US3862318A

US3862318A - Microbiocidal naphthenyl imidazolines

Info

Publication number: US3862318A
Application number: US267607A
Authority: US
Inventors: Phillip Adams; Alfonso N Petrocci
Original assignee: Millmaster Onyx Corp
Current assignee: Stepan Co
Priority date: 1969-12-09
Filing date: 1972-06-29
Publication date: 1975-01-21
Anticipated expiration: 1992-01-21

Abstract

WHEREIN R is the residue of a naphthene-carboxylic acid as a microbiocidal preservative agent.

A method of preserving cosmetics by admixing with the cosmetic formulation a microbiocidally effective amount of 1-aminoethyl-2naphthenyl imidazoline, having the structure:

Description

Adams et al.

[ MlCROBlOCIDAL NAPHTHENYL IMIDAZOLINES [75] Inventors: Phillip Adams, Murray Hill; Alfonso N. PetroccLGlen Rock, both of NJ.

[73] Assignee: Millmaster Onyx Corporation, New

York, NY.

[22] Filed: June 29, 1972 [21] Appl. No.: 267,607

Related US. Application Data [63] Continuation-in-part of Ser. No. 883,641, Dec. 9,

1969, Pat. No. 3,705,027.

[52] US. Cl 424/200, 424/69, 424/70, 424/273 [51] Int. Cl. A0ln 9/22, A61k 7/00 [58] Field of Search 424/273, 69, 70, 198, 200

[56] References Cited UNITED STATES PATENTS 2,832,715 4/1958 Jezl et al 424/30 3,705,027 12/1972 Adams et al 424/273 1 Jan. 21, 1975 Primary ExaminerVincent D. Turner Attorney, Agent, or FirmArthur A. Jacobs, Esq.

[ ABSTRACT wherein R is the residue of a naphthene-carboxylic .acid as a microbiocidal preservative agent.

5 Claims, N0 Drawings MICROBIOCIDAL NAPHTHENYL IMIDAZOLINES' II 11 II c on HQNCI-hCH -N N wherein R is the residue of a naphthene-carboxylic acid.

It has been discovered that the above-naphthenyl imidazolines have a high order of microbiocidal effectiveness which is greatly superior to other imidazolines having different acid residues.

They are especially utilizable to preserve cosmetics so as to prevent phase separation, discoloration and other effects of microbial proliferation, including that of pathogenic strains of microorganisms which may cause serious or minor infection of the skin or mucosa.

Naphthenic acids are well-known to the art and are available commercially, primarily as the result of various extractive procedures carried out in refining naturally occurring petroleums and petroleum fractions, particularly gas-oil distillates boiling in the range of 400700F. Naphthenic acids are found particularly in petroleums originating in the western part of the United States, especially in California; in the northern part of South America, especially Venezuela, Colombia and Aruba; in the southern part of Europe, especially Rumania, and, to a lesser extent, in crude oils originating in Louisiana, along the Texas gulf coast, in

Peru, Mexico, Poland, the Soviet Union and Germany.

The chemical 'nature of these naphthenic acids is more or less ill-defined, but they all have in'common the characteristic of possessing alicyclic nuclei. These may be five or six membered carbon atom ring systems, various condensed ring systems, and other related materials' as disclosed in Fieser, Organic Chemistry, 3rd ed. 1956, pages 97-98.

EXAMPLE 1 2,324 grams (or 9.28 mols) of Enjays Refined Naphthenic Acid having an acid number of 224, and 1,265 grams (or 12.07 mols) of diethylene triamine were charged into an agitated flask fitted with apacked fractionating column system for the purpose of separating and removing water formed in the reaction and return ing stripped amine to the reactor. Aquametric titration of the charged amine indicated a water content of 1.17%.

The mixture was agitated and heated under reduced pressure at about 150C. pot temperature and at 216 mm pressure, gradually raising the pot temperature to about 200C. during a period of about 12 hours. The water of reaction distilled along with some of the diethylene triamine, through the fractionating column, which stripped off the water and returned the amine to the reactor. When no more water distilled, the excess amine was distilled off at about 5 mm pressure and. 190C.

The total amount of water collected was 321 grams;

correcting for the initial water content, [7 mols of water was obtained, or 91.5% of the theoretical amount for the formation of the imidazoline.

A weighed sample was titrated potentiometrically to the first break with HCl in alcohol, indicating 87.4% activity. After reacting the non-tertiary nitrogen with phenyl isothiocyanate, titration with perchloric acid indicated 95.2% reaction.

The product was found to be effective against aerobic bacteria at from 25 to parts per million at 37C. during 4 hours.

EXAMPLE 2 The product was assayed bacteriologically by the Standard Broth Dilution Test Method. Aliquots of a solution of the aminoethyl naphthenyl imidazoline were added to appropriate broth culture media contained in test tubes, so that various concentrations were obtained. The tubes so prepared were inoculated with 24 hour broth cultures of the test bacteria, or 14 day aqueous spore suspensions of the test fungi, or 7 day broth cultures of the algae. Theinoculated tubes were incu bated as follows: bacteria for 72 hours at 37C.; fungi for 14 days at 28C.; algae for 7 days at 25C. Following the aforementioned incubation periods the tubes were examined for the presence or absence of macroscopic growth. The lowest concentration of test material not permitting macroscopic growth is designated as the Minimum lnhibitory Level.

The test organisms employed were: Escherichia coli E.c.; Pseudomonas aeruginosa ps.a.; Staphylococcus aureus 8a; Streptococcus faecalis S.f.; Asprgillus niger A.n., Penicilium-expansum P.e.; and Chlorella pyrenoidosa C.p.

Table 1 Parts per million of l-aminoethyl-2-naphthenyl imidazoline AT 0.5% of l-aminoethyl-2-naphthenyl imidazoline as a component of face creams and lotions, microbial growth on storage was found to be negligible. In the case of other cosmetic preparations, such as baby 10- tions, hair-set preparations, powders,. shampoos, and the like, preservation action was excellent in the range of 0.1% to 2% by .weight.

This compound may be employed either as the free amine or as its salts of inorganic or organic acids. Such acids may include, for example, hydrochloric, sulfuric, phosphoric, acetic, lauric, oleic, gluconic, oxalic, tartaric, citric, benzoic and substituted benzoic, paratoluene sulfonic, sulfamic, and the like.

EXAMPLE 4 Non-ionic Baby Lotion (sorbitan monooleate) Naphthenyl imidazoline 0.5 Distilled Water 0.5. to make l00.0

Here, and'in the succeeding examples, naphthenyl imidazoline or more simply, imidazoline will be understood to represent the l-aminoethyl-2-naphthenyl imidazoline of the invention. Although the free amine is named, as readily soluble in the oily it may also be employed in an aqueous phase as one of its salts.

The oil, lanolin, cetyl alcohol, Tween and Span were combined and mixed and heated to 60C. The water was heated to 62C and slowly added to the mix with propeller agitation. The resulting emulsion was allowed to cool to room temperature under agitation. The product had a pH of about 7.0.

sorbitol beeswax derivative) Naphthenyl imidazoline 0.5 Distilled water, 0.5. to make l00.0

The mineral oil, beeswax, imidazoline and the surfactants were combined and heated under agitation to 70C; the water was heated to 72C. and then added slowly, with propeller agitation, to the oily phase.

The cream was allowed to cool with adequate agitation to the set-point, and poured into jars.

The pH was in the range of about 6.5 to 7.0.

EXAMPLE 6 Shampoo Component Parts by Weight Onyx Chemical Co.'s Maprofix 563" 12.0

(99% active sodium lauryl sulfate) Onyx Chemical Co.'s Super Amide L 9C 3.0 (methyl laurate-diethanolamine condensate 97% paste) Naphthenyl imidazoline 0.5 Distilled water 0.8. to make 100.0

Heat the water to 50C. Slowly add the Maprofix while agitating, until it is completely dissolved. Add the Super Amide, previously melted and the imidazoline. Agitate until clear, while cooling.

Adjust the pH to 7.0.

EXAMPLE 7 Creme Rinse Component Parts by Weight Onyx Chemical Co.s Ammonyx 4" 7.5

(25% active) Cetyl alcohol 03 Potassium chloride 0.75 lmidazoline 0.5

Distilled water 0.5. to make 1000 EXAMPLE 8 Body Lotion Component Parts by Weight Amerchol Cholesterol Products, Inc. 5.0

Amerchol L-lO" Amerchols Acetulan" Triple-pressed stearic acid Glyceryl monostearate Propylene glycol Triethanolamine lmidazoline Distilled water 5 Q. S. to m ke 100.0-

The first four components and the imidazoline" are combined and are heated together to C. The mixed water, propylene glycol and triethanolamine are separately heated to 85C and added slowly to the oily phase while mixing. The agitation is continued while cooling to room temperature.

The pH of the product is about 8.0.

The invention claimed is:

l. A method of inhibiting the growth of bacteria or fungi in creams, lotions and shampoos subject to such growth which comprises applying to said bacteria or fungi an amount sufficient to inhibit their growth of the compound 1-aminoethyl-2-naphthenyl imidazoline or a salt thereof selected from the group consisting of the hydrochloric, sulfuric, phosphoric, acetic, lauric, oleic, gluconic, oxalic, tartaric, citric, benzoic, paratoluene, sulfonic and sulfamic acid salts.

2. The method of claim 1 wherein the cosmetic is a lotion.

3. The method of claim 2 wherein the cosmetic is a cold cream.

4. The method of claim 1 wherein the cosmetic is a shampoo.

5. The method of claim 1 wherein the cosmetic is a creme rinse.

Claims

2. The method of claim 1 wherein the cosmetic is a lotion.
3. The method of claim 2 wherein the cosmetic is a cold cream.
4. The method of claim 1 wherein the cosmetic is a shampoo.
5. The method of claim 1 wherein the cosmetic is a creme rinse.