US3907873A - Novel fragrance materials and process - Google Patents

Abstract

A novel ester comprising the reaction product of longifolene and formic acid, perfume and fragrance compositions containing same and process therefor.

Description

United States Patent Wight et al.

[451 Sept. 23, 1975 NOVEL FRAGRANCE MATERIALS AND PROCESS Inventors: Christian F. Wight, Mount Kisco, v

N.Y.; John B. Hall, Rumson, NJ.

International Flavors & Fragrances Inc., New York, N.Y.

Filed: May 29, 1973 Appl. No.: 364,918

Related u.s. Application Data Continuation of Ser. No. 37,333, May I4, 1970, abandoned.

Assignee:

US. Cl 260/489; 252/522; 260/497 R Int. Cl. C07C 67/04; CO7C 69/07 Field of Search 260/489, 497 R, 488 B References Cited UNITED STATES PATENTS 3/1972 Curtis et al. 260/489 Primary Examiner-Vivian Garner.

FOREIGN PATENTS OR APPLICATIONS 1,225,158 3/1971 United Kingdom .i 260/488 OTHER PUBLICATIONS Chem. Abstracts, 55:11458a (196] Attorney, Agent, or FirmBrooks Haidt l-laffner & Delahunty [57] ABSTRACT 5 Claims, No Drawings NOVEL FRAGRANCE MATERIALS AND PROCESS This is a continuation of Application Ser. No. 37,333, filed May 14, 1970, now abandoned. Y

The present invention relates in general to perfumery and in particular to the provision of-a novel-substance beneficially adapted for use in connection with .the preparation of perfume and fragrance compositions.

The use of perfume ingredients in the manufacture of a wide variety of industrial products such as soaps, de tergents, deodorants, cosmetic preparations and the like for purposes of imparting thereto an esthetically pleasing odor characteristic comprises, of course, well established practice. The commercial importance of perfume agents is, of course, to a great extent self evident and especially as regards applications primarily cosmetic in nature. However, in many instances, e.g., soaps and detergents manufacture, esthetic rather than functional considerations may well be determinative of product marketability and thus, considerations associated with product appearance, fragrance and the like assume rather critical importance.

Natural essential oils are widely exploited perfumery agents but have several disadvantages which detract from their commercial desirability. Hence, considerable industrial activity has centered around the research and development of synthetic perfume agents by suitable derivatization of natural occurring materials. Occasionally one comes across an abundant low cost essential oil with a major component which can be upgraded via suitable derivatives. One of the important advantages is the new body of matter is often a single controllable material free of theunavoidable variations connected with whole natural oils, differing from year to year and from lot to lot because they are obtained by variable primitive techniques. Moreover, a single chemical entity also affords a more predictable performance regarding compatability, stability, uniform fragrance strength and character in the multiplicity of end products in which perfumes are required. When such a derivative has great power coupled with low cost and a high degree of odor quality only obtainable by the use of expensive alternate materials, a valuable tool is presented to the perfumer.

Thus, a primary object of the present invention resides in the provision of a perfume and fragrance composition wherein certain disadvantages are eliminated and a novel perfume agent of superior functionality is provided.

Other objects and advantages of the present invention will become more apparent hereinafter as the description proceeds.

The attainment of the foregoing and related objects is made possible in accordance with the present invention which in its broader aspects includes the provision of a novel perfuming agent, compositions containing same .as well as processing therefor and wherein said perfume agent comprises an ester which is the reaction product of longifolene and formic acid.

The longifolene-formic acid reaction product provided in accordance with the present invention posthetically pleasing, provides an aroma of good intensity, the fragrance characteristics persisting for significant periods'of time as evidenced by dry-out evaluation.-

' The 'longifolene-formic acid reaction product may be readily prepared-by contacting at a temperature ranging from about 30C to about 90C, longifolene (C H i.e., 1,4-methanoazulene, decahydro-4,8,8- trimethyl-9 methylene, with formic acid in amounts sufficient to yield a mole ratio of formic acid to longifolene with the range of about 2 to about 10, said contacting being preferably carried out in the presence of an effective amount of a protonic acid such as sulfuric acid or a Lewis acid catalyst such as paratoluene sulfonic acid or methane sulfonic acid typified by boron trifluoride etherate, stannic chloride and the like and for a time sufficient to form the ester derivative; the latter may thereafter be recovered by any suitable separation technique, e.g., extraction, fractional distillation and the like.

The quantity of Lewis acid or protonic acid catalyst employed is not particularly critical apart from the requirement that it be present in effective amounts, i.e., quantities sufficient to permit the desired reaction rate. Thus, the catalyst component may be present in amounts varying from a small but effective amount, i.e., on the order of about 1% up to about 7% by weight of the formic acid.

The reaction may, if desired, be carried out in the presence of an inert solvent vehicle including, mobile liquid alkanes, e.g., propane, hexane, octane and the like; liquid aryl hydrocarbons, e.g., benzene, toluene, xylene, etc. However, since solvent materials are of an optional nature, their use is recommended against in order to minimize costs which would otherwise accrue in connection with necessary solvent-removal operations.

As previously indicated, the reaction is preferably carried out at a temperature within the range of from 30C to 90C. Within the. aforestatedv range, specific valueswill be selected having reference to the reaction rate desired, the latter beinginfluenced by the nature and type of solvent employed, if any, ratio reactants, amount of catalystand the like. The temperature selected should not be so high as to result in undesirable side reactions or degradative decomposition of one or more of the involved ingredients or so low as to cause extended reaction times. In general, it is found that optimum results obtain with the use of temperatures within the range of 40C to C, and accordingly, such range is particularly preferred for use herein.

Product yield can be improved appreciably by employing a holding period with agitation following complete additionof the reactants and catalyst. The length of any such holding period will depend, for example, on reactant ratio, agitation level, etc. In general, holding periods substantially in excess of 10 hours will not be required and particularly in view of the availability of modern, highly efficient processing equipment; thus, agitation is desirably carried out for periods ranging from aboutvone hour to about 6 hours.

The formicacidreactant is preferably employed in molar excess in order -to minimize quantities of unrea'cted longifolene, thereby facilitating product isolation and recovery while diminishing the formation of undesired by products. Inaccordance with preferred practice, the-formic acid is employed in a molar excess of 2-10 or more times.

Pressure is not particularly critical in the practice of the present invention and thus, the reaction can be car.- ried out under either subatmospheric or superatmospheric pressure conditions. However, such modes of proceeding require the use of specialized equipment which, in addition to the high cost involved, can prove burdensome from the standpoint of operation. Accordingly, it is in general preferred to employ atmospheric pressure.

The product can be recovered from the reaction medium by conventional means including washing, distillation, extraction, preparative chromatography, and the like. Fractional distillation under relatively high vacuum is particularly preferred, being especially conductive to effective separation and recovery. More specifically, upon completion of the desired reaction, it is generally recommended to wash the reaction mixture and to separate the organic layer. The aqueous layer can then be extracted with a suitable organic solvent such as benzene to recover the product as well as starting materials present therein. The organic solutions may then be combined and subjected to vacuum, fractional distillation whereby to provide the ester product.

The longifolene reactant employed in the aforedescribed process, comprises a cyclic terpene having the following structural formula:

Longifolene is widely distributed in nature, notably among species of the genus Pinus. One of the sources of longifolene is so-called Indian terpentine oil obtained from Pinus [ongifolia Roxb. It occurs in such Indian terpentine oil in amounts of about 30%, and is preferably purified before use herein to purities on the order of 80% or more.

The novel fragrance material provided in accordance with the present invention can be employed to advantage in a wide variety of applications to impart a rich, precious wood fragrance.

As olfactory agents, such material can be formulated into or used as a component of a perfume composition. Thus, such material, in addition to having an esthetically pleasing fragrance, exhibits excellent stability in a wide variety of perfume articles and perfume compositions. The terminology perfume composition as used in the context of the present invention, is intended to encompass a relatively Wide variety of relationships. Thus, the composition in question may comprise an ul timate perfume product or alternatively, a fragranceimparting composition adapted to be incorporated into a finished perfume for purposes of supplying a total fragrance impression or to enhance, modify or otherwise reinforce the natural fragrance characteristics of such product. Thus, suitable companion fragrance ingredients suitable for use in formulating the compositions comtemplated herein include, for example, natural and synthetic oils, alcohols including both saturated and unsaturated alcohols, ketones, esters, lactones, aldehydes, ethers, anthranilates; acetals, terpenes; carboxylic acids, diphenyl compounds, heterocyclic com- 4 pounds including azole s, quinolines, the macrocyclic musks including ketones, polycyclic musks including tetralin musks. Other ingredients which may be suitable in a particular instance-include, for example, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants and the like, depending upon the specific nature of the product being formulated, e.g., detergent, soap, space deodorant, cologne, bath preparation 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.

. In preparing perfume compositions, the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume compositions will be the sum of the effect of each ingredient. Thus, the ester derivative of the present invention may 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 term alter as used herein is intended to denote an effect on the fragrance impression, harmoniously blending with the other ingredient'materials to produce a novel bouquet, or alternatively, enhancing, fortifying or reinforcing an existing fragrance note. I

The amount of ester employed in a particular instance may vary over a relatively wide range and will be determined by a number of factors including, the nature and quantity of other ingredients, as well as the effects desired to be achieved. In any event, the essential requirement is that the ester reaction product be present in effective quantities, i.e., the amounts sufficient to alter the fragrance of the composition, e.g., carrier or vehicle. Thus, it has been found that perfume compositions containing a small but effective amount, e.g., as little as 2% by weight of the ester derivative, or even less, may be employed to advantage for purposes of imparting a pleasant wood aroma to soaps, cosmetics and other products. The amount employed can range up to 7% or higher, depending again upon the nature of the end product, the effect desired, as well as the particular fragrance sought. It will further be understood that the end product carrier or vehicle can be a liquid such as an alcohol, glycol or the like or alternatively, can be an absorbent solid such as talc or components for encapsulating the composition.

The following examples are given for purposes of illustration only and are not to be considered as necessarily constituting a limitation on the present invention.

EXAMPLE 1 PREPARATION OF LONGIFOLENE-FORMIC ACID REACTION PRODUCT Formic Acid Longifolene (88.7 moles) (40 moles) To the flask contents are added 600 g. of boron trifluoride etherate over a period of 15 minutes during which the temperature rises to 35C. The mixture thus ,formed is stirred for 4 hours at 50C and thereafter added to a receptacle containing 20 liters of water and 2 liters of benzene. The aqueous layer is decanted and extracted with 2 liters of benzene. The organic solutions are thereafter bulked and washed three times with 1.5 liters of a saturated aqueous solution of sodium bicarbonate. The benzene is then stripped off to a pot temperature of 110C., atmospherically, yielding 8748 g. of oil (acid value 1A=nil, ester value lS=4l.2%) containing about 35-40% of ester product. Fractional dis- ;tillation of the crude oil in the presence of 3% Prime] (refined mineral oil) and 0.1% lonox anti-oxidant at a pressure of 0.4 mm Hg, a reflux ratio of 2:1 and pot temperature of 100l30C. through a 12 inch X 44 mm. Goodloe packed column serves to remove lower boiling fractions determined by gas-liquid chromatography (GLC) to constitute essentially isolongifolene, such determination being confirmed by nuclear magnetic resonance (NMR). The desired product is therefore obtained by fractionally distilling the residue through a 12 inch X 44 mm. Goodloe packed column at a pressure of 0.3-0.7 mm. Hg at a reflux ratio of 9:1, (pot temperature l24l84C) and collecting the material having a boiling point of 89-92C. Yield: 3187.4

The product has an .ester value of 96.5% and a nil acid value.

A perfume of the following composition is prepared:

The resultant composition provides an interesting variation in the basic classic cologne blend, i.e., having a woody, amber-like fragrance note. Such fragrance exhibits good persistence on dry-out evaluation.

EXAMPLE 2 To a 2 liter flask fitted with stirrer, thermometer, additional funnel and reflux condenser are charged 480 g. longifolene and 480 g. of formic acid. To the flask contents 96 cc. of a 50%(v/v) sulfuric acid/water solution is added over a period of 30 minutes with good stirring. After the exotherm subsides the temperature is raised to 50C and the reaction mass stirred at 50C for another 6 hours. The mixture is then poured into 1.5 liters of water and the organic layer separated. The aqueous layer is extracted with toluene, the combined organic layer is washed neutral and the solvent stripped off. Distillation of the residual oil yields 220 g. of isolongifolene and g. of product. (Mainly a mixture of longifolene formates plus some alcohols.)

Perfume compositions similar to that described as Example 1 but prepared with the longifolene formate of Example 2 have a pleasant, woody fragrance note and exhibit good persistence on dry-out evaluation What is claimed is:

1. A product which is formed by the reaction of longifolene and formic acid, the product being formed by contacting longifolene and formic acid in the presence of sulfuric acid, boron trifluoride etherate, or stannic chloride acid catalyst at a temperature of about 30C to about 90C in a mole ratio of formic acid to longifolene within the range of about two to 10.

2. A process for the preparation of the product of claim 1 which comprises contacting at a temperature of between about 30C to about 90C longifolene with formic acid, in amounts sufficient to yield a mole ratio of formic acid to longifolene within the range of about two to about 10, said contacting being carried out in the presence of sulfuric acid, paratoluene sulfonic acid, methane sulfonic acid, boron trifluoride etherate, or stannic chloride acid catalyst to form said product, and thereafter recovering said product.

3. A process according to claim 2, wherein said catalyst is boron trifluoride ethereate.

4. A process according to claim 2 wherein the catalyst component is present in amounts of from about 1 percent up to about 7 percent by weight of the formic acid.

5. A process according to claim 2 wherein the contacting is carried out from about one to about 6 hours.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,907,873

DATED September 23 1975 |NVENTOR(S) CHRISTIAN F. WIGHT and JOHN B. HALL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 0

Col. 3, line 59, after "perfume" and before "for" insert -producta C01. 6, line 6 at the beginning of the line,

"-ditional" should read -dition Signed and Scaled this Q Twentieth Day of July 1976 [SEAL] Arrest.

0 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'Parenrs and Trademarks

Claims (5)

1. A PRODUCT WHICH IS FORMED BY THE REACTION OF LONGIFOLENE AND FORMIC ACID, THE PRODUCT BEING FORMED BY CONTACTING LONGIFOLENE AND FORMIC ACID IN THE PRESENCE OF SULFURIC ACID, BORON TRIFLUORIDE ETHERATE, OR STANNIC CHLORIDE ACID CATALYST AT A TEMPERATURE OF ABOUT 30*C TO ABOUT 90*C IN A MOLE RATIO OF FORMIC ACID TO LONGIFOLENE WITHIN THE RANGE OF ABOUT TWO TO 10.

2. A process for the preparation of the product of claim 1 which comprises contacting at a temperature of between about 30*C to about 90*C longifolene with formic acid, in amounts sufficient to yield a mole ratio of formic acid to longifolene within the range of about two to about 10, said contacting being carried out in the presence of sulfuric acid, paratoluene sulfonic acid, methane sulfonic acid, boron trifluoride etherate, or stannic chloride acid catalyst to form said product, and thereafter recovering said product.

3. A process according to claim 2, wherein said catalyst is boron trifluoride ethereate.

4. A process according to claim 2 wherein the catalyst component is present in amounts of from about 1 percent up to about 7 percent by weight of the formic acid.

5. A process according to claim 2 wherein the contacting is carried out from about one to about 6 hours.