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. 2022 Dec 15;23(24):15997.
doi: 10.3390/ijms232415997.

The Reactions of N,N'-Diphenyldithiomalondiamide with Arylmethylidene Meldrum's Acids

Victor V Dotsenko  1   2 , Alexander V Aksenov  2 , Anna E Sinotsko  1 , Ekaterina A Varzieva  1 , Alena A Russkikh  1 , Arina G Levchenko  1 , Nicolai A Aksenov  2 , Inna V Aksenova  2
Affiliations

The Reactions of N,N'-Diphenyldithiomalondiamide with Arylmethylidene Meldrum's Acids

Victor V Dotsenko et al. Int J Mol Sci. .

Abstract

The Michael addition reaction between dithiomalondianilide (N,N'-diphenyldithiomalondiamide) and arylmethylidene Meldrum's acids, accompanied by subsequent heterocyclization, was investigated along with factors affecting the mixture composition of the obtained products. The plausible mechanism includes the formation of stable Michael adducts which, under the studied conditions, undergo further transformations to yield corresponding N-methylmorpholinium 4-aryl-6-oxo-3-(N-phenylthio-carbamoyl)-1,4,5,6-tetrahydropyridin-2-thiolates and their oxidation derivatives, 4,5-dihydro-3H-[1,2]dithiolo[3,4-b]pyridin-6(7H)-ones. The structure of one such product, N-methylmorpholinium 2,2-dimethyl-5-(1-(2-nitrophenyl)-3-(phenylamino)-2-(N-phenylthiocarbamoyl)-3-thioxopropyl)-4-oxo-4H-1,3-dioxin-6-olate, was confirmed via X-ray crystallography.

Keywords: Meldrum’s acid; Michael adducts; active methylene compounds; dithiomalonamides; heterocyclization.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
The diversity of reported dithiomalondianilide reactions.
Scheme 2
Scheme 2
Synthesis and reactions of the Michael adducts 6.
Scheme 3
Scheme 3
Synthesis of the Michael adduct 15a′.
Scheme 4
Scheme 4
The reaction between dithiomalondianilide 1 and arylmethylidene Meldrum acids 14: products and possible mechanistic pathway.
Figure 1
Figure 1
Hydrogen bonding in Michael adducts 15.
Figure 2
Figure 2
ORTEP drawing of X-ray structure for N-methylmorpholinium 2,2-dimethyl-5-(1-(2-nitrophenyl)-3-(phenylamino)-2-(N-phenylthiocarbamoyl)-3-thioxopropyl)-4-oxo-4H-1,3-dioxin-6-olate 15b (CCDC deposition number 2218133).
Scheme 5
Scheme 5
Synthesis and plausible mechanism of formation of 4-(2-chlorophenyl)-7-phenyl-3-(phenylimino)-4,5-dihydro-3H-[1,2]dithiolo[3,4-b]pyridin-6(7H)-one 17c.
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