Patent GB-592747-A (GB)
Title: Furyl and difuryl sulphonates
IPC: C07D307/52
Filed: 1943-09-02
Abstract: Furyl and difuryl substituted organic sulphonates are made by treating compounds of the general formul  <FORM:0592747/IV/1> wherein X represents -CO-Y, -COOY (Y being hydrogen or an aliphatic or aromatic radical), -CONZZ1 (Z and Z1 being hydrogen or organic radicals, which may form part of a ring), -CN or -NO2, and R and R1 represent hydrogen or organic radicals (which may form part of a ring), or vinylogues thereof, with a bisulphite (of a metal, ammonium or an amine) or with sulphurous acid.  The reaction is preferably carried out in an aqueous medium, e.g. a mixture of water and a water-miscible organic solvent.  The free sulphonic acids obtained by using sulphurous acid may be converted into metal, ammonium or amine (e.g. methylamine, dimethylamine, pyridine, triethylamine, mono-, di- or tri-ethanolamine) salts.  The products react with aldehydes to produce resinous materials having cation-active properties, and are also useful in the preparation of emulsifiers, wetting agents and dispersing agents.  The starting materials are obtainable by condensing respectively 1 mol. of furfural with 1 mol. of a substance containing a reactive methyl or methyline group, of the formula X-CH2-R or a vinylogue thereof, or 2 mols. of furfural with 1 mol. of a ketone containing reactive methyl or methylene groups.  In examples: (1) furfurylidene acetophenone is heated with sodium bisulphite in water to produce sodium 1 - a  - furyl - 1 - (3 - keto - 3 - phenylpropane) - sulphonate; (2) furfurylidene methyl ethyl ketone is prepared by condensing equimolecular proportions of methyl ethyl ketone and furfural in aqueous sodium hydroxide solution, and is heated with potassium metabisulphite in water to form potassium 1-a -furyl-3-ketopentanesulphonate; (3) furfurylidene methyl isobutyl ketone is prepared by condensing equimolecular proportions of methyl isobutyl ketone and furfural in aqueous alcoholic sodium hydroxide solution, and is treated as in (2) to produce potassium 1-a -furyl-3-keto-5-methylhexanesulphonate; (4) furfurylidene nitromethane is heated with potassium metabisulphite in aqueous ethanol, producing potassium 1-a -furyl-2 - nitroethanesulphonate; (5) ethyl furylacrylate is heated with potassium metabissulphite in water, forming ethyl 2-potassium-sulpho - 2 - a  - furylpropionate; (6) 2 - a  - furylacrolein similarly yields 2-potassium-sulpho-2-a -furylpropionaldehyde; (7) furfurylidene cyanacetamide similarly gives 1-cyano-2-potassium-sulpho-2-a -furylpropionamide; (8) difurfurylidene acetone is heated with sodium bisulphite in water to produce disodium 1 : 5-di-a  - furyl - 3 - ketopentane - 1 : 5 p  - disulphonate; (9) a suspension of difurfurylidene cyclohexanone in ethylene glycol monoethyl ether is heated with an aqueous solution of potassium metabisulphite, producing 2 : 6-bis-(a -furylpotassium - sulphomethyl) - cyclohexanone; (10) furfurylidene-methyl a -furfurylidene-ethyl ketone is prepared by heating 5 mols. of methyl ethyl ketone with 11 mols. of furfural in ethanolic sodium hydroxide solution, and is heated with potassium metabisulphite in water to form potassium furfurylmethyl furfurylethyl ketone disulphonate; (11) furfurylidene acetone similarly yields potassium 1-a -furyl-3-ketobutanesulphonate. Additional starting materials specified are the condensation products of 1 mol. of furfural with 1 mol. of methyl hexyl, di-n-butyl, methyl n-propyl or methyl n-butyl ketone, chloracetic, crotonic, sorbic, propionic, butyric, succinic, malonic, lauric, phenylacetic, oxalacetic or 3 : 5-dinitro-o-toluic acid, or esters (e.g. methyl, ethyl, benzyl or phenyl esters) or amides of these acids, crotonaldehyde, sorbic aldehyde, propionaldehyde, heptaldehyde, succinic aldehyde, phenylacetaldehyde, acetonitrile, propionitrile, lauronitrile, crotonic nitrile, succinonitrile, phenylacetonitrile, nitroethane, 1-nitropropane, 1-nitrobutane, 1-nitropropylene or 1-nitrooctylene-2, or of 2 mols. of furfural with 1 mol. of methyl hexyl, di-n-butyl, methyl n-propyl or methyl n-butyl ketone, the methylcyclohexanones or cyclopentanone. Other bisulphites which may be used are ammonium and calcium bisulphites.  The Specification as open to inspection under Sect. 91 comprises also alternative methods of preparing the products of the invention by (a) treating the furfurylidene compounds with a halogen halide followed by treatment with an alkali metal sulphite, or (b) condensing furfural with a halogen substituted ketone, e.g. chloracetone, followed by treatment either (i) with a hydrogen halide and then with a sulphite or (ii) with a mixture of a bisulphite and a sulphite, e.g. of an alkali or other metal, ammonia or an amine.  It also contains an additional example in which sodium 3-sodiumsulpho-3-a -furylpropionate is prepared from 3-a -furylacrylic acid and sodium sulphite.  This subject-matter does not appear in the Specification as accepted.