US3364213A - Dodecyl tertiaryaminoethyl sulfoxides - Google Patents

Description

United States Patent 3,364,213 DODECYL TERTEARYAlt IINOETHYL SULFOXEES Hill M. Priestley, North Bergen, and James H. Wiison, Demarest, Ni, assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. 'Continuation-in-part of application Ser. No. 365,437, May 6, 1964. This appiication May 1, 1967, Ser. No. 634,873

5 Claims. (Cl. 269-247 .1)

ABSTRACT OF THE DiSiILGSURE The novel sulfoxides, dodecyl Z-dimethylamino-ethyl sulfoxide, dodecyl Z-diethanolaminoethyl sulfoxide, dodecyl 2-morpholinoethyl sulfoxide and dodecyl 2-piperidinoethyl sulfoxide, are disclosed. The sulfoxides have suds-stabilizing activity and are germicides.

The present invention relates to novel dodecyl 2-aminoethyl sulfoxides which are useful as foam stabilizers and which have germicidal properties.

This application is a continuation-in-part of our copending application, Ser. No. 365,487, filed May 6, 1964, which in turn was a continuation-in-part of our applications, Ser. Nos. 725,505, filed Apr. 1, 1958, and 60,546, filed Oct. 5, 1960, all now abandoned.

Alkyl sulfoxides having a lOng chain fatty acid residue are known to have surface active properties. US. Patent No. 2,787,595 to Webb discloses the the use of alkyl sulfoxides as the essential active ingredient in detergent compositions. According to Webb, the sulfoxides may be employed per so as the essential active ingredient in detergent compositions, but preferably are employed in combination with inorganic builder salts. It is also stated in the patent that other synthetic detergents may be employed as detergency supplements in combination with the sulfoxides and that foam stabilizers may be added.

It is common practice in the industry to include foam stabilizers in detergent compositions to improve the persistence and stability of the foam produced by agitation of the washing solution containing the detergent composition. These foam stabilizers are particularly useful in detergent compositions based upon organic non-soap synthetic detergent compounds.

The present invention is concerned with compounds which stabilize the foam produced on agitation of an aqueous washing solution containing a suds-producing organic synthetic detergent. Foam persistence is generally used by the housewife as an index of the cleansing ability of the solution. Once the foam has collapsed and disappeared, the housewife believes that the fat emulsifying and other cleansing abilities of the solution have been used up. This is not necessarily true, however, as the foam may collapse before the cleansing ability of the solution has been consumed. The problem of stabilizing the foam of aqueous solutions of detergent compositions is thus an important one and is one which has received considerable attention by workers in the field.

In addition to stability, several other characteristics of the foam are involved. The original amount of foam produced on agitation of the aqueous solution is an important consideration. Furthermore, the texture of the foam,

ice

Le, whether it is open and coarse, or of a very fine, dense character, and the ability of the foam to rinse cleanly and quickly from the articles being washed are factors which must be taken into consideration.

The prior art compounds which function as foam stabilizers in detergent systems depend upon well known foam stabilizing functional linkages, such as amide, and alcoholic and phenolic hydroxyl groups. Examples of these materials include fatty alcohols such as lauric alcohol and fatty acid substituted amides such as lauric diethanol amide and lauric isopropanol amide. Parahydroxy laurophenone is an example of a foam stabilizing compound containing a phenolic hydroxyl group.

These prior art foam stabilizers have some degree of specificity, i.e., they are suitable for use in stabilizing the foams produced in aqueous solutions of certain sudsproducing organic detergent compounds. For example, parahydroxy laurophenone is effective only with sodium lauryl sulfate or mixtures of this with other compatible active detergents. Also, the above-mentioned amides are generally suitable for use with alkyl aryl sulfonates, and lauryl alcohol is generaliy suitable for use with alkyl aryl sulfonates, and lauryl alcohol is generally limited to use with alkyl sulfates.

Still another deficiency of prior art foam stabilizers is that while they are effective in experimental systems based on pure water, their effectiveness is considerably diminished or non-existent in the presence of soil or fatty materials.

In accordance with the present invention, novel compounds are provided having the following formula:

wherein R is an amino radical selected from the group consisting of dimethylamino, diethanolamino, morpholino and piperidino radicals.

The compounds falling within this description are dodecyl Z-dimethylaminoethyl sulfoxide,

C H SOCH CH N (CH 2 dodecyl Z-diethanolaminoethyl sulfoxide,

C H SOCH CH N(CH CH OH) dodecyl 2-morpholino-et-hyl sulfoxide,

C1zH25SOCH2CHzN /O CHE-CH3 and dodecyl 2-piperidinoethyl sulfoXide,

CHa-CHa CH1 GET-CH2 It has been found that the presence of small amounts of the sulfoxides described above improve the stability of the foam produced by agitating aqueous solutions of sudsproducing materials selected from the group consisting of anionic, ampholytic and nonionic organic synthetic detergents. In addition, these compounds impart germicidal characteristics to aqueous solutions containing them.

The term suds-producing materials selected from the group consisting of anionic, ampholytic and nonionic organic synthetic detergents, as employed herein, is intended to include those anionic, ampholytic and nonionic compounds which are commonly employed as the essential active ingredient of suds-producing detergent compositions.

Suitable anionic suds-producing organic synthetic detergents include the alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate or ammonium pentadecyl benzene sulfonate, and the methyl taurates, such as Igepon TK-32, a sodium N-methyl-N- tall oil acid taurate, and Igepon TE42, an N-methyl acyl taurate derived from tallow. Also included are the sulfated fatty alcohols, such as sodium lauryl sulfate and ammonium lauryl alcohol sulfate; the sulfated polyethylene oxide esters of resins or fatty acids, such as the ammonium salt of sulfated nonyl phenol condensed with four moles of ethylene oxide; and Sipon LT-6, a. triethanolamine lauryl alcohol sulfate.

Suitable nonionic suds-producing organic synthetic detergents which may be employed according to this invention include Oronite NI-8589, a dodecyl phenol condensed with more than 10, i.e., 20 to 30 moles of ethylene oxide; Triton X-100, an alkyl aryl polyether alcohol, i.e., octylphenol condensed with moles of ethylene oxide; and Tergitol NP-14, an alkyl phenol polyethylene glycol ether; Neutronyx 600, an aromatic polyglycol ether condensate; and Sterox A], a tridecyl alcohol condensed with 10 moles of ethylene oxide, and Sterox CD, a tall oil condensed with 10 moles of ethylene oxide.

Also suitable are Deriphat No. 154, a tallow disodium betaimino dipropionate, and sodium cocoglycinate. These are ampholytic substances.

Conventional soaps and inorganic builder salts, such as the phosphates, silicates, sulfates and the like, are not included within the term suds-producing materials selected from the group consisting of anionic, ampholytic and nonionic organic synthetic detergents used herein, although these materials can be used as auxiliary agents in the compositions of this invention. Also excluded from this class are the sulfoxides described in the aforementioned Webb patent as an essential active ingredient in detergent compositions. The benefits of this invention are not obtained by merely increasing the concentration of dialkyl sulfoxide in the detergent composition.

The level of sulfoxide required to provide optimum foam stability depends upon the particular organic synthetic detergent employed and upon the nature of the sulfoxide. Generally speaking, the sulfoxides are efiective at levels above about 0.1% in detergent compositions containing operable levels of suds-producing organic synthetic detergents. At levels below this range, little if any benefit is obtained.

A general type of reaction which may be employed in preparing sulfoxides of this invention is described in detail in US. Patent No. 2,787,595.

The following example illustrates a method of preparing pure sulfoxides in accordance with the present in- Vention.

Example 1 Dodecyl vinyl sulfoxide was prepared from dodecyl Z-hydroxyethiyl sulfide. The preparation is summarized by the following equations:

The intermediate chlorosulfinate C H SCH CH O SOCl is quite stable and was heated at 200 C. under reduced pressure to drive out all of the sulfur dioxide, leaving the dodecyl Z-chloroethyl sulfide. The latter, by oxidation with sodium hypochlorite solution or concentrated nitric acid, gave dodecyl 2-chloroethyl sulfoxide. This was converted to dodecyl 2-iodoethyl sulfoxide by action of sodium iodide in acetone solution. Dodecyl vinyl sulfoxide, M.P. 42, was formed by heating 2-iodoethyl sulfoxide with 10% aqueous sodium hydroxide for 2 hours at 80 C. with mechanical stirring.

Amino sulfoxides may be prepared from these intermediates. For example, dodecyl Z-dimethylaminoethyl sulfoxide is prepared by mixing 8 grams of dodecyl 2- chloroethyl sulfoxide, 16 ml. of a 45% dimethylamine solution in methanol, and 32 ml. of methanol and keeping the mixture in a magnesium citrate bottle for 3 hours at 50 C. and at room temperature overnight. The reaction product is added to 50 ml. of 1:1 HCl and the volume made up to 200 ml. with distilled water. The hydrochloride is filtered and washed with 50 ml. of 1:4 HCl, and dried. The dry hydrochloride was then washed with a little ethyl acetate. The yield was 9.1 grams of dodecyl Z-dimethylaminoethyl sulfoxide hydrochloride, M.P. 162-4" C. Dodecyl Z-diethanolaminoethyl sulfoxide, C12H25SOCH2cH N(CHgCHzOH)2, dodecyl 2-morph0- linoethyl sulfoxide,

/CH2-CH2 CuHzaSOCHaCHzN /O CH2CH3 and dodecyl 2-piperidinoethyl CH2CH1 /CH2 CHz-CH; were also prepared by this method, from diethanol amine, morpholine and piperidine, respectively.

The compounds found useful according to this inventron are listed below together with their melting point and the melting point of sulfones prepared therefrom.

C 12H25S O CHzCHzN Meltin M 112' No. Compound N arne Fonnnla Point, Plfllli i C. Sulfone,

l 1 Dodecyl Z-dimethylaminoethyl sulioxide 0 211 CHzCH2N(CH3)2 59 42 2- Dodecyl 2-diethanolaminoethyl sulfoxide C12H25SOCH2GH2N(CH2CH2OH)1 26 41 C Hzo Hz 3 Dodecyl 2-morpholinoethyl sulfoxide (21211 58 0 0 H O HZN 67 66 C H2C Hg C Hz-C H2 4 Dodecyl 2-piperidinoethyl sulfoxide 012112580 CHzCHzN CH2 57 42 C H -C H Example 2 This example shows a representative formulation of a heavy duty liquid detergent utilizing the sulfoxides of this invention. These materials are exceptionally useful in dishwashing and in heavy duty laundry detergents. The examples uses a combination of lauric isopropanol amide and dodecyl Z-aminoethyl sulfoxides of the present invention as the foam stabilizing additive. The resulting detergent composition produces an exceptionally stable foam in aqueous solution.

Ingredient: Percent Dodecyl benzene sulfonic acid (90% active) 7.0 Sodium xylene sulfonate (37% active) 18.9 Sodium silicate (37.5% solids) 7.0 Potassium hydroxide 2.4 Dodecyl 2-aminoethyl sulfoxide 3.5 Lauric isopropanol amide 1.7 Tetrapotassium pyrophosphate 19.1 Water and miscellaneous ingredients 40.4

Dodecyl Z-dimethylaminoethyl sulfoxide, dodecyl 2-Cliethanolaminoethyl sulfoxide, dodecyl 2-morphol-inoethyl sulfoxide, and dodecyl 2-piperidinoethyl sulfoxide were used and each produced an exceptionally stable foam in aqueous solutions.

We claim:

1. A compound of the formula References Cited UNITED STATES PATENTS 2,750,357 6/1956 Bredereck et a1 260247.1

ALEX MAZEL, Primary Examiner.

J. TOVAR, Assistant Examiner.