Thiomorpholine synthesis

An orchestrated six-step reaction sequence using seven different supported reagents has been described for the synthesis of a piperidino-thiomorpholine Hbrary... 

Both tetrahydro-l,4-oxazine (morpholine) and its thia analogue (thiomorpholine) find application as solvents and bases, morpholine having particular value in synthesis as it is often used to prepare enamines from ketones with a free a-hydrogen atom. TV-Acylation and -alkylation are readily accomplished and a great diversity of TV-substituted morpholines and thiomorpholines are encountered in the patent literature, some having biological activity. 

The solid-phase synthesis of 2,4,5-trisubstituted thiomorpholine-3-ones 22 from a resin-bound protected cysteine has been reported by Nefzi et al. 

A number of substituted thiirans have been obtained by displacement of chlorine from chloromethylthiiran. Aryloxymethylthiirans have been used for the synthesis of antidepressant thiomorpholine derivatives, and thiolcarbamates derived from 2-mercaptomethylthiiran are claimed to be herbicides. A dimethylthiiran substituted with a long carbon chain containing a dienoate group is said to be insecticidal. ... 

Metal Complexes.—In order to determine the effect of the presence of a nitrogen donor on the ortho-metallation of the thiobenzoyl function, Alper and Chan treated NN-dimethylthiobenzamide with di-iron enneacar-bonyl. However, no sulphur-donor ligand ortho-metallated complex was obtained, as happens in the case of thiobenzophenone, but instead the complexes (245) and (246) were formed. - NN-Dimethylthioacetamide similarly yielded the complexes (247) and (248), whereas the unsubstituted thiobenzamide on treatment with di-iron enneacarbonyl gave the complexes (249) and (250). The synthesis and properties of metal complexes of dithio-oxamides, dithiomalonamides, 2-thiocarbamoyl-l,10-phenan-throlines, thiomorpholine-3-thione, and 2,4-dithiouracil have also been described recently. 

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