Crystallization of racemic 4-arylsulfonyl-2(5H)-furanones: reproducibility of homochiral associates,conditions for the spontaneous resolution of enantiomers and the formation of racemic compounds,the role of intermolecular interactions

Crystallization of three 4-arylsulfonyl-2(5H)-furanones from chloroform leads to the formation of a conglomerate of sulfone with para-tolyl substituent and racemic crystals of chloro and bromo analogs. The high degree of similarity of the crystal packings of a homochiral crystal and racemic compounds, viz., the similar type of the homochiral hydrogen-bonded chains and analogous three-dimensional homochiral layers additionally stabilized by the interactions of the type C=O…C=O and C-H…O, allowed us to suggest the presence of the second, “missing” form for each sulfone. A directed search for the “missing” forms revealed the existence of the racemic modification of sulfone with the para-tolyl fragment formed during a very slow crystallization of the compound from benzene. No conglomerates of bromo and chloro analogs were found. Topological analysis of the electron density distribution performed by quantum chemical calculations using density functional theory (PBE1PBE, 6–31G(d,p)) showed the higher energy favorability of intermolecular interactions in the homochiral chains as compared to the hypothetical heterochiral associates.     

Dimephosphone analogues. 3. Molecular and crystal structure of dimephosphone pyridinoylhydrazones exhibiting antiphthisic activity

Molecular and crystal structures of dimephosphone nicotinoylhydrazone and dimephosphone isonicotinoylhydrazone exhibiting antiphthisic activity are studied. In contrast to aroylhydrazones of arylaldehydes, existing in the crystalline state as a mixture of two amide conformers, the studied hydrazones exist in the crystalline state in the single geometrical form E _C=N E _N-N Z _N-C(O).     

STRUCTURE OF SOME ADAMANTYL-CONTAINING UREAS AND HYDROGEN BONDS IN THEIR CRYSTALS

Journal of Structural Chemistry - Molecular and crystal structures of five substituted urea derivatives with bulky adamantyl fragments in their substituents are considered. It is shown that the...     

Reaction of alkyl 3-bromo-3-nitroacrylates with substituted hydrazines. Synthesis of N′-substituted alkyl 3-nitropyruvate hydrazones

Russian Chemical Bulletin - The reaction of alkyl 3-bromo-3-nitroacrylates with substituted phenylhydrazines and hydrazides of aromatic acids proceeds through the formation of aza-Michael adducts....     

Synthesis,Antibacterial, and Antioxidant Evaluation of Novel Series of Condensed Thiazoloquinazoline with Pyrido,Pyrano, and Benzol Moieties as Five- and Six-Membered Heterocycle Derivatives

A novel synthesis of thiazolo[2,3-b]quinazolines 4(a–e), pyrido[2′,3′:4,5]thiazolo[2,3-b]quinazolines {5(a–e), 6(a–e), and 7(a–e)}, pyrano[2′,3′:4,5]thiazolo[2,3-b]quinazolines 8(a–e), and benzo[4,5]thiazolo[2,3-b]quinazoloine9(a–e) derivatives starting from 2-(Bis-methylsulfanyl-methylene)-5,5-dimethyl-cyclohexane-1,3-dione 2 as efficient α,α dioxoketen dithioacetal is reported and the synthetic approaches of these types of compounds will provide an innovative molecular framework to the designing of new active heterocyclic compounds. In our study, we also present optimization of the synthetic method along with a biological evaluation of these newly synthesized compounds as antioxidants and antibacterial agents against the bacterial strains, like S. aureus, E. coli, and P. aeruginosa. Among all the evaluated compounds, it was found that some showed significant antioxidant activity at 10 μg/mL while the others exhibited better antibacterial activity at 100 μg/mL. The results of this study showed that compound 6(c) possessed remarkable antibacterial activity, whereas compound 9(c) exhibited the highest efficacy as an antioxidant. The structures of the new synthetic compounds were elucidated by elemental analysis, IR, ¹H-NMR, and ¹³C-NMR.     

On‐Line Monitoring of Chemical Reactions by using Bench‐Top Nuclear Magnetic Resonance Spectroscopy

Real‐time nuclear magnetic resonance (NMR) spectroscopy measurements carried out with a bench‐top system installed next to the reactor inside the fume hood of the chemistry laboratory are presented. To test the system for on‐line monitoring, a transfer hydrogenation reaction was studied by continuously pumping the reaction mixture from the reactor to the magnet and back in a closed loop. In addition to improving the time resolution provided by standard sampling methods, the use of such a flow setup eliminates the need for sample preparation. Owing to the progress in terms of field homogeneity and sensitivity now available with compact NMR spectrometers, small molecules dissolved at concentrations on the order of 1 mmol L^?1 can be characterized in single‐scan measurements with 1 Hz resolution. Owing to the reduced field strength of compact low‐field systems compared to that of conventional high‐field magnets, the overlap in the spectrum of different NMR signals is a typical situation. The data processing required to obtain concentrations in the presence of signal overlap are discussed in detail, methods such as plain integration and line‐fitting approaches are compared, and the accuracy of each method is determined. The kinetic rates measured for different catalytic concentrations show good agreement with those obtained with gas chromatography as a reference analytical method. Finally, as the measurements are performed under continuous flow conditions, the experimental setup and the flow parameters are optimized to maximize time resolution and signal‐to‐noise ratio.     

Local Vibrations of Oxygen-Containing Thermal Donors in Germanium

The vibrational absorption bands associated with some types of double thermal donors (TD) in Ge enriched with the oxygen isotopes ¹⁶O and ¹⁸O have been identified. The thermal donors were formed during heat treatment of Ge:O crystals at 300 and 350°C. Absorption spectra were measured at room temperature and at 10 K. The formation of the thermal donors was accompanied by the appearance of three absorption bands, which in the Ge:¹⁶O spectra at room temperature are located at 600, 740, and 780 cm^–1. In low-temperature measurements, the bands at 600 and 780 cm^–1 exhibited splitting into series of narrow lines (up to 9) associated with some types of thermal donors (TD1–TD9). The absorption spectra measured at 10 K after different cooling conditions display bistability of the first four types of thermal donors (TD1–TD4). In the samples cooled by illumination with light in the region of frequencies of the fundamental absorption of Ge, pairs of lines are observed that belong to the bistable thermal donors in the helium-like configuration of double donors (DD). After cooling the samples in the dark, these pairs of lines are replaced by three new bands, which belong to local vibrational modes of bistable thermal donors in the low-energy neutral configuration. Based on the isotopic shift of the local vibrational modes of the thermal donors in Ge:¹⁶O and Ge:¹⁸O, a rigorous proof of the oxygen atoms entering into the composition of thermal donors is obtained.     

Investigation of a wake decay behind a circular disk in a hydro channel at high Reynolds numbers

LDA and PIV techniques were used to study the decay of an axisymmetrical turbulent wake originated downstream an immobile disk in a water flume for Reynolds numbers Re = 1.5?2.4?10⁵. Data were compared with experiments performed with a set of thermo-anemometers behind a disk in a wind tunnel at lower Reynolds numbers (Re = 1.3?2.6?10⁴). Observations for a new range of Reynolds number confirmed that the velocity distribution in the disk wake keeps self-similarity. The decay of a wake by the power law ?2/3 in the presented experiments remains until the maximum deficit of velocity becomes comparable with the turbulent pulsation level in the free-stream (less than 2 %).