Patent GB-603463-A (GB)
Title: Improvements in and relating to the preparation and use of substituted methane compounds
IPC: C07F3/12
Filed: 1945-10-30
Abstract: Substituted methane compounds are manufactured by condensing certain arylsulphonic acids with compounds of aldehydic function, other than formaldehyde, or substances yielding such compounds, or with ketones, imides or amides, and converting the resulting tri- or tetra-substituted methane (T.S.M.) compounds or their salts into salt-like bodies by treatment with alkyl, aryl, aralkyl or heterocyclic organo-metallic compounds; or by first reacting the arylsulphonic acid with the organometallic compound and condensing the resulting salt-like compound with the aldehydic compound, ketone, imide or amide; or by introducing all three reaction components into one and the same solvent and reacting them together therein.  The arylsulphonic acids which may be employed are aryl mono-, di- or polysulphonic acids which may also carry hydroxy, halogen or other substituents provided one or more replaceable hydrogen atoms remain in the ring, or mixtures of such sulphonic acids, but excluding sulphonic acids which contain chromophoric or quinonoid groups or which will react with compounds of aldehydic function, ketones, imides or amides to produce compounds containing chromophoric groups. As compounds of aldehydic function, or substances yielding them, may be employed aliphatic, aromatic, cycloaliphatic or heterocyclic aldehydes, their polymers or acetals, or compounds having latent aldehydic properties such as the aldose sugars.  The preferred organometallic compounds are those of mercury, e.g. alkyl, aralkyl, aryl or heterocyclic mercuric hydroxides, or corresponding mercury salts which react with metallic salts of the T.S.M. compounds, e.g. sulphates to react with barium salts or halides with silver salts of the T.S.M. compounds.  The reaction may be carried out in solution, usually in water or, where necessary, in a non-aqueous solvent, with or without heating or agitation, and if desired in the presence of a condensing agent of a dehydrating nature such as sulphuric acid or phosphorus oxychloride.  The products, which have bactericidal and fungicidal properties which make them useful for treating burns, wounds or other lesions, for preserving protein, cellulosic material or timber, or as rot-proofing or mould preventing agents, are soluble in a solution of an excess of the corresponding T.S.M. compounds or of the parent sulphonic acids or of one or more different T.S.M. compounds or of di-substituted methane compounds, and solutions may in some cases be obtained directly by using the reaction components in other than stoichiometric proportions.  In examples: (1) the condensation product of piperonal with naphthalene-2-sulphonic acid is heated with phenyl mercuric acetate in aqueous ethyl alcohol; (2) the condensation product of acetaldehyde with naphthalene - 2 - sulphonic acid is similarly reacted with phenyl mercuric hydroxide; (3) the piperonal in (1) is replaced by vanillin, and (4) by anioaldehyde; (5) the condensation product of acetaldehyde with naphthalene-2 : 7-disulphonic acid is similarly reacted with approximately a half or one molecular proportion of phenyl mercuric acetate; the products may be dissolved in an aqueous solution of the T.S.M. compound or, in the case of the latter, of bis-(naphthalene-2-sulphonic acid)-methane; (6) the piperonal in (1) is replaced by acetone, and (7) by benzaldehyde; (8) one equivalent of phenyl mercuric acetate is added to 10 of fused naphthalene-2-sulphonic acid and the product is heated with 11 equivalents of acetaldehyde, producing a solution of the mercury complex in a solution of the T.S.M. compound, which may be diluted with water and neutralized with sodium hydroxide; (10) and (12) the condensation product of octyl aldehyde with 2-naphthol-6-sulphonic acid is reacted with phenyl mercuric acetate in aqueous ethyl alcohol; (11) the T.S.M. compound in (10) is replaced by bis-(2-naphthol-6-sulphonic acid)-diaminomethane, and (13) by bis-(2-naphthol-6-sulphonic acid) - diphenylmethane; (14) 4 - aminophenylarsonic acid is heated with an aqueous solution of a  : a -bis-(naphthalene-2-sulphonic acid)-ethane; (15) an aqueous solution of the T.S.M. compound of (2) is added to a hot ethanol solution of 3-pyridyl mercuric acetate; (16) 1 : 8-aminonaphthol-3 : 6-disulphonic acid is heated with acetaldehyde in aqueous solution and the product is heated with phenyl mercuric acetate in ethyl alcohol; (17) the piperonal in (1) is replaced by dextrose; (18) the product of (2) is dissolved in a solution of the parent T.S.M. compound and the resulting solution is neutralized with ammonia; (21) the condensation product of acetaldehyde with naphthalene-2-sulphonic acid is reacted with ethyl mercuric hydroxide in aqueous solution. Specifications 547,564, 552,751 and 584,196 are referred to.ALSO:As bactericides, fungicides and external remedies for the treatment of burns, wounds and other lesions may be employed the compounds obtained by condensing compounds of aldehydic function, other than formaldehyde, or ketones, imides or amides, with aryl mono-, di- or poly-sulphonic acids, which may also carry hydroxy, halogen or other substituents provided at least one replaceable hydrogen atom remains in the ring (but excluding sulphonic acids which contain chromophonic or quinonoid groups or which will react with aldehydic compounds, ketones, imides or amides to produce compounds having chromophoric groups) and simultaneously or subsequently converting the resulting tri- and tetra-substitued methane (T.S.M.) compounds or their salts into salt-like bodies by treatment with alkyl, aryl, aralkyl or heterocyclic organometallic compounds.  The products may be used in the form of solutions thereof in an aqueous solution of an excess of the corresponding T.S.M. compounds or of the parent sulphonic acids or of one or more different T.S.M. compounds or of di-substituted methane compounds.  These solutions may be prepared by dissolving the solid product in the said aqueous solution, or in some cases by condensing the reaction components in solution in other than stoichiometric proportions.  In examples: (5) the reaction products of one molecular proportion of acetaldehyde and two of naphthalene-2:7 disulphonic acid with a half or one of phenyl mercuric acetate are dissolved in an aqueous solution of bis-(naphthalene-2:7-disulphonic acid)-methylmethane, or in the case of the latter product, of bis-(naphthalene-2-sulphonic acid)-methane; (8) one equivalent of phenyl mercuric acetate is added to 10 of fused naphthalene-2-sulphonic acid and the product is heated with 11 equivalents of acetaldehyde producing a solution of the mercury complex in a solution of the T.S.M. compound, which may be diluted with water and neutralized with sodium hydroxide; (10) and (11) the products from 2-naphthol-6-sulphonic acid, octyl aldehyde or urea, and phenyl mercuric acetate are dissolved in an aqueous solution of their parent T.S.M. compounds or of bis-(naphthalene-2-sulphonic acid)-methane, or naphthalene-2-sulphonic acid; (14) the product from : -bis-(naphthalene-2-sulphonic acid)-ethane and 4-aminophenylarsonic acid is dissolved in water and the pH is adjusted to 4-4.5; (15) the product from naphthalene-2-sulphonic acid, acetaldehyde and 3-pyridyl mercuric acetate is dissolved in an aqueous solution of bis - (naphthalene - 2 - sulphonic acid)-methane; (18) the phenyl mercury complex of bis - (naphthalene - 2 - sulphonic acid)-methylmethane is dissolved in a solution of its parent T.S.M. compound and the solution is neutralized with ammonia and diluted with water; (19) to a similar solution (before neutralization) is added sodium fluoride, the mixture is diluted with water and the pH is adjusted to 4-4.5, and, if desired, sodium dichromate and dinitrophenol are added; (20) to a similar solution are added potassium dichromate and sodium fluoride.  Specifications 547,564, 552,751 and 584,196, [Group IV], are referred to.