Patent GB-603304-A (GB)
Title: Manufacture of quaternary mercurithioammonium salts and disinfectant preparations containing them
IPC: C07F3/10
Filed: 1945-08-03
Abstract: Quaternary mercurithioammonium salts of the general formula <FORM:0603304/IV(b)/1> wherein R represents an alkyl, cycloalkyl or aryl group such as methyl, ethyl, propyl, methyl-cyclohexyl or phenyl groups, R1 represents an alkylene or arylene group such as ethylene, propylene or phenylene, X represents two groups R2 and R3 (R2 and R3 each repre senting an alkyl group such as methyl, ethyl or propyl) separately bound to N, or two members of a ring containing N, or one member of a ring containing N and R1, R4 represents an alkyl group such as methyl, ethyl or propyl and A represents an anion, are prepared by forming a quaternary salt by treating with a reactive ester of an aliphatic alcohol a mercurithioamine of the general formula <FORM:0603304/IV(b)/2> where R, R1, R2 and R3 have the above significance, or by treating an organic mercury hydroxide or an organic mercury salt with an appropriate quaternary thioammonium salt.  As reactive esters of an aliphatic alcohol there may be urea dialkyl sulphates such as dimethyl or diethyl sulphate, alkyl-, aralkyl-, or arylsulphonic acid esters, for example, para-toluene sulphonic acid methyl ester or alkyl halides such as methyl chloride, bromide or iodide.  The reactions are advantageously conducted in the presence of a solvent such as alcohol.  The mercurithioamines of the above general formula used as starting materials may be obtained by treating an alkyl mercury hydroxide or an alkyl mercury salt with a thioamine such as thioalkylamine, e.g. an aminoalkyl-mercaptan or a diaminoalkyl disulphide.  As quaternary thioammonium salts there may be used mercaptans of the formula <FORM:0603304/IV(b)/3> or disulphides of the formula <FORM:0603304/IV(b)/4> wherein R1, R4, X and A have the above significance. The quaternary thioammonium salts are obtained by treating thioamines with the said reactive ester of an aliphatic alcohol. In examples: (1), (2), (3) ethyl-mercurithioethyl-dimethylamine is prepared by boiling ethyl mercury chloride and bromide suspended in alcohol with caustic soda solution and adding to a solution of dimethylaminoethyl mercaptan, or by boiling a solution of alcohol, sodium and ethyl mercury chloride and bromide and then adding a solution bis-dimethylaminoethyl disulphide in alcohol in which sodium is dissolved, and is then reacted with dimethyl sulphate, methyl chloride or para-toluene sulphonic acid to yield ethylmercurithioethyl-trimethylammonium methosulphate, ethylmercurithioethyl-trimethylammonium chloride or ethylmercurithioethyl-trimethylammonium paratoluene sulphonate; similarly dodecylmercurithioethyl - trimethylammonium metho - sulphate is prepared; (4) ethylmercurithioethyl-trimethylammonium methosulphate is obtained by refluxing ethyl mercury hydroxide, obtained as in (1) from ethyl mercury chloride and bromide, with mercaptoethyl - trimethylammonium methosulphate which is prepared by reacting dimethylaminoethyl mercaptan and dimethyl sulphate; (6) to (11) by a similar method to (1) the following compounds are prepared; ethyl - mercurithioethyl - diethyl - methylammonium methosulphate, ethyl-mercurithioethyl - piperidinium methyl methosulphate, n - propyl - mercurithioethyl - trimethyl - ammonium methosulphate, n-propyl-mercurithioethyl - diethyl - methyl - ammonium metho - sulphate, phenyl - mercurithioethyl - trimethyl - ammonium methosulphate, para - ethyl - mer - curithiophenyl - trimethyl - ammonium metho - sulphate, 2 - (ethyl - mercurithio) - N - methyl - pyridinium methosulphate and ethyl-mercurithioethyl - trimethyl - ammonium bromide and iodide.  In addition, ethyl-mercurithioethyldimethyl - ethyl - ammonium ethosulphate and ethyl - mercurithioethyl - trimethyl - ammonium para-toluene sulphonate are specified.  A sample has been furnished under Sect. 2 (5) of 2 - ethyl - mercurithio - N - methyl - pyridinium methosulphate which is prepared by reacting ethyl-mercury hydroxide with a -mercapto-N-methyl-pyridine methosulphate obtained by treating 2-mercapto-pyridine with dimethyl sulphate.  Quaternary quinolyloxyalkyl- or phenoxyalkylammonium compounds are prepared by treating quinolyl- or phenyl-oxy-alkylamines with a reactive ester of an aliphatic alcohol.  The following compounds are mentioned: [b -(5 : 7-dichloro - quinolyl - (8) - oxy) - ethyl] - dimethyl - dodecyl - ammonium bromide, [b  - (5 : 7 - di - chloro - quinolyl - (8) - oxy) - ethyl] - dimethyl - hexadecyl - ammonium bromide, [b  - (2 - methyl - 5 : 7 - dichloro - quinolyl - (8) - oxy) - ethyl] - di - methyl - dodecyl - ammonium bromide, b -phenoxyethyl - dimethyl - dodecyl - ammonium chloride and bromide, b -phenoxyethyl-dimethyl-hexadecyl - ammonium bromide, b  - (p - chloro - phenoxy) - ethyl - dimethyl - dodecyl - ammonium bromide, b -(p-methyl-phenoxy)-ethyl-dimethyl-dodecyl-ammonium bromide and b -(p-tertiaryoctyl - phenoxy) - ethyl - dimethyl - dodecyl - ammonium bromide.  The Specification as open to inspection under Sect. 91 refers generally to the preparation of compounds of the general formula <FORM:0603304/IV(b)/5> wherein R, R1, R2, R3 and R4 represent organic residues and A represents an anion.  For example, R may be alkyl, cycloalkyl, aryl or heterocyclic group such as methyl, ethyl, propyl, ethoxyethyl, methyl-cyclohexyl, phenyl or pyridyl; R1 may be an alkylene, aralkylene or arylene group such as ethylene, propylene, phenylene-methylene or phenylene; R2, R3 and R4 may be alkyl groups such as methyl, ethyl or propyl groups or aryl groups such as phenyl, R2 may form a ring together with R1 or R3 and N, for example, it may form a pyridine ring with R1 or a piperidine or morpholine ring with R3; A may be the residue of an alkyl sulphuric acid, an alkyl, aralkyl or aryl sulphonic acid or a halogen atom such as chlorine or bromine.  In addition to the quaternary mercurithioammonium salts specified above, the following compound also is specified, viz. pyridyl-mercurithioethyl-trimethyl-ammonium methosulphate.  This subject-matter does not appear in the Specification as accepted.ALSO:Disinfectant compositions contain quaternary mercurithioammonium salts of the general formula <FORM:0603304/VI/1> wherein R represents an alkyl, cycloalkyl or aryl group such as methyl, ethyl, propyl, methyl-cyclohexyl or phenol groups, R1 represents an alkylene or arylene group such as ethylene, propylene or phenylene, X represents two groups R2 and R3 (R2 and R3 each representing an alkyl group such as methyl, ethyl or propyl), separately bound to N or two members of a ring containing N and R1, R4 represents an alkyl group such as methyl, ethyl or propyl and A represents an anion such as methyl or ethyl sulphate, chloride, bromide or iodide or the residue of an alkyl-, aralkyl- or arylsulphoric acid ester, for example, paratoluene sulphonic acid methyl ester. The quaternary mercurithioammonium salts may be used in the form of a salve, solution or powder or in admixture with other compounds which may or may not have disinfectant properties e.g. water, alcohol and water, colouring and odiferous substances, "Vaseline" (Registered Trade Mark), paraffin oil, wool fat and water, starch, sugar and urea or any other inert substance, quaternary quinolyloxy-alkyl- or phenoxy-alkyl-ammonium compounds. Specified quaternary mercurithioammonium salts are para - ethyl - mercurithiophenyl - trimethyl-ammonium methosulphate, ethylmercurithioethyl - trimethyl - ammonium methosulphate, ethyl-mercurithioethyl-trimethyl ammonium chloride, bromide or iodide, ethyl - mercurithioethyl - diethyl-methyl-ammonium methosulphate, propylmercurithioethyl - trimethyl - ammonium methosulphate, dodecyl-mercurithioethyltrimethyl-ammonium methosulphate, propyl - mercurithioethyl - diethyl-methyl - ammonium methosulphate, ethyl-mercurithioethyl - piperidinium-methyl-methosulphate, ethyl-mercurithioethyl-dimethylethyl-ammonium ethosulphate, ethyl-mercurithioethyl - triethyl - ammonium paratoluene sulphonate, phenyl-mercurithioethyl-trimethyl-ammonium methosulphate and 2-(ethyl-mercurithio)-N-methyl-pyridinium methosulphate.  Specified quaternary quinolyloxyalkyl- or phenoxyalkyl-ammonium compounds are [b -(5 : 7-dichloroquinolyl-(8)-oxy)-ethyl] - dimethyl-dodecyl-ammonium bromide, [b -(5:7-dichloro-quinolyl-(8)-oxy)-ethyl] - dimethyl - hexadecyl-ammonium bromide, [b -(2-methyl-5 : 7-dichloro-quinolyl-(8)-oxy)-ethyl] - dimethyl-dodecyl-ammonium bromide, b -phenoxyethyl-dimethyl-dodecyl-ammonium choride or bromide, b -phenoxyethyl-dimethyl-hexadecyl-ammonium bromide, b -(para-chloro-phenoxy) - ethyl-dimethyl - dodecyl-ammonium bromide, b -(para-methyl-phenoxy)-ethyl-dimethyl-dodecyl-ammonium bromide and b -(para-tertiary-octyl-phenoxy)-ethyl - dimethyl-dodecyl-ammonium bromide.  The Specification as open to inspection under Sect. 91 refers generally to disinfectant compositions containing compounds of the general formula <FORM:0603304/VI/2> wherein R, R1, R2, R3 and R4 represent organic residues and A represents an anion.  For example: R may be an alkyl, cycloalkyl, aryl or heterocyclic group such as methyl, ethyl, propyl, ethoxyethyl, methyl-cyclohexyl, phenyl or pyridyl; R1 may be an alkylene, aralkylene or arylene group such as ethylene, propylene, phenylene-methylene or phenylene; R2, R3 and R4 may be alkyl groups such as methyl, ethyl or propyl groups or aryl groups such as phenyl, R2 may form a ring together with R1 or R3 and N1, for example, it may form a pyridine ring with R1 or a piperidine or morpholine ring with R3; A may be the residue of an alkyl sulphuric acid, an alkyl, aralkyl or aryl sulphonic acid or a halogen atom such as chlorine or bromine. Pyridyl-mercurithioethyl-trimethyl-ammonium methosulphate is specified in addition to the compounds specified above.  This subject-matter does not appear in the Specification as accepted.