text: the compounds of this invention are prepared by general known methods . see , for example , u . s . pat . no . 2 , 333 , 468 describing the oxidative condensation of dithiocarbamic acids and primary or secondary amines to yield n , n - dialkylthiocarbamoyl sulfenamides . to further illustrate , n , n - dimethylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicylohexylsulfenamide is prepared as follows : a mixture of 100 ml ccl 4 , 39 . 6g 25 % aqueous solution of dimethylamine and 36 . 2g dicyclohexylamine is placed in a reaction vessel and cooled to 10 ° c . 114 ml of 14 % aqueous solution of naocl is added and the mixture is stirred for 15 minutes at 10 °- 15 ° c . after addition of 200 ml nahco 3 -- na 2 co 3 buffer solution , the mixture is warmed to 20 ° c and admixed with 15 . 2g cs 2 with stirring . the mixture is agitated for 40 minutes at 32 ° -═° c . after settling , the nonaqueous phase is separated out and filtered . ccl 4 is evaporated by heating under reduced pressure . the residual liquid is added to 150 ml methanol resulting in a precipitation of a solid . the methanol slurry is cooled to 10 ° c and filtered . the recovered solid is white crystalline material having a melting point of 80 °- 2 ° c . the yield is 44 . 1g . relatively small amounts of the antibacterial agents are sufficient to obtain the advantages of the invention . satisfactory results are obtained when the weight of the antibacterial agent is from 0 . 1 to 5 percent of the total weight of the detergent composition . the preferred range is 1 to 3 percent based on the weight of the detergent composition . however , it should be understood that greater amounts will be effective but without further substantial advantages . those skilled in the art will be able to determine , according to known practice , what the effective amount for a given application and / or desired germicidal or biostatic effect must be . the germicidal agents of this invention can be added to soap or other alkaline skin cleaning agent by any of the common employed methods which result in a uniform distribution of the antibacterial agent throughout the entire mass . shampoo and soap formulations can , of course , contain any of the usual additives such as coloring agents , perfume , thickeners , solvents , opacifiers , suds builders , conditioning agents , preservatives , buffers , and anti - static agents . the detergent may be soap as well as non - soap surface active agents of the anionic , cationic , nonionic and amphoteric type . anionic detergents include both the soap and non - soap detergents . examples of suitable soaps are the sodium , potassium , ammonium and alkanolammonium salts of higher fatty acids ( c 10 - c 20 ). particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow . examples of anionic non - soap detergents are alkyl glyceryl ether sulfonates , alkyl sulfates , alkyl monoglyceride sulfates or sulfonates , alkyl polyethoxy ether sulfates , acyl sarcosinates , acyl esters of isothionates , acyl n - methyl taurides , alkyl benzene sulfonates , and alkyl phenol polyethoxy sulfonates . in these compounds the alkyl and acyl groups , respectively , contain 10 to 20 carbon atoms . they are used in the form of water - soluble salts , the sodium , potassium , ammonium and alkanolammonium salts , for example . specific examples are sodium lauryl sulfate , potassium n - methyl lauroyl tauride ; and triethanolamine dodecyl benzene sulfonate . suitably useful cationic detergents are exemplified by dilauryldimethyl ammonium chloride , diisobutyl phenoxy ethoxy dimethylbenzyl ammonium chloride , cetyl trimethyl ammonium bromide , n - cetylpyridinium bromide and benzethonium chloride , which are classed as quaternary ammonium salts . suitable examples of amphoteric detergents are alkyl beta - iminodipropionates , and alkyl beta - amino propionates , wherein the alkyl group contains 10 to 20 carbon atoms , and basic quaternary ammonium compounds derived from 2 - alkyl - substituted imidazoline . the properties of the preferred embodiments of the invention were evaluated and the results are set forth in the following examples and tables . bacteriostatic activity per se was tested by milling into ivory soap ( made according to u . s . pat . no . 2 , 295 , 594 ) 1 percent test material based on the weight of the soap and by compressing it into plugs . plugs ( 0 . 5 inch in diameter and 0 . 25 inch thick ) of each of the test soaps were placed on agar plates seeded with one of three representative test bacteria , bacillus subtilis , staphylococcus aureus , and salmonella typhosa . after incubation at 37 ° c . for 24 hrs ., the clear zone of inhibition ( lack of bacterial growth ) was measured and reported as average diameter of zone inhibition ( diameter of clear zone less the diameter of the soap plug ), and tabulated in table ia . for the test of substantivity or retention of bacteriostat by the skin after washing with the test soap , untanned calf - skin hide buttons were soaked in an 8 percent solution of the test soap containing 1 % bacteriostat , rinsed four times with distilled water , placed on seeded agar plates and incubated for 24 hrs ., at optimum temperature of the test bacteria , bacillus subtilis , staphylococcus aureus and salmonella typhosa . the zones of inhibition was measured and reported as in the soap plug test , and tabulated in table ia . the results set forth in table ia demonstrate the good microorganism inhibiting and skin substantive properties possessed by the compositions of this invention . moreover , the unexpected effectiveness of the thiocarbamoyl sulfenamides of this invention in detergent compositions is apparent from comparison with the ineffectiveness of structurally similar compounds . employing the identical test procedure previously described , bacteriostatic activity for some thiocarbamoyl sulfenamides not falling within the formula of this invention was evaluated . the results , tabulated in table ib , demonstrate a lack of substantial bacteriostatic activity and substantivity in soap for these related compounds and thus the unpredictability of useful efficacy . table ia__________________________________________________________________________bacteriostatic activity and substantivity in soap average diameter of inhibited zone in mmactive ingredients ( a ) activity in soap ( b ) hide substantivity in soap b . subtilis s . aureus s . typhosa b . subtilis s . aureus s . __________________________________________________________________________ typhosan , n - dimethylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicyclohexylsulfenamide 12 12 10 3 4 2n , n - diethylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicyclohexylsulfenamide 15 16 12 2 3 2n , n - dimethylthiocarbamoyl - n &# 39 ;- phenyl - sulfenamide 24 22 19 3 6 2n , n , n &# 39 ;, n &# 39 ;- bis ( 2 , 2 &# 39 ;- oxydiethylene )- thiocarbamoylsulfenamide 5 12 4 4 10 2__________________________________________________________________________ table ib__________________________________________________________________________thicarbamoyl sulfenamides without substantial bacteriostatic activity andsubstantivity in soap__________________________________________________________________________ average diameter of inhibited zone in mm activity in soap hide substantivity in soapactive ingredients b . subtilis s . aureus s . typhosa b . subtilis s . aureus s . __________________________________________________________________________ typhosan , n - di - n - butylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicyclohexylsulfenamide 6 0 0 0 0 0n , n - diethylthiocarbamoyl - n &# 39 ;- phenyl - sulfenamide 0 0 0 0 0 0bis ( 3 , 5 - dimethyloxydiethylene )- thiocarbamoyl sulfenamide 0 0 0 0 3 0n , n - dieicosylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicyclohexylsulfenamide 0 0 0 0 0 0__________________________________________________________________________ the skin substantivity test was repeated using shampoo formulations as follows : shampoo a shampoo b percent percentingredients by weight by weight______________________________________sodium salt of sulfated coconutfatty alcohol 23 -- sodium stearate 8 . 7 -- sodium alkyl glyceryl ethersulfonate . sup . 1 -- 28 . 3sodium acyl sarcosinate . sup . 2 -- 5 . 0sodium sulfate 0 . 8 2 . 6sodium chloride -- 6 . 6trisodium phosphate 2 . 1 -- diethanolamide of coconutfatty acids -- 2 . 0perfume 1 . 0 0 . 4active ingredient 2 . 0 2 . 0water , made up to 100 % -- -- ph 7 . 7 7 . 4______________________________________ . sup . 1 alkyl radicals derived from fatty alcohol , 25 . 3 % from coconut and 3 % from tallow . sup . 2 acyl radicals derived from coconut fatty acids untanned calf - skin buttons were soaked in an 8 percent solution of the test shampoo containing 2 % bacteriostat , rinsed four times with distilled water , placed on seeded agar plates and incubated for 24 hrs . at optimum temperature of the test bacteria , bacillus subtilis , staphylococcus aureus and salmonella typhosa . the zones of inhibition were measured and reported as in the soap plug test and tabulated in table ii . table ii__________________________________________________________________________hide substantivity in shampoo average diameter of inhibited zone in mm shampooactive ingredient composition b . subtilis s . aureus s . typhosa__________________________________________________________________________n , n - dimethylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicyclo - hexylsulfenamide a 4 0 2do . b 11 11 13n , n - dimethylthiocarbamoyl - n &# 39 ;- phenyl - sulfenamide a 10 8 5do . b 18 20 14n , n , n &# 39 ;, n &# 39 ;- bis ( 2 , 2 &# 39 ;- oxydiethylene ) thio - carbamoylsulfenamide a 14 14 9do . b 12 13 11n , n - diethylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicyclohexyl - sulfenamide a 11 11 3do . b 12 10 6__________________________________________________________________________ to test the color stability of detergent compositions , a soap plug containing n , n - dimethylthiocarbamoyl - n &# 39 ;, n &# 39 ;- dicyclohexylsulfenamids as active ingredient was cut in two , and one portion was exposed to sunlight for 40 hrs . upon comparison to the unexposed portion of the soap , no color change was observed . thus , there have been disclosed n , n - dialkylthiocarbamoyl sulfenamides which unexpectedly possess excellent germicidal and substantive properties which are retained in the presence of detergents . these properties , as well as the color stability of the compounds of the invention , indicate the applicability of the compounds as active ingredients in germicidal or medicinal soaps , shampoos and other skin - cleansing compositions .