Patent GB-537221-A (GB)
Title: Manufacture of new condensation products
IPC: C07C335/32
Filed: 1939-10-16
Abstract: 537,221. Condensation products ; dyeing textiles ; waterproofing. SOC. OF CHEMICAL INDUSTRY IN BASLE. Oct. 16, 1939, Nos. 27971, 27972, 27973, 27974, 27975 and 27976. Convention dates, Oct. 14, 1938, Nov. 19, 1938, Jan. 4, 1939, Jan. 12, 1939, Jan. 25, 1939, and Sept. 23, 1939. Samples furnished. [Classes 2 (iii) and 15 (ii)] [Also in Group VIII] Condensation products are made by treating carboxylic amides containing at least one free hydrogen atom attached to the nitrogen atom with an α:α<SP>1</SP>-dihalogenodimethyl ether. The products may be rendered water-soluble by converting the halogen atom into a thiosulphuric ester group, a quaternary ammonium group, or a substituted amino or imino group, or residue containing such group, in salt form, including residues containing a thiourea group, a dicyandiamide group or at least one basic nitrogen atom and at least one mercapto group. The amide may be treated with 1, 1.5 or 2 molecular proportions of the dihalogenodimethyl ether. A large number of aliphatic, araliphatic and aromatic amides suitable as parent materials as specified, including amides of acetic, propionic, butyric, valerianic, caproic, lauric, myristic, palmitic, stearic, behenic, undecylenic, oleic, linoleic, linolenic, chloracetic, bromacetic, α-bromolauric, benzoic, salicylic; naphthoic, oxynaphthoic, phenylacetic, hexahydrobenzoic, naphthenic and resin acids, the amides being made by treating the corresponding acid chloride or esters with ammonia. Secondary amides containing the group -CONHR, where R is a substituted or unsubstituted hydrocarbon residual or an ocyl group may also be used; such amides are derived from primary amines (including methylamine, ethylamine, propylamine, isopropyl amine, butylamine, amylamine, hexylaminedodecylamine, diethylaminoethylamine, ethanolamine, polyalkylenepolyamines, cyclohexylamine, aniline, chloraniline, p-dimethylaminoaniline, toluidines, naphthylamines and benzylamine), from ureas (including monomethyl-, monoethyl-, monododecyl-, N:N<SP>1</SP>-dimethyl-, N:N<SP>1</SP>-diethyl-, N:N<SP>1</SP>-diphenyl- and N:N<SP>1</SP>-didocecylureas), and from methanes, e.g. the N-monosubstituted methanes obtainable from chloroformic ester and a primary amine. Secondary amides such as diacetamide, dibenzamide, and dilaurylamide are also suitable. Methylene diamides, such as methylene diformamide, methylene diacetamide, methylene bismonochloracetamide, methylene distearamide &c. may be used ; also methylene diurethanes and methylene diureas, including the unsymmetrical methylene diamides made by the process of Specification 533,220. As α:α<SP>1</SP>- dihalogenodimethyl ethers, the dichloro and dibromo compounds are specified. The products containing an aliphatic or cycloaliphatic residue of more than 12 carbon atoms are wetting, softening and waterproofing agents. When heated or treated with a saponifying agent they are decomposed ; if the decomposition is effected on a substratum, e.g. a textile, the latter acquires waterproofing qualities fast to washing, which in some cases is combined with a softening effect. The products, particularly those containing the thiourea residue, may also improve the affinity of animal and cellulose fibres for acid dyes, the fibres being impregnated with a solution or dispersion of the product and then dried and heated. Cellulose treated in this way can be dyed with direct dyes, and with sulphuric esters of vat dyes or with dyestuff esters or amides such as those described in Specifications 480,358, 482,184 and 505,504. Acid dyestuffs absorbed by the treated cellulose may in some cases be diazotzed on the fibre and developed by means of azo components, or may be treated on the fibre with diazo compounds. In examples : (1) the following amides are reacted with α:α<SP>1</SP>-dichlorodimethyl ether and the products converted into the pyridinium or thiourea compounds : stearic acid amide and N-methylamide, the amide of hydrogenated whale oil fatty acids, lauric amide, butyric amide, benzamide, p-stearoylaminobenzamide, formanilide, acetanilide, p-acetamido-dimethylaniline, acetylamylamine, acetylcyclohexylamine, propionic anilide, stearic anilide, stearic α-naphthylamide, the azo dyestuff monoacetylm - phenylenediamine # 2 : 3 - oxynaphthoic anilide, 2-acetylaminonaphthalene, methylene distearamide, N-acetyl-N-stearoylmethylene diamine, and methylene dibenzamide ; (2) the product from stearic acid amide and α:α<SP>1</SP>- dichlorodimethyl ether is reacted with piperidine ; and (3) the amide of hardened whale oil fatty acids is reacted with α:α<SP>1</SP>-dichlorodimethylether and the product condensed with 2-mercaptothiazoline, 4-methyl-2-mercaptothiazole, or diczyandiamide. Examples of the use of the products in softening and waterproofing textile materials, and in dyeing viscose or cotton with (a) the condensation product from m-benzoylchloride - sulphonic acid and the azo dyestuff 2:5-dichloraniline - 2:3-oxynaphthoic o-anisidide, (b) the condensation product from mbenzoylchloride-sulphonic acid and the product from cyanuric chloride (1 mol.), aniline (1 mol.) and 2-aminoanthraquinone (2 mols.),(c) Indigosol Green J.B, Indigosol Blue JCB, or Indigosol O4B, and (d) Cloth Fast Red R. Samples have been furnished under Sect. 2 (5) of the products obtained from α:α<SP>1</SP>-dichlorodimethylether and (a) stearic amide and sodium thiosulphate, (b) whale oil acids amide and allylthiourea, (c) diphenylurea and thiourea, (d) octadecyl carbamate and thiourea, (e) dibenzamide and thiourea, and (f) methylenediurethane and thiourea. Specifications 471,130, 517,474, 517,631 and 517,632 also are referred to. The Specification as open to inspection under Sect. 91 comprises also the use of any α:α<SP>1</SP>- dihalogenodialkyl ether in the preparation of initial products, and the treatment of the products with any agent adapted to exchange halogen for a water-solubilizing group, including a polyglycol ether group. This subject-matter does not appear in the Specification as accepted.