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Title: The synthesis of optically active thiols and related compounds (1) ; and, The oxidation of some thiocarbonates (2)
Author: Anisuzzaman, Abul Kashem Mohammad
Awarding Body: University of London
Current Institution: Imperial College London
Date of Award: 1966
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Part 1 : (R)- and (S)-2,3-dimercaptopropanols, (R)-3-mercaptopropane-1,2-diol, (S)-2-mercaptopropanol and related compounds have been synthesised by stereospecific routes from D-mannitol via (S)-1,2-0-isopropylideneglycerol. These thiols, of known absolute configurations, thus provide reference compounds of potential use for other stereochemical correlations. A racemic product was obtained when attempts were made to synthesise (R)-2,3-dimercaptopropanol from 1,2,5,6-tetradeoxy-3,4-0-isopropylidene-1,2:5,6-di(thiocarbonyldithio)-L-iditol by a process involving the reduction of (R)-2,3-(carbonyldithio)glyceraldehyde. This fact suggested that a carbanion stabilised by resonance involving a 3d orbital of sulphur and the carbonyl group might be an intermediate during the reduction of the aldehyde. Pat 2 The oxidation of a number of cyclic thiocarbonates was studied. It was observed that the nature of the product depends on the structure of the thiocarbonate, the nature of the oxidant, and the experimental conditions. Thus trans-1,2-(thiocarbonyldithio)cyclohexane on oxidation with lead tetra-acetate (or peracetic acid) gave trans1,2-(oxythiocarbonyldithio)cyclohexane. With an excess of peracetic acid, the same trithiocarbonate yielded trans-cyclohexane-1,2-disulphonic acid and trans-1,2- (methylenedisulphonyl)cyclohexane. Similar results were also obtained with trans-2,3-(thiocarbonyldithio)tetralin. With an excess of peracetic acid, trans-1,2-(carbonyldithio)cyclohexane yielded only trans-cyclohexane-1,2- disulphonic acid. trans-1,2-(Thiocarbonyldioxy)cyclohexane gave trans-1,2-(carbonyldioxy)cyclohexane on oxidation with either lead tetra-acetate or perphthalic acid. Similarly, the thiocarbonyl group of trans-(thiocarbonyloxythio)cyclohexane was converted to the carbonyl group by lead tetra-acetate. A disulphide of unusual structure was obtained from 1,2-(thiocarbonyldioxy)benzene by oxidation with lead tetra-acetate.
Supervisor: Owen, L. N. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available