US2504107A - Aluminum methionate - Google Patents

Description

Patented Apr. 18, 1950 ALUMINUM METHIONATE John Edward Christian and Glenn L. Jenkins, La Fayette, Ind., assignors to Purdue Research Foundation, a corporation of Indiana No Drawing. Application October 4, 1946,

Serial No. 701,091

1 Claim. 1

This invention relates to new astringent agents, the preparation of such agents and to cosmetic anti-perspirants including them.

Up to the present time the conventional antiperspirants have been salts of weak metals, such as aluminum, with strong inorganic acids, such as hydrochloric and sulfuric. The usually employed compounds have been aluminum chloride and aluminum sulfate, although zinc, thorium and other metal salts have been known to be equivalent. These astringent salts of weak metals and strong acids are effective in reducing perspiration, but by themselves are corrosive to clothing and may cause skin irritation. While this corrosion may be inhibited, the inhibitors are relatively expensive.

We have now discovered that certain organic salts of weak metals, such as aluminum, are effective anti-perspirants but are harmless to skin and fabrics. The preferred member of the group is aluminum methionate, or aluminum methane disulfonate having the formula:

80: (C: )IAh 501 Other aluminum alkyl sulfonates are likewise effective as anti-perspirants. Aluminum methionate, aluminum ethane disulfonate and aluminum methane trisulfonate are considered the most active astringents of those prepared and tested.

The compositions appear to require the following three characteristics:

(1) The aluminum ion or its equivalent.

(2) One or more sulfo groups.

(3) An alkyl group.

In general, the more sulfo groups, the greater is the astringency and the fewer the carbon atoms in the alkyl groups, the greater is the astringency.

Aluminum methionate may be prepared as follows:

100 gm. of calcium methionate is dissolved in 250 cc. of warm water and 102 gm. (98% of theory) of crystalline aluminum sulfate, dissolved in 250 cc. of water, is added slowly with stirring. The mixture is digested for ten minutes, filtered, and the calcium sulfate washed with water, the water being added to the original filtrate. The filtrates may be concentrated and aluminum methionate solution used as such. The pure salt may be isolated as follows: The aluminum methionate solution is concentrated until a super saturated solution is obtained. A1-

cohol is added and the aluminum salt crystallizes out. The salt may be further recrystallized from water and alcohol.

Aluminum methionate is hygroscopic and, therefore, does not tend to dry out. It does not tend to crystallize out of astringent creams. It is soluble in water and may be included in concentrations as high as 25 per cent. I

Aluminum ethane disulfonate having the structural formula may be prepared by dissolving 5 gm. of barium ethane disulfonate in 200 cc. of hot water and slowly adding 3 gm. of theory) of A12(SO4)3. 18 H2O dissolved in 10 cc. of water with stirring. The barium sulfate formed is illtered off. The filtrate is evaporated to about 10 cc. and ethyl alcohol added to precipitate the aluminum salt. The salt is filtered, washed with water, and dried.

Aluminum methane sulfonate having the structural formula may be prepared by reacting methane sulfonic acid and aluminum sulfide.

57 gm. of methane sulfonic acid is placed in a suitable flask containing 15.5 gm. (5% excess) of aluminum sulfide. Distilled water is added in excess and the mixture heated on an electric hot plate and allowed to react until no more H28 was evolved. The excess aluminum sulfide is filtered off and the filtrate concentrated almost to dryness. The product is allowed to crystallize and then washed with acetone to remove the remaining water present.

Aluminum methane trisulfonate having the structural formula may be prepared by reacting the barium salt with aluminum sulfate in the same manner described in connection with the aluminum ethane disulfonate.

Aluminum sulfo-acetate having the structural formula Solc2-O O 0- All may be prepared by reacting the barium salt with aluminum sulfate in the same manner described 3 in connection with the aluminum ethane disulfonate.

Aluminum o-sulfo-benzoate having the structural formula "Iegacid" regular pounds 20 Stearic acid do 4 White protopet do /2 Distilled water do 35 Glycerlne -do- 1 Gum tragacanth owder do Aluminum methionate (71- /1% Sol.) do 33% Formaldehyde (37% solution) do Perfume ounces 3 Tegacid is the trade name for a mixture of glyceryl monostearate and a wetting agent presumably of the sulfated fatty alcohol compound type. White protopet is white petrolatum, U. 8.59.

4 We claim: As a new composition of matter, aluminum methionate.

JOHN EDWARD CHRISTIAN GLENN L. JENKINS.

REFERENCES CITED The following references are of record in the file of this :patent:

UNITED STATES PATENTS Number Name Date 59,239 Lewis Oct. 30, 1866 1,438,101 Divine Dec. 5, 1922 2,145,583 Carlson Jan. 31, 1939 2,236,387 Wallace et a1 Mar. 25, 1941 2,316,670 Colgate et al Apr. 13, 1943 2,430,815 Hersberger et al. Nov. 11, 1947 FOREIGN PATENTS Number Country Date 354,443 Great Britain of 1931 568,209 Germany Jan. 23, 1933 OTHER REFERENCES Drug and Cosmetic Industry, July 1937, vol. 41, page 117.

Beilstein, Handbuch der Org. Chem, vol. 4, (4th Ed. 1922) page 11.

Beilstein, Handbuch der Org. Chem, vol. 4, first Supplement (4th Ed. 1929) page 310.

Chemical Abstracts, Abstracts of four publications by Becker et al., at the following pages: vol. 24, page 82-8 (1930), vol. 25, page 915 (1931), Vol.26, page 962 (1932) (two articles).