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United States, Patent ()?iice. __ 3,964,048 Patented Nov. 13, 1952 2 1 3,064,048 PROCESS FOR PREPARENG 3,4',5-TRIBROMO SALICYLANILIDE IN THE PRESENCE OF A WETTING AGENT Charles H. Sehrannn, Easton, Pa., and Henry Lemaire, Leonia, NJZ, assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine It is not desirable to add all of the bromine required for the reaction to produce the tribromo product at the start of the reaction, since too high an initial bromine concentration may lead to the production of a higher proportion of brominated products containing more than three bromine atoms per molecule. Thus, the bromine can be added dropwise or in small increments over a period of from one-half to three hours. After all of the bromine has been added, the reaction mixture is held at 10' the reaction temperature for a suf?cient time to allow The present invention relates to a process for the prep reaction to proceed to completion, usually in about one aration of a novel chemical compound, 3,4’,5-tribromo half to two hours’ time. The reaction mixture then can No Drawing. Filed July 10, 1958, Ser. No. 747,568 10 Claims. (Cl. 26ti—559) salicylanilide. > be allowed to cool to room temperature, and is ?ltered to Polyhalosalicylanilides can be made in good yield by the direct condensation of a halogenated salicylic acid 15 and a halogenated aniline. Although this method is sat isfactory in the laboratory, it is economically undesirable commercially because of the necessity for separately halo genating the salicylic acid and the aniline portions prior to condensation. However, the halogenation of salicyl 20 remove the desired product which also is insoluble in the reaction medium. anilide by methods known in the art results in compara 3,4',5 - tribromosalicylanilide. tively- poor yields. quite ?ne particles, i.e., below 200 mesh, others quite ’ Any organic surfactant can be employed. The anionic, cationic, and nonionic surfactants are the known classes of surfactants, and any of these, alone or in admixture, give satisfactory results. The choice of any particular surfactant will depend upon the particle size desired of the Some surfactants yield In accordance with the invention, 3,4',5-tribromosali coarse particles, i.e., above 20 mesh, and others interme cylanilide is obtained in a high yield by the bromination diate these extremes. This phenomenon is at present un of salicylanilide with three moles of bromine. In this 25 explained. bromination, it is theoretically possible to obtain a wide There are many types of anionic surfactants which will variety of polybrominated products, the bromine being at once occur to those skilled in this art. substituted in any of several combinations of one, two and three positions in the two rings. However, in ac sulfonates are a class of surfactant well known in the art under this name. One example thereof are the sulfonated cordance with the invention the bromine entering the rings is oriented to give the 3,4’,5-tribromo isomer by effecting branched chain structure of polypropylene and a tertiary The alkyl aryl phenylpolypropylene alkanes, characterized by the the bromination in a medium composed of from 0.1 to alkyl'carbon at the benzene ring, and having the following 2% of an organic surfactant and from 99.9 to 98% water. general structure: The reaction mixture will contain small amounts not in excess of about 30% and usually not exceeding 20% of 35 the 3,5 and 4’,5-dibromo derivatives and the 2',3,4’,5 tetrabromo derivative. The surfactant and water when present in a concentra tion within the ranges stated by some unknown mecha nism shift the reaction in favor of the 3,4',5-tribromo 40 derivative. Bromination in water alone yields a product SOsM having a dark color, the reaction proceeds more slowly, where M is hydrogen, an alkali metal or an organic amine and the total yield is appreciably lower, due to the forma cation, and R1 and R2 are alkyl, of the type formula tion of the tarry products imparting the dark color. CDHZHH, and at least one R is a polypropylene group, the Salicylanilide is insoluble in the reaction medium at the 45 Whole alkyl group containing preferably twelve to ?fteen reaction temperatures. Stirring therefore is essential carbon atoms. These are known compounds, whose prep throughout the reaction in order to keep the system uni aration and properties are set forth in US. Patent No. form. Enough of the reaction medium should be used 2,477,383 to Lewis, issued July 26, 1949; they are avail to ensure complete suspension of the salicylanilide, but able in commerce under the trade names “Oronite”, apart from this the amount is in no way critical. The “Ultrawet” and “Neolene”. larger‘,- the volume of reaction medium, the more di?icult Another example thereof are the alkyl aryl sulfonates the mix is to handle and the more dilute will be the suspen sion, so that the reaction will proceed more slowly. A made by chlorinating a keryl hydrocarbon, and condens ing this with benzene, followed by sulfonating. reaction medium having a concentration of less than about These give a ?ne particle size of 3,4’,5-tribromosalicyl 5% salicylanilide thus would not be used. At a concen 55 anilide. tration in excess of about 12%, the reaction mixture be Also useful are the aliphatic acyl amino alkane sul comes quite thick and dif?cult to stir. Usually, a con fonates of the type described in Patent No. 1,932,180, the centration of from 8% to 10% is preferred. sodium alkanoyl and alkenoyl methyl taurides. They The reaction proceeds smoothly at a temperature with have the formula: in the range from about 40° to about 70° C. Preferably, 60 from 50° to 65° C. is employed, since at the more elevated temperatures the color of the product may be dark. At temperatures below 40° C. the reaction proceeds too slow ly to be practical. where R is an aliphatic hydrocarbon radical, such as alkyl or alkenyl, having nine to seventeen carbon atoms, R1 is 3,064,048 d. 3 hydrogen or a lower alkyl radical of one to six carbon unsaturated hydrocarbon group having ‘from eight to atoms such as methyl, ethyl, propyl, butyl, amyl, and eighteen carbon atoms or an aralkyl group having a straight or branched saturated or unsaturated hydro carbon group of from eight to eighteen carbon atoms at tached to the aryl nucleus, and attached to A through the hexyl, and n and X are the same as that de?ned in con nection with the aminocarboxylates. Examples are lauro yl, oleoyl and stearoyl taurides, methyl taurides and amino aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylate and thiocar methane sulfonates. These give a relatively ?ne particle 3,4',5-tribromo salicylanilide, about 2% of which is above 200 mesh. There can also be employed the aliphatic hydrocarbon boxylate groups and x is a number from eight to thirty. R can for example be a straight or branched chain octyl, 10 nonyl, decyl, lauryl, myristyl, cetyl, or stearyl group, or aminocar-boxylates, of the general formula: an alkyl aryl group such asoctylbenzene, nonylbenzene, decylbenzene, stearylbenzene, etc. When R is alkyl it will be evident that the surfactant can be regarded as derived from an alcohol, mercaptan, where R is an aliphatic hydrocarbon radical, such as alkyl or alkenyl, having one to eighteen carbon atoms, 15 oxy or thio fatty acid of high molecular weight, by condensation with ethylene oxide. Typical of this type and R1 is hydrogen or the same as R or some other of alkyl ether are the condensation products of oleyl or dodecyl alcohol or mercaptan with “Emulfor ON,” “Nonic 218” and “Sterox SE” and “SK”. Typical alkyl aliphatic hydrocarbon radical, such as alkyl or alkenyl, having one to eighteen carbon atoms, the total number of carbon atoms of R and R1 being not less than eight esters are “Gl226” and “Renex” (polyoxyethylene ester and not more than twenty-two, n is a whole number of one to ?ve, preferably one or two, and x is a salt of tall oil acids), “Sterox CD”, “Neutronyl 330” and “331” (higher fatty acid esters of polyethylene glycol). forming cation, more particularly sodium, potassium, When R is aralkyl, the surfactant can be derived from an alkyl phenol or thiophenol. calcium, magnesium, and amine, an ethanolamine, etc. Examples of such compounds are alkyl or alkenyl aminopropionates, such as the sodium salt of dodecyl The oxyethylated alkyl phenols and thiophenols have the following general formula: ?-alanine, octadecenyl-B-alanine, dodecyl methyl amino propionate, diamyl aminopropionate, oleyl ethyl amino propionate, the sodium salt of alkyl or alkenyl glycines, such as sodium dodecyl glycine, and sodium octadecenyl 30 glycine. R These give a fairly coarse particle 3,4',5-tribromo ‘salicylanilide, about 50% of which is above 200 mesh. Any alkyl sulfate Whose alkyl group has from about eight to about twenty-two carbon atoms is suitable, for where R is a straight or branched saturated or un saturated hylrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, A is example, lauryl, myristyl, stearyl and cetyl sulfates, and oxygen or sulfur and x is a number ‘from eight to thirty. also sulfates derived from mixed fatty alcohols obtained from fatty oils, such as coconut oil fatty alcohols and R can, for example, be a straight or branched chain octyl, palm oil fatty alcohols. are the condensation products of octyl and nonyl phenol with from eight to seventeen moles of ethylene oxide, nonyl, decyl, lauryl, myristyl, cetyl or stearyl. Typical ' These give a relatively ?ne particle 3,4',5-tribromo salicylanilide. 40 available commercially under the trade names “Oronite Also useful are the sulfated ethoxynated alkyl phenols having the following general formula: NIW,” “Antarox A400,” “Igepal CA” and “CO,” “Triton X—l00,” “Neutronyx 600” and “Tergitol NPX.” Also useful are the alkyl carboxyamido condensation products (condensation products of ethanolamine with fatty carboxylic acids and fatty thiocarboxylic acids) having the following general formula: where R is a straight or branched chain saturated or un saturated hydrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, A is The compound has at least one RA or R'A group, usually one or two, R and R’ are straight or branched chain satu oxygen or sulfur, x is a number from three to eight, and rated or unsaturated hydrocarbon groups having from eight to eighteen carbon atoms, R” is hydrogen, an alkyl M is hydrogen or an alkali metal, e.g., sodium, potassium, and ammonium, or_an organic amine cation. The amine can be any of those listed hereinafter. group of one to about twenty-four carbon atoms, or a R is usually a second branched chain hydrocarbon group and can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. H [0112011201 or group AR’ . These give a relatively ?ne particle 3,4',5-tribrorno salicylanilide. Exemplifying the amines are water-soluble strongly basic amines such as triethanolarnine, dietha nolamiue, monoethanolamine, ethylenediarnine, diethyl 'enetriamine, tetraethanol ammonium hydroxide, morpho line, mixed isopropanolamines, monoisopropanol amine, diethylene glycol ‘amine, and amino ethyl ethanolamine. The alkylolamines, either mono-, preferred. ' 1 di- or tri-,‘ ‘are ' There are many types of nonionic surfactants known to ‘those skilled in the- art, and any of these or mixtures thereof could bev employed, including, for example, alkyl oxy- and thioether and oxy- and thioester surfac tants having the following general formula: I R_A_[cH2cH2O1g—_—CH2CH2-or1 where R is a straight or branched chain saturated or (if) A is selected from the group consisting of carbonyl 0:0 and thiocarbonyl (:8 groups, and x is a whole number equal to the valence of RA or R'A. For example, if one of RA or R’A is a dicarboxylic acid, x is at least two, with a possibility of longer chains of amido- and ester-linked acid and ethylene units. Usually x is from one to four. R, R’ and R” can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl group. The Pluronics are a group of nonionic surfactants hav ing the'formula: . CH3 HO[CH?CH20]m[OHaéHOLJCIIzCHzOhUH These are fully described in US. Patent No. 2,674,619 to L. G. Lundsted, dated April 6, 1954; see especially ‘seems . . . . 5 . . column 3, lines 55 to 71. See 2,677,700 to D. R. Jackson et al., m and m’ represent the average units, and n the average number also U.S. Patent No. dated May 4, 1954. number of oxyethylene of oxypropylene units. See U.S. Patent No. 2,674,619. The sum of m and m’ 5 Typical compounds are those where R is oleyl, stearyl and palmityl. The following examples are illustrative: EXAMPLES 1 TO 6 Salicylanilide (213 g., one mole) was suspended in 2.5 liters of water containing 2 g. (basis active) surfactant preferably is within the range from ?fteen to forty-one, and n preferably is within the range from seventeen t0 thirty-one. and brought to 55° C. The surfactant was as listed in These give a ?ne particle 3,4’,5-tribr0m0salicylanilide. the table below. The suspension was stirred and 480 g. The process of the invention as stated also can be based 10 (three moles) of bromine was added dropwise while upon cationic surfactants. These are characterized by maintaining a temperature from 55° to 60° C. The the fact that the hydrophobic group forms part of cation bromine addition required ninety minutes, and the mix when the compound is dissolved in water. The amines and quaternary ammonium salts are the preferred groups ture was held at 55 ° C. for an additional hour. At the end of this time the product was cooled to room tem of cationic surface active agents, but any such agents 15 perature, neutralized, and ?ltered. The ?lter cake was known to those skilled in the art can, of course, be used. washed twice with methanol and dried. The yield in The quaternary ammonium compounds are soluble in both all cases was about 95—98% of material containing 70 basic and acidic media. The primary, secondary, and to 79% 3,4’,5-tribromosalicylanilide, from 1 to 4% 4',5 tertiary amines containing a hydrophobic group suf?dibromosalicylanilide, from 12 to 17% 3,5-dibromo ciently large to be in the surface active range are less 20 salicylanilide and from 4 to 15% 2’3,4’,5-tetrabromo soluble in water and in alkaline solutions, and usually Salicylanilide. The yields and particle sizes obtained are require solubilization with an organic solvent. They are, listed in Table I: Table 1 Percent Yield Percent ' Example No. 1 Surfactant Retained Percent on 200 Mesh Bromine 5 Percent 3,4/,& 1 Percent 435 2 Percent 3,5 3 Percent 2’3,4’.=. 4 78 1 13 8 2.31 52.63 79 4 13 4 70.57 51.21 70 3 12 15 43. e3 52. 82 74 2 12 12 2.92 52.23 17 9 3. 37 51. 20 14 6 0. 27 51. 53 Igepon T (sodium oleyl methyl taurideip ______________________ __ Cetyltritnethylammonium bromide (Ce-tab) ______________ __ Sodium salt of coco~beta~alanine (Deriphat- XD-151) _ _ __ Sodium lauryl sulfate. _ Ammonium saltofsulin dn0u_ - phenol-4 mole ethylene oxide condensate 6 _______ __ (Alipal 00-436, NPES-4) _ _ Sodium salt of dodeeylbenzene sullonate ______________________ -. 74 75 5 l 3,4’,s-tribromosalicylanilide. 2 4’,5-dibromosalicylanilide. 3 3,S-dibromosalicylanilide. 4 2'3,4’5-tetrabromosalicylnnilide. _ _ I _ 5 Analysis based on entire mixture; theoretleal for 3,4’,?-tribromosal1cylani11de—5329%. however, soluble in acidic solutions where the pH is low enough to convert the bases to their amine salts. In addition to these classes of materials, there are the surface active agents based upon guanidines, hydrazines, amine oxides and nitrogen-containing heterocyclic substances, as well as sulfonium compounds containing long-chain hydrophobic groups. The quaternary ammonium compounds have at least one long aliphatic chain having from about twelve to about eighteen carbon atoms, and the remaining valences of the nitrogen are taken with short-chain aliphatic radi cals usually having from one to ?ve carbon atoms, or by hydrogen. These compounds have the general formula EXAMPLE 7 Salicylanilide (213 g., one mole) was suspended in 2.5 liters of water containing 5 g. (40% active) of an aqueous sodium dodecylbenzenesulfonate paste. The suspension was stirred and heat was applied to bring the temperature of the mixture to 55 ° C. Two-thirds (320 g., two moles) of the bromine was added during this period and the remaining one-third (160 g., one mole) was added at 55—60° C. The bromine addition required ninety minutes, and the reaction temperature was held at 65° C. for an additional hour. At the end of this time, the product was cooled to room temperature and 175 cc. of an aqueous 10% sodium bisul?te solution was added. R1R2R3R4NX, wherein one R is a long-chain aliphatic radical as described, and the remaining R’s are additional 60 After neutralization with 130 g. (in 500 cc. of water) of sodium hydroxide to pH 4, the crude, 3,4’,5-tribromo long-chain or short-chain aliphatic radicals, or hydrogen, Salicylanilide was ?ltered and dried. The yield was and X is an anion such as halogen, for example halide or 440 g. (98%) of material containing 77% 3,4',5-tribrom0 bromide, sulfate, nitrate, and the like. Typical quaternary ammonium compounds having surface active properties are palmityl trimethyl ammonium chloride, stearyl di methyl benzyl ammonium chloride, oleyl trimethyl am~ monium chloride, cetylpyridinium bromide, and coconut fatty alkyl dimethyl benzyl ammonium chloride (Roccal, Triton K60). These give a quite coarse particle 3,4’,5 tribromosalicylanilide. Salicylanilide, 4% 4’,S-dibromosalicylanilide, 13% 3,5 dibromosalicylanilide and 6% 2',3,4’,5-tetrabromosalicyl anilide. The material was vcomposed of ?ne particles below 200 mesh. EXAMPLE 8 Salicylanilide (213 g., 1 mole) was suspended in' 2.5 70 liters of water containing 2 g. Pluronic F68. The sus pension was stirred vand heat was applied to bring the temperature of the mixture to 55° C. Two-thirds (320 g., two moles) of the bromine was added during this period has from nine to seventeen carbon atoms. These com and the remaining one-third (160 g., one mole) was pounds are available under the trade name “Sapamines.” 75 added at 5 5—610‘‘ C. The bromine addition required ninety Another well known class of cationic detergents have the formula RCONHC2H4N(C2H5)2, where R is a long chain hydrophobic group derived from a fatty acid and aoeacas " 7 minutes, and the reaction temperature was held :at 65° C. is therefore no need to free the 3,4',5-tribromosalicyl for an additional hour. At the end of this time, the anilide of these di- andjtetrabromo. derivatives. The mix product was cooled to room temperature and 1775 cc. of tures of di-, tri- and tetrabromo derivatives can be used an aqueous 10% sodium bisul?te solution was added. directly in soap and nonsoap compositions, and these After neutralization with 130 g. (in 500 cc. of water) of 5 compositions show excellent germicidal effectiveness. sodium hydroxide to pH 4, the crude 3,4',5-tribromo The following example is illustrative: salicylanilide was ?ltered and dried. The yield was 440 EXAMPLE ll g. (98%) of material containing 77% 3,4',5-tribrorno Soap-synthetic chips (30 lbs.) containing 24.9% so salicylanilide, 3% 4',5-dibromosalicylanilide, 16% 3,5 dibromosalicylanilide and 4% 2’,3,4’,5-tetrabromosalicyl dium tallow soap, 35% sodium coconut oil soap, 18% acyl methyl taurate prepared from 40—I.V. tallow fatty acids, 5% miscellaneous unidenti?ed matter from the soap and taurate, 10% stearic acid, 0.02% butylated hy anilide. The material was composed of gritty particles. EXAMPLE 9 Salicylanilide (213 g., one mole) was suspended in droxy toluene, 0.8% perfume, 0.0022% dye (FD&C 2.5 liters of water containing 2 g. of the condensation 15 Red #4), 0.3% TiO2, and the balance water, were weighed into a chip mixer. All percentages shown above product of an average of 12 moles ethylene oxide with are expressed on the weight of the whole mixer com decanol. The suspension was stirred and heat was ap position. To these chips were added 0.5% (whole-com position basis) of a mixture containing 76% 3,4’,5-tzi bromosalicylanilide, 2% 4',5-dibromosalicylanilide, 10% 3,S-dibromosalicylanilide and 12% 2’3,4’,5-tetrabromo salicylanilide. The batch was mixed, milled, and plodded plied to bring the temperature of the mixture to 55° C. Two-thirds (320 g., two moles) of the bromine was added ‘during this period and the remaining one-third (160 g., one mole) was added at 55-605 C. The bromine addi tion required ninety minutes, and the reaction tempera into bars. 8% aqueous solutions were prepared from one of these soap bars and subjected to the Finger Imprint Test. ture was held at 65° ,C. for an additional hour. At the end of this time, the product was cooled to room tempera~ ture and 175 cc. of an aqueous l0% sodium bisul?te solution was added. After neutralization with 130 g. The mixture composed‘predominantiy of the 3,4’,5-tri bromosalicylanilide gave a rating of 3.2. In contrast, 4’,5-dibromosalicylanilide in a germicidal soap bar pre crude 3,4’,5-tribromosalicylanilide was ?ltered and dried. pared in the same way and of the same composition The yield was 440 g. (98%) of material containing 80% 3,4’,5 - tribromosalicylanilide, 4% 4',5 - dibromosalicyl 30 gave a rating of 0.9. A bar prepared in the same way and of the same composition but containing no germicide anilide,, 10% 3,S-dibromosalicylanilide and 3% 2’,3,4',5 had a rating of 0. tetrabromosalicylanilide. The material was composed of Only small amounts of 3,4’,S-tribrornosalicyanilide are ?ne particles below 200 mesh. required to render soap germicidal. An amount as low EXAMPLE 10 35 as 0.01% based on the weight of the soap produces a soap composition having excellent antibacterial potency. Salicylanilide (213 g., one mole) was suspended in As much as 5% has been used to advantage. There is no 2.5 liters of water containing 2 g. of the condensation need to employ more than is required to give the de product of tridecyl alcohol with an average of 10 moles sired germicidal effect, and in general for this reason ethylene oxide. The suspension was stirred and heat was ‘applied to bring the temperature of the mixture to 55 ° C. 40 from 0.2 to 2% would be preferred. Increasing the con centration of the compound beyond 5% merely increases Two-thirds (320 g., two moles) of the bromine was added (in 500 cc. of water) of sodium hydroxide to pH 4, the during this period vand the remaining one-third ( 160 g., ' the cost of the soap and might tend to reduce the de one mole) was added at 55-60“ C. The bromine addi tergent properties of the composition. tion required ninety minutes, and the reaction tempera be seen that the concentration is not critical, but would It will readily ture was held at65° C. for an additional hour. At the end of this time, the product was cooled to room tem perature and 175 cc. of an aqueous 10% sodium bisul?te solution was added. After neutralization with 130 g. (in be determined from a consideration of these factors as ' long as enough is used to give the desired antibacterial effect. In the quantities in which the compound or mixture thereof with di- and tetrabromo salicylanilides is used 500 cc. of water) of sodium hydroxide to pH 4, the crude in soaps, it does not produce skin irritation, is not toxic, 3,4’,S-tribromosalicylanilide was ?ltered and dried. The yield was 440 g. (98%) of material containing 77% 50 and is compatible with the usual soap components. The term “soap” as used herein refers to alkali met? 3,4’,5 - tribromosalicylanilide, 2% 4’,5 - dibromosalicyl soaps of the saturated and unsaturated higher fatty acids anilide, 18% 3,S-dibrornosalicylanilide and 3% 2',3,4',5 having from about eight to about twenty-six carbon atoms, tetrabromosalicylanilide. The material was composed of such as capric, caprylic, lauric, myristic, palmitic, stearic, oleic, linoleic, linoienic, arachidic, behenic, margaric, ?ne particles below 200 mesh. 3,4’,S-tribromosalicylanilideis a novel compound hav ing the structure: Br OH l I tridechoic, and cerotic acids and the mixtures of such acids naturally occurring in fats, oils, waxes, and rosins, such as the soaps of coconut oil fatty ‘acids, tallow fatty acids, pig fat, ?sh oil fatty acids, beeswax, palm oil fatty 60 I Br 3,4’,5rtiibromosalicylanilide is a white compound, solid acids, sesame oil fatty acids, peanut oil fatty acids, olive oil fatty acids, palm kernel oil fatty acids, cottonseed oil fatty acids, soyabean oil fatty acids, corn oil fatty acids, babassu oil fatty ‘acids, rosin acids, abietic ‘acid, and at room temperature, insoluble in water, soluble in hot acetone and ,very soluble in dimethylformamide. This greases. compound has extraordinary bactericidal properties, and those skilled in the art in order to achieve this result, these properties are retained in the presence of soap. the following procedure is recommended: The soap chips 'are weighed into the mixer and followed immediately by addition of the remaining components of the mix, for example, perfume and dye, in the form of a solution if desired, and mixing is continued for a long enough Soap and nonsoap compositions containing 3,4',5-tri bromosalicylanilider'have shown excellent germicidal ef fectivenessr'when subjected to standardized tests. The 3,4’,S-tribrornosalicylanilide as obtained by the process of the invention will contain small amounts of the 3,5 and 4’,S-dibromosalicylanilide and the 2’3,4’,5 tetrabromosalicylanilides. These also have germicidal properties, particularly the tetrabromo isomer, and there While several mixing procedures will be apparent to period to ensure a thorough dispersion. Thereafter the 3,4',5-tribromosalicylanilide or mixture thereof with di~ and tetrabromo salicylanilides is added with complete and adequate mixing only for the time to ensure uniformity 3,064,048 of dispersion. The ?nal mix then can be treated in the ‘conventional ways to produce the desired soap. To form a bar, for example, the mix can be plodded and extruded using conventional equipment. The 3,4’,5-tribromosalicylanilide soaps in accordance: with the invention can be formed as bar soaps, powdered soaps, chip soaps, ?ake soaps, bead soaps, bar and cake soaps and soap compositions intended for toilet, wash 10 ethylene oxide, and the higher fatty acid esters of sorbitan ethylene oxide condensates, such as sorbitan monostearate ester of polyoxyethylene glycol. They may be in any of the forms described heretofore, including cakes or pow ders, and may include various ?llers, sudsing agents and ingredients conventionally employed in detergent formu lations. They may be compounded for various purposes, such as for shampoo, dishwashing, textile laundering, toilet soaps and similar preparations. ing and disinfectant purposes in addition to their use as detergents. The compositions can be dried in any 10 The 3,4’,S-tribromosalicylanilide or mixture thereof desired way; ‘spray drying is convenient in many in with di- and tetrabromo salicylanilides may be included stances. It is desirable to hold the temperature to which in compositions which contain soap or other surface active the mix is subjected during conversion into its ?nal form agents not intended primarily for detergent use, such as below the temperature at which the 3,4',5-tribromo salicylanilide would be decomposed. Soap mixtures in 15 accordance with the invention have been subjected to temperatures up to 215° F. for periods of up to one hour without disadvantage. various powdered cosmetics. This application is a continuation-in-part of applica tion Serial No. 700,732, ?led December 5, 1957, and now abandoned. We claim: The compositions of the invention meet all of the re 1. A process for preparing a mixture of brominated quirements for germicidal soaps, as is evident from tests 20 derivatives composed predominantly of 3,4',5-tribromo which have been carried out on them, and are indis salicylanilide which comprises brominating one mole of tinguishable in appearance from ordinary soaps. They salicylanilide with three moles of bromine in a reaction can be used as ordinary detergent soaps and are especially medium consisting essentially of from 99.9 to 98% water recommended for uses in which both detergent ‘and de and from 0.1 to 2% of an organic surfactant. germing characteristics are desired. The test results show 25 2. A process in accordance with claim 1, the bromine that the compositions used routinely for a period of from being added dropwise. one to two weeks lower the bacterial ?ora of the skin to 3. A process in accordance with claim 1, in which the a very low level. The compositions are particularly surfactant is anionic. valuable for routine surgical and hospital use ‘and gen 4. A process in accordance with claim 3, in which the erally useful in the prevention of infections arising from 30 surfactant is an alkylaryl sulfonate. skin bacteria. 5. A process in accordance with claim 3, in which the Those skilled in the art will perceive many variations surfactant is an aliphatic hydrocarbon acyl amino alkaue in the compositions of the invention. For example, the sulfonate. 6. A process in accordance with claim 3, in which the and tetrabromo salicylanilides need not be the only 35 surfactant is an alkyl sulfate. germicidal agent; other germicides, such as 2,2'-dihy 7. A process in accordance with claim 1, in which the droxy halogenated diphenyl methanes, can be included, if surfactant is cationic. desired. 8. A process in accordance with claim 7, in which the The soap compositions, in addition to the soap and surfactant is a quaternary hydrocarbon substituted am germicide, will also usually contain ?llers, coloring ma 40 monium compound. terials and perfumes, as desired, as is familiar to those 9. A process in accordance with claim 1, in which the skilled in the art. surfactant is nonionic. The compositions containing the 3,4’,5-tribromosalicyl-' 10. A process in accordance with claim 9, in which the anilide or mixture thereof with di- and tetra-bromo surfactant is an alkyl oxyethylene condensation product. salicylanilides may contain mixtures of detergents, such 45 as soap and anionic nonsoap, or soap and a nonionic non References Cited in the ?le of this patent soap. Typical satisfactory anionic nonsoaps are the alkyl UNITED STATES PATENTS 3,4’,5-tribromosalicylani1ide or mixture thereof with di sulfates, typi?ed by sodium lauryl sulfate, known in the trade as Duponol C, the alkyl aryl sulfonates, typi?ed by 2,511,784 O’Neal ______________ __ June 13, 1950 the sodium polypropylene benzene or toluene sulfonates, 5 O and the sodium keryl benzene or toluene sulfonates, the 2,675,409 2,802,029 Orlotf et a1 ___________ _.. Apr. 13, 1954 Schuler ______________ __ Aug. 6, 1957 180,961 516,037 Austria ______________ .._. Nov. 19, 1954 Belgium _____________ __ Dec. 31, 1952 937,646 Germany ____________ __ June 12, 1956 sulfated ethoxynated phenols, typi?ed by the ammonium salt of sulfated ethoxynated nonyl phenol, prepared by condensation of nonyl phenol with ?ve moles of ethylene oxide, and the sodium fatty acid esters of taurine, typi?ed 55 by sodium palmitic or oleic methyl tauride or mixtures thereof, and the esters of higher fatty acids and hydroxy ethane sulfonates such as oleic acid ester of hydroxy ethane sodium sulfonate. Also useful are nonionic non soaps, such as the polyethylene glycol esters of the higher 60 fatty acids, typi?ed by polyoxylene ethylene and propyl ene glycol stearates, the polyethylene glycol ethers of a1 kyl phenols, typi?ed by the condensation product of octyl and nonyl phenol with ?ve to twelve moles of FOREIGN PATENTS OTHER REFERENCES Hirwe et al.: Proc. Ind. Acad. Sci., vol. 5A, pages 321-325 (1937). Hirwe et al.: J. Indian Chem. Soc., vol. 16, pages 281 284 (1939). Judhev et _al.; I. University of Bombay, vol. 20, See. A, pt. 3, pages 97—100 (1951).