Easy, inexpensive and effective oxidative iodination of deactivated arenes in sulfuric acid

Two ‘model’ deactivated arenes, benzoic acid and nitrobenzene, were effectively monoiodinated within 1 h at 25-30 °C, with strongly electrophilic I⁺ reagents, prior prepared from diiodine and various oxidants (CrO₃, KMnO₄, active MnO₂, HIO₃, NaIO₃, or NaIO₄) in 90% (v/v) concd sulfuric acid (ca. 75 mol% H₂SO₄). Next, an I₂/NaIO₃/90% (v/v) concd H₂SO₄ exemplary system was used to effectively mono- or diiodinate a number of deactivated arenes. All former papers dealing with the direct iodination of deactivated arenes are briefly reviewed.     

Structures and energies of seleno derivatives of biuret.Ab Initio comparative studies of diselenobiuret, selenobiuret, and selenothiobiuret

Ab initio studies (LCAO-MO method) on conformers of three seleno derivatives of the biuret molecules diselenobiuret [I], selenobiuret [II], and selenothiobiuret [III] were carried out at the Hartree-Fock (HF) and MP2 levels. The molecular geometries of these species were fully optimized at the HF level and characterized by analysis of the harmonic vibrational frequencies using a split-valence triple-zeta basis set augmented by a set ofd polarization functions on heavy atoms andp polarization functions on hydrogen atoms [TZP(d, p)]. The total energies of the HF-optimized structures were calculated at the MP2 (frozen core) level using a larger TZP (2df, 2pd) basis set. The potential energy searches revealed a total of 11 minimum-energy conformers (assigned astrans-trans, trans-cis, cis-trans, andcis-cis) and seven transition-state species for the title molecules. The two predicted conformers for diselenobiuret (Ia=trans-trans andIc=cis-cis) are characterized byC ₂ and the third byC _s symmetry. For selenothiobiuret two forms (IIIa=trans-trans andIIId=cis-cis) possessC ₁ and two (IIIb=trans-cis andIIIc=cis-trans) possessC _s symmetries, respectively. For selenobiuret, four formsIIa=trans-trans (C₁),IIb=trans-cis (C _s),IIc=cis-trans (C ₁), andIId=cis-cis (C₁), were obtained as a result of gradient optimization. Comparison of the relative energies for the considered species indicated that thecis-trans forms are the most stable conformations for all three systems at both the HF and MP2 levels of theory.     

A method for determination of the structure of the intramolecular hydrogen bond in the cations of unsymmetrically substituted 1,8-bis(dimethylamino)naphthalenes in solution

Alkylation of 8-dimethylamino-1-methylamino-4-nitronaphthalene in the CD₃I/KOH/DMSO system afforded a 4-nitro derivative containing the N(CD₃)Me group in position 1. Direct proof of the structure of the intramolecular hydrogen bond in solutions of monoprotonated 4-R-1,8-bis(dimethylamino)naphthalenes was obtained for the first time. ¹H NMR study revealed that the chelated NH proton is shifted to the N(8) atom for R = NO₂ and NH₃ ⁺ and to the N(1) atom for R = NH₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 159–162, January, 2006.     

Thermodynamic study of the three isomers of bromo and iodobenzoic acids. Part II

Using our technique of combustion of small amount of a substance, we determined by calorimetry the standard molar enthalpy of formation in the condensed state and atT=298.15 K of the three isomers of bromo and iodobenzoic acids. Associating to these values their standard molar enthalpies of sublimation previously measured, it was possible to determine their standard molar enthalpies of formation in the gaseous state and atT=298.15 K. The experimental values of the thermodynamic properties _f H _m ^o (cr, 298.15 K), _f H _m ^o (cr, 298.15 K), _sub H _m ^o (298.15 K), and _f H _m ^o (g, 298.15 K) are given for the two series. From the experimental value of the standard molar enthalpy of atomization, it was possible to determine an enthalpy value for the C_b-Br and C_b-I bonds. The experimental and theoretical values of the resonance energy of bromo and iodobenzoic acids are compatible. The relative stability of some monosubstituted derivatives of benzoic acid studied in our laboratory is also discussed.Part I is concerned with Ref. 22 (for bromobenzoic acids) and with Ref. 23 (for iodobenzoic acids).     

La-Ba系氧化物催化剂用于甲烷氧化偶联

以La_2O_3为基础,碱土金属作为第二组分的二元氧化物催化剂均具有较高的生成C_2活性,特别是La-Ba-O系催化剂具有优良的甲烷氧化偶联活性和稳定性,当La/Ba原子比为2.5时,C_2收率可达20.3％。第三组分的添加有助于提高C_2选择性,特别是添加碱金属,可以抑制完全氧化反应,并提高乙烯/乙烷比。在La:Ba:Na=2.5:1:0.1的催化剂上进行了500/小时的寿命实验,在整个反应期间,催化剂的活性和选择性相当稳定。X-射线物相分析表明,新鲜催化剂除有少量的碳酸钡外,主要是氧化镧和氧化钡的混合物。500小时后的物相基本上是氧化镧和碳酸钡。使用前后催化剂的比表面积及表面La和Ba的分布均无改变。较高的CH_4/O_3比对提高C_2选择性有利,当CH_4:O_2=4:1时,C_2选择性和收率分别为65.1％和19.1％。     

Strong intramolecular hydrogen bond N—H...O in 2-(2-acyl-1-phenylethenyl)-5-phenylpyrroles

The molecular structure of 2-(2-benzoyl-1-phenylethenyl)-5-phenylpyrrole and 2-(2-furoyl-1-phenylethenyl)-5-phenylpyrrole was studied by X-ray diffraction analysis at 110 K and quantum chemistry methods (B3LYP/6-31G*). In the crystalline state, both compounds have cyclic structures closed by strong intramolecular hydrogen bond N—H...O. Canonic zwitterionic structure contributes largely to the ground state of the molecules. This is probably due to synergism of the H-bonding and -electron interactions.     

Intramolecular hydrogen bonds and conformations of the 1,4-butanediol molecule

IR and Raman spectra of 1,4-butanediol (BD) versus variations in the medium (CCl₄, CH₃CN), concentration, temperature, and phase state were obtained. The observed changes attest to the conformational variety of BD molecules under the experimental conditions. On the basis of the analysis of the v(OH) region it is concluded that both in the gas phase and in CCl₄ solution conformers of BD with free OH groups coexist with conformers with O-H...O intramolecular hydrogen bonds. The difference in enthalpies, H, for the groups of conformers with and without intramolecular hydrogen bonds was found from the temperature dependence of the v(OH)_free and v(OH)_intra band intensities. The structures and energies for 70 possible spectrally and energetically distinguishable conformers of BD that do not take into account intramolecular hydrogen bonds were calculated by molecular mechanics with account of electron lone pairs of oxygen atoms. Using the experimental values of H and the calculated relative conformer energies,E, the intramolecular hydrogen bond energyE _intra= 3.7 kcal mol^–1 was found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1572–1577, September, 1993.     

Solvatochromism and prototropism of diaminodiphenyl sulphones and 2-aminodiphenyl sulphone: a comparative study by electronic spectra

A comparative study of absorption and fluorescence maxima of 4,4′-diaminodiphenyl sulphone (4DADPS), 3,3′-diaminodiphenyl sulphone (3DADPS) and 2-aminodiphenyl sulphone (2ADPS) in different solvents reveals that (i) solvatochromic shifts are found to be mainly due to interaction of solvents with amino group, (ii) in any one solvent the net solvatochromic shifts of two amino groups are less than that of one amino group, (iii) fluorescence shift from cyclohexane to water is a maximum for 4DADPS and a minimum for 2ADPS and (iv) 4DADPS and 3DADPS possess more twisted intramolecular charge transfer character than 2ADPS. The excited-state acidity constants, determined by fluorimetric titration and Förster cycle methods, have been reported and discussed.     

Selective oxidation of isobutane over Mo-V-Te mixed oxide catalysts with different tellurium contents

A series of MoV_0.3Te_x (x = 0−0.3) mixed oxides were prepared and investigated for the selective oxidation of isobutane. Among them, MoV_0.3Te_0.23 showed the best methacrolein and methacrylic acid selectivity (as high as 17% and 16%, respectively), and the yield to methacrolein and methacrylic acid reached 3.6% and 3.5%, respectively, at 21.3% isobutane conversion at 440°C.