C-13 MAS NMR spectra of cis,cis-mucononitrile in liquid-crystalline media and in the solid state. Orientation of the carbon chemical-shift tensors

The spinning sidebands observed in the C-13 MAS NMR spectra of cis,cis-mucononitrile oriented in liquid-crystalline media and of the neat sample in the solid state are studied. There are differences in the sideband intensity patterns in the two cases. These differences arise because the order parameters which characterize the orientation of the solute in the liquid-crystalline media differ for different axes. It is shown that, in general, the relative intensities of the sidebands contain information on the sign and magnitude of an effective chemical-shift parameter which is a function of the sum of the products of the principal components of the chemical-shift tensor and the corresponding order parameters with respect to the director. A method for obtaining the orientation of the carbon chemical-shift tensor is proposed. The carbon chemical-shift tensors obtained from gauge-including atomic orbital calculations are also presented for comparison. (C) 1996 Academic Press, Inc.

Molecular-Conformation of 1,3-Pyridylphenylureas by H-1 and C-13 NMR-study

1H and 13C NMR spectra are reported for several 1,3-pyridylphenyl ureas. Analysis of the spectra yielded the chemical shifts. The variations in the chemical shifts have been discussed in terms of the molecular conformations.

Studies of Phosphazenes. Part 13.' Thermal Rearrangement Reactions of Some Met hoxycyclo phosp hazenes

The methoxycyclophosphazenes [NP(OMe),], (n = 3-6) rearrange on heating to give oxocyclophosphazanes, [N(Me)PO(OMe)],. Isomeric products are formed when n = 4-6. The lH, ,lP, and 13C n.m.r. data for the starting materials and the products are presented. The ethoxy- and n-propoxy-derivatives N,P,( OR)* do not undergo the above rearrangement. The geminal derivatives N,P,R,(OMe), (R = Ph or NHBut) on heating yield both fully and partially rearranged products, namely dioxophosphaz-1 -enes and oxophosphazadienes, as shown by 270- MHz lH n.m.r. spectroscopy. The non-geminal derivative N,P,( NMe,),(OMe), gives only the fully rearranged product N,Me,P,(NMe,),O,(OMe), whose structure has been established from its lH and 31P n.m.r. spectra.

Phase relations between Al2O3---Cr2O3 and FeAl2O4---FeCr2O4 solid solutions at 1823 K

Tie-lines between the corundum and spinel solid solutions have been determined experimentally at 1823 K. Next, activities of FeCr2O4 and FeAl2O4 in the spinel solid solution were determined by combining the tie-line data with literature values for the activities of Cr2O3 and Al2O3 in the corundum phase. Activities and the Gibbs energy of mixing for the spinel solid solution were also obtained from a model based on cation distribution between nonequivalent crystallographic sites in the oxide lattice. The difference between the Gibbs energy of mixing obtained experimentally and from the model has been attributed to a strain enthalpy term which is relatively unchanged in magnitude from the reported at 1373 K. The integral enthalpy of mixing obtained from experimental data at 1373 and 1823 K using the second law is compared with the model result.

Hydrogen- 1 and Carbon- 13 Magnetic Resonance Studies of Nonactin-Calcium Complex

For an understanding of the cation selectivity and general binding characteristics of macrotetralide antibiotic nonactin (NA) with ions of different sizes and charges, the nature of binding of divalent cation, Ca2+, to NA and conformation of the NA-Ca2+ complex have been studied by use of 270-MHz proton nuclear magnetic resonance ('H NMR) and carbon-13 nuclear magnetic resonance (13C NMR). The calcium ion induced significantly large changes in chemical shifts for H7, H2, H3, and H5 protons of NA and relatively small changes for H18 and H2' protons. Changes in I3C chemical shift were quite large for carbonyl carbon, C,; it is noteworthy that in the NA-K+ complex, H2 and H2' protons practically do not show any change during complexation and carbonyl carbon shows a much smaller chemical shift change.

Theoretical investigations of the two-bond proton-carbon-13 coupling constants. Angular variations of the couplings involving carboxyl carbon

A formulation has been developed using perturbation theory to evaluate the π-contribution to the nuclear spin coupling constants involving nuclei at least one of which is an unsaturated center. This fromulation accounts for the π-contribution in terms of the core polarization and one-center exchange at the π-center. The formulation developed together with the Dirac vector model and Penney-Dirac bond-order formalisms was employed to calculate the geminal (two-bond) proton coupling constants of carboxyl carbons in α-disubstituted acetic acids. The calculated coupling constants were found to have an orientational dependence. The results of the calculation are in good agreement with the experimental values.

Aspects of tautomerism. 13. Alkaline hydrolysis of .gamma.-, .delta.-, and .epsilon.-keto esters and their desoxy analogs. Geometrical constraints on keto participation

The rates of alkaline hydrolysis of methyl &benzoylpropionate (I), methyl y-benzoylbutyrate (11) and methyll6-benzoylvalerate (In) decrease in the order I > I1 > III. Keto participation is the predominant pathway in the case of y-keto esters. Evidence has also been obtained for keto participation in the case of 6-keto esters, whereas no such evidence is available in the case of r-keto esters studied.

Applications of the Vilsmeier reaction. 13. Vilsmeier approach to polycyclic aromatic hydrocarbons

The Synthesis of three typical polycyclic hydrocarbons (PAH) has been described, wherein the Vilsmeier reaction plays a major role. Vilsmeier reaction of the tetraloll gives the dihydronaphthaldehyde 2 which on cyclodehydration gives the dihydroarene 3. Ita dehydrogenation affords 3-methoxybenz[a]anthracene (4). Vilsmeier reaction on the dimethoxydihydronaphthalene 5 gives the versatile dimethoxydihydronaphthaldehyde 6 which has been converted to the dimethoxybenzo[c]fluorene 7 by direct cyclodehydration and the fulvene 10 by cyclodehydration of allylic alcohol 8 derived from 6 followed by dehydrogenation. The saturated alcohol 12 corresponding to 8 undergoes cyclodehydration to give the dimethoxyhexahydrobenzo[c]phenanthrene (13). Some of the advantages of the Vilsmeier approach to PAH have been pointed out.

Structure of pentacyclo[7.4.2.02,6.06,15.011,14]pentadec-4-ene-7,13-dione, a novel pentacyclic C15 quinane system

C 15H 1602 (a synthetic precursor to dodecahedrane), monoclinic, P21/n, a = 12.171 (5), b = 6.976(5), c = 13.868 (3) A, B = 102.56 (3) ° , Z = 4, D m = 1.30, D c = 1.318 g cm -3, F(000) = 488, g(Mo K¢t) = 0.92 cm- 1. Intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.077 (R w = 0.076) for 1337 observed reflections. All the five-membered rings are cis fused and have envelope (C s symmetry) conformations.

Presence of Lipids in Mycobacteriophage 13

The presence of lipids has been demonstrated in mycobacteriophage 13. The total lipid was composed of 69% phospholipids and 31% neutral lipids. More than two-thirds of phospholipids present in the phage were synthesized in the host prior to infection. The fatty acid composition of the phage differed markedly from that of its host, both in chain length and the degree of saturation. The phage lipid was mostly composed of saturated fatty acids of which more than 50% were short chain fatty acids. Changes in growth temperatures reflected variations in fatty acid composition, characteristic of the phage, and which were distinctly different from those of the host. Electron microscopic observations revealed that the phage has a membranous bilayer structure. The presence of lipids may facilitate the phage-host interaction especially in lipid-rich organisms like mycobacteria.

Evolution of Grain-Boundary Microstructure and Texture in Interstitial-Free Steel Processed by Equal-Channel Angular Extrusion

The equal-channel angular extrusion (ECAE) of Ti-bearing interstitial-free (IF) steel was performed following two different routes, up to four passes, at a temperature of 300 degrees C. The ECAE led to a grain refinement to submicron size. After the second pass, the grain size attained saturation thereafter. The microstructural analysis indicated the presence of coincident-site lattice (CSL) boundaries in significant fraction, in addition to a high volume fraction of high-angle random boundaries and some low-angle boundaries after the deformation. Among the special boundaries, Sigma 3 and Sigma 13 were the most prominent ones and their fraction depended on the processing route followed. A deviation in the misorientation angle distribution from the Mackenzie distribution was noticed. The crystallographic texture after the first pass resembled that of simple shear, with the {112}, {110}, and {123} aligned to the macroscopic shear plane.