US2216842A - Germicidal compounds - Google Patents

Description

Patented Oct. 8,119.0

UNITED- STATES cnamcmar. corrrotmns' Carl Johnson, Maplewood, N. 1., and William M. Allison, New York, N. Y., assignors to Oakite Products, Inc., a corporation of New York No Drawing. Application July 2'1, 19.35, Serial No. 33,602

6 Claims.

The invention relates to germicidal compounds, and further to detergent, disinfecting and deodorizing mixtures containing such compounds.

A considerable number of materials having germicidal action, and which'maybe used in various cleaning processes where both cleaning and sterilizing are to be accomplished in one operation, have heretofore been used. However,

I such materials have been unsatisfactory for vari- 10 ous reasons- For example, chlorine is frequently used but constant additions of chlorine, compounds are necessary in order to maintain the germicidal property of cleaning solutions. Other materialsare unsatisfactory, as they may attack the articles being cleaned .or have other disadvantageous properties.

One object of the present invention is to provide an odorless material to be used in cleaning which is inert to, and is not affected by, the

miscellaneous inert organic materials with which it comes in contactjand which acts only on bacteria and other living micro-organisms at any pH value of the cleaning solution that may be desired. There are a number of advantages 'in a solution having such properties.

In the first place, the solutions made according to the invention remain sterile at all times and need not be used immediately after they have been made. They possess substantially the same bactericidal properties at the end of the cleaning operation as at the beginning, at least if there has been no great dilution of the solution during the cleaning; Large amounts oforganic matter removed during the cleaning process do not appear to affect the sterilizing power of the solution.

A' further advantage is that the sterilizingpower may be easily determined at any time since it remains constant where there isno dilution, simply by determining the alkalinity or acidity which will indicate'the extent of dilution.

o of alkali are required only to retard the growth.

of bacteria, since the cleaning alone can be accomplished by concentrations of 1% or lower.,

These strong alkali solutions will however react withand corrode the glass. Therefore, a further 55 object of the invention is to provide a such asaz'sulfonic acid or one of its salts.

' product.

'sulfonic acid salt, which will not have the same corrosive effect as an alkali. 1

which will have a minimum reaction with the articles being cleaned, and which therefore may be used with detergents of such low concentration as not to destroy the articles.

A further object of the invention is to provide a material which is inexpensive and the use of which involves a relatively small amount of labor. In prior art processes, costly apparatus has been necessary to control the application of sterilizing materials and methods, the materials used 10 have been effective only for a short time, and have not been dependable. A further object of the invention is to provide a material in which considerations of tempera- .ture may be avoided, thus making accurate ll control of this feature of the cleaning process unnecessary.

The present invention contemplates a series of new compounds which have germicidal action, and furthermore an admixture of such com- 20 pounds with a detergent which results in a further increase in the germicidal power.

We have found that an.organic germicide which is...either a base or a salt, and which is aromatic, will react with a sulfonic compound, 25

The reaction may take place either between an acid and a base; an acid and a salt, a salt and a base, or two salts. Preferably an aliphatic sulfonic compound is used, although the aromatic com- 30 pounds will also react to produce this type of The resulting product is obviously a Amongthe materials which may be used as 86 organic germicides are aromatic mercuryl compounds which are toxic to bacteria, such as phenyl mercuric hydroxide, phenyl mercuric nitrate, phenyl m'ercuric chloride, para nitro toluene mercurici'cetate, alpha nitro naphthalene mer- 4o Curio acetate, alpha naphthyl-amine mercuric acetate, and the like. In other words, these compounds are aromatic mercuryl hydroxides, or derivatives or salts thereof, which are hereinafter referred to as aromatic mercuryl compounds-or 45 organic mercury germicides. The preferred compounds are those mercury germicides which have the ggler'al formula Rr-HgX in which R is an arylradical and X is an acid radical or a hydroiwl group. The germicidal power of all such compounds, andparticularly of the mercuryl compounds, is increased by their combination with the sulfonic compounds. 1 Among the sulfonic compounds which may be used, we prefer to use the aliphatic compounds such as the aliphatic sulfonic acids, aliphatic acid sulfates, higher fatty acid amido sulfonic acids, higher fatty acid esters of sulfonated aliphatic amido compounds or the higher fatty acids altered in other ways to prevent reaction of the carboxyl group, the acid sulfates or sulfonates of the higher alcohols containing at least 8 carbon atoms and sulfonated higher fatty acids,

The highest bactericidal activity is obtained where the two compounds to be combined are present in substantially molecular proportions, so that no excess of either remains in the product.

' This is particularly true where the two are added to water to produce a germicidal solution for use, with or Without detergents.

The process of producing these compounds may be carried out for instance according to one of the following examples:

1. 389 grams of methyl-oleamide-ethyl-sulfonic acid and 295 grams of phenyl mercuric hydroxide are reacted together, yielding 666 grams of methyl oleamide ethyl phenyl mercuric sulfonate and 18 grams of water.

2. 238 grams of decyl hydrogen sulfate are reacted with 295 grams of phenyl mercuric hydroxide, yielding 515 grams of decyl phenyl mercuric sulfate and 18 grams of water.

3. 295 grams of phenyl mercuric hydroxide and 173 grams of sulfanilic acid are reacted, yielding 450 grams of phenyl mercuric sulfanilate and 18 grams of water.

4. 407 grams of amino sulfon phenyl mercuric chloride and 195 grams of sodium sulfanilate are mixed together in water. The resulting product contains 543 grams of amino sulfon phenyl mercuric sulfanilate and 59 grams of sodium chloride.

The above yields are theoretical yields which are obtainable in actual practice because the reactions involved are neutralizing reactions or double decomposition reactions resulting in the formation of water or a neutral salt. The product may be recovered by evaporating the water, alcohol, or other solvent used as a reaction medium, as any neutral inorganic salt such as sodium chloride is not detrimental to the product. It is not necessary that the reacting materials be completely dissolved in the reacting medium as the materials will react merely by digesting them together in the specified proportions in an aqueous or alcoholic medium, after which the resulting product may be filtered and dried.

We have found that such compounds are much more effective in their germicidal action than the combined effects of the individual constituents. Tests of the constituents and of the final compounds were made in the following manner:

. A sample of water was treated with the various mixtures, and this sample was then contaminated with some bacteria culture. It was found that the control solution contained approximately 5000 bacteria per milliliter. test solution was plated in a Petri dish on nutrient agar medium for 48 hours at 37 C., and then the colonies, if any, which had developed were counted.

The following tables indicate the efficiency of the various materials so tested:

The following mercury compounds, due to their slight solubility, were used in the form of saturated aqueous solutions.

Count after- Germicide, parts per million 5 10 minute minutes minutes Trisodium phosphate 7500 and para nitro toluene mercuric acetate Trisodiurn phosphate 7500 and para nitro toluene mercuric acetate and methyl oleamide ethyl sodium sulfonate l0 'Insodium phosphate 7500 and alphanitro naphthalene mercuric acetate Trisodium phosphate 7500 and alpha nitro naphthalene mercuric acetate and methyl oleamide ethyl sodium sulfonate 10 Tnsodlum phosphate 7500 and alpha naphthylamine mercuric acetate l0 0 O 'lrisodium phosphate 7500 and alpha naphthylamine mercu icacetateandmethyl oleamide ethyl sodium sulfonate 10 0 0 0 According to a further feature of the invention, we have discovered that the germicidal effectiveness of these new compounds is still further increased by admixture with a detergent, and particularly with an alkaline detergent. As suitable materials may be mentioned such alkalies or alkaline salts ,as caustic soda, sodium carbonate, disodium phosphate, sodium tetraborate, sodium metaborate, sodium metasilicate, and sodium orthosilicate, and corresponding potassium compounds and ammonium compounds wherever these exist. However, for certain types of cleaning operations, acids or acid salts having a detergent action may be employed, such as hydro- One milliliter of the a Only a relativelysmall proportion of the germicide .is necessary to reach such results. The

germicide does not exceed 10%, and'preferably is not over 1 or 2% of the detergent. In addition to the examples given in the table, mixtures may be provided in which the germicide and the sulfonic compound are mixed with the detergent, and permitted. to react and form the new compound when the mixture is added to water for use.

In the washing of bottles in the machine generally used for that purpose, we prefer a composition having as a detergent base a mixturecontaining a considerable proportion of caustic soda.

This mixture also contains soda ash, trisodium phosphate and, possibly, sodium meta-silicate. When a small quantity of a germicidal compound produced according to the invention is added, it is possible to use such a cleansing material in a concentration of one ounce to the gallon, where four ounces have heretofore been necessary for obtaining satisfactory germicidal action. The mixture may contain as much as used either with the new compounds or with the germicidal compound-detergent mixtures.

The compounds and mixtures described above are stable and eifectivein solutions at relatively high temperatures throughout the entire pH 5 range. In fact, their germicidal activity increases at elevated temperatures.

It is not necessary that the compounds heretofore described be formed in advance of the cleaning operation. For example, the i'ngredil0 ents'may be mixed in dry form and allowed to react only when they are dissolved in water to form the cleaning and disinfecting solution. We may for instance mix an organic germicide and a sulfonic compound, with or without a detergent 1 and/or an active oxygen compound, in the dry state. As soon as sucha mixture is added to water the materials will react to produce the new compounds.

The terms detergent" and' "alkaline deter- 20 gent" as used herein are intended to mean not only the specific compounds listed above but also such mixtures and combinations thereof as may be useful for any specific cleaning process, as well as other chemical compounds, acid or alka- 25 line, having detergent action.

The term sulfonic compound as usedin the specification and claims is intended to cover both aliphatic and aromatic sulfonic acids and the salts thereof, and also other materials such as the acid sulfates of higher alcohols or their salts.

1. A new organic mercury compound of the general formula (CsHeHg) .R1, in which R1 represents a radical of a higher fatty compound contalning a sulfonic group.

'2. A new organic mercury compound of the general formula R.Hg.R.1, wherein R represents an aromatic radical and R1 represents a radical of a higher fatty compound containing a sulfonic w emu 32A new organic mercury compound of the general formula R.Hg.R1, wherein It represents an aromatic radical and R1 represents the methyl-oleamide-ethyl-sulfonate radical.

4. Methyl-oleamide-ethyl-phenyl-mercuric sulfonate.

5. A neworganic mercury compound of the general formula R.Hg.Ri. wherein R represents an aromatic radical and R1 represents the decylso sulfate radical.

6. Decyl-phenyl-mercuric sulfate.

CARL JOHNSON. wnmsu M. ALLISON.