Transformations of pyridiniums derived from amino-alcohols and from diamines : Novel ring closures

Pyridiniums derived from amino alcohols cyclise to ethers or rearrange to aldehydes on heating. Monopyridiniums from diamines can be acylated or converted into ureas or thioureas: these products cyclise on heating in solution to give dihydro-thiazoles, -4H-thiazines, -oxazoles, -4H-oxazines, or tetrahydro-3H-thiazepines.     

Vibrational and high pressure conformational studies of 1,1,2-trichloroethane

The infrared spectra of 1,1,2-trichloroethane were recorded from 4000 to 50 cm^?1 in the vapour and liquid states. Additional spectra above 200 cm^?1 of the low temperature crystal and of two crystalline solids, prepared by compressing the sample in a diamond anvil cell, were obtained. Also, infrared spectra of the liquid and of the compound dissolved in CS₂ were recorded at increased pressures. Raman spectral data of the liquid (including polarization measurements) and of the low temperature crystal were obtained.The fundamental frequencies for each of the two conformers, C₁ and C_s, were assigned and the results checked by normal coordinate analysis. The same diagonal and off-diagonal force constants were employed for the two conformers and the force fields were derived by means of a least squares refinement, including data for chloroethane, 1,1-dichloroethane and various deuterated species. A standard deviation of 3 % was obtained in the final fit.From the changes in relative intensities for infrared bands belonging to the C₁ and C_s conformers with increasing pressure, the volume differences (ΔV¯between the conformers were determined in CS₂ solution and in the pure liquid.     

Automated development of analytical chemical methods : The determination of senun calcium by the cresolphthalein complexone method

The cresolphthalein complexone method for serum calcium determination was investigated by means of a modified Technicon Autoanalyzer II under computer control. Simplex optimization of reagent concentrations, followed by response-surface mapping in the region of the optimum produced a method yielding 8.5% greater calcium sensitivity and 15% lower baseline absorbance than the standard method, with comparable insensitivity to interferences, and only a very slight sacrifice in linearity; a comprehensive operational understanding of the chemical system was also obtained.     

Atomic and molecular absorption spectra of indium in air-acetylene flame

Absorption spectra of both atomic and molecular species in the air-acetylene flame, which are produced when the aqueous solutions of indium dissolved in HNO₃, HF, HCl, HBr and HI were aspirated into the flame, have been investigated in the u.v. region. Numerous atomic absorption lines of indium have been observed in the absorption spectra. Most of these lines were previously listed only as emission lines. Those atomic lines have been ascribed to the electronic transitions from the ground states of 5p ²P_1/2⁰ and 5p ²P_3/2⁰ to the excited states such as ls ²S_1/2, md ²D_3/2, nd ²D_5/2, 4p^{2 4}P_1/2, 4p^{2 4}P_3/2 and 4p^{2 4}P_5/2, respectively, where 13 l 6 and 14 m,n 5. The molecular absorption bands for InF, InCl and InBr in the airacetylene flame have been also observed near 234 nm, 267 nm and 282 nm, respectively, as the electronic transition of ¹Σ⁺ → ¹Π₁ Those absorption bands show fine structures due to the molecular vibrations. The spectral parameters for the molecular vibrations have been obtained from the simulations of the observed spectra. The molecular absorption band for InI was not observed because of the decomposition of the molecule in the flame. In addition, the molecular absorption band for InO has been observed near 273 nm and those for NO near 205 and 215 nm.     

Infrared and Raman multi-phonon spectra and structure of PbWO4

Improved Raman spectra of PbWO₄ show previously reported spectra contain large polarization and/or orientation errors. New spectroscopic information, obtained from polarized IR reflection and Raman spectra, allowed us to assign the IR and the previously unreported Raman multi-phonon bands. It was also used to show that it determines uniquely the C_4h factor group of PbWO₄. The use of IR reflection vs. infrared transmission spectra in the vibrational determination of crystal structures is also discussed.     

Some observations on the interdependence of cyanide concentration and atomization efficiency in the nitrous oxide-acetylene flame

A relationship is derived between CN concentration and atomization efficiency in the C₂H₂-N₂O flame. The relationship is examined under various experimental conditions and β values are estimated for a number of elements. The possibility of complex vapour phase oxide formation by U is considered.     

The NMR spectra of porphyrins—14: Self-aggregation of zinc(II) meso-nitro and meso-dinitro octaethylporphyrins

Complex formation in zinc(II) meso-nitro-octa-ethylporphyrin (1) and the corresponding α,β-dinitro (2) and α, γ-dinitro (3) zinc(II) chelates has been studied using proton NMR at 220MHz. This allows complete resolution of all the distinct groups in the proton spectrum, and the large concentration dependence of the spectra of 1 and 2 can be analysed to afford the monomeric and monomer-dimer shifts for all protons in these molecules. In contrast 3 shows no concentration dependence, nor any change upon addition of pyrrolidine, which immediately dissociates the aggregates of 1 and 2. The monomeric ¹H and ¹³C shifts are reported, together with those of zinc(II) octaethylporphyrin (4), and the complete assignment given allows the substituent shifts of the meso nitro groups in the porphyrin to be obtained. Analysis of the monomer-dimer shifts in terms of the ring current model gives the detailed geometries of the dimers, which have an inter-ring separation of ca 4.5 Å and a lateral displacement from the vertical of ca 1.0 Å. The results also allow the distinction between two different molecular complexes considered previously, and fully confirm our earlier suggestions that binding is due to metal-to-porphyrin, rather than metal-to-substituent, interactions.     

Geometry optimised ab inttio calculations on 1,5- and 1,2-dicarba-closo-pentaborane (5)

Geometry optimised ab initio LCAO- MO-SCF calculations for the isomeric carboranes 1,5- and 1,2-dicarba-closo-pentaborane (5) are reported. The optimised geometry of the 1,5-isomer agrees with the experimental geometry and for this isomer greater thermo-dynamic stability is predicted. The framework bonding is due mainly to interactions between the apical atoms and those in the equatorial plane, while within this equatorial plane there is very weak bonding.     

Microwave spectrum and substitutional structure of CH2DF

Forty-two transitions of the microwave spectrum of CH₂DF have been observed in the region between 75 and 450 GHz. The measurement of both a-type and b-type transitions makes possible the analysis of the spectrum and the accurate calculation of the rotational constants (in MHz): = 119 675.0535 ± 0.074, = 24 043.4415 ± 0.072, ? = 22959.3732 °0.072, °j = 0.049371 ±0.00011, °_jk = 0.34268 ±0.0006, 2_k = 3,3774 ± 0.0035, δ _j = 0.002329 ± 0.000045, δ_k = 0.0687 ± 0.036. These constants, in combination with the results of earlier work on the symmetric speci r_s structure calculation based entirely on high-accuracy microwave data. The structural parameters are r_CH = 1.100 Å, r_CF = 1.383 Å, and ∠HCH = 110° 37'.     

On the contributions of resonance,hybridization and nonbonded interactions to the structure of butadiene

A recent ab initio molecular orbital calculation on butadiene has been interpreted by Skaarup, Boggs and Skancke as indicating that the shortness of the central C-C bond is due primarily to hybridization. Resonance was considered to make a minor contribution and nonbonded interactions were judged to be unimportant. Unfortunately, this analysis failed to take into account the crucial role of geminal nonbonded interactions, and the calculations were, accordingly, not designed to discriminate between the hybridization and nonbonded models. A more direct investigation of intramolecular nonbonded interactions based on ab initio computations has been earned out on other systems, however, providing evidence that the effects of nonbonded contributions are substantial.     

Classification of monosubstituted phenyl rings by branching tree methods using infrared and raman peak heights

A branching tree scheme is proposed and evaluated for classifying monosubstituted benzenes by the structure of the part of a substituent which lies near the phenyl ring. A large group having the same atom attached to the phenyl ring is divided into subgroups having a more highly defined structure. Each subgroup is then further divided into still smaller subgroups having still more highly defined structures. Combined sets of infrared and Raman peak heights for bands characteristic of the phenyl ring vibrations are used as pattern vectors. A statistical linear discriminant method is used to correlate the peak heights of groups having similar near-the-ring structure. The stepwise and overall success rates are given for each level of classification.     

The coulometric titration of bromate with cuprous copper

A coulometric procedure has been developed by which 18 to 240 μg quantities of bromate may be determined to within 0.3 μg. The bromate is allowed to react with bromide in an acid solution and electrolytically generated cuprous copper is used for the titration. A dual platinum electrode indicator system is used in an amperometric end-point procedure     

Construction of small data bases for trace element determinations

Construction of a small data base intended as a model for personal use in the area of trace element determinations is described. A MELCOM 7000 computer is used and several types of on-line conversational retrieval systems are discussed.     

A spectral and polarographic study of the acid--base and complexing behaviour of bromazepam.

A method for the microdetermination of periodate in the presence of iodate is presented. It is based on reduction of periodate to iodate by leucothionine generated in situ by photochemical reaction between EDTA and blue thionine. Biamperometric curves are used for evaluation, representing reduction time for the periodate versus the current generated in the oxidation of the T_red in excess after the end-point. A polarographic study of the process is presented. An applied potential of 100 mV is suitable for the biamperometric measurements with Pt—Pt electrodes. The method is applicable for 0.4–45 ppm periodate. Iodate does not interfere up to IO^-₃ : IO^-₄ ratios of 100:1.     

An ab initio MO calculation of the electronic structure and geometry of protonated methanol

Protonated methanol, CH₃ OH₂⁺, has been studied using the LCAO—MO—SCF method with a 7, 3 and 9, 5, 1 Gaussian orbital basis set on the heavy atoms and 4s on hydrogen. It is found that the ground state is non-planar around oxygen, in contrast with previous calculations, with an inversion barrier of 3 kcal mol^?1. The changes in electron distribution in the reacting systemCH₃⁺ + H₂O → CF₃OH₂⁺is also examined.     

Supernucleophiles—II: Orbital interactions and nucleophilicity

The role of adjacent lone pair centers upon the nucleophilic reactivity of various amines with p-nitrophenyl acetate has been studied. The kinetics of appropriately substituted hydroxy- and methoxyamines, as well as unsubstituted analogs are presented. The effect of orbital orientation was evaluated theoretically for 1-aminoethanol using CNDO/2. The results of the theoretical study imply a small through-bond and an even smaller through-space lone pair interaction. Kinetically, rate enhancements resulting from such interactions are not observed.     

The use of the CNDO method in spectroscopy: VII. Changes in dipole moment upon excitation

The results of the calculations of changes in dipole moment upon excitation of some organic molecules are discussed in connection with recent high resolution spectroscopic measurements of the same quantities. Calculations are reported for several substituted benzenes, several azines, and for formaldehyde, propynal, formyl fluoride, difluorodiazirine and azulene. The calculations were carried out within the CNDO/S parametrization scheme.     

Vibrational spectra and molecular configuration of hexafluoroazomethane

Twenty-one of the 24 fundamental frequencies of CF₃N=NCF₃ have been identified from the infrared and Raman spectra of the vapor and condensed states. The spectra reveal a total lack of infrared-Raman coincidence, i.e., the rule of mutual exclusion is obeyed. This evidence strongly supports the existence of hexafluoroazomethane in the trans configuration and negates the results of a recent electron diffraction study which favor the cis form.     

Vapor phase infrared spectrum and coriolis coupling constants of pentacarbonyl(thiocarbonyl)chromium(0)

Several band contours have been successfully resolved in the high-resolution IR spectrum of pentacarbonyl(thiocarbonyl)chromium(0) vapor at ~312 K. However, PQR separations are only clearly discernible for the three v(CO) fundamentals (v₁,v₂ and v₁₆). The good agreement between the observed and calculated PR separations of the two a₁v(CO) modes (v₁ and v₂) verifies the C_4v prolate symmetrical top geometry of the molecule. From band shape analyses, the Coriolis coupling constants of the ev(CO) mode (v₁₆) and the e δ (CrCO) mode (v₁₇) are estimated to be —0.45 ± 0.05 and —0.80 ± 0.15, respectively.