Addition dipolaire-1,3 aux olefines portant une substitution captodative: reactivite comparee des α et des β amino acrylnitriles vis a vis des arylazides.

Arylazides reacted with α amino-acrylonitriles $\text{1}$ to produce 1-aryl-5-amino-triazoles, and with β amino-acrylonitriles $\text{2}$ to give 1-aryl-4-cyanotriazoles. Kinetics showed the Hammett ρ to be > o and therefore, these reactions are controlled by LUMOazide-HOMOolefin interaction. Despite the captodative substitution in $\text{1}$ and $\text{2}$ (ΔΔ E^≠～ 500 cal.M^?1) does'nt agree with a diradical intermediate.     

The photochemical reactions of α,β,γ,δ -unsaturated diazo compounds at low temperature

The α,β:γ,δ-unsaturated tosylhydrazone lithium salts (4) undergo photolysis at ?60°C to give vinylcyclopropenes (10) and [l,2]diazeto[l,4-a] pyrroles (11) and/or (12). The formation of (11, X=H) establishes the intermediacy of (8, X=H) in the formation of the 3$\text{H}$-1,2-diazepine (9). The diazoalkene (5, X=Me) showed opposite electrocyclisation periselectivity to its thermal cyclisation and gave (11, X=Me) $\text{via}$ (8, X=Me), rather than the pyrazoles (2) and (3).     

High-performance liquid chromatographic analysis of dianhydrogalactitol in plasma by derivatization with sodium diethyldithiocarbamate.

A high-performance liquid chromatographic method is described for measuring submicrogram quantities of dianhydrogalactitol, a promising anti-neoplastic agent, in plasma. The drug is derivatized directly in plasma with sodium diethyldithiocarbamate to form a bis(dithiocarbamoyl) ester which absorbs UV light at 254 nm (am 17,000). The derivatized product is then extracted quantitatively into chloroform and separated by normal phase chromatography (muBondpak CN column). Dianhydrogalactitol concentration below 50 ng/ml of plasma can be detected in the eluent.     

Massenspektren neuer Phloroglucide,insbesondere solcher mit Valerylseitenketten

Mass spectra of phloroglucinol derivatives recently isolated from African Dryopteris species are presented. Phloroglucides with n-valeryl side chain were found in these ferns for the first time. In the mass spectra they show strong peaks corresponding to loss of propene (C₃H₆) produced by McLafferty rearrangement, as shown in model compounds. Aside of the rottleron change (discussed formerly) this must be considered in order to avoid wrong interpretation, particularly when mass spectra are used to analyse mixtures of homologues, as usually present in the plants. If valeryl side chains are present other methods must be used therefore to measure the amount or show the absence of lower homologues with acetyl side chains.     

Study of the structure of the lectins ofDatura innoxia seeds. III. Resistance of the lectins to the action of various proteases

The capacity of the lectins ofDatura innoxia for being digested by proteases with various specificities and pH optima has been studied. Under the conditions of limited proteolysis the hemagglutinating activity did not decrease, and the degree of hydrolysis determined from the reaction with trinitrobenzenesulfonic acid was close to zero.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 93–95, January–February, 1996. Original article submitted July 3, 1995.     

Parametric analysis of oscillatory oxidation reactions

A complete parametric analysis, concerning an overall kinetic model for oscillating catalytic deep oxidation of alcohols, carbon monoxide or hydrogen, is presented. The model contains four parameters.     

Efficient and eco-friendly synthesis of dihydropyrimidinones, bis(indolyl)methanes, and N-alkyl and N-arylimides in ionic liquids

Dihydropyrimidinones, bis(indolyl)methanes, and N-alkyl and N-arylimides were synthesized efficiently under mild reaction conditions in the presence of two types of ionic liquids. In each section, effects of different ILs on the yield of reactions were investigated. The use of ionic liquids offer improvements for the synthesis of title compounds with regard to the yield of products, simplicity in operation, short reaction times and green aspects by avoiding toxic catalyst and organic solvents.     

Identification of soy protein in meat by pyrolysis-high-resolution gas chromatography

Pyrolysis-gas chromatography was applied to the characterization of ground beef and soy protein isolate and its mixtures at the 50, 30 and 10% levels. A cryogenic trap pyrolysis mode was employed and the volatile pyrolysates were analysed by a high-resolution capillary gas chromatograph. Two phenolic derivatives, o-methoxy- and dimethoxyphenol, as well as 2,3-dithiabutane are uniquely observed at a large concentration in the soy pyrolysate. Quantification of these characteristic compounds allow the estimation of the level of soy inclusion in the mixture. This approach effectively denotes soy addition up to the 10% level in comminuted beef.     

Algorithms for high-level data processing in gas chromatography

Computer processing of gas chromatographic data is discussed, with special emphasis on the numerical operations needed. The CHADIC program is described. This program enables optimal separation conditions to be determined and isothermal gas chromatograms to be processed for qualitative and quantitative analysis.