Heterocyclic compounds from 3,3‐dimercapto‐1‐aryl‐2‐propen‐1‐ones. Note 1. 4‐Ary1‐1,3‐dihydro‐2H‐1,5‐benzodiazepine‐2‐thiones

Abstract

A series of new 4‐aryl‐1,3‐dihydro‐2H‐1,5‐benzodiazepine‐2‐thiones (3) has been synthesized by condensing the 3,3‐dimercapto‐1‐aryl‐2‐propen‐1‐ones with o‐phenylenediamine. The structure was established by the results of acid cleavage and by nmr spectra. The alkylation of compounds 3 gave 2‐alkylthio‐4‐aryl‐3H‐1,5 benzodiazepines (10).

Reactivity Studies on a Novel 4-(2-hydroxyphenyl)-1,3-dihydro-1,5-benzodiazepine-2-thione

“…In an attempt to functionalise the thiolactam moiety to form the corresponding hydrazino-amidine, compound 4 (or the iminothioether 5) was treated for two hours with a slight excess of hydrazine hydrate in ethanol at room temperature, affording a single product 9 which was formulated as 5-(2-aminophenylamino)-3-(2-hydroxyphenyl)-1H-pyrazole. In fact, as formation of the tautomeric form 8β may also be envisaged, 13 and since this and compound 9 cannot be distinguished on the base of simple spectral data ( 1 H and 13 C NMR); a NOESY experiment was carried out, which revealed the correlation between the pyrazolic H-4 (s, 6.40 ppm) and the aromatic H-6'' (brd, 7.56 ppm) of the 2-aminophenylamino residue. This is consistent with the proposed structure 9, rather than the hydrazino-amidine 8β (Scheme 4).…”

“…IR spectra were recorded with a Perkin-Elmer Spectrum BX FT-IR apparatus, as films on NaCl. 1 H (500.13 MHz), 13 C (125.77 MHz) and two-dimensional NMR experiments were performed with an Avance-500 Bruker spectrometer. Chemical shifts are measured in ppm on the δ scale.…”

4-Phenyl-1-(prop-2-yn-1-yl)-1H-1,5-benzodiazepin-2(3H)-one

“…For the pharmacological effects of benzodiazepines, see: Meldrum & Chapman (1986). For examples of synthetic pathways of new benzodiazepines, see: Aatif et al (2000); Baouid et al (2001); Boudina et al (2007); Nardi et al (1973). For previous work from our groups on organic crystals, see: Fernandes et al (2011); Amarante, Figueiredo et al (2009); ; Paz & Klinowski (2003); Paz et al (2002).…”

“…The precursor, 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one (II), was prepared following literature procedures (Nardi et al, 1973) A mixture of 1 g (4.6 mmol) of II, 0.43 g (2.3 mmol) of benzyltriethylammonium chloride (TBA-Cl) and 3 ml of a 50% sodium hydroxide aqueous solution in benzene (25 ml) was stirred at ambient temperature. After 15 min, propargyl bromide was added slowly.…”

3-Dimethylaminomethylene-4-phenyl-1,3-dihydro-2H-1,5- benzodiazepin-2-one

“…0.47 g (1.98 mmol) of 4-phenyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one 1[2,3] in 4.5 ml of dimethylformamide-dimethylacetal (DMF-DMA) was stirred at 100 °C for 4 hours and then cooled to room temperature. Filtration and washing with a little cold diethyl ether gave 0.46 g (75%) of 3-dimethylaminomethylene-4-phenyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one 2.…”