Patent GB-636430-A (GB)
Title: A process for treating olefinic aldehydes
IPC: C07C47/19
Filed: 1947-12-16
Abstract: Polymers and condensed products are obtained as still residues when a -olefinic aldehydes are reacted with water in the presence of an acidic hydration catalyst to give a hydroxy-aldehyde.  The products may be hydrogenated with or without prior isolation.  For details of the process and reactants (see Group IV (b)).  Prior to hydrogenation the products would appear to be analogous to the hydroxy polyaldehydes formed by the Michael polycondensation of acrolein and its homologues, cf. (J.A.C.S. 60, 1737, 1911 (1938)). In three examples substantial proportions of resinous products are obtained as still bottoms when aqueous acrolein solutions are reacted with dilute sulphuric acid at 70-80 DEG  C. in the presence of hydroquinone, the products being hydrogenated with Raney nickel catalyst without previous isolation.ALSO:Hydroxyaldehydes or saturated non-aldehydic hydroxy compounds are obtained by reacting an a -olefinic aldehyde with water in the presence of a small proportion of an acidic hydration catalyst until a substantial proportion of hydroxyaldehyde is formed and then, if desired, hydrogenating one or more of the reaction products in the presence of a hydrogenation catalyst.  It is preferred that the a -olefinic aldehyde has a terminal methylene group the double bond of which is in conjugate relation to the carbonyl group of the aldehyde.  The hydration may be accompanied by condensation to give various hydroxy polyaldehydes, cf. Michael (J.A.C.S., 60, 1737, 1911, (1938).  Many a -olefinic aldehydes are specified of the aliphatic, aromatic and cycloaliphatic series and they may be substituted by, e.g. heterocyclic, amino, hydroxy and halide radicles.  Acrolein is the preferred aldehyde.  Catalysts instanced are hydrochloric, sulphuric, hydrofluoric, phosphoric, oxalic, tartaric and acetic acids, acid salts and sulphonic acids. Acids such as hypochlorous acid which have an oxidizing action may not be used.  Sulphuric acid of strength less than 10 per cent, e.g. 0.5 to 1 per cent, by weight is preferred.  In general, the acidic catalyst should result in a reaction medium of pH 0.5 to 7. Polymerization inhibitors such as hydroquinone may be present. Difficulty soluble a -olefinic aldehydes may be treated by the addition of a mutual solvent such as dioxane.  Hydration temperatures instanced are between 75 DEG  and 100 DEG  C.  The hydroxyaldehyde may be recovered from the reaction mixture before hydrogenation by adding a salt to form an insoluble sulphate which is filtered off and the hydroxyaldehyde is obtained by fractionation under reduced pressure.  Hydrogenation catalysts instanced are Raney nickel, Adkin's copper-chromium oxide, and other conventional compounds. Preferred temperatures are not above 100 DEG  C., e.g. 80-100 DEG C., and pressures up to 5000 lbs./sq. inch.  The whole reaction mixture or its separated products may be hydrogenated.  It is stated that a -meth-acrolein may be hydrated to 2-methylpropanol-3-al which may be hydrogenated to 2-methylpropane diol-1.3.  In examples, n-propyl alcohol, trimethylene glycol and 1.5-dihydroxy-2-methylol pentane are obtained in various proportions by reacting in the presence of hydroquinone: (1) 21.2 per cent aqueous acrolein with 0.5 per cent weight per cent of sulphuric acid for 8 hours at 70-80 DEG C., followed by hydrogenation with Raney nickel at 32-40 DEG  C., and 1000 lbs./sq. inch pressure for 5 hours; (2) 10 per cent aqueous acrolein with 0.5 per cent weight per cent of sulphuric acid for 2 hours at 75 DEG  C. with hydrogenation as above; and (3) 10 per cent aqueous acrolein with 1 per cent weight per cent sulphuric acid for 2 hours at 75 DEG  C., followed by hydrogenation for 1 hour at 79-88 DEG  C. and 1000 lbs./sq. inch in the presence of Raney nickel.