Patent GB-620142-A (GB)
Title: Manufacture and application of new urea derivatives
IPC: D06M13/432
Filed: 1946-04-04
Abstract: A compound containing the group-<FORM:0620142/IV (b)/1> or <FORM:0620142/IV (b)/2> , or a methylene derivative of such a compound, is converted (a) into a compound containing at least one <FORM:0620142/IV (b)/3> group by condensation with at least one mol. of formaldehyde under alkaline conditions or (b) into a compound containing at least one <FORM:0620142/IV (b)/4> group, where X is halogen, by condensation with formaldehyde in the presence of hydrogen halide or by reaction with an a ,a 1-dihalogen-dimethyl ether.  The products may then be treated to replace at least one terminal hydroxy group or at least one halogen atom by a water-solubilizing group.  The starting materials are obtainable by condensing an amide or urethane with formaldehyde and a urea, simultaneously or in succession, specified compounds suitable for this reaction being acetamide, caprylamide, lauramide, stearamide, octadecylurethane, urea, methylurea and biuret.  The methylene derivatives which may also be used as starting materials are obtainable by treating the amideor urethane-condensation products with formaldehyde under acid conditions.  The introduction of a water-solubilizing group into a compound containing a terminal hydroxy group may be effected by reaction with (a) thioureas capable of reacting in the iso-form or (b) water-soluble salts of tertiary amines, e.g. pyridine hydrochloride.  The introduction of a water-solubilizing group into a compound containing a halogen atom may be effected by treatment with (a) a tertiary amine, e.g. pyridine, triethylamine or dimethylcyclohexylamine, (b) a primary or secondary amine, (c) a thiourea capable of reacting in the iso-form, (d) dicyandiamide or like compound, (e) an oxycarboxylic or oxysulphonic acid, e.g. glycollic acid or b -oxyethanesulphonic acid, (f) a mercaptocarboxylic or mercaptosulphonic acid, e.g. thioglycollic acid, (g) glycols or ethers thereof, particularly polyglycols or (h) salts of halogen-carboxylic acids followed, in this case, by further treatment to introduce a water-solubilizing group.  The reaction of the starting materials with formaldehyde and the introduction of the water-solubilizing group may also be effected simultaneously, suitable reagents for this purpose being water-soluble salts of tertiary amines, hydrohalides of thiourea, and mercaptocarboxylic acids.  The products are useful as assistants in the treatment of fibrous materials, such as textiles, leather and paper.  In the examples: (1) a condensation product from stearic acid methylolamide and urea is treated in acetic acid with paraformaldehyde and a little sulphuric acid; a methylene derivative of the initial condensation product is so obtained, and is treated with paraformaldehyde and hydrogen chloride to yield a chloromethyl derivative, which is treated with pyridine or (example 2) with triethylamine or (example 3) with diethylene glycol or (example 4) with glycollic acid or (example 5) with thiourea; (6) the methylene compound of example (1) is treated with paraformaldehyde and thioglycollic acid; (7) the chloromethyl derivative of example 1 is treated with dimethylcyclohexylamine; (8) a condensation product from stearic acid methylolamide and urea is heated with a ,a 1-dichlorodimethyl ether and the product is treated with pyridine; (9) a condensation product from stearic acid methylolamide and urea is treated in pyridine solution with paraformaldehyde and the methylol compound so obtained is heated with thiourea.  Specification 533,220 is referred to.ALSO:A compound containing the group <FORM:0620142/IV (c)/1> : or <FORM:0620142/IV (c)/2> , or a methylene derivative of such a compound, is converted (a) into a compound containing at least one <FORM:0620142/IV (c)/3> group by condensation with at least one mol. of formaldehyde under alkaline conditions or (b) into a compound containing at least one <FORM:0620142/IV (c)/4> group, where X is halogen, by condensation with formaldehyde in the presence of hydrogen halide or by reaction with an a ,a 1-dihalogen-dimethyl ether.  The products may then be treated to replace at least one terminal hydroxy group or at least one halogen atom by a water-solubilizing group.  The starting materials are obtainable by condensing an amide or urethane with formaldehyde and a urea, simultaneously or in succession, specified compounds suitable for this reaction being acetamide, caprylamide, lauramide, stearamide, octadecylurethane, urea, methylurea and biuret.  The methylene derivatives which may also be used as starting materials are obtainable by treating the amide- or urethane-condensation products with formaldehyde under acid conditions.  The introduction of a water-solubilizing group into a compound containing a terminal hydroxy group may be effected by reaction with (a) thioureas capable of reacting in the iso-form or (b) water-soluble salts of tertiary amines, e.g. pyridine hydrochloride.  The introduction of a water-solubilizing group into a compound containing a halogen atom may be effected by treatment with (a) a tertiary amine, e.g. pyridine, triethylamine or dimethylcyclohexylamine, (b) a primary or secondary amine, (c) a thiourea capable of reacting in the iso form, (d) dicyandiamide or like compound, (e) an oxycarboxylic or oxysulphonic acid, e.g. glycollic acid or b -oxyethanesulphonic acid, (f) a mercapto-carboxylic or mercapto-sulphonic acid, e.g. thioglycollic acid, (g) glycols or ethers thereof, particularly polyglycols, or (h) salts of halogen-carboxylic acids followed, in this case, by further treatment to introduce a water-solubilizing group.  The reaction of the starting materials with formaldehyde and the introduction of the water-solubilizing group may also be effected simultaneously, suitable reagents for this purpose being water-soluble salts of tertiary amines, hydrohalides of thiourea and mercapto-carboxylic acids.  The products are useful as assistants in the treatment of fibrous materials, such as textiles, leather and paper.  Those containing an aliphatic or cycloaliphatic residue of about twelve carbon atoms are useful as wetting agents.  The products may be used alone or with other appropriate substances, e.g. salts of weak acids.  In the examples: (1) a condensation product from stearic acid methylolamide and urea is treated in acetic acid with paraformaldehyde and a little sulphuric acid; a methylene derivative of the initial condensation product is so obtained, and is treated with paraformaldehyde and hydrogen chloride to yield a chloromethyl derivative, which is treated with pyridine or (example 2) with triethylamine or (example 3) with diethylene glycol or) (example 4) with glycollic acid or (example 5) with thiourea; (6) the methylene compound of example 1 is treated with paraformaldehyde and thioglycollic acid; (7) the chloromethyl derivative of example 1 is treated with dimethylcyclohexylamine; (8) a condensation product from stearic acid methylolamide and urea is heated with a ,a 1-dichlorodimethyl ether and the product is treated with pyridine; (9) a condensation product from stearic acid methylolamide and urea is treated in pyridine solution with paraformaldehyde and the methylol compound so obtained is heated with thiourea.  Specification 533,220 is referred to.