Metallation of benzyl selenides and of α-aryl selenoacetals. Scope and limitations.

α-Metallo benzylselenides and α-metallo selenoacetals derived from aromatic aldehydes have been conveniently prepared by metallation of the corresponding carbon acids. KDA in THF proved among the various basic systems tested, the most efficient.α-Metallo benzylselenides and α-metallo selenoacetals derived from aromatic aldehydes have been conveniently prepared by metallation with KDA of the corresponding carbon acids. These reactions have been used for the synthesis of arylalkanes, including those bearing a trialkylated benzylic carbon, from aromatic aldehydes.     

Arylsulfimide Polymers. IV. Prototype Transamidations–A Comparison of the Reactions of Benzamides,Benzimides, Sulfonamides,Sulfonimides, and Saccharins

Transamidation reactions of nonpolymerizing systems involving benzamides, phthalimides, arylsulfonamides, benzenedisulfonamides and -disulfonim-ides, and saccharins are described. The study includes reactions of both N-substituted and unsubstituted amides and imides with anilines and aniline hydrochlorides. An evaluation of the results of these reactions, aimed at establishing the optimum conditions for transamidations in polymerizing systems, is also presented.     

Study of N,N′-dihydroxyethyldithiooxamide by X-ray diffraction,u.v.-vis,NMR, Raman and i.r. spectroscopy

The vibrational, NMR and electronic spectra of HO(CH₂)_xNHCSCSNH(CH₂)_xOH (x = 2,3,5,6) are discussed. A vibrational analysis has been proposed for the N,N′-dihydroxyethyldithiooxamide (x = 2) and its deuterated (NH/ND, OH/OD) analogue. The structure of N,N′-DHEDTO was solved by X-ray analysis. M_r = 208, monoclinic, space group P2₁/n, a = 9.8800(5) Å, b = 11.3260(7) Å, c = 9.7806(8) Å, β = 119.366(5)°, V = 953.8 ų, Z = 4, Dc = 1.365 Mgm⁻¹,μ(CuKα) = 0.47 mm⁻¹, F(000) = 440.00, T = 300 K. Final conventional R-factor = 0.036, R_w = 0.037, for 1608 unique reflections with I > 3.σ(I) out of 1800 measurements. The structure was solved using the automatic programs PATSYS and DIRDIF. The two νOH bands in the i.r. spectrum are in agreement with the crystallographic structure, which proposes that the unit cell of the compound consists of two independent molecules.     

Synthesis and Properties of Azoles and Their Derivatives. 47. Regioselectivity, Stereoselectivity and Kinetics of [2+3] Cycloaddition Reaction of Z-C,N-Diphenylnitrone with E-β-Nitrostyrenes

The [2+3] cycloaddition of Z-C,N-diphenylnitrone with E--nitrostyrenes leads to (3SR, 4SR, 5SR)- and (3SR, 4RS, 5RS)-2,3-diphenyl-4-nitro-5-arylisoxazolidines as the only reaction products. The kinetics of the reaction was studied by using the HPLC method. It was found that total rate constants increase with increasing substituent Hammett -constants. The substituent effect is rationalized in terms of FMO theory.     

Aminoamidines. 5. Synthesis and acetylation of N,N1,N2-triaryl-substituted β-aminoamidines

Triaryl-substituted -aminoamidines were obtained by the reaction of ,-unsaturated N-arylimidoyl chlorides with arylamines. Acylation of the products gave the products from monosubstitution at the -amino group. Triaryl-substituted -aminoamidines react with phosgene and with oxalyl chloride to form 4-aryliminoperhydropyrimidin-2-ones and 5-aryliminoperhydro-1,4-diazepine-2,3-diones, respectively.For previous communication, see [1].A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2633–2642, November, 1992.     

A review of: “The Effects of Hostile Environments on Coattings and Plastics,Acs. D. P. Garner and G. A. Stahl (Editors): Symposium Series 229, American Chemical Society,Washington, D.C., 1983, 339 pp., U.S. and Canada $47.95, export $57.95.”

Rh‐catalyzed polymerization of a new N‐propargylamide monomer having a galactose residue was investigated. The polymerization proceeded in a mixed solvent of THF and water to produce the galactose‐carrying poly(N‐propargylamide) consisting of cis‐isomer. The copolymerization of the monomer with the N‐propargylamide having the alkyl chain was also carried out.     

Experimental thermochemical study of the enthalpies of formation and sublimation of isonicotinamide,picolinamide, nicotinamide,isonicotinamideN-oxide,and nicotinamideN-oxide. The dissociation enthalpies of the N–O bonds

The standard (p ^∘  =  0.1MPa) molar enthalpies of combustion in oxygen, at T =  298.15 K, for crystalline picolinamide (2-NH₂COPy), nicotinamide (3-NH₂COPy), isonicotinamide (4-NH₂COPy), nicotinamide N -oxide (3- NH₂COPyNO), and isonicotinamide N - oxide (4-NH₂COPyNO) were measured by static-bomb calorimetry. These values were used to derive the standard molar enthalpies of formation of the crystalline compounds. The standard molar enthalpies of sublimation, at T =  298.15 K, for the three pyridinecarboxamide isomers were measured by microcalorimetry and the standard molar enthalpies of sublimation for the two pyridinecarboxamide N -oxide compounds were measured by a mass-loss effusion technique. From the enthalpies of formation of the gaseous compounds, the molar dissociation enthalpies D_m^oof the (N ⁺ – O ⁻ ) covalent bonds were derived. Comparison has been made with D_m^o(N–O) values in pyridine N -oxide derivatives.