Patent GB-825538-A (GB)
Title: Dithiocarbamic acid ester derivatives containing sulphonic groups and their production
IPC: C23F11/04
Filed: 1956-01-03
Abstract: The invention comprises dithiocarbamic acid ester derivatives having the general formula <FORM:0825538/IV (b)/1> wherein R represents hydrogen or an alkyl, cycloalkyl or aralkyl group, substituted or unsubstituted, R1 represents a saturated divalent aliphatic group, Me represents an alkali metal or ammonium and X represents an aliphatic, araliphatic or aromatic group, which may contain substituents especially sulphonic acid groups or alkali or ammonium salts thereof, the last-mentioned class of derivatives having the general formula <FORM:0825538/IV (b)/2> wherein X1 represents a divalent aliphatic, araliphatic or aromatic group, substituted or unsubstituted, and Me11 is an alkali metal or ammonium which need not be identical with Me1. The invention also comprises the preparation of the above compounds by a process comprising in a first stage reacting an alkali metal or ammonium salt of an amino-saturated aliphatic sulphonic acid in which the amino group is unsubstituted or is mono-substituted by an alkyl, cycloalkyl or aralkyl group which may itself be substituted, with carbon disulphide in the presence of an equimolar amount of an alkali metal hydroxide or ammonium hydroxide, suitably at room or slightly elevated temperature. This stage yields salts of dithiocarbamic acids of the general formula <FORM:0825538/IV (b)/3> Me1 being an alkali metal or ammonium.  The amino sulphonic acid reagents may contain two amino groups in which event either or both may be reacted with the carbon disulphide.  The product from the first stage is, in a second stage, esterified by means of an alkylating agent whereby the radical Me1 is replaced by the desired radical X.  The alkylating agents specified include dimethyl sulphate, ethyl bromide, allyl chloride and benzyl chloride; in order to obtain products wherein X contains a sulpho group there are used sultones or halogencontaining sulphonic acids including 4-chloro-3-nitro benzene sulphonic acid, or their alkali metal or ammonium salts.  Both stages are preferably effected in aqueous medium but organic solvents may be used.  The final products are useful as corrosion inhibitors (see Group II), vulcanization inhibitors and fungicides.  Examples describe the preparation of N-aliphatic sulphonate S-hydrocarbon-substituted thiocarbamates, N:S-bis-aliphatic sulphonate substituted thiocarbamates and ethylene - bis - (dithiocarbamic acid - N - S - bis - propyl - o  - sodium sulphonate) and in some examples the amino sulphonates used as reagents are prepared by reacting the appropriate amine with a suitable sultone and adding the resulting inner salt of the aminosulphonic acid to caustic alkali.  A disclaimer refers to Specification 823,152.  Reference has been directed by the Comptroller to Specifications 764,340 and 764,613.ALSO:Dithio carbamic acid ester derivatives having the general formula: <FORM:0825538/II/1> wherein R represents hydrogen or a substituted or unsubstituted alkyl, cycloalkyl or aralkyl group, R1 represents a saturated divalent aliphatic group, Me represents an alkali metal or ammonium and X represents an aliphatic, araliphatic or aromatic group which may contain substituents especially a sulphonic acid group or its alkali metal or ammonium salt thereof, may be used as corrosion inhibitors, especially in the treatment of metals in acid baths.  The preparation of the inhibitors is described (see Group IV(b)) a disclaimer refers to Specification 823,152 [Group IV(b)]