, a dish detergent or hard- surface detergent. |
Technical field
The present invention relates to the field of perfumery. More particularly, it concerns some nitrile derivatives of formula (I), as defined herein below, and their use as perfumery ingredients. The present invention concerns also the compositions and the consumers' articles containing said nitrile derivatives.
Prior art
To the best of our knowledge, only few of the compounds of formula (I) are reported in prior art documents. For instance one may cite 4-isopropylcyclohexanecarbonitrile (reported in US 20020028969 as chemical intermediate) or 4-terbutylcyclohexanecarbonitrile (reported in Org. Lett., 2004, 6, 501 as chemical intermediate).
However, said prior art documents citing a compound of formula (I) do not report or suggest any organoleptic properties of the compounds of formula (I), or any use of said compounds in the field of perfumery. Indeed they all report their use or preparation as chemical as such.
The usefulness of the compounds of formula (I) as perfuming ingredients is surprising in view of the prior art perfuming ingredients. Indeed, to the best of our knowledge, only few cycloalkylnitriles are known as being useful perfuming ingredients (see WO 09/060378 or WO 08/117254). However said prior art ingredients possess a very different odor and chemical structure, and therefore do not suggest any organoleptic properties of the compounds of formula (I), or any use of said compounds (I) in the field of perfumery.
Description of the invention
We have now surprisingly discovered that a compound of formula
I (T) in the form of any one of its stereoisomers or a mixture thereof, and wherein n represents 0 or 1, and R represents a C3_7 linear, branched or cyclic alkyl or alkenyl group optionally comprising an oxygen atom;
can be used as perfuming ingredient, for instance to impart odor notes of the nitrile and/or citrus type, and in particular of the nitrile and citrus type.
According to a particular embodiment of the invention, n is 1, i.e. the invention's compound is a cyclohexyl derivative.
According to a particular embodiment of the invention, n is 1 , and compound (I) is in the form of its trans isomer.
According to a particular embodiment of the invention, R represents a C 4 _6 linear, branched or cyclic alkyl or alkenyl group optionally comprising an oxygen atom.
According to a particular embodiment of the invention, R represents a C 4 _6 branched or cyclic alkyl or alkenyl group, in particular alkyl. Said compounds are also new chemicals, except 4-isopropylcyclohexanecarbonitrile, l,l'-bi(cyclohexyl)-4- carbonitrile and 4-terbutylcyclohexanecarbonitrile, and are therefore also another object of the present invention.
As mentioned above, said compound of formula (I) is in the form of any one of its stereoisomers or a mixture thereof. In particular, said compound can be in the form of a mixture of cis and trans isomers wherein the trans isomers represent more than 50% w/w, or even 70% w/w, of the mixture. In particular said compound can be in the form of a trans isomers.
It is understood that other particular embodiments of the invention may be those comprising several of the above definitions.
As specific examples of the invention's compound, one may cite, as non-limiting example, 4-isobutylcyclohexanecarbonitrile (cis/trans = 30/70), which possesses nitrile, citrusy notes with an interesting and characteristic verbena note.
Although having a quite different chemical structure, said compound is olfactively related to the geranyl/citronellyl nitrile family. For instance, in applications, the invention's compound displays performances which are above those of citronellyl nitrile and as good as 3,7-dimethyl-2,6-nonadienenitrile and methyl geranyl nitrile. However
4-isobutylcyclohexanecarbonitrile odor distinguishes itself from the one of geranyl/citronellyl nitrile family by being less fatty and more lemony/verbena. As other example one may cite cis 4-isobutylcyclohexanecarbonitrile, which possesses an odor similar to the one mentioned above but distinguishing itself by having a stronger nitrile note as well as a bit weaker lemony note.
As other specific, but non-limiting, examples of the invention's compounds, one may cite the following ones in Table 1 :
Table 1 : Invention's compounds and their odor properties
According to a particular embodiment of the invention, the compounds of formula (I) are : cis 4-isobutylcyclohexanecarbonitrile, trans 4-isobutylcyclohexane- carbonitrile, or 4-isobutylcyclohexanecarbonitrile in the form of a mixture of isomers cis/trans = 30/70.
When the odor of the invention's compounds is compared with the one of the prior art compounds described in WO 09/060378 or WO 08/117254, then the invention's compounds distinguish themselves by possessing nitrile/citrus notes and by lacking of, or by not possessing significant, patchouli or lactonic/jasminic/celery/apricot notes so characteristic of the prior art compounds. Similarly the prior art compounds do not possess the characteristic nitrile/citrus notes of the present inventions' compounds. Said differences lend the invention's compounds and the prior art compounds to be each suitable for different uses, i.e. to impart different organoleptic impressions. Indeed the compounds (I) are well suited to impart citrus notes, especially in functional perfumery, while the prior art compounds are not suited for such use.
As mentioned above, the invention concerns the use of a compound of formula (I) as perfuming ingredient. In other words it concerns a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least a compound of formula (I). By "use of a compound of formula (I)" it has to be understood here also the use of any composition containing compound (I) and which can be advantageously employed in perfumery industry as active ingredients.
Said compositions, which in fact can be advantageously employed as perfuming ingredient, are also an object of the present invention.
Therefore, another object of the present invention is a perfuming composition comprising:
i) as perfuming ingredient, at least one invention's compound as defined above;
ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and
iii) optionally at least one perfumery adjuvant.
By "perfumery carrier" we mean here a material which is practically neutral from a perfumery point of view, i.e. that does not significantly alter the organoleptic properties of perfuming ingredients. Said carrier may be a liquid or a solid.
As liquid carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive. However, one can cite as non-limiting example solvents such as dipropyleneglycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2- ethoxyethoxy)-l-ethanol or ethyl citrate, which are the most commonly used.
As solid carrier one may cite, as non-limiting examples, absorbing gums or polymers, or yet encapsulating materials. Examples of such materials may comprise wall- forming and plasticizing materials, such as mono, di- or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins, or yet the materials cited in reference texts such as H. Scherz, Hydrokolloids : Stabilisatoren, Dickungs- und Gehermittel in Lebensmittel, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitat, Behr's VerlagGmbH & Co., Hamburg, 1996. The encapsulation is a well known process to a person skilled in the art, and may be performed, for instance, using techniques such as spray-drying, agglomeration or yet extrusion ; or consists of a coating encapsulation, including coacervation and complex coacervation techniques.
By "perfumery base" we mean here a composition comprising at least one perfuming co-ingredient.
Said perfuming co-ingredient is not of the formula (I). Moreover, by "perfuming co-ingredient" it is meant here a compound, which is used in perfuming preparation or composition to impart a hedonic effect. In other words such a co-ingredient, to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.
The nature and type of the perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of its general knowledge and according to intended use or application and the desired organoleptic effect. In general terms, these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds.
For the compositions which comprise both a perfumery carrier and a perfumery base, other suitable perfumery carrier, than those previously specified, can be also ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol (origin: Dow Chemical Company). By "perfumery adjuvant" we mean here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in perfuming bases cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.
An invention's composition consisting of at least one compound of formula (I) and at least one perfumery carrier represents a particular embodiment of the invention as well as a perfuming composition comprising at least one compound of formula (I), at least one perfumery carrier, at least one perfumery base, and optionally at least one perfumery adjuvant.
It is useful to mention here that the possibility to have, in the compositions mentioned above, more than one compound of formula (I) is important as it enables the perfumer to prepare accords, perfumes, possessing the odor tonality of various compounds of the invention, creating thus new tools for their work.
Preferably, any mixture resulting directly from a chemical synthesis, e.g. without an adequate purification, in which the compound of the invention would be involved as a starting, intermediate or end-product could not be considered as a perfuming composition according to the invention.
Furthermore, the invention's compound can also be advantageously used in all the fields of modern perfumery to positively impart or modify the odor of a consumer product into which said compound (I) is added. Consequently, a perfumed article comprising: i) as perfuming ingredient, at least one invention's compound, as defined above; and ii) a perfumery base;
is also an object of the present invention.
The invention's compound can be added as such or as part of an invention's perfuming composition.
For the sake of clarity, it has to be mentioned that, by "consumer product base" we mean here a consumer product which is compatible with perfuming ingredients. In other words, a perfumed article according to the invention comprises the functional formulation, as well as optionally additional benefit agents, corresponding to a consumer product, e.g. a detergent or an air freshener, and an olfactive effective amount of at least one invention's compound. The nature and type of the constituents of the consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of its general knowledge and according to the nature and the desired effect of said product.
Non-limiting examples of suitable perfumery bases can be a perfume, such as a fine perfume, a cologne or an after-shave lotion; a fabric care product, such as a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, or a bleach; a body-care product, such as a hair care product (e.g. a shampoo, a coloring preparation or a hair spray), a cosmetic preparation (e.g. a vanishing cream or a deodorant or antiper spirant), or a skin care product (e.g. a perfumed soap, shower or bath mousse, oil or gel, or a hygiene product); an air-care product, such as an air freshener or a "ready to use" powdered air freshener; or a home care product, such as a wipe, a dish detergent or hard-surface detergent.
Some of the above-mentioned consumer product bases may represent an aggressive medium for the invention's compound, so that it may be necessary to protect the latter from premature decomposition, for example by encapsulation or by chemically bounding it to another chemical which is suitable to release the invention's ingredient upon a suitable external stimulus, such as an enzyme, light, heat or a change of pH.
The proportions in which the compounds according to the invention can be incorporated into the various aforementioned articles or compositions vary within a wide range of values. These values are dependent on the nature of the article to be perfumed and on the desired organoleptic effect as well as the nature of the co -ingredients in a given base when the compounds according to the invention are mixed with perfuming co- ingredients, solvents or additives commonly used in the art.
For example, in the case of perfuming compositions, typical concentrations are in the order of 0.001 % to 15 % by weight, or even more, of the compounds of the invention based on the weight of the composition into which they are incorporated. Concentrations lower than these, such as in the order of 0.01% to 5% by weight, can be used when these compounds are incorporated into perfumed articles, percentage being relative to the weight of the article.
The invention's compounds can be prepared according to a method comprising the transformation of corresponding aldehyde into the nitrile derivative, Examples of such a method are given herein below in the Examples. Examples
The invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade (°C); the NMR spectral data were recorded in CDCI 3
(if not stated otherwise) with a 360 or 400 MHz machine for 1 H and 13 C, the chemical shifts δ are indicated in ppm with respect to TMS as standard, the coupling constants J are expressed in Hz.
4-Bicyclohexyl-carbonitrile is prepared as described in J. Am. Chem. Soc. 1948, 70, 3177.
Example 1
Synthesis of compounds of formula (I)
A) Preparation of 4-isobutylcyclohexanecarbonitrile
Preparation of4-isobutylcyclohexyl)methanol
1 kg of 4-sec-butylbenzaldehyde (described in J.Med.Chem. 1987, 2121) was added in an autoclave with the 500ml of methanol and lOg of Ru 5% on Alox. Then the reaction was heated at 80°C and let overnight under a pressure of 400 bar of hydrogen and vigorous stirring. Then, the reaction was filtered, the organic phase was washed with brine, dried with sodium sulfate and concentrated to give 1080 g of the pure 4-isobutylcyclohexyl)methanol in a 70/30 cis/trans ratio (quantitative yield). From this cis/trans mixture, a careful distillation on a Fischer column (B.p. 83°C under 2.5 mbar) gave a fraction of cis 4-isobutylcyclohexyl)methanol (97% cis).
13 CNMR of the cis/trans mixture: 22.9(q), 22.9(q), 24.8(d), 25.1(d), 25.4(t), 29.0 (t), 29.5(t), 32.6 (d), 32.9 (t), 35.3 (d), 38.4(d), 40.7(d), 43.5(t), 47.0 (t), 66.3(t), 68.8(t)
13 C NMR of the cis isomer: d 22.9 (q), 25.1 (d), 25.4 (t), 29.0 (t), 32.6 (d), 38.4 (d), 43.5 (t), 66.3 (t)
Preparation of4-isobutylcyclohexanecarbaldehyde
Following the procedure of oxidation procedure described in WO 2003/064362, from 15. Og of 4-isobutylcyclohexyl)methanol (97/3 cis/trans) were obtained 7.5g (46% yield) of 4-isobutylcyclohexanecarbaldehyde (83/17 cis/trans). "C NMR of the cis/trans mixture: 22.8 (q), 24.0 (t), 24.7 (d), 26.0 (t), 29.7 (t), 32.1
(t), 33.7 (d), 34.7 (d); 45.4 (t), 46.7 (t), 47.5 (d), 50.6 (d), 204.9 (d), 205.6 (d) A partial isomerisation of this aldehyde occurs during the distillation (B.p. 80°C under 10 mbar) to give a 30/70 cis/trans quality. The equilibrium (15/85 cis/trans) was obtained by treatment with potassium hydroxide in methanol overnight at room temperature.
13 CNMR of the trans isomer: 22.8 (q), 24.7 (d), 26.0 (t), 32.1 (t), 34.7 (d), 46.7 (t), 50.6 (d), 204.9 (d)
Preparation of4-isobutylcyclohexanecarbonitrile
At 30-40°C, 50g of a 50% solution in water of hydroxylamine (757mmol) was added to a solution of 4-isobutylcyclohexanecarbaldehyde (84g, 83/17 cis/trans) in 100ml isopropanol. At the end of the reaction, followed by GC, the organic phase was washed with water, brine, dried with sodium sulfate and concentrated to give 70g of the crude oxime.
This crude oxime was added, over a period of 4 hours, to 56g of acetic anhydride at 110°C. The reaction was cooled down and 100 ml of pentane was added. Then, the organic layer was washed with water, dried over magnesium sulfate and concentrated to give 46g of the crude nitrile with the same cis/trans ratio as the starting aldehyde. A careful distillation of this quality of nitrile on a Fischer column (B.p. 75-80°C under 0.5 mbar) gave fractions with high percentage of cis isomer (cis/trans ratio 93/7).
13 CNMR of the cis isomer: 22.8 (q), 24.6 (d), 27.3 (d), 28.3 (t), 29.1 (t), 34.2 (d), 46.0 (t), 122.3 (s)
Starting from a 30/70 cis/trans quality of 4-isobutylcyclohexanecarbaldehyde and following the procedure described above, were obtained 4-isobutyl cyclohexanecarbonitrile (30/70 cis/trans) in 40% yield after distillation.
1 3 CNMR of the cis/trans mixture: 22.77(q), 24.59(d), 24.63(d), 27.31(d), 28.38(d),
29.09(t), 29.79(t), 31.81 0, 33.78(d), 34.18(d), 46.02(t), 46.02(t), 46.22(t),
46.22(t), 122.26(s), 122.85(s)
Preparation of 4-(ethoxymethyl)cvclohexanecarbonitrile
Preparation of 4-ethoxymethyl-l-cyclohexanecarbaldehyde Following the oxidation procedure described in WO 2003/064362, from 37g of 4-ethoxymethyl-l-cyclohexylmethanol (J.Mass Spectrometry 1995; 30; 1421) were obtained 19g of 4-ethoxymethyl-l-cyclohexanecarbaldehyde (16/84 cis/trans) after distillation.
1 3 CNMR for the cis/trans mixture: 15.2(q), 23.7(d) 25.5(t), 26.5(t), 28.8(t), 36.8(d),
37.7 (d), 47.3 (d), 50.5(d), 66.4(t), 75.2(t), 76 (t), 204.6 (d), 204.7 (d) 13 C NMR trans isomer: d 15.2 (q), 25.5 (t), 28.8 (t), 37.7 (d), 50.5 (d), 66.4 (t), 76.0 (t), 204.6 (d)
Preparation of 4-( ethoxymethyl)cyclohexanecarbonitrile
Starting from 19g of trans-4-ethoxymethyl-l-cyclohexanecarbaldehyde described above and following the procedure described for 4-isobutylcyclohexanecarbonitrile, were obtained lOg of 4-(ethoxymethyl)cyclohexanecarbonitrile (16/84 cis/trans). 13 C NMR trans isomer: 15.1 (q), 28.3 (d), 28.4 (t), 29.3 (t), 36.8 (d), 66.4 (t), 75.4 (t), 122.7 (s)
13 C NMR for the cis/trans mixture: 15.1 (q), 25.8 (t), 27.2 (d), 27.8 (t), 28.3 (d), 28.4 (t), 29.3 (t), 36.8 (d), 37.2 (d), 66.4 (t), 75.4 (t), 75.5 (t), 122.6 (s); 122.7 (s) Preparation of 3-pentylcyclopentanecarbonitrile
Preparation of2-( tert-butoxymethylene )-5-pentylcyclopentanone
In a 100ml two-necked flask, 60g of 2-(hydroxymethylene)-5-pentylcyclopentanone (Org.Let. 2001, 12; 1897) was dissolved in cyclohexane (160ml). After addition of 59,91 ml of tert-butanol and 100 mg of p-toluenesulfonique acid monohydrate, the mixture was heated under reflux 4 hours while the water formed was collected by a
Dean-Stark trap. The reaction mixture was added to an ice cooled solution of NaHC0 3 (200ml) and extracted with diethylether (200ml). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to give 70.18g of crude product. Distillation (B.p. 150°C under 0.4 mbar) gave 2-(tert-butoxymethylene)-5-pentylcyclopentanone in 71% yield
13 C NMR: 14.1 (q), 22.6 (t), 23.1 (t), 27.0 (t), 27.2 (t), 28.3 (q), 30.3 (t), 31.9 (t), 49.7 (d), 79.6 (s), 116.3 (s), 148.1 (d), 209.2 (s) Preparation of (3-pentyl-l-cyclopenten-l-yl)methanol
To a solution of 2-(tert-butoxymethylene)-5-pentylcyclopentanone (40.64g) in ethanol (400ml) was added NaBH 4 (7.42g). The reaction mixture was stirred for 2 days.
Then poured onto in water (200ml) and HC1 (10%) (100ml), extracted with diethyl ether (200ml). The organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 30.94g of a mixture of 46% 3-pentyl-l-cyclopentene-l-carbaldehyde and 22% (3-pentyl-l-cyclopenten- l-yl)methanol.
A distillation on a Widmer column (B.p. 55-76°C under 0.6-0.4 mbar) gave 22.5g of pure aldehyde.
13 C NMR of the aldehyde: 14.0 (q), 22.6 (t), 27.5 (t), 27.8 (t), 29.8 (t), 31.9 (t), 34.7
(t), 46.7 (d), 146.9 (s), 156.7 (d), 190.1 (d)
1 3 C NMR of the alcohol: 14.1 (q), 22.7 (t), 27.7 (t), 30.5 (t), 32.0 (t), 32.1 (t), 36.1
(t), 45.5 (d), 62.2 (t), 129.9 (d), 143.6 (s)
Preparation of 3-pentylcyclopentanecarbaldehyde
To a solution of 3-pentyl-l-cyclopentene-l-carbaldehyde (14.63g) in ethylacetate (40ml) was added 10% Pd on charcoal (150mg ).The reaction mixture was stirred under atmospheric pressure of hydrogen for 6 hours, then filtered, concentrated under reduced pressure to give 13.9g of crude product. Distillation (B.p. 90°C 0.41mbar) gave l lg of pure 3-pentylcyclopentanecarbaldehyde (70/30 cis/trans; 87% yield).
13 C NMR of the major isomer : 14.1 (q), 22.7 (t), 25.8 (t), 28.3 (t), 32.1 (t), 32.2 (t), 33.4 (t), 35.5 (t), 40.8 (d), 51.6 (d), 204.0 (d)
Preparation of 3-pentylcyclopentanecarbonitrile
Starting from 2.57g of 3-pentylcyclopentanecarbaldehyde described above and following the procedure described for 4-isobutylcyclohexanecarbonitrile, were obtained 2.05 g of crude 3-pentylcyclopentanecarbonitrile.
Then a bulb-to-bulb distillation (90-100 °C / 0.27 mbar) gave 1.75 g of pure product (2 isomers 30/70). "C NMR : Major isomer: 14.0 (q), 22.6 (t), 27.4 (d), 28.2 (t), 30.4 (t), 31.6 (t), 32.0
(t), 35.5 (t), 38.0 (t), 40.1 (d), 123.5 (s)
Minor isomer: 14.0 (q), 22.6 (t), 27.6 (d), 28.1 (t), 30.9 (t), 31.6 (t), 32.0 (t), 35.3 (t),
37.3 (t), 39.2 (d), 125.0 (s)
D) Preparation of 4-(4-methylpentyl)-l-cyclohexanecarbonitrile
Starting from 2g (9.89mmol) of 4-(4-methylpentyl)-l-cyclohexanecarbaldehyde (described in Bul.Soc.Chim.Fr. 391; 1956) and following the procedure described for 4-isobutylcyclohexanecarbonitrile, were obtained 1.99 g of crude 4-(4- methylpentyl)-l-cyclohexanecarbonitrile. Bulb-to-bulb distillation at 115 °C/ 15 mbar gave 1.63 g.
13 C NMR: 22.6 (q), 24.4 (t), 27.9 (d), 28.4 (d), 29.8 (t), 31.6 (t), 36.3 (d), 37.0 (t), 39.2 (t), 122.9 (s)
Example 2
Preparation of a perfuming composition
A powder detergent's perfuming composition, of the lemon type, was prepared by admixing the following ingredients :
Ingredient Parts by weight
Linalyl acetate 130
Anisic aldehyde 30
C IO aldehyde 70
C 8 aldehyde 30
MNA aldehyde 90
Carvone Gauche 110
Citral 135
l,l-Diethoxy-3,7-dimethyl-2,6-octadiene 10
Verdyl acetate 70
Verdyl propionate 60
Eucalyptus essential oil 30
Geraniol 160 Linalool
Hedione ® 0
10%* Neobutenone Alpha ® 2)
10%* Cis-2-methyl-4-propyl-l,3-oxathiane 3)
Terpenes ex orange
Verdox ® 4)
Vertofix Cceur ® 5)
2,4-Dimethyl-3-cyclohexene- 1 -carbaldehyde
2100
* in dipropyleneglycol
1) methyl cis-dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland
2) l-(5,5-dimethyl-l-cyclohexen-l-yl)-4-penten-l-one; origin: Firmenich SA, Geneva, Switzerland
3) origin: Firmenich SA, Geneva, Switzerland
4) 2-tert-butyl-l-cyclohexyl acetate; origin : International Flavors & Fragrances, USA
5) methyl cedryl ketone; origin: International Flavors & Fragrances, USA
The addition of 200 parts by weight of 4-isobutylcyclohexanecarbonitrile (cis/trans = 30/70) to the above-described composition imparted to the letter a reinforced lemon connotation, which was more clean and functional. The use of the prior art cycloalkylnitriles provided totally different results.
Example 3
Preparation of a perfuming composition
A dish wash's perfuming composition, of the verbena type, was prepared by admixing the following ingredients :
Ingredient Parts by weight
Benzyl acetate 150
Cis-3-Hexenol acetate 10
Nonanyl acetate 100
Terpenyl acetate 250 Hexyl acetate 30
Anisic aldehyde 20
10%* Benzoic aldehyde 20
C 10 aldehyde 20 C 11 aldehyde 20
C 8 aldehyde 15
C 9 aldehyde 10
Hexylcinnamic aldehyde 200
Amione 10 Methyl anthranilate 10
Amyl butyrate 5
Cis-3-Hexenol 10
Citronellal 40
Citronellol 200 Coumarine 20
Cis-2-pentyl-l-cyclopentanol l) 40
10%* Damascenone Total l) 20
10%* Damascone Alpha 40
Decal 10 Diethyl 1 ,4-cyclohexane dicarboxylate de l) 80
Geraniol 500
Clove essential oil 20
Hedione ® 2) 250 l,3-Benzodioxole-5-carbaldehyde l) 20 Helvetolide ® 3) 30
Iso E Super ® 4) 100
Lavandin Grosso 20
Lemongrass Oil 40 l-P-menthene-9-carbaldehyde 100 Linalool 200
10%* Menthone 40
10%* Muscenone Delta 0 40
10%* Cis-2-methyl-4-propyl-l,3-oxathiane 5) 20 1%* (2E,6Z)-2,6-Nonadienal
Amyl salicylate
Sclareolate ® 6)
Undecalactone gamma
* in dipropyleneglycol
1) origin: Firmenich SA, Geneva, Switzerland
2) methyl cis-dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland
3) (lS, R)-2-[l-(3',3'-dimethyl-l'-cyclohexyl)ethoxy]-2-methylpropyl propanoate; origin: Firmenich SA, Geneva, Switzerland
4) l-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-l-ethanone; origin: International Flavors & Fragrances, USA
5) 3-methyl-5-cyclopentadecen-l-one; origin: Firmenich SA, Geneva, Switzerland 6) propyl (S)-2-(l,l-dimethylpropoxy)propanoate; origin: Firmenich SA, Geneva,
Switzerland
The addition of 250 parts by weight of 4-isobutylcyclohexanecarbonitrile (cis/trans = 30/70) to the above-described composition imparted to the letter a clear lemony, verbena aspect.
If instead of the invention compounds were used other lemony nitrile (i.e. geranyl nitrile, citronellyl nitrile, 3,7-dimethyl-2,6-nonadienenitrile) the result was a reinforcement of the lemony aspect but without imparting/reinforcing a verbena character.
Again, the use of the prior art cycloalkylnitriles provided totally different results.