Regioselective synthesis of heterocyclic N-sulfonyl amidines from heteroaromatic thioamides and sulfonyl azides

N-Sulfonyl amidines bearing 1,2,3-triazole, isoxazole, thiazole and pyridine substituents were successfully prepared for the first time by reactions of primary, secondary and tertiary heterocyclic thioamides with alkyl- and arylsulfonyl azides. For each type of thioamides a reliable procedure to prepare N-sulfonyl amidines in good yields was found. Reactions of 1-aryl-1,2,3-triazole-4-carbothioamides with azides were shown to be accompanied with a Dimroth rearrangement to form 1-unsubstituted 5-arylamino-1,2,3-triazole-4-N-sulfonylcarbimidamides. 2,5-Dithiocarbamoylpyridine reacts with sulfonyl azides to form a pyridine bearing two sulfonyl amidine groups.

Silver derivatives of multi-donor heterocyclic thioamides as antimicrobial/anticancer agents: unusual bio-activity against methicillin resistantS. aureus,S. epidermidis, andE. faecalisand human bone cancerMG63cell line

A series of biosafe mixed-ligand complexes of silver with heterocyclic thioamides have been studied for their antimicrobial/anticancer activity.

Bismuth(III) bromide-thioamide complexes: synthesis, characterization and cytotoxic properties

New bismuth(III) bromine compounds of the heterocyclic thioamides were prepared and structurally characterized. The reaction of heterocyclic thioamides with bismuth(III) bromide resulted in the formation of the {[BiBr2(μ2-Br)(MMI)2]2·CH3COCH3·H2O} (1), {[BiBr2(MBZIM)4]·Br·2H2O} (2), {[BiBr2(μ2-Br)(tHPMT)2]2·CH3CN} (3), {[BiBr2(μ2-Br)(PYT)2]2·CH3CN} (4) and {[BiBr2(μ2-Br)(MBZT)2]2 2CH3OH} (5) complexes (MMI: 2-mercapto-1-methylimidazole, MBZIM: 2-mercaptobenzimidazole, tHPMT: 2-mercapto-3,4,5,6-tetrahydro-pyrimidine, PYT: 2-mercaptopyridine and MBZT: 2-mercaptobenzothiazole). The complexes 1–5 were characterized by melting point (m.p.), elemental analysis (e.a.), molar conductivity, Fourier-transform infrared (FT-IR), Fourier-transform Raman (FT-Raman), nuclear magnetic resonance (1H and 13CNMR) spectroscopy, UV-Vis spectroscopy and thermogravimetric-differential thermal analysis (TG-DTA). The molecular structures of 1–5 were determined by single-crystal X-ray diffraction. Complex 2 is a first ionic monomuclear octahedral bismuth(III) bromide, while the complexes 1, 3–5 are the first examples of dinuclear bismuth(III) bromide derivatives. Complexes 1–5 were evaluated in terms of their in vitro cytotoxic activity against human adenocarcinoma breast (MCF-7) and cervix (HeLa) cells. The toxicity on normal human fetal lung fibroblast cells (MRC-5) was also evaluated. Moreover, the complexes 1–5 and free heterocyclic thioamide ligands were studied upon the catalytic peroxidation of the linoleic acid by the enzyme lipoxygenase (LOX).

Вплив комплексних сполук купруму (ІІ), кобальту (ІІ) та цинку з ароматичними і гетероциклічними тіоамідами на посівні властивості деяких сільськогосподарських культур

Встановлено вплив комплексних сполук купруму (ІІ), кобальту (ІІ) та цинку з ароматичними та гетероциклічними тіоамідами на рістрегулюючу активність деяких сільськогосподарських рослин. Доведено вплив досліджуваних комплексів на схожість насіння та приріст біомаси паростків пшениці, кукурудзи, соняшнику, салату та квасолі. Отримані результати свідчать про те, що досліджені координаційні сполуки покращують посівні якості насіння та сприяють формуванню веґетативної маси деяких сільськогосподарських рослин. The influence of complex compounds of Copper (II), Cobalt (II) and Zinc with aromatic and heterocyclic thioamides on the seeding properties of the seeds of some agricultural plants has been studied. As potential plant growth promoters, the coordination compounds of Copper (II), Cobalt (II) and Zinc with deprotonated ligands based on aromatic (N-p-tolylthiobenzamide; N-p-anisylthiobenzamide) and heterocyclic (N-phenylpyridine-2-carbothioamide, N-p-phenylbenzimidazole-2-carbothioamide) thioamides have been investigated. In experiments, indole-3-acetic acid was used as a standard plant-growing regulator. To compare the plant-growing activity of pure thioamides with the corresponding coordination compounds, N-p-tolylthiobenzamide has been investigated. Control samples have not been processed by preparates. The plant-growing activity has been determined by the germination of the seeds, the increase of the mass of their seedlings, the length of the 2nd internode and the increase of the raw vegetative mass of some agricultural plants. The laboratory germination of the seeds of wheat, corn, sunflower and salad increased in comparison with the control sample in 1.10–1.48 times, with the standard – in 1.00–1.39 times and with the thioamide – in 1.00–1.14 times. It has been determined that the optimal concentration, in which the best parameters of plant-growing activity of the investigated compounds on seeds and seedlings of wheat, corn, sunflower and salad are recorded, is the concentration of 10 mg/l. In the greenhouse conditions we have studied the effect of the investigated compounds on the length of the second internode of the seedlings and the increase of the raw vegetative mass of bean germs after their treatment with doses of 4 mg/volume (5 kg/ha) and 0.025 mg/volume (0.031 kg/ha). According to the obtained results, the optimal dose of preparates has been determined – 0.031 kg/ha. Obtained results indicate that coordination compounds of Copper (II), Cobalt (II) and Zinc with aromatic and heterocyclic thioamides improve crop properties of the seeds and promote the formation of the vegetative mass of some agricultural plants. Among the studied compounds the highest plant-growing activity has been shown by the complex of Cobalt (II) with N-p-phenylbenzimidazole-2-carbothioamide.

Coordination variability of Copper(I) in multidonor heterocyclic thioamides.

The chemistry of copper(I) with scarcely studied heterocyclic thioamides, namely, 2,4,6-trimercaptotriazine, purine-6-thione, 2,4-dithiouracil, 2-thiouracil and pyrimidine-2-thione is described. The interaction of 2,4,6-trimercaptotriazine (tmtH3) with [Cu(CH3COO)(PPh3)2] gave rise to a pair of bond isomers : [Cu(κ1N-tmtH2)(PPh3)2] (6a), [Cu(κ1N,κ1S-tmtH2)(PPh3)2] (6b) and with copper(I) bromide and PPh3, it has formed a trinuclear complex, [Cu3Br2(κ1N,κ1S,κ2S-tmtH2)(PPh3)6] (7) with anionic tmtH2- in these complexes. The 2,4-dithiouracil with copper halides (CuCl, CuBr) and PPh3 yielded dinuclear complexes: [Cu2(κ2Cl)(κ1S,κ1S-dtucH)(PPh3)4] (4) and [Cu2(κ2Br)(κ1S,κ1S-dtucH)(PPh3)4] (5) with unusual eight membered metallacyclic rings. Pyrimidine-2-thione (pymSH) coordinated to CuI as N,S-chelated anion yielding mononuclear complex, [Cu(κ1N,κ1S-pymS)(PPh3)2] (1), while 2-thiouracil (tucH2) with copper(I) chloride and PPh3 yielded a tetrahedral complex, [CuCl(κ1S-tucH2)(PPh3)2] (3). Purine-6-thione (purSH2) coordinated to CuI in two different modes yielding mono- and di-nuclear complexes, [Cu(κ1N,κ1S-purS)(PPh3)2].CH3OH (2a) and [Cu2(κ1N,κ2S-purS)2(PPh3)2] (2b). The existence of bond isomers (6a and 6b), synthesis of novel dinuclear ( 4 and 5) and rare trinuclear (7) complexes with unusual bonding patterns and uncommon chelation to CuI by pymS- in 1 are the novel features of the present study. Complexes have shown intense emission bands in the visible region, λmax 490 to 495 nm.