Synthesis and fungicidal activity of novel 1,3‐disubstituted 1H‐diazirine derivatives

Abstract

A convenient method for synthesis of novel 1- [pyrimidinyl], 1-[1,3,5-triazin-2-carbonyl], and 1-[thiazol-5-carbonyl] derivatives of 3-thioxo-diaziridine 1, 3, 5, and 7 from corresponding hydrazides, CS2, and KOH is elaborated. The highest reaction yield was observed when these initial reagents were taken in molar ratio of 1:1.7:2.0, respectively. By alkylation of compounds 1, 3, 5, and 7 that proceeds exclusively at sulfur atom, the 3-sulfanyl derivatives of 1-[pyrimidinyl]-, 1-[1,3,5-triazin-2-carbonyl]-, and 1-[thiazol-5-carbonyl]-diazirines 2, 4, 6, and 8 were formed. The structures of synthesized compounds were confirmed by proton and carbon nuclear magnetic resonance (NMR), mass spectra (MS), and elemental analysis. The fungicidal activities of S-substituted derivatives were studied. Data of preliminary biological tests testify that these compounds can be of interest in search for new fungicides.

New Trends in Diaziridine Formation and Transformation (a Review)

“…In general, conventional methods for the synthesis of diaziridines with HOSA have been performed in various solvents, such as water [79], methanol [80], or pure liquid ammonia [81]. When conventional methods were used for the reaction of cyclooctanone 92, benzylamine 93, and HOSA, the corresponding bicyclic diaziridine, 1,2 diazaspiro [2,7]decane 94 (Figure 13), was produced with quite a low yield (~20%) [81]. In order to achieve a better understanding of this, the solvent dependency of the N-monosubstituted diaziridine 94 yield was studied by means of GC-MS [82].…”

“…When an excess of the mixture of CS 2 and KOH was added to hydrazide 109 spirit boiling solution, the hydrogen sulphide evolved in the reaction. As a result of the elimination of hydrogen sulphide, three-membered diaziridine 110 was formed, along with another product, 1,3,4-thiadiazolidine [2]. Although the amounts of CS 2 and KOH were varied, the same substances were formed, with the amount of CS 2 affecting only the yield of the final product.…”

“…A single reagent that is able catalyze multiple mechanistically distinct processes in a chemical reaction known as an auto-tandem catalyst [98], and the transition metal used for this process is gold(I). The ring opening of diaziridines [99] is started by the synthesis of N-monosubstituted diaziridine by the conventional method of reacting ketone 144, benzyl, and the aminating reagent NH 2 OSO 3 H. A minimal modification at the free Nterminal of diaziridine resulted in 1-benzyl-1,2-diazaspiro [2,5]octane 145, which was then used as the starting material for an auto-tandem catalysis reaction mediated by gold(I). The model reaction was conducted by reacting diaziridine 145 with phenylacetylene 146, and it was found that the product 3-pyrazoline 147 was preferentially obtained using Ph 3 AuNTf 2 as the catalyst, rather than other catalysts.…”

“…An important intermediate and precursor in organic chemistry, diaziridine [1] is a highly strained three-membered heterocycle with two nitrogen atoms [2]. The other excellent properties of diaziridine include a weak N-N bond, low toxicity, hydrazine aminal duality [3], and neurotropic activity [4].…”