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. 2014 Jul 17:10:1638-44.
doi: 10.3762/bjoc.10.170. eCollection 2014.

Chemistry of polyhalogenated nitrobutadienes, 14: Efficient synthesis of functionalized (Z)-2-allylidenethiazolidin-4-ones

Viktor A Zapol'skii  1 , Jan C Namyslo  1 , Mimoza Gjikaj  2 , Dieter E Kaufmann  1
Affiliations

Chemistry of polyhalogenated nitrobutadienes, 14: Efficient synthesis of functionalized (Z)-2-allylidenethiazolidin-4-ones

Viktor A Zapol'skii et al. Beilstein J Org Chem. .

Abstract

The reaction of mercaptoacetic acid esters with pentachloro-2-nitro-1,3-butadiene (1) provides an appropriate precursor for the synthesis of special thiazolidin-4-ones. Applying different anilines as the second constituent for the requisite cyclization step, a series of (Z)-2-allylidenethiazolidin-4-ones was obtained in yields up to 81%. Some subsequent reactions have been examined too, such as the formation of perfunctionalized 1H-pyrazoles upon treatment with hydrazine. Thiazolidinones are as well known for their physiological activities as for their application in optoelectronics.

Keywords: 1H-pyrazoles; 2-nitroperchlorobutadiene; atropisomers; cyclization; thiazolidin-4-ones.

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Figures

Scheme 1
Scheme 1
SNVin reactions of pentachloro-2-nitro-1,3-butadiene (1).
Scheme 2
Scheme 2
Formation of thiazolidin-4-ones 7–19.
Figure 1
Figure 1
Hindered rotation in the case of ortho- or meta-substituted aniline precursors.
Figure 2
Figure 2
X-ray analysis of thiazolidin-4-one 11.
Scheme 3
Scheme 3
Assumed mechanism for the formation of thiazolidin-4-ones 7–18.
Scheme 4
Scheme 4
Substitution reactions of the precursors 3 and 5 with additional amines.
Scheme 5
Scheme 5
Synthesis of 5-arylmethylidenethiazolidin-4-ones 22–26 and 1H-pyrazoles 27, 28.
Scheme 6
Scheme 6
Assumed mechanism for the formation of 1H-pyrazole 27.
Scheme 7
Scheme 7
Formation of ethyl propanoate 29 and subsequent reactions.
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References

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