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Publication numberUS3325369 A
Publication typeGrant
Publication dateJun 13, 1967
Filing dateMar 26, 1964
Priority dateMay 3, 1963
Also published asDE1213942B, USRE27332
Publication numberUS 3325369 A, US 3325369A, US-A-3325369, US3325369 A, US3325369A
InventorsEdward J Shuster, Willard T Somerville
Original AssigneeInt Flavors & Fragrances Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Perfume compositions containing geranonitrile, cinnamyl nitrile or 2-nonenyl nitrile
US 3325369 A
Abstract  available in
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Description  (OCR text may contain errors)

United States Patent 3,325,369 PERFUME COMPOSITIONS CONTAINING GERAN- ONlTRILE, CINNAMYL NTTRILE OR Z-NONENYL NITRlLE Willard T. Somerville, Fair Haven, N.J., and Edward J. Shuster, Brooklyn, N.Y., assignors to International Flavors & Fragrances, Inc., New York, N.Y., a corporation of New York N Drawing. Filed Mar. 26, 1964, Ser. No. 355,071 6 Claims. (Cl. 167-94) This invention relates to larly to perfume mixtures for use space deodorants and the like.

Soaps and similar compositions are generally blended with perfume mixtures containing at least one ingredient selected to impart a pleasing odor. Often o e-unsaturated aldehydes are used to impart the desired odor. It has been found that one of the most pleasant and acceptable odors is the fresh, citrusy, lemon-like odor which is obtained by blending citral either alone or as an ingredient in a perfume mixture in soaps and like compositions. Other desirable odors are imparted with other aldehydes such as cinnamaldehyde and 2-nonenyl aldehyde.

This application is a continuati0n-in-part of our earlier application Ser. No. 277,695, filed May 3, 1963, now abandoned.

We have found that citral and other such aldehydes have poor stability. Thus citral, when incorporated in various compositions either alone or in a mixture discolors on standing and its odor becomes degraded. The principal object of the our invention, accordingly, is to find a substitute for .u o-unsaturated aldehydes such as citral which, while possessing the desirable characteristics of the aldehydes can be blended in the compositions mentioned either alone or as part of a perfume mixture without substantial deterioration with respect to odor, color or other desirable qualities.

We have found in accordance with our invention that geranonitrile, which is a known substance having the formula in soaps, cosmetics,

has the desired citr-usy, lemon-like odor of citral and when blended in compositions including soap, detergents, cosmetics, space deodorants and the like, shows substantially no discoloration or degradation of odor on storage for long periods of time.

We have also discovered that cinnamonitrile has the quality characteristic of cinnamaldehyde, but with a special green top note. In soap and other compositions, it is decidedly superior to the corresponding aldehyde in both color and odor stability.

In addition, we have found that 2-nonenyl nitrile has the cinnamon-like characteristics of the corresponding aldehyde. The fragrance quality of the latter, however, disappears so rapidly in all media that it is worthless as a perfume. The nitrile, however, is stable and retains its fragrance characteristics as a perfume and in perfume mixtures when used in compositions such as soaps, powders and others as referred to above.

The invention comprises the novel products, the specific embodiments of which are described hereinafter by way of example and in accordance with which we now prefer to practice the invention.

As produced by us geranonitrile contain-s approximately one-third cis form and two-thirds trans form by weight. This isomer mixture is substantially similar in odor properties with citral, and we prefer to use it either alone or in mixtures in compositions such as those mentioned. Simperfumes, and more particuv 3,325,369 Patented June 13, 1967 ilar effects may be obtained if the isomer ratio is not exactly adhered to.

Cinnamonitrile and 2-nonenyl nitrile are prepared in accordance with standard procedures for example from the corresponding oxime and may be obtained either as pure isomers or as mixtures of cis and trans forms. Whether utilized as isomers or as mixtures, the compounds are re markably stable in odor and color.

. We have found in accordance with our invention that the aforesaid nitriles may be utilized alone, as above stated, for example in sachets for use in bureaus and in closets, and in other ways that compositions are normally employed. They may also be employed alone or in mixtures in detergents, cosmetics, soaps, space deodorants and other formulations.

In this connection, we have found unexpectedly that geranonitrile may be combined with soaps which have an alkaline reaction in use, or.in some detergents which have an acid reaction, without changing. its stability with respect to color or odor. Compositions of this sort which include geranonitrile have an extremely long shelf life, while citral, when included in the same compositions, has a relatively short shelf life, as shown by the test below. Similar results are obtained with the nitriles mentioned above and similar nitriles.

The following are examples of the perfume mixtures and soap and other formulations as we now prefer to produce them. It is to be understood that these compositions are preferred examples and the invention is not to be considered as restricted thereto xcept. as indicated in the appended claims.

A total of 100 grams of soap chips were mixed with one gram of the perfume mixture given below until a substantially homogeneous composition was obtained. Another soap composition-was identically prepared except that the geranonitrile of the perfume mixture was replaced with three times the amount of citr-al. Both soap compositions manifested a characteristic lemon-like odor despite the lesser amount of geranonitrile employed.

The perfume mixture consisted of the following ingredients in the parts by weight indicated:

Geranium bourbon 175 Citronellol 150 Geraniol 100 Phenyl ethyl alcohol s Amyl cinnamic aldehyde 200 Cyclamal 20 Lyral n Tetrahydro linalool 37.5 Tetrahydro myrcenol 37.5 Linalool -i 75 Citronellyl acetate Phenyl ethyl'acetate 5 Phenyl acetaldehyde dimethyl acetal l0 Cinnamic alcohol 35 Terpineol a 100 Linalyl acetate 25 Musk ketone 10 Indole 10 Geranonitrile l0 1 Lyral is the registered trademark-0f International Flavors & Fragrances, Inc., for 4-(4methyl, 4-hydroxy amyl)A -cycl0- hexene carboxaldehyde.

Example II.- Testing of soups containing geranortitrile containers in an oven at 140 F. for five days, after which they were compared with duplicate samples kept in closed containers at room temperature. In all cases, soaps containing citral were discolored. The odor of citral was al-' ready in the process of degradation. In contrast, the soaps containing geranonitrile were unchanged both in color and odor.

Example IlI.Preparation of detergent compositions containing geranonitrile A total of 100 grams of a detergent were mixed with 0.15 gram of the perfume mixture given below until a substantially homogeneous composition was obtained. Other detergent compositions were similarly prepared ex- 'cept that the geranonitrile was replaced with three times the amount of citral. Both compositions manifested a characteristic lemon-like odor of substantially equal strength despite the lesser amount of geranonitrile used.

The compositions were identically tested in accordance with the procedure described in Example II with the same results.

The perfume mixture used in preparing the detergents of this example consisted of the following ingredients in parts by weight indicated:

Decyl aldehyde, solution in diethyl phthalate 4 Toilet soap bars were prepared and tested as in Example V. It was found that the aldehyde caused distinct yellowing of the soap bars and that the soap bars containing the nitrile remained white. Moreover, the bars containing the nitrile retained their original fragrance and odor balance whereas the odor balance was noticeably altered in the accelerated tests of toilet soap bars containing the aldehyde.

Example VII .-Liquid detergent containing cinnamonitrile Concentrated liquid detergent samples containing, in the one case 0.2% by weight of cinnamonitrile and in the other 0.2% by weight of cinnamaldehyde were held at room temperature for ten days and compared with one another. At the end of this period an examination showed that the nitrile imparted a more powerful cassia note than the aldehyde, and that with the nitrile there was no change Terpinyl acetate a 100 Terpineol 40 Linalyl acetate 100 Orange oil 350 Geranyl acetate 100 Geraniol Coumarin 2 Geranonitrile 3.5

Example IV.-Preparation of cosmetic powder composition containing geranonitrile A cosmetic powder was prepared by mixing 100 grams of powder with 0.25 gram of geranonitrile in a ball mill.

A second cosmetic powder was similarly prepared except that the geranonitrile was replaced with citral.

These cosmetic powders were oven tested as described in Example II at 100 F. for two weeks and it was ob- I served that the powder containing the citral was discolored and its odor completely degraded, whereas the powder containing the geranonitrile was substantially unchanged in both color and odor.

Example VI .-T oilet soap composition with a perfume composition containing cinnamonitrile A perfume mixture containing the following ingredients in the parts by weight indicated was prepared:

Musk ambrette 4 Coumarin 20 Geraniol 12 Eugenol 24 Cinnamic aldehyde or cinnamo nitrile 24 Methyl diphenyl ether 24 Bois de Rose Oil 12 Lavender spike 34 Rosemary tunisian 36 from the water white color of the original unperf-umed liquid detergent base, while the aldehyde containing sample had changed to a lemon yellow color.

The detergent samples were further tested under use conditions by dissolving 0.5 gram of the perfumed detergents in separate 200 gram portions of warm water. When each was compared with freshly prepared samples of detergent the detergent containing the aldehyde in water exhibited evidence of degradation by change of the characteristic odor and loss of such odor, whereas the comparable nitrile-containing composition retained its full strong cinamon-like odor, without loss of color, whereas the aldehyde containing composition exhibited a yellowish discoloration.

Example VIII .-Powder detergent containing cinnamonitrile A comparison experiment was carried out in which detergent base powder samples containing 0.2 gram of cinnamaldehyde or 0.2 gram of cinnamonitrile per grams of unperfumed detergent base powder were thoroughly mixed in a high speed rotary roller blender. The samples were examined after 10 days storage in closed glass containers at room temperature. It was found that the odor of the aldehyde had lost its characteristics very rapidly, and that the powder had acquired a yellowish cast. The sample containing the nitrile retained its typical cinnamon note in full volume, and there was no change in color.

Example IX .--Cosmetic powder containing cinnamonitrile A comparison experiment was carried out in which cosrnetic talcum powder samples containing one gram of cinnamaldehyde or one gram of cinnamonitrile per 100 grams of unperfumed talcum powder were thoroughly mixed in a high speed rotary blender. The samples were stored in closed glass containers in an oven for one week at 100 F. In this medium the aldehyde note was completely altered and the talcum powder acquired a pale, ivory tint, whereas the nitrile retained its typical note with no discoloration of the powder base.

Example X .C0smetic powder containing trans-Z-nonenyl nitrile Separate mixtures, used as described in the following paragraph, were prepared containing one part trans-2- 'nonenyl nitrile in 1,000 parts of methyl ionone and one part trans-Z-nonenal in 1,000 parts of the same substance.

Comparison experiments were carried out, in which 1% by weight of each mixture was incorporated in cosmetic talcum powder. The cosmetic compositions were tested in the same manner as the previous example, and it was found that there was a complete loss of the aldehyde aroma, whereas in the case of the nitrile the waxy, plantlike odor persisted at the end of the test period.

Example XI.Sap bars containing trans-Z-nonenyl nitrile Separate mixtures were prepared containing one part trans-Z-nonenyl nitrile in 1,000 parts para tertiary amyl cyclohexanone and one part trans-Z-nonenal in 1,000 parts of the same substance.

These mixtures were incorporated into chips, at 1% by weight, mixed and plodded into bars. Some bars containing each perfume mixture were held at room temperature in closed containers for seven days. Other bars containing each mixture were held in closed containers in an oven at 140 F. for the same length of time. It was found that with the aldehyde, even with the samples held at room temperature, there was a noticeable loss of aroma. In the accelerated tests at 140 F. the loss was practically complete. With the nitrile containing samples, in both cases the original strength and balancing effect continued undiminished.

The same tests as above were carried out using 0.1% mixtures of said aldehyde and said nitrile in methyl ionone. The methyl ionone blend with the aldehyde was not much different than methyl ionone alone at the conclusion of the tests. The sample with said nitrile, on the other hand, maintained an unaltered floral and waxy note over the normal woody character of the methyl ionone.

The same tests were carried out using 0.1% mixtures of said aldehyde and said nitrile in diethyl phthalate. Aldehyde-containing soap bars held at 140 F. for only three days showed a marked fatty odor followed by progressive disappearance, until at the end of seven days the soap bars were almost devoid of starting odor. The said nitrilecontaining soaps under the same circumstances retained the typical floral and waxy aroma.

The use of nitriles in cosmetic powders is an especially rigorous test of their stability, since in powders, degradation due to oxidation is accelerated because of the enormous surface area of the powder.

In the standard age acceleration tests used in the above examples a temperature of 110 F. for one week is equivalent to six months at ordinary temperature.

The amount of nitrile which will be effective in our compositions depends upon many factors, including for example, the selected nitrile, the other ingredients present, their amounts and the effects which are desired. We have found that perfume mixtures containing as little as 0.02% by weight of nitrile or even less may be usefully employed. For certain mixtures as much as 12% by Weight or even higher is useful. When these perfume mixtures are used in soaps and other products the amount is the same as is generally employed with ordinary perfume mixtures, i.e., from about 1% to about 3% by weight. Thus, as little as 0.0002% 'by weight of the selected nitrile may be employed to impart desirable aroma characteristics to soaps, cosmetics and other products.

While the description of our invention has been given in terms of what are presently considered the preferred embodiments, it will be obvious to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. It is the intention therefore, that the appended claims cover all such changes and modifications as fall within the spirit and scope of the invention.

In each of the above examples:

The soap base and soap chips used consisted of unperfumed sodium base toilet soap made from tallow and coconut oil.

The substance referred to as detergent powder was a powder obtained from Lever Bros, Co. being sold under the trademark Rinso.

The substance referred to as liquid detergent was a product manufactured by Ultra Chemical Co., known as P-87 Liquid Detergent Base.

What is claimed is:

1. A perfume mixture containing an effective amount of a nitrile selected from the group consisting of geranonitrile, cinnamyl nitrile, 2-noneny'l nitrile and mixtures thereof characterized by substantial freedom from discoloration and odor degradation on storage.

2. A composition comprising a soap together with a perfume mixture containing an effective amount of a nitrile selected from the group consisting of geranonitrile, cinnamyl nitrile, 2-nonenyl nitrile and mixtures thereof characterized by substantial freedom from discoloration and odor degradation on storage.

3. A composition comprising a detergent together with a perfume mixture containing an effective amount of a nitrile selected from the group consisting of geranonitrile, cinnamyl nitrile, 2-nonenyl nitrile and mixtures thereof characterized by substantial freedom from discoloration and odor degradation on storage.

4. A composition comprising a cosmetic together with a perfume mixture containing an effective amount of a nitrile selected from the group consisting of geranonitrile, cinnamyl nitrile, 2.-nonenyl nitrile and mixtures thereof characterized by substantial freedom from discoloration and odor degradation on storage.

5. A composition comprising a space deodorant together With a perfume mixture containing an effective amount of a nitrile selected from the group consisting of geranonitrile, cinnamyl nitrile, 2-nonenyl nitrile and mixtures thereof characterized by substantial freedom from discoloration and odor degradation on storage.

6. A perfume consisting of a mixture of cis and trans isomers of geranonitrile having a citrusy lemon-like odor substantially identical with that of citral but substantially free from discoloration and odor degradation.

No references cited.

ALBERT T. MEYERS, Primary Examiner.

J. D. GOLDBERG, Assistant Examiner.

Non-Patent Citations
Reference
1 *None
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4277377 *Mar 19, 1980Jul 7, 1981Bush Boake Allen LimitedPerfume compositions containing dimethyl heptenonitriles
US4863631 *Jun 24, 1988Sep 5, 1989International Flavors & Fragrances Inc.Dimethyl substituted alkyl nitriles, perfume and bleach compositions containing same organoleptic uses thereof and process intermediates for producing same
US4962089 *Oct 20, 1989Oct 9, 1990International Flavors & Fragrances Inc.Cyano-substituted sulfur-containing compounds, and compositions containing same and organoleptic uses thereof
US4983579 *Jun 29, 1990Jan 8, 1991International Flavors & Fragrances Inc.Reacting geranonitrile with thioacetic acid
US4985402 *Apr 25, 1990Jan 15, 1991International Flavors & Fragrances Inc.2-Methyl-1-nitrilo-2-methyl -1-hydroxylamino-3-(methoxyphenyl) propane, organoleptic uses thereof and processes for preparing same
US5105005 *Sep 12, 1990Apr 14, 1992Haarmann & Reimer GmbhOrganoleptic
US6475473Jul 6, 1999Nov 5, 2002Quest International B.V.Perfume compositions
US6743768Jul 20, 2001Jun 1, 2004Givaudan SaMixture of (9e)-undecenonitrile, (9z)-undecenonitrile, and 10-undecenonitrile; perfumes
US7955839Jun 25, 2007Jun 7, 2011Recology Inc.Systems and methods for converting organic waste materials into useful products
US7985577Jul 24, 2006Jul 26, 2011Recology, Inc.Systems and processes for treatment of organic waste materials with a biomixer
US8809038Mar 20, 2006Aug 19, 2014Recology Inc.Process for treatment of organic waste materials
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DE2910282A1 *Mar 15, 1979Oct 4, 1979Unilever NvNicht keimtoetende, desodorierende toiletteseife, verfahren zu ihrer herstellung und ihre verwendung
EP1174116A1 *Jul 21, 2000Jan 23, 2002Givaudan SAFragrance composition comprising a mixture of nitriles
EP1174117A1 *Jul 12, 2001Jan 23, 2002Givaudan SAFragrance composition comprising a mixture of nitriles
WO2000001360A1 *Jul 6, 1999Jan 13, 2000Behan John MartinPerfume compositions
Classifications
U.S. Classification424/76.4, 512/6
International ClassificationC11D9/44, A61L9/01, C11B9/00, C11D3/50
Cooperative ClassificationC11B9/0061, A61L9/01, C11D3/50, C11B9/0023, C07C255/00, C11B9/0065, C11D9/442
European ClassificationC07C255/00, C11D9/44B, C11B9/00B6, C11D3/50, C11B9/00F, C11B9/00F2, A61L9/01