N-N(+) Bond-Forming Intramolecular Cyclization of O-Tosyloxy β-Aminopropioamidoximes and Ion Exchange Reaction for the Synthesis of 2-Aminospiropyrazolilammonium Chlorides and Hexafluorophosphates.

Our research area is related to the spiropyrazolinium-containingcompounds, which are insufficiently studied compared with pyrazoline-containing compounds. Nitrogen-containing azoniaspiromolecules have also been well studied. In drug design and other areas, they are a priori important structures, since rigid spirocyclic scaffolds with the reduced conformational entropy are able to organize a closely spaced area.

Crystal structure and antidiabetic activity of 2-aminospiropyrazolinium tosylates and the product of O-tosylation of β-(benzimidazol-1-yl)propioamidoxime.

2-Amino-1,5-diazaspiro[4.5]dec-1-en-5-ium salts possess bioactivity tuned by the nature of the heteroatoms in the six-membered ring and the counter-ion. The molecular environment of these cations in solids provides an opportunity to establish the conformations and hydrogen-bonding patterns typical for this family.

Reaction Products of β-Aminopropioamidoximes Nitrobenzenesulfochlorination: Linear and Rearranged to Spiropyrazolinium Salts with Antidiabetic Activity.

Nitrobenzenesulfochlorination of β-aminopropioamidoximes leads to a set of products depending on the structure of the initial interacting substances and reaction conditions. Amidoximes, functionalized at the terminal C atom with six-membered -heterocycles (piperidine, morpholine, thiomorpholine and phenylpiperazine), as a result of the spontaneous intramolecular heterocyclization of the intermediate reaction product of an S2 substitution of a hydrogen atom in the oxime group of the amidoxime fragment by a nitrobenzenesulfonyl group, produce spiropyrazolinium or -nitrobenzenesulfonates. An exception is -nitrobenzenesulfochlorination of β-(thiomorpholin-1-yl)propioamidoxime, which is regioselective at room temperature, producing two spiropyrazolinium salts (-nitrobezenesulfonate and chloride), and regiospecific at the boiling point of the solvent, when only chloride is formed.

Redetermination of the structure of 2-amino-8-thia-1,5-di-aza-spiro-[4.5]dec-1-en-5-ium chloride monohydrate.

The reaction of β-(thio-morpholin-1-yl)propio-amidoxime with tosyl chloride in CHCl in the presence of DIPEA when heated at 343 K for 8 h afforded the title hydrated salt, CHNS·Cl·HO, in 84% yield. This course of the tosyl-ation reaction differs from the result of tosyl-ation obtained for this substrate at room temperature, when only 2-amino-8-thia-1,5-di-aza-spiro-[4.5]dec-1-ene-5-ammonium tosyl-ate was isolated in 56% yield.