Patent GB-625840-A (GB)
Title: Manufacture of organic nitrogen compounds
IPC: D06P3/20
Filed: 1946-09-30
Abstract: Organic nitrogen compounds useful as textile assistants (see Group IV (c)) are manufactured by replacing an amino-hydrogen atom, present in an acetal-like cyclic ether of a primary or secondary propylamine containing at least two hydroxy groups, by an acyl, alkyl or aralkyl residue by treatment with an acylating agent or with a mineral acid ester of an aliphatic or araliphatic alcohol and, if desired, splitting of the carbonyl compound, bound in the manner of an acetal, by treatment with an acid.  The acyl residue introduced may be that of a carboxylic acid (of the aliphatic, aromatic, aliphatic-aromatic, cycloaliphatic or heterocyclic series, and including dicarboxylic and substituted carboxylic acids, e.g. chlorofatty acids), a sulphonic acid (e.g. of the aliphatic series, with or without chlorine substituents, or of the benzene or naphthalene series), or a sulpho-carboxylic acid, examples of each type being given.  Acylation may be effected by the action of a reactive derivative of the acid, e.g. the anhydride or an ester thereof, or especially an acid halide (advantageously in the presence of an acid-binding agent and a solvent or diluent), or, in the case of a carboxylic acid, by heating with the acid itself (if necessary in the presence of an agent promoting the splitting off of water, e.g. boric acid). Carbamic acid residues may be introduced by the action of carbamic acid halides or isocyanates, whilst chloroformic esters (e.g. those of aliphatic alcohols of high molecular weight) may be reacted (preferably in the presence of an acid-binding agent) to yield urethanes.  As mineral acid esters of aliphatic or araliphatic alcohols may be employed alkyl (including hydroxy alkyl) or aralkyl halides, of which examples are given, this treatment also being advantageously carried out in the presence of an acid-binding agent.  Suitable starting materials are compounds of the general formul  <FORM:0625840/IV (b)/1> wherein R1 and R2 each represent hydrogen or a hydrocarbon residue.  Examples describe the treatment of imino-d-(g -propylene-isopropylidene dioxide) with commercial stearic acid chloride or oleic acid chloride (in ether, with or without the addition of potassium carbonate), with coconut oil fatty acid chlorides (in ether), with commercial stearic acid (in the presence of boric acid), with octadecyl bromide and with p-nitrobenzoyl chloride (in ether), of g -amino-propylene-isopropylidene dioxide with coconut oil fatty acid chlorides (in ether), with dodecyl bromide (under pressure) and with butyric acid chloride (in ether), and of imino-di-(g -propylene-ethylidene oxide) with commercial stearic acid chloride (in ether), followed in most cases by splitting of the acetal grouping.  Aminoacetals of the kind employed as starting materials are obtainable by heating an acetal-like cyclic ether of a halogen-propyl alcohol containing at least two hydroxy groups, e.g. (g -chloropropylene)-methylene or -isopropylidene dioxide, with ammonia or a primary amine, e.g. at 130-140 DEG  C., advantageously under pressure in the case of ammonia or a volatile amine.  The Specification as open to inspection under Sect. 91 comprises also other methods of replacing the amino-hydrogen atom by any organic residue different from any residue already present in the starting materials, e.g. replacement by a hydroxyalkyl residue by the action of 1 : 2-alkylene oxides, such as ethylene oxide, propylene oxide or glycide.  This subject-matter does not appear p  in the Specification as accepted.ALSO:Compounds useful as textile assistants are obtained by replacing an amine-hydrogen atom, present in an acetal-like cyclic ether of a primary or secondary propylamine containing at least two hydroxy groups, by an acyl, alkyl or aralkyl residue, and, if desired, splitting the acetal grouping to form the free polyhydroxy compound (see Group IV (b)).  The products of low molecular weight may be used as wetting agents in concentrated solutions of electrolytes, e.g. mercerizing liquors.  The polyhydroxy compounds which contain an aliphatic or cycloaliphatic residue of at least 8 carbon atoms are applicable as wetting, dispersing, washing or softening agents, as assistants in the dyeing industry, and as agents for preventing the agglomeration of fibres in the manufacture of staple fibres of regenerated cellulose.  The N-acylated polyhydroxy compounds of which the acyl residue is derived from a fatty acid of at least 12 carbon atoms can be used as washing agents in acid liquors and as assistants in wool dyeing, especially in dyeing with complex metal compounds, e.g. complex chromium compounds of mordant dyestuffs. The products may be used alone or in conjunction with other additions.  In examples: (13) wool yarn is wetted with an aqueous solution of coconut oil fatty acid-N-bis-(a  : b -dihydroxy-g -propyl-amide; (14) raw wool is washed in dilute sulphuric acid containing stearic acid-N-bis-(a  : b -dihydroxy-g -propyl)-amide; (15) wool is dyed brown with a mixture of the complex chromium compounds of the azo dyestuffs 1-hydroxy-2-amino-4-nitrobenzene - 6 - sulphonic acid --> 1 - phenyl - 3-methyl - 5 - pyrazolone, 1 - hydroxy - 2 - amino - 4 - chlorobenzene - 6 - sulphonic acid --> 2 : 4 - dihydroxyquinoline, 1 - hydroxy-2 - amino - 4 - nitrobenzene - 6 - sulphonic acid --> acetoacetanilide and 1 - hydroxy - 2-amino - 4 : 6 - dinitrobenzene --> 1 - aminonaphthalene-4-sulphonic acid from a bath containing sulphuric acid and oleic acid-N-bis-(a  : b -dihydroxy-g -propyl)-amide.