Patent GB-670861-A (GB)
Title: Sulphonamido compounds
Inventor: FRIEDRICHSEN WILHELM
IPC: C07C311/37
Filed: 1950-06-08
Abstract: The invention comprises sulphanilamido derivatives of the general formula <FORM:0670861/IV (b)/1> in which one X stands for the radical of a cyclic acetal and the other X stands for hydrogen or the radical of a cyclic acetal, the acetal being derived from an aliphatic aldehyde having one or two carbon atoms and an aliphatic glycol in which the hydroxy groups are separated by two or three carbon atoms, the sulphonamido group being attached to a carbon atom of the cyclic acetal which is in b -position with reference to one of the oxygen atoms of the nucleus.  The invention also comprises a method for making them by reacting the corresponding amino-substituted 1,3-dioxane or dioxalane with a sulphonic acid halide of the benzene series containing a group capable of subsequent conversion to an amino group.  Groups capable of conversion to amino groups include acylamino, urethane, urea, nitro, azo and azo-methine groups.  In examples: (1) the 4-aminobenzene-1-sulphonic acid amide of 4-o -aminomethyl-4-methyl-1,3-dioxane is prepared by mixing 4-o -aminomethyl-4-methyl-1,3-dioxane with N-acetyl-sulphanilic acid chloride in the presence of aqueous sodium carbonate and hydrolyzing the product with hydrochloric acid in methanol; (2) the 4-aminobenzene sulphonic acid amide of amino-4-methyl-1,3-dioxane (a mixture of 4-o -aminomethyl-1,3-dioxane and 4-methyl-5-amino-1,3-dioxane) is made by reacting amino-4-methyl-1,3-dioxane with N-acetylsulphanilic acid chloride in presence of sodium carbonate; (3) the 4-aminobenzene-1-sulphonic acid amide of 4-aminomethyl-dioxalene is made by reacting N-acetyl-sulphanilic acid chloride with 4-aminomethyl-dioxalane in presence of sodium carbonate solution and the product hydrolysed as in (1); (4) the 4-aminobenzene-1-sulphonic acid amide of 2-aminomethyl-4-methyl-1,3-dioxane is made as in (2); and the 4-aminobenzene sulphonic acid amide of di-4-methyldioxanyl-amine is made by reacting N-acetylamino-sulphanilic acid chloride with di-(4-methyl-1,3-dioxanyl)-amine and hydrolysing the product with aqueous caustic soda.  4 - o  - Aminomethyl - 4 - methyl - 1,3 - dioxane is made by heating 4-o -chloromethyl-4-methyl-1,3-dioxane (prepared by condensing formaldehyde with isobutenyl chloride) with excess of aqueous ammonia in the presence of copper sulphate.  A mixture of 4-o -aminomethyl-1,3-dioxane and 4-methyl-5-amino-1,3-dioxane is prepared by heating chloro-4-methyl-1,3-dioxane (prepared by chlorinating 4-methyl-1,3-dioxane in the dark) with ammonia in a closed vessel. 4-Aminomethyl-dioxalane is made by heating 4-o -chloromethyl-dioxalane (prepared by condensing 3-chloro-1,2-dihydroxypropane with formaldehyde) with ammonia under pressure.  2-Aminomethyl-4-methyl-1,3-dioxane is made by heating 2-bromomethyl - 4 - methyl - 1,3-dioxane with aqueous ammonia under pressure.  Di-(4-methyl-1,3-dioxanyl)-amine is made by the action of ammonia on the chloro-4-methyl-1,3-dioxane described above.  Other general methods of obtaining the chlorinated 1,3-dioxanes and dioxalane derivatives used as starting materials are (a) causing formaldehyde or acetaldehyde to act on olefines such as ethylene, propene, n- and iso-butene, n- and iso-pentene, hexenes and heptenes in the presence of water and strong mineral acids or acidic salts such as zinc chloride, followed by halogenation in the dark; (b) re-acetalization of a 1,3-dioxane with 2-halogen-acetaldehyde; and (c) acetalization of a 1,2-glycol with formaldehyde or acetaldehyde followed by halogenation or acetalization of a 1,2-glycol with 2-halogen-acetaldehyde.