2-(N,N-Disubstituted Amino)thiazoles with Electron-withdrawing Groups at Position 5: Prepaeation and Investigation on Structural Features

DOI: 10.1039/P19840000147

Source and publish data:

Journal of the Chemical Society. Perkin transactions I p. 147 - 153 (1984)

Update date:2022-08-04

Topics:

Authors:

Birkinshaw, Timothy N.

Gillon, David W.

Harkin, Shaun A.

Meakins, G. Denis

Tirel, Malkom D.

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Article abstract of DOI:10.1039/P19840000147

A convenient procedure for preparing N-mono- and NN-di-substituted cyanamides from cyanogen bromide has been developed.N,N-Disubstituted thioureas, obtained from the cyanamides, were condensed with α-bromo-α-cyanoketones to give 5-cyano-2-(N,N-disubstituted amino)thiazoles and with α-bromo-ketones to give 2-(N,N-disubstituted amino)thiazoles.Substitution in the latter products afforded 5-trifluoroacetyl- and 5-nitro-2-(N,N-disubstituted amino)thiazoles; nitration is greatly facilitated by the presence of a 4-aryl group.The average values of the barriers of rotation of the barriers to rotation of the 2-NR2 groups (ΔG^<*>₂₉₈) in the 5-substituted thiazoles were established by variable temperature 1H n.m.r. spectrometry to be 57.4 kJ mol ^-1 (5-NO2), 56.2 (5-COCF3), and 51.5 (5-CN).I.r. examination showed that the 5-trifluoroacetyl compounds adopt one rotational form preferentially; this is probably the carbonyl O,S-syn-conformation.