The reaction of thiosemicarbazide with N cyanoguanidine in an acidic medium afforded 3,5 diamino 1 thiocarbamoyl 1,2,4 triazole, whose condensation with α halo ketones gave 3,5 diamino 1 thiazol 2 yl 1,2,4 triazoles 7a-d. The latter were also prepared by the inde pendent synthesis from 2 hydrazinothiazoles and N cyanoguanidine. Acylation of compounds 7a,d under mild conditions and their condensation with aldehydes occur at the C(3´)NH 2 group. The structure of aroyl derivative 11c was established by X ray diffraction. Acylation of diaminothiazolyltriazole 7a in boiling Ac 2 O afforded 3,5 diacetylamino 1 (4 phenylthiazol 2 yl) 1,2,4 triazole. Hydrogenation of arylidene derivatives 14b,c and aroyl derivative 11c gave the corresponding benzylaminotriazoles 15a,b.

Triazole derivatives R 0280Reaction of Thiosemicarbazide with N-Cyanoguanidine: Synthesis of 3,5-Diamino-1-thiocarbamoyl-and 3,5-Diamino-1-thiazol-2-yl-1,2,4-triazoles. -The reaction of thiosemicarbazide (II) with N-cyanoguanidine (I) followed by condensation of the resulting triazole (III) with haloketones affords thiazolyl-1,2,4-triazoles (V). Their acylation under mild conditions and their condensation with aldehydes proceed selectively at the 3-amino group. -(CHERNYSHEV*, V. M.; KOSOV, A. E.; GLADKOV, E. S.; SHISHKINA, S. V.; TARANUSHICH, V. A.; DESENKO, S. M.; SHISHKIN, O. V.; Russ.

<div>Nickel(II) complexes with pyrazole-based ligands are widely employed in catalysis of ethylene</div><div>oligomerization and subsequent Friedel-Crafts alkylation of toluene. We have prepared ten new</div><div>nickel(II) dibromide complexes with various substituted bis(azolyl)methanes. They have been</div><div>characterized using ¹H NMR, IR, MALDI-TOF and elemental analysis. The structures of three</div><div>complexes have been unambiguously established using X-ray diffraction. It was found that these</div><div>complexes in the presence of Et₂AlCl or Et₃Al₂Cl₃ are active both in ethylene oligomerization and</div><div>Friedel-Crafts alkylation processes (activity up to 3720 kgoligomer·mol[Ni]⁻¹·h⁻¹). The use of Et₃Al₂Cl₃</div><div>results in the higher share of alkylated products (up to 60%). Moreover, catalytic systems activated with</div><div>Et₃Al₂Cl₃ produced small amounts of odd carbon number olefins (up to 0.8%). The Friedel-Crafts</div><div>alkylation was used as a trap for previously undetected short-chain odd carbon number olefins (C₃ and</div><div>C₅).</div>