Patent GB-1041984-A (GB)
Title: Improvements in or relating to organic disulphides and uses thereof
Inventor: BROOKS LESTER ALLAN
IPC: C10L1/24
Filed: 1964-01-13
Abstract: A bacteriostatic cleansing composition comprises a detergent or dry-cleaning solvent and a carbamoyl thiocarbamoyl disulphide of the general formula <FORM:1041984/C4-C5/1> where R1, R2, R3 and R4 are the same or different and are each a saturated aliphatic or araliphatic hydrocarbon radical containing from 1 to 10 carbon atoms or R1 plus R2 and/or R3 plus R4 together with the adjoining nitrogen atom form a heterocyclic ring (Division C2).  Examples are given in which the bacteriostatic activity of carbamoyl thiocarbamoyl disulphides is determined in soap, alkyl aryl sulphonate detergent and dry cleaning solvents such as trichlorotrifluoroethane and trichloroethylene.  In the examples various substituted carbamoyl thiocarbamoyl disulphides were tested at a specific concentration, dimethyl carbamoyl dimethyl thiocarbamoyl disulphide was further tested at concentrations varying between 0.05% and 0.1% by weight, the effect of storage on these bacteriostatic soaps was also investigated, and in a further example the effect of washing one hand in medicated soap and the other hand in non-medicated soap was investigated by counting the bacterial colonies found in the wash water which had been cultured for a specified period.  The disulphide of the above formula may be formed in situ in the composition from the corresponding thiocarbamyl monosulphide.ALSO:Water used in paper mills may be treated with 0.1-0.3 by weight of a compound of the general formula <FORM:1041984/C1/1> in which R1, R2, R3 and R4 are the same or different and are each a saturated aliphatic or araliphatic hydrocarbon radical containing from 1 to 10 carbon atoms or R1 plus R2 and/or R3 plus R4 together with the adjoining nitrogen atom form a heterocyclic ring, in order to combat the growth of organisms (Division C2).ALSO:Carbamoyl thiocarbamoyl disulphides of the general formula <FORM:1041984/C2/1> where R1, R2, R3 and R4 are the same or different and are each a saturated aliphatic or araliphatic hydrocarbon radical containing from 1 to 10 carbon atoms or R1 plus R2 and/or R3 plus R4 together with the adjoining nitrogen atom form a heterocyclic ring are obtained by passing into a thiocarbamyl monsulphide of the formula <FORM:1041984/C2/2> where R1, R2, R3 and R4 are defined as above, at least about a stoichiometric amount of free oxygen containing gas, and introducing into said thiocarbamyl monosulphide at least a trace amount of nitrogen tetroxide per mole of the monosulphide sufficient to cause the formation of carbamoyl thiocarbamoyl disulphide, at a temperature low enough to avoid substantial decomposition of the reaction products and separating the resulting carbamoyl thiocarbamoyl disulphide from the reaction mixture.  Water or an inert solvent such as toluene, benzene or chloroform can be used as a reaction medium.  The compounds may also be prepared by the action on thiuram monosulphides of oxidizing agents forming nitrogen tetroxide in situ, e.g. a nitrite salt such as sodium nitrite in the presence of an acid such as hydrochloric acid may be used provided the reaction mixture is agitated vigorously in the presence of air. Examples are given in which the R groups represent methyl, ethyl, butyl, hexyl, benzyl and together with the nitrogen atom R3 plus R4 represent piperidyl and morpholyl.  The products may be used as bacteriostats and fungistats in cleansing compositions including dry cleaning compositions and vinyl resin compositions; as agricultural fungicides, and anti-fouling agents (Divisions A2, A5, C1, C3, C5 and D2).ALSO:A stabilized vinyl resin composition comprises a vinyl resin and a fungistatic and bacteriostatic amount of a carbamoyl thiocarbamoyl disulphide of the general formula <FORM:1041984/C3/1> where R1, R2, R3, and R4 are the sam or different and are each a saturated aliphatic or araliphatic hydrocarbon radical containing from 1 to 10 carbon atoms or R1 plus R2 and/or R3 plus R4 together with the adjoining nitrogen atom form a heterocyclic ring (see Division C2). An example is given where dimethyl carbamoyl dimethyl thiocarbamoyl disulphide is incorporated as a fungicide into a vinyl resin composition comprising the following:-vinyl chloride-vinyl acetate copolymer resin, dioctyl phthalate, ricinoleate type plasticizer, stearic acid, barium-cadmium type stabilizer, and chelating stabilizer.ALSO:A composition useful in the preservation of material normally subject to attack by fungus and/or bacteria comprises a detergent, a dry cleaning solvent, a jet fuel or a vinyl resin and at least one carbamoyl thiocarbamoyl disulphide of the general formula <FORM:1041984/A5-A6/1> where R1, R2, R3 and R4 are the same or different and are each a saturated aliphatic or araliphatic hydrocarbon radical containing from 1 to 10 carbon atoms or R1 plus R2 and/or R3 plus R4 together with the adjoining nitrogen atom form a heterocyclic ring (Division C2).  Examples are given in which (1) the compounds are mixed with a soft clay, a dispersing agent (e.g. the sodium salt of mixed alkyl aryl sulphonate) and a wetting agent (e.g. a high molecular weight alkyl benzene sodium sulphonate); (2) the wetting agent was a liquid nonionic surfactant, nonyl phenyl polyethylene glycol ether and an anti-foaming agent was also added, the compositions obtained in these examples may be applied to potato plants, sugar beet seeds, wax bean seeds and fruit trees; (3) the compounds are blended with a detergent such as alkyl aryl sulphonate or a soap; (4) the compounds were added to dry cleaning solvents such as trichloro-trifluoroethane and trichloroethylene; (5) the compounds were added to a jet fuel; and (6) the compounds were added as fungicides to a vinyl resin containing vinyl chloride-vinyl acetate co-polymer resin, dioctyl phthalate, ricinoleate type plasticiser, stearic acid, barium-cadmium type stabilizer and a chelating type stabilizer.ALSO:Paper mill slime is treated for combating organisms therein by incorporating in the aqueous liquid of the paper mill a carbamoyl fluocarbamoyl disulphide of the general formula:- <FORM:1041984/D1-D2/1> where R1, R2, R3 and R4 are the same or different and are each a saturated aliphatic or araliphatic hydrocarbon radical containing from 1 to 10 carbon atoms or R1 plus R2 and/or R3 plus R4 together with the adjoining nitrogen atom form a heterocyclic ring (Division C2).  An example is given where samples of slime recovered from paper mills were collected and each cultured for 7 consecutive days.  Each slime culture was used as the moculum in a separate Zone of Inhibition test.  Dimethyl carbamoyl dimethyl thiocarbamoyl disulphide was found to inhibit the growth of organisms when used in concentrations in the range 0.1 to 0.3% by weight.