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Publication numberUS3926860 A
Publication typeGrant
Publication dateDec 16, 1975
Filing dateDec 17, 1974
Priority dateJan 28, 1974
Publication numberUS 3926860 A, US 3926860A, US-A-3926860, US3926860 A, US3926860A
InventorsRobert L Chappell
Original AssigneeInt Flavors & Fragrances Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Fragrance materials containing cis-2-n-pentyl cyclopropane-1-carboxylic acid
US 3926860 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent [191 1 Dec. 16, 1975 Chappell Robert L. Chappell, Moorestown, NJ.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

[22] Filed: Dec. 17, 1974 [21] Appl. No.: 533,637

Related US. Application Data [63] Continuation-in-part of Ser. No. 436,846, Jan. 28,

1974, abandoned.

[75] Inventor:

[52] US. Cl. 252/522; 252/89; 252/106; 260/468 l-l; 260/514 H [51] Int, Cl. A61K 7/46; C11B 9/00; C07C 61/04 [58] Field of Search 252/89, 522

[56] References Cited UNITED STATES PATENTS 3,786,052 l/1974 Martel et al. 260/240 OTHER PUBLICATIONS Julia and Descoins: Bull. Soc. Chim. France 1970, p. 1805.

Descoins and Julia: Bull. Soc. Chim. France 1970, p. 1816.

D'Yakonov et al.: Zh. Obschei. Khim. 35, 2169 (1965).

Buehler et 211.: Organic Syntheses, pp. 63 and 760-762 (1970).

Arctander Perfume and Flavor Chemicals (Aroma Chemicals) Vol. 1, compound No. 1187 (1969).

Primary ExaminerI-lerbert Levine Assistant Examiner-G. E. Schmitkons Attorney, Agent, or Firm-Arthur L. Liberman, Esq.; l-larold Haidt, Esq.

[57] ABSTRACT Described are perfumed articles, colognes and fragrance compositions containing cis-2-npentylcyclopropane-l-carboxylic acid (substantially in the absence of trans-2-n-pentylcyclopropane-lcarboxylic acid) which imparts thereto long lasting patchouli-like animal, leathery note. The novel compound, cis-2-n-pentylcyclopropane-l-carboxylic acid so useful is prepared by means of a process comprising the steps of (i) first preparing cis-2-n-penty1cyclopr0- pane-l-methanol from cis-2-octen-1-o1; then (ii) oxidizing the cis-n-Z-pentylcyclopropane-l-methanol to form a mixture of cis-2-n-pentylcyc1opropane-1- carboxaldehyde and trans-2-n-penty1cyclopropane-1- carboxaldehyde; (iii) oxidizing the mixture of cis and trans-2-n-pentylcycl0propanel-carboxaldehyde to form a mixture of cis and trans-2-n-pentylcyclopropane carboxylic acids; and (iv) using column chromatography separating the mixture of cis and trans-2-n-penty1cyclopropane carboxylic acids to form the desired product.

6 Claims, No Drawings FRAGRANCE MATERIALS CONTAINING CIS-Z-N-PENTYL CYCLOPROPANE-l-CARBOXYLIC ACID RELATED APPLICATION This application is a continuation-in-part of application for US. Letters Patent Ser. No. 436,846 filed on Jan. 28, 1974, and now abandoned.

BACKGROUND OF THE INVENTION Materials which can provide patchouli-like animal and leathery notes are desirable in the art of perfumery. The natural material, patchouli oil, which provides such fragrance notes and contributes desired nuances to perfumery compositions is high in cost, and varies in quality from one batch to another and is subject to the 'usual variations of natural products.

There is accordingly a continuing effort to find synthetic materials which will replace the essential fr'agrance notes provided by natural patchouli oil. Unfortunately, many of the synthetic materials either have, the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the compositions. The search for materials which can provide a more refined patchouli-like fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.

The prior art is replete with synthetic materials which purport to contribute patchouli-like fragrances, for

example, Buchi et al., 83 J.Am.Chem.Soc., 927 (1961) is disclosed as Compound 487 in Perfume and Flavor Chemicals (Aroma Chemicals) Volume 1, Arctander published 1969 as having a powerful, winey, herbais a key component for patchouli fragrance having a patchouli-like animal, leathery note and having the capability of imparting such notes to perfumes and cosmetic compositions. Surprisingly, this novel compound has fragrance properties which are surprisingly different in kind from other known compounds and compositions in the prior art, to wit:

i. Beilstein, Volume E III 9, page 101 disclosing 2-nhexyl-cyclopropane-carboxylic acid-(1) (no disclosure of aroma);

ii. Snejkal et al., Collection Czech. Chem. Communications 25, 1746-50 (1960) discloses interalia, cisisobutyl cyclopropane carboxylic acid (no disclosure of aroma);

iii. Danilkina and Dyakonov, Zh. Obshch. Khin., 34 (9) 3129-30 (1964) discloses 2-butyl cyclopropane carboxylic acid (cis/trans mixture with no aroma disclosed);

iv. Dolgii et al., Farmakol. Toksikol. 30 (2 199-203 (1967) discloses 2-n-pentylcyclopropane carboxylic acid (no reference made to isomeric configuration or to aroma);

v. Dyakonov et al., Zh. Obschei. Khim. 35, 2169 (1965) discloses mixtures of cis and trans-Z-pentylcyclopropane carboxylic acid, the trans acid being in the major proportion. No reference is made to aroma;

vi. Julia et a1. Bull Soc. Chim. France 1970, 1805 discloses cis-2-n-butyl cyclopropane carboxylic acid ethyl ester at page 1808 without reference being made to its aroma.

THE INVENTION The invention comprises the use in perfumery of the novel compound, cis-Z-n-pentylcyclopropane-l-carboxylic acid, novel fragrance compositions, perfumed articles and Colognes containing cis-2-n-pentylcyc1opropanel-carboxylic acid, substantially in the absence of trans-2-n-pentylcyclopropane-l carboxylic acid, the specific embodiments of which are described hereinafter by way of example and in accordance with which it is now preferred to practice the invention.

Briefly, the present invention provides cis-2-n-penty1- cyclopropane-l-carboxylic acid having the structure:

+ (CHZI 2 Zn- Cu couple H ii. Conversion of the cis-2-n-pentylcyclopropane methanol to a mixture of cis and trans-2-n-pentylcyclopropane carboxaldehyde per the following 35 The second reaction, the oxidation of the mixture of cis and trans-2-n-pentylcyclopropane methanol to the mixture of cis and trans-2-n-pentylcyclopropane carboxaldehyde is most preferably carried out using a chromic acid oxidizing agent. Other oxidizing agents which may be used in this reaction in place of chromic acid are potassium permanganate, oxygen and air. It is most preferable to carry out this second oxidation reac- IQ H OH I tion in the presence of a solvent such as pyridine al- I though other solvents are also useful, such as alphapicoline, beta-picoline, gamma picoline, piperidine and.

reaction: ethanol amine.

0 5 I z N VIO} a trans C H N aldehyde H H (py n H H iii. Conversion of the mixture of cis and trans-2 -npentylcyclopropane carboxaldehyde to a mixture of cis and trans-2-n-pentylcyclopropane carboxylic acid; and

iv. Separation of the mixture of cis and trans-2-n-pentylcyclopropane carboxylic acids thereby recover ing 2-cis-n-pentylcyclopropanel -carboxylic acid.

2. Recovery of cis-2-pentylcyclopropane-l-carboxylic acid from patchouli oil using chromatographic techniques as more fully described in Example II, infra.

In the synthesis of cis-2-pentylcyclopropane-l-carboxylic acid, the first of the three reactions is carried out using an excess of diiodomethane and cis-2-octen-l -ol. The reaction is most preferably carried out in an inert solvent such as diethyl ether or cyclohexane. The reaction is carried out preferably under reflux conditions at atmospheric pressure (thus, in the case of the use of diethyl ether as a solvent, the temperature of 65 reaction is 36-46C). The reaction takes place in the presence of a zinc-copper couple prepared by admixing the Zinc dust cuprous chloride powder and solvent be used in the reaction.

The third reaction which is the oxidation of the mixture of cis and trans-2-n-pentylcyclopropane carboxaldehydes to the mixture of cis and trans-Z-n-pentylcyclopropane-l-carboxylic acids is most preferably carried out using a silver oxide oxidizing agent in base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate in aqueous solution. This second oxidizing reaction is preferably carried out in a solvent such as ethanol or benzene or any other suitable solvent.

The fourth step of this process involves the separation of the cis isomer from the trans isomer of 2-n-pentylcyclopropane-l-carboxylic acid. Such a separation is carried out using chromatographic techniques such as column chromatography techniques as further exemplified in Example I (D), infra.

[t has been found that cis-n-pentylcyclopropane-lcarboxylic acid useful in the practice of this invention possesses patchouli-like animal, leathery note with good intensity and persistence. This fragrance quality particularly adapts cis-Z-n-pentylcyclopropane-l-carboxylic acid for incorporation into patchouli perfume compositions, and fragrance modifying compositions. It will be appreciated by those skilled in the art from the present disclosure that the fragrance. character of the finished perfume compositions can-be tailored to specific uses as more fully described hereinafter.

Purified cis-2-n-pentylcyclopropanel -carboxylic acid is an olfactory agent and can be incorporated into a wide variety of compositions which will be enhanced by its patchouli-like animal, leathery note. Cis-2-n-pentylcyclopropane-l-carboxylic acid can be added to perfume compositions in its pure form or it can be added to mixtures of materials in fragrance imparting compositions to provide a desired fragrance character for finished perfume material. The perfume and fragrance compositions obtained according to this invention are suitable in a wide variety of perfumed articles, and can also be used to enhance, modify or reinforce natural fragrance materials. It will thus be appreciated that cis-2-n-pentylcyclopropane-l-carboxylic acid is useful as an olfactory agent and fragrance.

The term perfume composition is used herein to mean a mixture of compounds, including, for example, natural oils, synthetic oils, alcohols, aldehydes, ketones, esters, lactones, and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain (a) the main note or the bouquet or foundationstone of the composition; (b) modifiers which roundoff and accompany the main note; (0) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually low-boiling fresh-smelling materials. Such perfume compositions of this invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, and the like.

In perfume compositions the individual components contribute their particular olfactory characteristics, but the overall efiect of the perfume composition will be the sum of the effect of each ingredient. Thus, the cis-2-n-pentylcyclopropane-l-carboxylic acid of this invention can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient of the composition.

The amount of cis-2-n-pentylcyclopropane-l-carboxylic acid of this invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as much as 50% or as little as 3.0% by weight of mixtures or compounds of this invention, or even less can be used to impart a patchouli-like, leather, animal note to soaps, cosmetics and other products. The amount employed will depend on considerations of cost, nature of the end product,

IICHZ OH the effect desired in the finished product, and the particular fragrance sought. i

The cis-2-n-pentylcyclopropane-l-carboxylic acid disclosed herein can be used alone, in a fragrancemodifying composition, or in a perfume composition as an olfactory component in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil, bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun screens; powders such as talcs, dusting powders, face powder and the like. When the cis-2-npentylcyclopropane-l-carboxylic acid of this invention is used in perfumed articles such as the foregoing, it can be used in amounts of 0.1% or lower. Generally, it is preferred not to use more than about 10% in the finished perfumed article, since the use of too much will tend to unbalance the total aroma and will needlessly raise the cost of the article.

The following examples serve to illustrate embodiments of the invention as it is now preferred to practice it. It will be understood that these examples are illustrative and the invention is to be considered restricted thereto only as indicated in the appended claims.

EXAMPLE I A. Preparation of cis-2-n-pentylcyclopropane methanol Zn-Cu lr ICH (couple) H A suspension of 38 gms. of zinc dust and 58 gms. of cuprous chloride powder in 125 ml of ether are stirred under reflux for 30 minutes. Diiodomethane (24.8 ml) is added dropwise over a 20 minute period. No external heat is required and the addition is carried out at a rate sufficient to maintain reflux (3641C). The alcohol is then added dropwise over a 20 minute period without external heating. Reflux is maintained (4146C) throughout addition of alcohol. The reaction mass is refluxed daily for 8% hours for 5 days (42 hours in all) adding more ether and diiodomethane as required. The course of the reaction is followed by GLC (20' X A" 5% SE-30 prog. -220C at 4/min.):

Sample Starting No. Cl-l l Material Product 1 10 hours 19% 39.7% 30.7% 11 24 hours 52.3% 22.6% 20.1% 111 33 hours 44.0% 21.9% 28.6%

Fr. Vapor Liq. No. Temp. Temp. Vacuum Comments (mm/Hg) 1 60/70 65/73 1 2/14 diiodomethane GLC analysis of FR. No. 7 shows the mixture to be C H CH C H A C 11 H 5 11 H NaOH bowax column, programmed l00200C at 4/min.) shows one major product (82.3%). The crude aldehyde is not purified nor submitted for spectral data but is immediately oxidized to the acid with silver oxide.

C. Preparation of cis and trans-2-n-pentylcyclopropane- 1 -carboxylic acid Silver oxide is prepared by adding 100 ml of sodium hydroxide to a stirred solution of gms. of

silver nitrate in ml of water. The resulting precipi- 70.7% product and 19.1% starting material. (GLC 30 tate is filtered and dried.

conditions: 20 X A 5% Carbowax column, programmed 100-200C at 4/min.).

CrO

CH OH 3 Chromium trioxide (25 gms.) is dissolved in 25 ml of water. The aqueous chromic acid solution is then added slowly to pyridine 250 ml cooled to 5C. The alcohol is then added dropwise to the solution at 05C with stirring in 5 minutes. The reaction is allowed to warm to room temperature (22C) and is stirred overnight. The reaction is worked up by pouring into 500ml of water and then removing any remaining solids by filtration. The aqueous mixture is extracted with 250 ml of ether and twice more with ml portions of ether. The ether extracts are bulked and washed twice with equal volumes of water and once with 5% hydrochloric acid to remove any remaining pyridine. One final wash with water and the ether solution is dried over magnesium sulfate. Stripping the ether under house vacuum gives 1 1 gms. of residue. An Ir rum on the Perkin-Elmer 237 shows the product to be mostly aldehyde. GLC analysis (20 X A 5% Car- Silver oxide (20 gms.) is placed in 500 ml reaction flask along with 200 ml of 2 B alcohol. Aqueous sodium hydroxide ml, 20%) is added and 10 gms. of npentylcyclopropane2-carboxaldehyde in 20 ml of 2 B 5 11\ /cno Pyridine H i 1.4 H

H eye 1 alcohol is added dropwise in 3 minutes. The mixture is times with ml portions of ether. The aqueous layer is acidified with 10% hydrochloric acid and then extracted with 100 ml of ether. The ether extract is washed twice with an equal volume of water and dried over magnesium sulfate. The filtered ether solution is evaporated to net 5.5 gms. of acid. This acid is characterized as follows: 1 gram of the acid is treated with an excess of diazomethane in ether to make the methyl ester..The excess diazomethane is consumed with a few drops of acetic acid and excess acetic acid is removed with aqueous sodium bicarbonate. Ether solution is dried and stripped of solvent. The remaining (ca. 4 gms) acid is combined with 3 gms. of Primol and distilled over a three inch micro-Vigreaux column without reflux:

Fr. Vap. Liq. No. Temp. Temp. Vacuum Wt. (gms.)

Residue: 0.4 gms.

Both the cis and trans isomers of the methyl ester are trapped from a X A1." 5% Carbowax column at 145C (isothermal). The mixture is found to be 70% trans isomer and 30% cis isomer.

Mass Spectral Analysis Only two major peaks are detected, both with an apparent molecular weight of 170. Fragmentations are almost identical with the exception of peak inversion at m/e 138 and 139 and also at m/e 127 and 128. In peak No. 1 (cis isomer) m/e 138 and 128 are the more intense; whereas in the scan of peak No. 2 (trans isomer) m/e 139 and 127 are the more intense. Also the scan of peak No. 1 corresponds with the mass spectral analysis of the ester of the natural isolate prepared according to the above procedure (See page 21 referring to TLC Spot No. 2).

The infrared analysis spectrum of peak No. l (the cis isomer) is identical with that of the isolate methyl ester from TLC spot No. 2 (prepared according to the procedure set forth on page 21, infra).

I Value:

Carbowax 20M SE-30 Peak No. 1 (Minor) 8.67 8.00 Peak No. 2 (Major) 8.87 8.19

D. Isolation of cis 2-n-pentylcyclopro pane- 1 -carboxylic acid The 4.0 gms. of the 5.5 gms. of cis and trans isomers of 2m-pentylcyclopropane-l-carboxylic acid prepared in Part (C) are dissolved in benzene and applied to a sllicic acid column and developed carefully using methylene chloride-methanol (3:1). The eluates containing the cis acid are combined, concentrated to dryness and characterized using NMR analysis. The NMR results EXAMPLE II Isolation of cis-Z-N-pentylcyclopropanel -carboxylic acid from patchouli oil Patchouli oil (4 kg.) is diluted with 4 liters of ethyl ether in an open-head separatory funnel. The solution is extracted with four liters of 10% sodium hydroxide solution stirring vigorously with a mechanical stirrer. The aqueous layer is separated and washed four times with 2 liters of ether (total). The aqueous solution is acidified with ice-cold 20% hydrochloric acid to a pH of 2. and then extracted three times with a total of 2 liters of ether. The combined ether portions are washed twice with water, dried over magnesium sulfate and evaporated under reduced pressure to net 46.2 gms. of an amber colored oil.

Twenty grams of the 46 gms. of amber colored oil produced as indicated above is dissolved in 200 ml. of ethyl ether. The solution is extracted three times with 200 ml. portions of 10% sodium bicarbonate solution. The combined aqueous extracts are acidified to a pH of 2.0 with 20% hydrochloric acid and extracted twice with 200 ml. portions of ether. The combined ether portions are washed with saturated salt solution till neutral, dried over magnesium sulfate, and evaportated under reduced pressure to net 4 gms. of the bicarbonate soluble acids. The ether solution of the bicarbonate-insoluble phenolic acids is washed neutral with saturated salt solution and dried over magnesium sulfate. The ether is evaporated under reduced pressure to net 16 gms. of the phenolic acid portion (yellow oil). The 4 gms. of the bicarbonate-soluble patchouli acids are treated with a slight excess of diazomethane to give a mixture of methyl esters which are submitted for GC-MS, capillary GLC and I values.

A portion of the bicarbonate-insoluble phenolic acids (10.6 gms.) is combined with 21.3 gms. of Primol and distilled over a microvigreaux column (3 inch vacuum jacket without reflux head):

Fr. Nos. 3 and 4 solidified. The solid fractions are bulked and recrystallized twice from methanol to give a white crystalline solid (0.9 gms.), m.p. 4244C.

The remaining portion of the patchouli acid mixture is taken up in 1 10 ml. of ether and extracted twice with equal volumes of 10% cold sodium bicarbonate solution. The aqueous layers is combined and washed three times with 200 ml. portions of ether. The combined ether layers (including the ether layer from the bicarbonate extraction) is extracted with 300 m1. of 5% aqueous sodium hydroxide solution and separated. The ether layer is dried and stripped of solvent to net 0.3 gms. of residue. The aqueous layer is acidified with 43 ml. of concentrated hydrochloric acid to a pH of 3.0 at 05C. The acidified aqueous layer is extracted three times with 200 ml. portions of ether. The combined ether portions are washed neutral with saturated brine, dried over magnesium sulfate and stripped of solvent to net 16.6 gms. of the Phenolic Acids.

The aqueous layer is acidified with 22 ml. of concentrated hydrochloric acid to a pH of 3.0 at O5C. The acidified aqueous layer is extracted three times with ml. portions of ether. The aqueous layer is discarded and the ether layer is washed neutral with saturated brine and dried over magnesium sulfate. The ether is stripped under reduced pressure to give 4.3

gms. of the bicarbonate-soluble acids. The acids are tested with an excess of diazomethane to give the methyl esters.

A preliminary TLC analysis (is performed on 0.25 mm precoated TLC plates silica gel F-254 distributed by EM Reagents Div. of Brinkmann Instruments, Inc. X 20 cm). A number of solvent systems are tried (i.e. tert.-Butanol-ammonium hydroxide-95:5, CH Cl CH Ol-I 3:1 CH Cl -CH OH (3: 1 NH vapor. The latter is found to give the best results. The NH vapor is introduced into the system by simply placing a few ml. of concentrated ammonium hydroxide solution in a beaker and placing the beaker in the developing tank allowing the system to come to equilibrium prior to placing the TLC plates in the tank) of the phenolic acid portion shows six spots. The six spots are scraped from the plate and the silica from each spot is collected separately. The spots are located under short wave U.V. light. Each of the six samples of silica gel collected are extracted with 5 ml. of ether. Evaporation of the ether solutions on perfume testing blotters shows that only materials from spots Nos. 2, 5 and 6 have any odor at all. Spot No. 3, the most intense and largest spot, is found to have the same retention time (TLC) as samples of the two pyrones isolated and characterized.

Large samples of the odoriferous TLC isolates are obtained using 20 X 20 cm preparative TLC plates. Plates are prepared 1 mm thick using silica gel HG-254 (Brinkmann) and are developed in the same manner with methylene chloride-methanol 3:1 saturated with ammonia vapor. A total of 40 prep. plates are prepared, streaked with an ether solution of the phenolic acids developed and examined under UV light. A separation comparable to that obtained with the precoated plates are observed and the three odoriferous sections are removed carefully and separately from the plates. The three portions of silica gel collected from the appropriate areas of the TLC plates are extracted separately with ether in Soxhlet extractors for approximately 4-5 hours. The ether solutions obtained are concentrated with a stream of nitrogen gas. Standard GLC analysis (20' X W 50% carbowax column and 5% SE-30 column programmed 150220C at 2/min.) shows that none of the three odoriferous isolates are homogeneous.

The odoriferous component of TLC spot No. 2 was extracted in ether and a portion is treated with a slight excess of diazomethane and the major component of the methylated mixture is trapped (20 X /4 5% SE-30 column, programmed 100200C at C/min.) and submitted for spectral tests. The free acid obtained from the above ether extract of TLC spot No. 2 is trapped from a 8' X /4" carbowax-isophthalic acid column and submitted for spectral tests and odor evaluation.

No odoriferous components could be trapped from TLC spot No. 6.

TLC spot No. 5 has a strong phenolic, smokey odor and the major peak is trapped for spectral data (IR). A white crystal-line compound precipitated from the ether solution (extract) upon concentration. The solid is filtered and recrystallized from ether. This compound is submitted for spectral tests and the IR is found to be identical with that of the trapped major peak from the ether solution. This component is later shown to be an artifact.

12 TLC spot No. 2 (major peak trapped on an 8' X A" 20% carbowax-isophthalic acid column, programmed l30220C at 2/min.).

NMR:

Chemical Shift(8) Description Assignment 1.10 0.82 6H multiplets a&b

1.30 8H multiplets c 1.50 1H multiplet d H Cl (a) (b) A H 1; 2)4 CO H Mass Spectral Analysis A parent peak at m/e 156 is apparent. The five most abundant peaks in decreasing order of abundance are: m/e 73, 55, 41, 56 and 84. A strong m-18 is also noted.

v max: 2.9-3.9 to OH (carboxylic acid) 5.90; C=O U.V. and Raman The acid obtained from TLC spot No. 2 is converted to the methyl ester with diazomethane. The major peak is trapped and submitted for spectral tests:

Mass Spectral Analysis Parent peak at m/e 170 is apparent and a strong m-31 (m/e 139 is noted (RC o, indicative of methyl esters). The six most abundant peaks in decreasing order of abundance are: m/e 87, 55, 27, 41, 29, 96

max: 1728 cm" C=O (conjugated ester) but no C=C absorption in IR or Raman.

Based on the above spectral data, the structure of the isolate from TLC spot No. 2 is2-n-pentylcyclopropanel-carboxylic acid. The cis-Z-n-pentylcyclopropane-lcarboxylic acid is synthesized as described in Example I and is found to be identical with the isolate from TLC spot No. 2.

EXAMPLE Ill Perfume Formulation The following woody cologne perfume formulation is prepared:

Parts Ingredients by Weight Bergamot oil Orange oil 200 Lemon oil 50 Eugenol l0 4-(4-methyl-4-hydroxy amyl) A cyclohexene carboxalde'hyde 40 3aMethyl-dodecahydro-6,6,9a-

trimethylnaphtho-(2,l-b) furan 5 Product produced by reaction of acetic I anhydride, polyphosphoric acid and 1,5,9-trimethyl cyclododecatrienel 5.9 according to the process of Example I of US. Pat. No. 3,7l8,697 Cis-2-n-pentylcyclopropane- I -carboxylic acid prepared according to Example I (D) LII Cis-2-n pentylcyclopropane-l-carboxylic acid imparts a warm patchouli-like character to this woody cologne composition. i

EXAMPLE IV Preparation of a Soap Composition A total of 100 gm. of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil are mixed with 1 gm. of the perfume composition set forth in Example III until a substantially homogenous composition is obtained. The soap composition manifests a characteristic woody cologne aroma having a warm patchouli-like character.

EXAMPLE V Preparation of a Soap Composition A total of 100 gm. of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil is mixed with 1 gm. of cis-2-n-pentylcyclopropane-l-carboxylic acid until a substantially homogeneous composition is obtained. The soap composition manifests a warm patchouli-like animal, leathery character.

EXAMPLE VI Preparation of a Detergent Composition A total of 100 gm. of a detergent powder sold under the trademark RINSO are mixed with 0.15 gm. of a perfume composition containing the mixture obtained in Example III until a substantially homogeneous composition having a woody cologne fragrance with a warm patchouli-like character is obtained.

EXAMPLE VII Preparation of a Cosmetic Base A first cosmetic powder is prepared by mixing 100 gm. of talcum powder with 0.25 gm. of the perfume composition of Example III in a ball mill. A second cosmetic powder is similarly prepared except that the mixture produced in Example III is replaced with the product produced in Example II, cis-2-n-pentylcyclopropane-l-carboxylic acid. The cosmetic powder containing the material of Example III has a woody cologne fragrance with a warm patchouli-like character. The cosmetic powder produced using the material of Example II has a warm patchouli-like animal, leathery character.

EXAMPLE VIII Liquid Detergent Containing cis-2-n'pentylcyclopropane- 1 -carboxylic acid Concentrated liquid detergents with a patchouli-like odor containing 0.2%, 0.5% and 1.2% of the product produced in accordance with the process of Example II, cis-Z-n-pentylCyclopropane-l-carboxylic acid, are prepared by addingthe appropriate quantity of cis-2-npentylcyclopropane-l-carboxylic acid to the liquid detergent known as P-87. The patchouli-like animal, leathery aroma of the liquid detergent increases with increasing concentration of the cis-2-n-pentylcyclopropane-l-carboxylicacid of this invention.

. EXAMPLE IX Preparation of Cologne and Handkerchief Perfume The composition of Example III is incorporated in a cologne having a concentration of 2.5% in aqueous ethanol; and into a handkerchief perfume in a concentration of 20% (in ethanol). The use of the composition of Example III affords a distinct and definite woody cologne aroma having a warm patchoulilike character to the handkerchief perfume and to the cologne.

EXAMPLE X Cologne and Handkerchief Perfume The cis-Z-n-pentylcyclopropane-l-carboxylic acid produced by the process of Example II is incorporated into a cologne having a concentration of 2.5% in 85% ethanol; and into a handkerchief perfume in a concentration of 10% (in 95% ethanol). The cis-2-n-pentylcyclopropane-l-carboxylic acid produced in Example [I affords a distinct and definite warm patchouli-like animal, leathery aroma to the handkerchief perfume and to the cologne.

What is claimed is:

1. An olfactory sense affecting composition of matter selected from the group consisting of perfume compositions, perfumed articles and colognes comprising cis-2-n-pentylcyclopropane carboxylic acid in the absence of trans-2-n-pentylcyclopropane carboxylic acid and a composition of matter selected from the group consisting of:

Natural perfume oils; Synthetic perfume oils; Alcohols;

Aldehydes;

Ketones;

Esters;

Lactones;

Detergents;

Soaps;

Bath Preparations; Hair Preparations; Cosmetic Preparations; and Powders 2. A perfume composition comprising cis-2-n-pentylcyclopropane-lcarboxylic acid substantially in the absence of trans-2-n-pentylcyclopropane carboxylic acid and at least one adjuvant selected from the group consisting of natural perfume oils; synthetic perfume oils, alcohols, aldehydes, ketones, esters and lactones.

3. A perfumed article comprising cis-2-n-pentylcyclopropane-l-carboxylic acid substantially in the ab- 15 sence of trans-2-n-pentylcyclopropane-l-carboxylic acid and a detergent, soap, bath preparation, hair preparation, cosmetic preparation, or powder.

4. A process for producing a perfumed composition comprising the step of admixing a composition of matter selected from the group consisting of natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, esters, lactones, a detergent, soap, bath preparation, hair preparation, cosmetic preparation, or powder with a fragrance imparting amount of cis-2-n-pentylcyclopropane-l-carboxylic acid substantially in the absence of trans-2-n-pentylcyclopropane-l-carboxylic acid.

5. A cologne composition comprising cis-2-n-pentylcyclopropane-l-carboxylic acid substantially in the absence of trans-2-n-pentylcyclopropanel-carboxylic acid, ethanol and water.

6. An olfactory sense affecting composition of matter comprising (1) a product produced by a process comprising the steps of:

16 i. Treating cis-2-octen-l-ol with methylene diiodide in the presence of a copper-zinc couple to produce cis-2-n-pentylcyclopropanel -methanol;

Oxidizing said cis-2-n-pentylcyclopropane-lmethanol to form a mixture of cis and trans-2-npentylcyclopropanelcarboxaldehydes;

iii. Oxidizing said mixture of cis and trans-2-n-pentylcyclopropane-l-carboxaldchydes to form a mixture of cis and trans-n-pentylcycloproane-l-carration, cosmetic preparation or powder.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4049706 *Sep 24, 1975Sep 20, 1977Air Products And Chemicals, Inc.Selective oxidation of chrysanthemyl alcohol
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US7074828 *Dec 5, 2002Jul 11, 2006The Governors Of The University Of AlbertaCompounds that stimulate glucose utilization and methods of use
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US7473706Mar 6, 2006Jan 6, 2009The Governors Of The University Of AlbertaCompounds that stimulate glucose utilization and methods of use
US7524885 *Feb 23, 2005Apr 28, 2009The Governors Of The University Of AlbertaCompounds that stimulate glucose utilization and methods of use
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US8202901Mar 12, 2009Jun 19, 2012The Governors Of The University Of AlbertaCompounds that stimulate glucose utilization and methods of use
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CN102432570A *Nov 10, 2010May 2, 2012江苏德峰药业有限公司Synthetic method of 6.6-dimethyl-3-oxadicyclo[3.1.0] hexane-2.4-dione
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Classifications
U.S. Classification512/8, 510/488, 560/124, 510/102, 562/506
International ClassificationC11B9/00, C07C31/133, C07C45/29
Cooperative ClassificationC07C31/1333, C11B9/003, C07C45/292
European ClassificationC07C45/29C, C07C31/133A, C11B9/00D2