US3479301A

US3479301A - Perfume compositions including ether-ketones

Info

Publication number: US3479301A
Application number: US615858A
Authority: US
Inventors: Arno Cahn; Allan H Gilbert
Original assignee: Lever Brothers Co
Current assignee: Lever Brothers Co
Priority date: 1962-07-26
Filing date: 1966-07-25
Publication date: 1969-11-18
Anticipated expiration: 1986-11-18

Description

3,479,301 PERFUME COMPOSITIONS INCLUDING ETHER-KETONES Arno Cahn, Pearl River, N.Y., and Allan H. Gilbert, West Englewood, N.J., assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Original application July 26, 1962, Ser. No. 212,706, now Patent No. 3,316,305, dated Apr. 25, 1967. Divided and this application July 25, 1966, Ser.

Int. Cl. Cllb 9/00 US. Cl. 252522 7 Claims ABSTRACT OF THE DISCLOSURE Perfume compositions including novel ether-ketones having desirable fragrances.

This is a divisional application of Ser. No. 212,706, filed July 26, 1962, now US. Patent No. 3,316,305 granted April 25, 1967.

This invention relates to novel chemical compounds and more particularly to ether-ketones having desirable fragrances and to methods for the preparation of such compounds.

In the manufacture of cleansing compositions containing detergents, it has been found necessary to incorporate materials having pleasant fragrances in order to mask undesirable odors in the detergent composition thereby to increase consumer acceptance of the product. The wellknown fragrant materials of the ester class such as benzyl acetate and benzyl propionate are examples of such additives. However, since most detergent formulations contain alkali, perfumery materials such as the aforementioned esters are decomposed by hydrolysis either during storage or during use in aqueous solutions.

A further problem which has arisen in the use of perfumery materials in cleansing compositions concerns the presence of bleaching ingredients. The latter materials tend to oxidize erfumery additives and it has been found that the perfumes are decomposed upon storage in the presence of many bleaching ingredients.

It is an object of this invention to synthetically produce perfu'mery materials having desirable fragrances.

A further object is the production of compounds with desirable odor characteristics which retain their fragrances in the presence of bleaching ingredients and which are stable in alkaline media.

Other objects and advantages of the invention will be apparent from the following description.

It has now been found that the above objects and advantages can be attained by a compound of the formula:

RO(CR R (CR R (CR R COR wherein R is a straight or branched-chain alkyl group having at least 4 carbon atoms; R R R R R and R each are radicals selected from the group consisting of hydrogen and straight or branched-chain alkyl groups having from 1 to about 3 carbon atoms with not more than two of the radicals being alkyl; R is a straightchain or branched-chain alkyl group having from 1 to about 4 carbon atoms; m, n and p are integers whose sum is greater than 2; the total number of carbon atoms in the molecule being no more than about 20. Preferred compounds are those in which R ranges from 4 to about 12 carbon atoms and the sum of m, n and p is less than 6. Examples of compounds coming within the above formula are the following: 5-isobutoxy-pentanone-2; 5-(2, 4-dimethyl-pentoxy)-pentanone-2; 5 (n-pentoxy)-pentanone-2; Z-methyl-6-isobutoxy-hexanone-3; 4-methyl-5-isobutoxy-pentanone-2; 6-isobutoxy-hexanone-2; etc.

United States Patent 0 Patented Nov. 18, 1969 Each of these materials is endowed with a pleasant fragrance and is suitable for use in a perfume base. The compounds have strong lasting fragrances and are stable in detergent compositions containing alkali and/or bleaching ingredients. Furthermore, many of the compounds of the invention have a low aflinity for hard surfaces which is advantageous when they are employed in dishwashing formulations because of the low residual perfume content which remains on glassware washed with the formulation.

The ether-ketones of the invention may be prepared by various procedures, some of which have a general application while other methods are peculiar to particular compounds. However, any method of preparation known to those skilled in the art may be employed.

In the preparation of 5-alkoxy-2-pentan0nes, a suitable method has been developed which involves the use of alpha-acetyl-gamma-butyrolactone as a starting material. The reaction equation is as follows:

A detailed description of this method is set forth in Example 4, infra.

Another procedure for preparing some of the etherketones of this invention involves the free-radical addition of aldehydes such as acetaldehyde to allyl ethers:

It is necessary to carry out this reaction under carefully controlled conditions to obtain satisfactory yields. Thus, for optimum results ditertiary-butyl peroxide should be employed as the free-radical catalyst using glass-lined equipment and a temperature within the range of about 115-130 C. The allyl ether may contain alkyl substituents of 1-3 carbon atoms attached to the allyl radical to produce ether-ketones having alkyl-substituted methylene radicals, i.e., some of the radicals R are alkyl.

The following examples illustrate the preparation of materials according to the invention. It will be understood, however, that these examples are included merely for purpose of illustration and are not intended to limit the scope of the invention as described herein, unless otherwise specifically indicated.

EXAMPLE 1 15.6 grams of 2,4-dimethylpentyl allyl ether (0.1 mole), 1.5 grams of ditertiary butyl peroxide (0.01 mole) and 13.2 g. of acetaldehyde (0.3 mole) were placed in a glasslined pressure reactor and heated at 115-125 C. for 24 hours. Excess pressure was vented and the contents of the reactor removed and distilled to yield 9.3 g. of 5-(2,4- dimethylpentoxy)-2-pentanone, B. 107-112 C./10 mm., n =1.4274. This material retained its fragrance when subjected to C1 and alkali for two weeks at F.

Scent characteristics Odor: lavender, fruity, jasmin. Intensity: strong. Retention: good.

Effect of Temperature-Table 1 below shows the effect of temperature on the yield of 5-(2,4-dimethylpentoxy)- 2-pentanone. Different catalysts were used in these experiments to obtain approximately equal half-lives at the temperatures employed.

TABLE 1.-MOLAR RATIOS OF REACTANTS 2,4-dimethylpentylallyl Auetal- Temp, Time, Yield,

ether dehyde Catalyst 0. hrs. percent aa-azodi-isobutyronitrile. b Benzoyl peroxide. v Ditertiary butyl peroxide.

Effect of Glass-Lining In the Pressure Vessel.Table 2 shows a comparison of two runs carried out in a reactor with and without a glass lining, respectively.

12.8 grams of isobutyl-methallyl ether (0.1 mole), 1.5 grams of ditertiary butyl peroxide (0.01 mole) and 13.2 g. of acetaldehyde (0.3 mole) were placed in a glasslined pressure reactor and heated at 115-125 C. for 24 hours. Excess pressure was then vented, the contents of the reactor removed and distilled to yield 7.7 g. of S-isobutoxy-4-methyl-2-pentanone, B. 7982.5 C./1 mm. n =1.4212.

Scent characteristics Odor: green, natural, geranium-like, ketonic. Intensity: stronger than linalool. Retention: good.

EXAMPLE 3 33.8 grams of 3-isobutoxypropyl chloride (0.22 mole) was refluxed with stirring with 5.8 g. (0.24 mole) of magnesiurn and a crystal of iodine in 150 ml. of anhydrous ether. The Grignard product gradually formed over a period of hours. 12.8 g. of isobutyronitrile (0.186 mole) in 20 ml. of ether was then added at the reflux temperature and the mixture refluxed for an additional 1 /2 hours after which it was left overnight. Ice was then added to decompose the complex, followed by 200 ml. of 50% sulfuric acid. The product was isolated by ether extraction and distilled to give 245 g. of 2-methyl-6-isobutoxy-hexanone-3, a pleasant smelling colorless oil, B. 114-116 C. at 25 mm., n =1.4206.

Scent characteristics Odor: pineapple, ester-like. Intensity: stronger than linalool. Retention: good.

EXAMPLE 4 5-chloro-2-pentanone was prepared in 76% yield from a-acetyl-gamma-butyrolactone and hydrochloric acid. 90.5 grams of this ketone (0.75 mole) and 62 grams of ethylene glycol (1 mole) were refluxed in 600 ml. of benzene containing 1 gram of p-toluenesulfonic acid using a Dean- Stark trap to remove the water' formed in the reaction.

After 6 hours, the benzene solution was washed with sodium bicarbonate solution and water, and then distilled to yield 106.4 grams of 5-chloro-2-pentanone dioxolane as a colorless oil, B. 6668 C./ 0.4 mm., n =1.4478.

75 grams of the dioxolane (0.46 mole) was added to a solution of 10.6 grams (0.46 mole) of sodium in 2.96 grams (4 moles) of isobutyl alcohol and the mixture refluxed for 16 hours. 500 ml. of water was added followed by enough concentrated hydrochloric acid to make the solution distinctly acid to litmus paper. The solution was then refluxed for 1 hour after which the product was isolated by ether extraction. Distillation gave 57.6 grams of 5-isobutoxy-2-pentanone, a colorless pleasant smelling oil, B. 9495 C./0.2 mm., n =1.4169.

This compound displayed a fragrance resembling rose and lavender. It is chemically stable in soap and detergent formulations and is well retained by such media. Its manner of use in perfumery is illustrated by the following formula:

Rose lavender Parts by weight This perfume mixture displayed an adequate fragrance level when used at 0.8 to 1.0%.

The compounds 5-(n-pentoxy)-pentanone-2 and 6-isobutoxy-hexanone-2 were prepared by methods similar to those described above. The scent characteristics of the respective compounds are as follows:

5-(n-pentoxy)- fi-isobutoxypentanone-Z hexanone-Z Odor Lovage, celery-like, Green, sharp, camphor,

ketonic. natural, ketonic. Intensity Equals linalool Equals linalool. Retention Good Good.

The retention characteristics of the compounds were assessed qualitatively by determining the disappearance of fragrance on a perfumers blotter impregnated with the test compound.

We claim:

1. A perfume composition comprising a mixture of at least two perfumes in which one perfume has the generic formula:

RO(CR R (CR R (CR R CO--R" wherein R is an alkyl group having at least 4 carbon atoms; R R R R R and R are each radicals selected from the group consisting of hydrogen and alkyl groups having from 1 to about 3 carbon atoms with not more than two of the total R -R radicals being alkyl; R is an alkyl group having from 1 to about four carbon atoms; m, n and p are integers whose sum is greater than 2; the total number of carbon atoms in the molecule being no more than about 20.

2. The perfume composition according to claim 1 in which one perfume has the formula:

(CH CHCH O (CH COCH 3. The perfume composition according to claim 1 in which one perfume has the formula:

(CH CHCH CH (CH -CH -O'(CH -CO--CH 5 6 4. The perfume composition according to claim 1 in References Cited which one perfume has the formula: UNITED STATES PATENTS 3( 2)4 2)3 3 2,560,770 7/1951 Ladd 260-594 5. The perfume composition according to claim 1 in 5 .v OTHER REFERENCES Which one perfume has the formula:

(CH CH-CH -O-(CH CO-CH CH 2 6. The perfume composition according to claim 1 in ALBERT MEYERS Pnmary Exammer which one Perfume has the formula: 10 A. FAGELSON, Assistant Examiner (CH CH-CH --OCH CH(CH U.S. Cl. X.R.

-CH CO-CH 7. The perfume composition according to claim 1 in which one perfume has the formula:

Nerdel, J. Prakt. Chem., V01. 8, 1959, pp. l7l80.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 479,501 Dated November 18, 1969 Invent r( Arno Cahn et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

COLUMN line 45, "c./:. m." should be --c./1o mm.-; COLUMN line 1 Fm/0.2 mm." should be --c./o.24 mm.--.

SIGNED AN'D SEALED JUN 2 31970 GEAL) Anew mma, In WILLIAM E. -0: a a, T officer Oomlutom of Patents