Patent GB-470636-A (GB)
Title: Alcohols and process for making same
Filed: 1936-01-08
Abstract: Phenolic aralkylaminoalcohols, of the probable general formula HO.R.CH2.N(X).  Alkylol, where R is an aromatic or heterocyclic nucleus which may be substituted and X is hydrogen, methylol or an alkylolaminomethylene group, are manufactured by condensing a phenol having a hydrogen atom o- or pto the hydroxyl group, and free from acidic groups, with at least one molecular proportion each of formaldehyde and an aliphatic or alicyclic aminoalcohol having a primary amino group, e.g. b  - aminoethanol, g  - aminopropanol, 1-amino - 2 - hydroxypropane, 4-amino-1-hydroxybutane, amino-tert.-butanol, 1 : 2-aminocyclohexanol, 3 - amino - 1 : 2 - dihydroxypropane and their homologues.  The reaction may be effected at ordinary temperatures by mixing the three components in any order, advantageously in an inert organic solvent, e.g. alcohol or dioxane, or may be accelerated by heating at about 60--100 DEG  C. The condensation with formaldehyde, or with formaldehyde and the aminoalcohol, may be repeated indefinitely until finally a nitrogenous resinoid is obtained.  Suitable phenols are monohydric or polyhydric, mononuclear or polynuclear phenols, which may contain as additional nuclear substituents halogen, acyl, nitro, amino, alkoxy, alkylol or hydrocarbon groups, e.g. phenol, o-, m- or p-cresol, 1 : 3 : 5 - xylenol, psec-or tert. - butylphenol, thymol, p-tert.-amylphenol, o-, m-, or p-phenylphenol, o- or p-cyclohexylphenol, p-benzylphenol, a -a -g -g -tetramethylbutylphenol or -o-chlorophenol, b -naphthol, resorcinol, guaiacol, hydroquinone, pyrocatechol, o-, p  m-or p-chlorophenol, o-, m-, or p-nitrophenol, p-aminophenol, saligenin, 8-hydroxyquinoline, p-benzoylphenol, bis-(p-hydroxyphenyl)-di-methylmethane, p-p<1>-dihydroxydiphenyl, 2-or 4-chloro-o-phenylphenol, o-chloro-p-nitrophenol, butylphenols, amylphenols, hexylphenols, octylphenols, amylcresols, laurylphenols and cetylphenols, and also the fusible ("A" stage) resinous condensation products of formaldehyde with phenols or cresols.  The products possess the properties of phenols, alcohols and amines: e.g. with sodium hydroxide solution they yield phenates; with monobasic or polybasic acids, acyl halides or anhydrides they yield alcoholic esters; with sulphuric acid they yield sulphuric esters which are wetting, cleansing and emulsifying agents; with inorganic or organic acids they yield amine salts, many of which, particularly those of phosphoric, lactic, acetic or gluconic acid are soluble in water to yield antiseptic or germicidal solutions, whilst those in which the phenols used contain long alkyl chains or large hydrocarbon radicles in the aromatic nucleus yield aqueous solutions of very low surface tension and strong foaming properties and are useful as wetting, emulsifying, dispersing and cleansing agents; with waterinsoluble acids, e.g. higher fatty acids, naphthenic or resin acids, such as oleic, lauric, stearic, linoleic, palmitic, ricinoleic or abietic acids, they yield salts which are soluble in hydrocarbons or in fatty oils and are useful as emulsifying agents for oils, fats and waxes; with sulphonated oils or sulphated higher alcohols, e.g. lauryl or cetylsulphuric acid, they yield salts which are soaps and wetting agents of high phenol coefficient.  Such of the products as contain a secondary nitrogen atom react with acyl halides to form amides, which are intermediates for the preparation of soaps, wetting or emulsifying agents by sulphonation of the alcoholic hydroxyl group or the aromatic nucleus, especially if the acyl group is a fatty chain of six or more carbon atoms, e.g. caproyl, oleyl, stearyl or palmityl.  Products containing a tertiary nitrogen atom yield quaternary ammonium bases by treatment with alkylating or aralkylating agents, e.g. benzyl chloride, dimethyl or diethyl sulphate.  Products obtained from nuclear chlorinated phenols are mothicides or antiseptics, alone or in the form of their salts. All the products, and their esters, amides and salts, are convertible into resins when heated, especially in the presence of excess of formaldehyde, and may therefore be employed in coating, laminating and moulding compositions.  The lactic, phosphoric and acetic acid salts of the "A" stage resins are soluble in water, yielding solutions which can be used for impregnating porous substances such as paper, textiles, vegetable or animal fibres. Solutions of salts of volatile acids, e.g. acetic or formic acid, which acids are expelled on heating the salt above 100 DEG  C., are useful for crease-proofing fabrics.  Salts with higher fatty acids may be dissolved in volatile aromatic, aliphatic or hydroaromatic hydrocarbons or in fatty glycerides and used as coating or impregnating compositions.  The products may also be used as antioxidants in oils or rubber, as pickling inhibitors, insecticides, metal cleaning compositions, and in dyeing, tanning or mordanting operations.  In examples: (1) o-phenylphenol is condensed with 1 mol. each of formaldehyde and b -aminoethanol or with 1 mol. of N-methylolaminoethanol to produce 2-hydroxy-3-phenylbenzylaminoethanol together with some of its N-methylol derivative, which may also be obtained by treating the main product with 1 mol. of formaldehyde or by condensing o-phenylphenol with 2 mols. of formaldehyde and 1 mol of b -aminoethanol; by treating the 2-hydroxy-2-phenylbenzyl-aminoethanol with 1 mol. each of formaldehyde and b -aminoethanol or with 1 mol. of N-methylolaminoethanol, or by condensing o-phenylphenol with 2 mols. each of formaldehyde and b -aminoethanol there is obtained a higher condensation product which resinifies on warming; (2) p-tert.-amylphenol is condensed with 1 mol. each of formaldehyde and b -aminoethanol to produce 2-hydroxy-5-tert.-amylbenzylaminoethanol; this may be transformed by heating with 1 mol. of formaldehyde into its N-methylol derivative, which yields a resin on further heating; (3) p-tert.-butylphenol similarly yields 2-hydroxy-5-tert.-butylbenzylaminoethanol; (4) p-cyclohexylphenol similarly yields 2-hydroxy-5-cyclohexyl-benzylaminoethanol; (5) p-nitrophenol similarly yields 2-hydroxy-5-nitrobenzylaminoethanol; (6) a -a -g -g -tetramethylbutylphenol is similarly condensed; (7) resorcinol or hydroquinone is used, the latter yielding a watersoluble resin; (8) p-benzoylphenol is condensed with a solution prepared by mixing 1 mol. each of formaldehyde and b -aminoethanol, to produce 2-hydroxy-5-benzoyl--benzylaminoethanol; (9) phenol is condensed with an equimolecular amount of N-methylolaminoethanol; the sodium salt of the product and its salts with phosphoric, lactic, acetic, acrylic, oxalic, sulphuric, hydrochloric, tartaric, crotonic, citric, gluconic, maleic, oleic ricinoleic, elaeostearic, naphthenic, stearic and palmitic acids and linseed and coconut oil fatty acids are referred to; the free base and its salts form resins when heated to 100--150 DEG  C.; by using excess of formaldehyde in the condensation a faster curing resin is obtained; (10) phenol is condensed with 2 mols. each of formaldehyde and N-hydroxymethylaminoethanol; the product forms salts with oxalic, lactic, phosphoric, hydrochloric, hydrosilicofluoric, sulphuric and oleic acids; the base and its salts form resins when heated; (11) bis-(p-hydroxyphenyl)-dimethylmethane is condensed with 2 mols. of formaldehyde and 1,06 mols. of b -aminoethanol, or with larger proportions of these substances; (12) p-cresol is condensed with 1 mol. each of formaldehyde and b -aminoethanol; (13) 2-chlor-o-phenylphenol is condensed with formaldehyde and b -aminoethanol to produce 2-hydroxy-3-(o-chlorophenyl)-benzylaminoethanol; (14) o-chlorophenol is condensed with 2 mols. of formaldehyde and 1 mol. of b -aminoethanol; (15) a "Novolak" resin from 1 mol. of phenol and 0,7 mol. of formaldehyde is condensed with formaldehyde and b -aminoethanol; (16) 4-chloro-o-phenylphenol is used in place of the 2-chloro-compound in the process of (13).ALSO:As emulsifying agents may be employed the sulphuric esters of phenolic aralkylamino-alcohols, of the probable general formula HO.R.CH2.N(X). Alkylol, where R is an aromatic or heterocyclic nucleus which may be substituted and X is hydrogen, methylol or an alkylolaminomethylene group, obtained by condensing a phenol having a hydrogen atom o- or pto the hydroxyl group, and free from acidic groups, with at least one molecular proportion each of formaldehyde and an aliphatic or alicyclic aminoalcohol having a primary amino group.  The amine salts formed by inorganic or organic acids with those of the above phenolic aralkylaminoalcohols in which the phenols used contain long alkyl chains or large hydrocarbon radicles in the aromatic nucleus may be similarly employed.  The salts of the phenolic aralkylaminoalcohols with water-insoluble acids, e.g. higher fatty acids, naphthenic or resin acids are useful as emulsifying agents for oils, fats and waxes.  Emulsifying agents are also obtained by sulphonation of the alcoholic hydroxyl group or the aromatic nucleus of the compounds obtained by treating such of the phenolic aralkylaminoalcohols as contain a secondary nitrogen atom with acyl halides, especially those containing a fatty chain of six or more carbon atoms.ALSO:As antioxidants for rubber may be employed phenolic aralkylaminoalcohols, of the probable general formula HO.R.CH2.N(X). Alkylol, where R is an aromatic or heterocyclic nucleus which may be substituted and X is hydrogen, methylol or an alkylolaminomethylene group, obtained by condensing a phenol having a hydrogen atom o- or pto the hydroxyl group, and free from acidic groups, with at least one molecular proportion each of formaldehyde and an aliphatic or alicyclic aminoalcohol having a primary amino group, or the salts, esters or amides of the above compounds.