Patent GB-579370-A (GB)
Title: Manufacture of new condensation products having capillary activity
IPC: C07D231/26
Filed: 1943-03-08
Abstract: Condensation products are obtained by condensing at a raised temperature and/or in the presence of an acid-binding agent a compound having at least one reactive hydrogen atom attached to a carbon atom directly connected to a carbonyl group with an alkyl or aralkyl halide having at least 9 carbon atoms, in which an ether bridge may form part of the aliphatic or araliphatic residue or an aromatically bound hydroxyl group may be present as a substituent in the araliphatic residue, and introducing a water-solubilizing group if not present in the starting materials. Compounds having a reactive hydrogen in the position stated and which exhibit enolisation include pyrazolones, such as 1 - phenyl - 3 - methyl-, 1 - (21-methylphenyl) - 3 - methyl-pyrazolones, and esters or amides of acetoacetic and cyanoacetic acids, such as acetoacetic and cyanoacetic acid anilides. These may contain such groups as sulphonic acid, neutralized carboxyl, sulphuric acid ester or thiosulphuric acid which impart solubility.  Examples of such starting materials are 1-phenyl-3-methyl-pyrazolone-31 or 41-sulphonic acid, 1-(21-methylphenyl or chlorophenyl)-3-methyl-pyrazolone-41 or 31-sulphonic acid, 1-phenyl - pyrazolone - (5) - carboxylic acid - (3) - sulphonic acid-41), 1-phenyl-3-methyl-pyrazolone-disulphonic acid-(31, 51), pyrazolone-(5)-carboxylic acid-(3), and acetoacetic acid orthoanisidide sulphonic acid.  Alkyl halides specified are dodecyl bromide, cetyl iodide and octylchlormethyl ether. Suitable aralkyl halides are chlormethyl aromatic or partially hydrogenated aromatic compounds such as chlormethylxylene, and -cumene, 2-chlormethyl-cymene, 1-chlormethyl-naphthalene, chlormethyl-tetrahydronaphthalene, e.g. ar-2-chlormethyl-tetrahydronaphthalene, chlormethyl - cyclohexyl - benzene, chlormethyl-anthracene, -octahydro - anthracene and -octahydrophenanthrene.  Such chlormethyl compounds can be made by the action of gaseous hydrogen chloride on a mixture of the hydrocarbon, formaldehyde, hydrochloric acid, and, if desired, zinc chloride, at about 60-70 DEG  C.  Chlormethyl derivatives of hydroxyaryl compounds and their ethers may also be used, for example of the phenolic addition product of phenol and dipentene or of the ether obtained by condensing dipentene with b -naphthol. Condensation of, for example, an aralkyl chloride may be effected with an alkali salt of the sulphonated starting material in aqueous solution at 60-70 DEG  C., sodium hydroxide being added to keep alkaline. Reaction products which still contain a reactive hydrogen atom adjacent a carbonyl group may be reacted with halogen-carboxylic or -sulphonic acids, e.g. chlor-acetic or bromethane sulphonic, and those containing aromatic nuclei or hydroxy groups with sulphonating agents, e.g. sulphuric acid or addition products of sulphur trioxide with tertiary amines.  The products are used as textile assistants, e.g. as wetting agents for mercerising and like baths, as dispersing, washing, softening, levelling and foaming agents, alone or with such substances as inorganic salts.  In examples: (I) ar-2-chlormethyl-tetrahydronaphthalene is added in 1 or 2 molecular proportions to an alkaline solution of 1-phenyl-3-methyl-pyrazolone-41-sulphonic acid at 65-70 DEG  C., kept alkaline by addition of caustic soda, the mixture heated for 68 hrs., neutralized, evaporated to dryness, extracted with alcohol, and evaporated to give a product having high wetting capacity; (2) and (3) 2-chlormethyl-cymene is reacted in like manner with the same pyrazolone derivative or with the corresponding 31-sulphonic acid; (4) chlormethyl-cumene is similarly condensed with the same 31-sulphonic acid; (5) 1-(21-methylphenyl)-3-methyl-pyrazolone-41-sulphonic acid is condensed with 2-chlormethyl-cymene; (6) 1 - (21-chlorphenyl) - 3 - methyl - pyrazolone - 31 - sulphonic acid is reacted with 2-chlormethyl-cymene; (7) acetoacetic acid-ortho-anisidide is mixed with boric acid and added at 0-10 DEG  C. to sulphuric acid containing sulphur trioxide to produce the sulphonic acid which is reacted with 1 or 2 molecular proportions of 2-chlormethyl-cymene; (8) 1-phenyl-3-methyl-pyrazolone-31-sulphonic acid and dodecyl bromide are added to propyl alcohol containing sodium in solution, and heated in a closed vessel at 170-175 DEG  C. for 8 hrs.; (9) the product of (1) is used in a bath for washing wool yarn; (10) the product of (2) with sodium sulphate is used in a bath for pre-wetting cotton or wool yarn.  The Specification as open to inspection under Sect. 91 comprises the use of alkyl or aralkyl halides of 8 carbon atoms, for example actyl chloride, 2-ethyl-hexyl bromide and chlormethyl-toluene. This subject-matter does not appear in the Specification as accepted.