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. 2023 Jan 6;28(2):609.
doi: 10.3390/molecules28020609.

Alkyl 4-Aryl-6-amino-7- phenyl-3-(phenylimino)-4,7-dihydro- 3H-[1,2]dithiolo[3,4-b]pyridine-5-carboxylates: Synthesis and Agrochemical Studies

Victor V Dotsenko  1   2 , Anna E Sinotsko  1 , Vladimir D Strelkov  1 , Ekaterina A Varzieva  1 , Alena A Russkikh  1 , Arina G Levchenko  1 , Azamat Z Temerdashev  3 , Nicolai A Aksenov  2 , Inna V Aksenova  2
Affiliations

Alkyl 4-Aryl-6-amino-7- phenyl-3-(phenylimino)-4,7-dihydro- 3H-[1,2]dithiolo[3,4-b]pyridine-5-carboxylates: Synthesis and Agrochemical Studies

Victor V Dotsenko et al. Molecules. .

Abstract

The reaction between dithiomalondianilide (N,N'-diphenyldithiomalondiamide) and alkyl 3-aryl-2-cyanoacrylates in the presence of morpholine in the air atmosphere leads to the formation of alkyl 6-amino-4-aryl-7-phenyl-3-(phenylimino)-4,7-dihydro-3H-[1,2]dithiolo[3,4-b]- pyridine-5-carboxylates in 37-72% yields. The same compounds were prepared in 23-65% yields by ternary condensation of aromatic aldehydes, ethyl(methyl) cyanoacetate and dithiomalondianilide. The reaction mechanism is discussed. The structure of ethyl 6-amino-4-(4-methoxyphenyl)-7-phenyl-3-(phenylimino)-4,7-dihydro-3H-[1,2]dithiolo[3,4-b]pyridine-5-carboxylate was confirmed by X-ray crystallography. Two of the prepared compounds showed a moderate growth-stimulating effect on sunflower seedlings. Three of the new compounds were recognized as strong herbicide safeners with respect to herbicide 2,4-D in the laboratory and field experiments on sunflower.

Keywords: Michael addition; [1,2]dithiolo[3,4-b]pyridines; active methylene thioamides; cyanoacetic esters; dithiomalondianilide; herbicide safeners.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
The reported methods [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16] for construction of [1,2]dithiolo[3,4-b]pyridine system.
Scheme 2
Scheme 2
Two possible directions for heterocyclization reactions of active methylene thioamides with cyanoacetic esters or 2-cyanoacrylates.
Scheme 3
Scheme 3
Synthesis of compound 15a.
Figure 1
Figure 1
ORTEP drawing of the X-ray structure for ethyl 6-amino-4-(4-methoxyphenyl)-7-phenyl- 3-(phenylimino)-4,7-dihydro-3H-[1,2]dithiolo[3,4-b]pyridine-5-carboxylate 15a (CCDC deposition number 2219352). Thermal ellipsoids for non-hydrogen atoms are shown at 50% probability. Blue: nitrogen, gray: carbon atoms, red: oxygen atoms, yellow: sulfur atoms.
Scheme 4
Scheme 4
Synthesis of compounds 15a–g.
See this image and copyright information in PMC

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