GB1045888A - Process for the production of hydantoin derivatives - Google Patents

Abstract

The invention comprises hydantoins of the general formula <FORM:1045888/C2/1> where n = 18, 20 or 22. They are produced from the corresponding ketone <FORM:1045888/C2/2> e.g. cyclododecanone or cis-or trans-cyclodecene-2,3 or 7-one by addition of an alkali metal cyanide, e.g. KCN, and (1) NH4CO3, (2) NH3 and CO2 or (3) NH3 and a cyanate. The ketones may be prepared by hydrogenation of cyclododecadiones which in turn may be prepared by oxidation of cyclodeca-1,5,9-triene and rearrangement of the epoxide so formed. The oxidation may be performed by 1 mole of performic, peracetic or perbenzoic acids, or H2O2 per double bond and an organic acid or buffer solution in a single or multiphase system. A solvent, e.g. ethyl acetate or acetone, and a temperature of 0-50 DEG C. may be used. Rearrangement of the epoxide occurs at 115-125 DEG C. in the presence of 0.1-10% of a catalyst, e.g. MgI2. The product from cis, trans, transcyclododeca-1,5,9-triene is a mixture of cis, trans- and trans, trans-cyclododeca-1,5-diene-9-one and cis, trans-cyclododeca-1,5-diene-10-one. Cis, trans-cyclododeca-1,5-diene is oxidized to cis- and trans-5,6-oxidocyclododecene which rearrange to cis- and trans-cyclododecene-5 and 6-ones. Reaction of the ketone with KCN and NH3 may be carried out in a solvent, e.g. dioxan, MeOH, EtOH, PrOH, HOCH2CH2OH, glycerol, an alkyl ether of a polyglycol or a monoester of a polyhydric alcohol. Water may also be present. The reaction temperature may be 40-75 DEG C. at atmospheric pressure or 40-150 DEG C. at superatmospheric pressure. The resulting mixture may be neutralized with HCl after heating. In reactions (2) and (3) <FORM:1045888/C2/3> is an intermediate. Cyclododecadiene-1,5-one is treated with KCN and NH4CO3 in Example (1) and HCN, NH3 and CO2 in an unnumbered example.