Patent GB-877957-A (GB)
Title: New heterocyclic sulpho-compounds
Inventor: WILLMUND WOLF-DIETER
IPC: C23F11/16
Filed: 1958-04-09
Abstract: The invention comprises 5- and 6-membered hetero cyclic compounds having a single hetero cyclic ring and which contain in the hetero cyclic ring two or three <FORM:0877957/IV (b)/1> groups which are linked together directly or by carbon, nitrogen or sulphur to complete said ring, Z representing an -S-alkyl-, -S-cycloalkyl- or -S-aryl-sulphonic acid group, wherein the alkyl, cycloalkyl or aryl component may be substituted, and salts of the acids.  They may be prepared by reacting a 5- or 6-membered hetero cyclic compound having a single hetero cyclic ring, which ring contains two or three <FORM:0877957/IV (b)/2> groups linked together directly or by carbon, nitrogen or sulphur to complete the said ring, Y representing a halogen atom or a mercapto or mercaptide group, either with a sulpho-alkylating, -cyclo-alkylating or -arylating agent when Y is a mercapto or mercaptide group or with a mercapto-alkane sulphonic acid or salt thereof when Y is a halogen atom, the sulphogroup introducing reagents being present in molar proportions corresponding to the number of Ys in the hetero cyclic ring. Suitable hetero cyclic starting materials are 2:5-dimercapto- and 2:5-dichloro-1:3:4-thiadiazole, 3:5-dimercapto- and 3:5-dichloro1:2:4-thiadiazole, 2:5-dimercapto-1:3:4-triazole, 2:4-dimercapto- and 2:4-dichloro-1:3:5-triazine, 2:4:6-trimercapto- and 2:4:6-trichloro (or tribromo)-1:3:5-triazine and 3:6-dichloro pyridazine.  The sulpho-alkylating and -arylating agents are those agents which react with a compound containing active hydrogen to replace the latter by an alkyl, cyclo alkyl or aryl radical containing a sulphonic acid group and if desired other substituents; for example, aliphatic, cyclo aliphatic and aromatic sultones of which propane sultone, butane sultone and 1:8-naphtha sultone are typical of many specified, haloalkyl and -aryl sulphonic acids and their salts including, for example, bromo methane sulphonic acid, 3-chloro-2-hydroxy propane sulphonic acid and 4-chloro methyl benzenesulphonic acid, and mixtures of sodium sulphite with alkane bis-halides, including for example, methylene bromide, 1:1-dibromo ethane and 1:4-dibromo butane, may be used.  The reactions using the mercapto-substituted hetero cyclic reagents are usually effected under alkaline conditions in aqueous, aqueous-alcoholic or alcoholic solution or suspension; the alkylene dihalides are preferably used in excess to provide a reaction medium, and the sodium sulphite may be used therewith jointly or successively.  The reaction of the halo-substituted hetero cyclic reactants with mercapto-alkane sulpho compounds, many of which compounds are given, is generally effected in aqueous sodium carbonate.  The products may be used as corrosion inhibitors, rubber adjuvants and fungicides and in electro plating baths (see Specification 847,841).  Examples describe (1) the tri-sodium salts of 1:3:5-triazine-2:4:6-(21-mercapto ethane sulphonic acid) and -(31-mercapto propane sulphonic acid): (2) the disodium salt of 1:3:4-thiadizole-2:5-bis (31-mercapto propane sulphonic acid) and (3) the disodium salt of pyridazine-3:6-bis-(31-mercapto propane sulphonic acid).  Reference has been directed by the Comptroller to Specifications 764,340, 775,026 and 787,254.