Patent GB-600706-A (GB)
Title: Manufacture of water-soluble amide derivatives
IPC: D06M13/322
Filed: 1944-04-05
Abstract: Water-soluble amide-derivatives containing an aliphatic or cycloaliphatic residue having at least 12 carbon atoms obtained by reaction of a compound, other than an amine, which contains at least one alcoholic hydroxyl group attached to a chain of at least two carbon atoms and also contains at least one further hydroxyl group or a sulphonic acid or carboxyl group or an exchangeable halogen atom with formaldehyde and an aliphatic or cycloaliphatic carboxylic acid amide or urethane containing at least two carbon atoms connected together and at least one amido hydrogen atom or with a methylol derivative of such an amide and when a halogen atom as aforesaid is present, conversion of such an atom into a quaternary ammonium salt by treatment with a tertiary amine or into an isothiourea in salt form by treatment with a thiourea capable of reacting in the iso-form (see Group IV (b)) may be used as dispersing agents.  Thus, a condensation product obtained by interaction of oleic acid methylolamide and a polyglycol comprising mainly triglycol in the presence of glacial acetic acid is used to prepare mineral oil-water emulsions.  Numerous other products and starting materials therefor are specified. Specification 583,031 is referred to.  The Specification as open to inspection under Sect. 91 relates to the use of amide derivatives which may be prepared as above from any amide having at least two carbon atoms connected together and at least one amido hydrogen atom and numerous additional amido starting materials are specified including ureas, hydrazides and sulphonamides.  It is also stated that the replaceable halogen atoms when present may be reacted with sulphites or sulphonates. This subject-matter does not appear in the Specification as accepted.ALSO:Water-soluble amide-derivatives are prepared by reacting a compound, other than an amine, which contains at least one alcoholic hydroxyl group attached to a chain of at least two carbon atoms and also contains at least one further hydroxyl group or a sulphonic acid or carboxyl group or an exchangeable halogen atom, with formaldehyde and an aliphatic or cycloaliphatic carboxylic acid amide or urethane containing at least two carbon atoms connected together and at least one hydrogen atom attached to at least one amido-nitrogen atom or with a methylol derivative of such an amide, the reaction being carried out in the presence of a concentrated water-soluble carboxylic acid which is free from alcoholic hydroxyl groups and contains at most 20 per cent by weight of water and when a halogen atom as aforesaid is present converting such an atom into a quaternary ammonium salt by treatment with a tertiary amine or into an isothiourea radical in salt form by treatment with a thiourea capable of reacting in the iso-form. Reaction is preferably carried out in the presence of glacial acetic acid or concentrated formic acid at 70-100 DEG  C. Advantageously, an excess of formaldehyde is employed.  A polymeric modification of formaldehyde is preferred, for example, paraformaldehyde.  The products may be used as textile assistants; in particular, those containing aliphatic or cycloaliphatic residues having at least 12 carbon atoms may be used as washing, wetting, foaming, dispersing (see Group III), softening or levelling agents and as agents for preventing the agglomeration of the fibrils in the working up of regenerated cellulose staple fibres into textile materials; those having an aliphatic residue containing 16 or more carbon agents may be used in rendering fibres water-repellent (see Group VIII).  They may be used in conjunction with other textile assistants, for example, inorganic salts.  Hydroxy groups present in the products may be converted into poly-glycol ether groups by means of ethylene oxide.  In examples, the following are interacted in glacial acetic acid which is subsequently distilled off, the residues obtained comprising light-coloured powders: (1) oleic, stearic or coconut fatty acid amides, paraformaldehyde and sodium b -hydroxyethane sulphonate; (2) stearic acid methylolamide and sodium b  - hydroxyethane sulphonate; (3) stearic acid methylol amide, or the methylol amides of oleic acid, coconut oil fatty acid or montanic acid, paraformaldehyde and sodium glycollate; (4) stearic acid methylol amide, paraformaldehyde and malic acid; (5) glycol chlorhydrin and stearic acid methylol amide, the product after removal of acetic acid being reacted with pyridine; (6) oleic acid methylolamide and a polyglycol consisting mainly of triglycol; (7) coconut oil fatty acid methylol amide and anhydrous glycose; (8) N-methyl stearamide, paraformaldehyde and sodium b -hydroxyethane sulphonate; (9) stearamide, paraformaldehyde and sodium glycollate. An example is given illustrating the use of a product, prepared as in (1) from stearamide, in the washing of wool.  Other amide starting materials specified include those of acetic, propionic, acrylic, butyric, caprylic, lauric, palmitic, linoleic, hardened train oil, adipic, chlor-acetic, chlor-propionic, or glycollic acids; the monoN-substitution products of these amides, for example N-methyl, ethyl, oxyethyl or dioxypropyl lauric acid amide; octadecylurethane and methylene dioctadecylurethane.  Additional hydroxy compounds mentioned are a  : b -dioxypropane sulphonic acid, chloro-oxypropionic acid, lactic acid, citric acid or their salts, glycol, glycerol, mannitol, polyethylene glycols, poly-glycerines, cane-sugar and glycerine chlorhydrin.  The methylol amide starting materials are prepared by reacting formaldehyde with a solution of the amide in a solvent such as water, alcohol, acetone, glacial acetic acid, benzene or pyridine, if desired, in the presence of a condensing agent.  Specification 583,031 is referred to.  A sample has been furnished under Sect. 2 (5) of a product prepared by reacting octadecylurethane, sodium oxyethane sulphonate and paraformaldehyde in glacial acetic acid.  The Specification as open to inspection under Sect. 91 includes the use of any amide having at least two carbon atoms connected together and at least one amido hydrogen atom or a methylol or halo-methyl derivative thereof, reaction preferably being carried out in the presence of an acid or a water-binding agent.  Further amido starting materials specified include benzoic, naphthoic, para-stearyl amino benzoic, hexahydro benzoic, tetrahydronaphthyl acetic, resin or naphthenic and chlormethyl benzoic acid amides, phthalimide, diketo-piperazine, ethyl-, phenyl-, dodedecyl and di-dodecyl ureas, hydrazides, and aliphatic and aromatic sulphonamides.  Products containing a halogen-atom may be reacted with a sulphite or sulphonate as well as the other reagents mentioned above.  In additional examples: (1) glycollic acid, stearamide and paraformaldehyde are interacted in the presence of dehydrated sodium sulphate or fused sodium acetate; (2) stearamide is reacted with a  : a 1-dichloro dimethyl ether and the product then reacted with glycollic acid or glucose in glacial acetic acid or with an acetone solution of the product obtained by evaporating to dryness a sulphuric acid solution of sodium oxyethane sulphonate.  This subject-matter does not appear in the Specification as accepted.ALSO:Water-soluble amide-derivatives prepared by reacting a compound, other than an amine, which contains at least one alcoholic hydroxyl group attached to a chain of at least two p carbon atoms and also contains at least one further hydroxyl group or a sulphonic acid or carboxyl group or an exchangeable halogen atom, with formaldehyde and an aliphatic or cycloaliphatic carboxylic acid amide or urethane containing at least two carbon atoms connected together and at least one hydrogen atom attached to at least one amido-nitrogen atom or with a methylol derivative of such an amide, under specified conditions (see Group IV (b)) and when a halogen atom as aforesaid is present converting such an atom into a quaternary ammonium salt by treatment with a tertiary amine or into an isothiourea radical in salt form by treatment with thiourea capable of reacting in the iso-form, may be used as textile assistants; in particular, those containing aliphatic or cycloaliphatic residues having at least 12 carbon atoms may be used as washing, wetting, foaming, dispersing, softening or levelling agents and as agents for preventing the agglomeration of the fibrils in the working up of regenerated cellulose staple fibre into textile materials.  They may be used in conjunction with other textile assistants, for example, inorganic salts. Examples describe products which yield foaming solutions with water and/or may be used as wetting or washing agents, which are obtained as light coloured powders by interaction of the following in glacial acetic acid which is subsequently distilled off: (1) oleic, stearic or coconut fatty acid amides, paraformaldehyde and sodium b -hydroxyethane sulphonate; (2) stearic acid methylolamide and sodium b -hydroxyethane sulphonate; (3) stearic acid methylolamide, or the methylolamides of oleic acid, coconut oil fatty acid or montanic acid, paraformaldehyde and sodium glycollate; (4) stearic acid methylol amide, paraformaldehyde and malic acid; (5) glycol chlorhydrin and stearic acid methylolamide, the product after removal of acetic acid being reacted with pyridine; (6) oleic acid methylolamide and a polyglycol consisting mainly of triglycol; (7) coconut oil fatty acid methylolamide and anhydrous glucose; (8) N-methyl stearamide, paraformaldehyde and sodium b -hydroxyethane sulphonate; (9) stearamide, paraformaldehyde and sodium glycollate. An example is given illustrating the use of a product, prepared as in (1) from stearamide, in the washing of wool.  Other amide starting materials specified include those of acetic, propionic, acrylic, butyric, caprylic, lauric, palmitic, linoleic, hardened train oil,