Gezielte Konformationsänderungen an cyclischen Systemen, 2. Mitt.: Konformere 2-Phenyl-1,3-dithiane

In 2-phenyl-1.3-dithiane (1) and its p-methyl derivative (2) theequatorial phenyl adopts a conformation coinciding with the symmetry plane of the molecule. For 2-(2′-methylphenyl)-1.3-dithiane (4) acisoid relation of theaxial hydrogen on C-2 and the aromatic methyl group was established. This conformation can be changed by substitution of position 2 by methyl: in this geminally substituted compound (3), phenyl no longer assumes theequatorial position, and the plane of the phenyl group isperpendicular to the symmetry plane of the molecule. These deductions depend on the deshielding effect of sulphur and the diamagnetic anisotropy of the aromatic ring in the NMR spectra influencing the chemical shifts of the orthoprotons and of the protons of the dithiane ring respectively. The influence of the conformation on both of these effects is taken into account.     

Diffusion of protons in silica hydrogel

The effect of preparation pH of silica hydrogel on the effective diffusion coefficient of protons in silica hydrogel (D _e , m²/s), on surface area of silica gel (S, m²/s) and on particle size of silica gel (D _p , mm) was studied. Silica hydrosols were obtained by adding water glass to sulfuric acid. The effective diffusion coefficient of proton in silica hydrogel was determined by the method of diffusion from silica hydrogel plane sheet to a stirred solution of a limited volume. A numerical solution was obtained for the diffusion equation using the Regula Falsi method. Regression analyses of experimental data were conducted.Diffusion of protons in silica hydrogel is a complicated process due to a decelerating effect of the porous structure of silica hydrogel and to the accelerating effects of slow ions such as Na⁺ and surface diffusion. The effective diffusion coefficient increased with surface area of silica gel, indicating the diffusion of protons on the surface of the silica particles.     

Zur Anwendbarkeit von Ringstrommodellen in der Konformationsanalyse

The classical (Johnson-Bovey) and quantum mechanical (Haigh-Mallion) approach accounting for the shielding contribution to protons in the proximity of aromatic nuclei are compared with respect to their applicability in conformational analysis. This is accomplished by means of the¹H-NMR spectra of various cyclophanes their geometries being fairly well known from X-ray data or other independent methods. The chemical shifts of the monitor protons (all of them being situated above or below the plane of the benzene ring considered) are consistent with shielding effects predicted by the classical theory notwithstanding the fact that the benzene hexagons are not strictly planar in any of these systems. In contrast, the quantum mechanical treatment considerably underestimates the shielding of protons in those regions.

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Mit 2 Abbildungen     

The structure of the proton skeleton in 1,3-butadieneiron Tricarbonyl as determined from the NMR spectra of oriented molecules

¹H NMR spectra of 1,3-butadieneiron tricarbonyl oriented in a nematic liquid crystal solvent have been analysed and used to derive the structure of the proton skeleton, which is found to be non-planar. The distance of the anti protons from the plane defined by the remaining four protons is 0.77 ± 0.06 ±.     

New tables of ‘ring current’ shielding in proton magnetic resonance

A new theory⁶ for ‘ring current’ effects on the chemical shifts of protons in or out of the plane of a benzene ring is summarized, and pictorially compared with the predictions of the earlier semi-classical theory of Johnson and Bovey.¹ In the Appendix are presented extensive numerical tables of the predicted shieldings.     

Synthesis and characterization of intermediate sitting-atop (i-SAT) complexes of free base meso-tetraarylporphyrins and tin(IV) chloride

The reaction of meso-tetraarylporphyrins (H₂T(X)PP) with SnCl₄ affords green intermediate sitting-atop (i-SAT) complexes, [(H₂T(X)PP)SnCl₄]. UV–Vis, ¹H NMR and ¹³C NMR spectral data show that the porphyrin core of the complexes is distorted, thus two nitrogen atoms of the pyrrolenine groups on one side of the porphyrin plane act as electron donors to the tin center of SnCl₄. The intermediate sitting-atop (i-SAT) complex is formed each time during the incorporation of the metal center, where in the intermediate state the pyrrolic protons still remain on the porphyrin.     

A reassignment of the 13C-NMR spectrum of the alkaloid ajmaline through the use of two-dimensional nmr techniques

The reassignment of the ¹³C chemical nmr spectrum of the alkaloid, ajmaline, is reported. An earlier assignment based on analogy to other alkaloids and deductions from molecular orbital theory was found to be partially in error. The present study uses broadband decoupled (both dimensions) proton-carbon shift correlation and long-range proton-carbon chemical shift correlation techniques. These experiments, in conjunction with earlier work by others on the assignment of the proton spectra, suffice to now unequivocably assign the ¹³C nmr spectrum of the title compound.     

1H NMR spectra. Part 30: 1H chemical shifts in amides and the magnetic anisotropy,electric field and steric effects of the amide group

The ¹H spectra of 37 amides in CDCl₃ solvent were analysed and the chemical shifts obtained. The molecular geometries and conformational analysis of these amides were considered in detail. The NMR spectral assignments are of interest, e.g. the assignments of the formamide NH₂ protons reverse in going from CDCl₃ to more polar solvents. The substituent chemical shifts of the amide group in both aliphatic and aromatic amides were analysed using an approach based on neural network data for near (≤3 bonds removed) protons and the electric field, magnetic anisotropy, steric and for aromatic systems π effects of the amide group for more distant protons. The electric field is calculated from the partial atomic charges on the N.C═O atoms of the amide group. The magnetic anisotropy of the carbonyl group was reproduced with the asymmetric magnetic anisotropy acting at the midpoint of the carbonyl bond. The values of the anisotropies Δχ_parl and Δχ_perp were for the aliphatic amides 10.53 and ?23.67 (×10^?6 ų/molecule) and for the aromatic amides 2.12 and ?10.43 (×10^?6 ų/molecule). The nitrogen anisotropy was 7.62 (×10^?6 ų/molecule). These values are compared with previous literature values. The ¹H chemical shifts were calculated from the semi‐empirical approach and also by gauge‐independent atomic orbital calculations with the density functional theory method and B3LYP/6–31G⁺⁺ (d,p) basis set. The semi‐empirical approach gave good agreement with root mean square error of 0.081 ppm for the data set of 280 entries. The gauge‐independent atomic orbital approach was generally acceptable, but significant errors (ca. 1 ppm) were found for the NH and CHO protons and also for some other protons. Copyright © 2013 John Wiley & Sons, Ltd.     

Conformational preferences of 2-methoxy-acetophenone

On the basis of the presence or absence of long-range spin–spin coupling constants between side–chain and ring nuclei in 2-methoxyacetophenone, some literature ambiguities about the conformational preferences of the side-chains in this compound can be resolved. The long-range coupling between the methoxy protons and the ring proton ortho to the methoxy group, ⁵J(H, CH₃)o, is (?)0.28 ± 0.02 Hz, as expected for a conformation in which the methoxy group lies in the benzene plane and cis to H-3. The methyl protons of the acetyl group do not couple to H-6, implying that this methyl group does not approach H-6 closely. However, the ¹³C nucleus of this methyl group couples by +0.4 Hz to H-5 and not to H-3. This stereospecific five-bond coupling implies that the acetyl group predominantly prefers an arrangement in which the carbonyl group lies trans to the other substituent, as would be expected electrostatically. Large twists out of the ring plane are not consistent with the observed couplings.     

470—The proton pump at work: Part I. The basic concept of excess proton/defect proton translocation

The Nagle-Morowitz proton pump, which is based on proton transport in water and ice, is shown to be inapplicable to weakly H-bonded proton transport systems. It is demonstrated that in weakly or non H-bonded systems protons can migrate either as excess protons H using a high-lying proton conduction band or as defect protons H′ using intermediate energy levels. As H? the protons act as positive charge carriers endowed with a very high mobility. As H′ they act as negative charge carriers. The H′ transport mechanism involves thermally activated proton tunneling. Owing to the very large mobility differences between H? and H′, > 10⁶, very high potentials can be self-generated in any situation which creates a concentration gradient. Proton conductivity data on inorganic model compounds are presented. Applying these results to proton transport across biomembranes, transmembrane potentials U_m, acidification Δ pH and transient phenomena can be explained as result of H? and H′ translocation.     

Zundel‐like and Eigen‐like Hydrated Protons on a Platinum Surface

The nature of hydrated protons is an important topic in the fundamental study of electrode processes in acidic environment. For example, it is not yet clear whether hydrated protons are formed in the solution or on the electrode surface in the hydrogen evolution reaction on a Pt electrode. Using mass spectrometry and infrared spectroscopy, we show that hydrogen atoms are converted into hydrated protons directly on a Pt(111) surface coadsorbed with hydrogen and water in ultrahigh vacuum. The hydrated protons are preferentially stabilized as multiply hydrated species (H₅O₂⁺ and H₇O₃⁺) rather than as hydronium (H₃O⁺) ions. These surface‐bound hydrated protons may play an important role in the interconversion between adsorbed hydrogen atoms and solvated protons in solution.     

Sensor activity, photodegradation and photostabilisation of a PAMAM dendrimer comprising 1,8-naphthalimide functional groups in its periphery

The colouristic and fluorescent characteristics of a new composite material based on a PAMAM dendrimer of second generation whose periphery is modified with 4-N,N-dimethylaminoethylamino-1,8-naphthalimide and polyamide-6 have been investigated. This dendrimer has been investigated with regard to its application as a heterogenic sensor capable of detecting metal cations and protons in aqueous solutions. In the presence of metal cations (Ni²⁺, Fe²⁺, Fe³⁺ and Co²⁺) and protons the fluorescence intensity of the composite increases due to their coordination with dendrimer molecule. The results obtained reveal the capacity of this system to act as a sensitive sensor of environmental pollution by metal cations and protons. It has been shown that in N,N-dimethylformamide solution the metal cations inhibit the processes of photodegradation of the dendrimer.     

Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand

A novel nickel(II) complex [Ni(L)₂Cl]Cl with a bidentate phosphinopyridyl ligand 6‐((diphenylphosphino)methyl)pyridin‐2‐amine (L) was synthesized as a metal‐complex catalyst for hydrogen production from protons. The ligand can stabilize a low Ni oxidation state and has an amine base as a proton transfer site. The X‐ray structure analysis revealed a distorted square‐pyramidal Ni^II complex with two bidentate L ligands in a trans arrangement in the equatorial plane and a chloride anion at the apex. Electrochemical measurements with the Ni^II complex in MeCN indicate a higher rate of hydrogen production under weak acid conditions using acetic acid as the proton source. The catalytic current increases with the stepwise addition of protons, and the turnover frequency is 8400 s^?1 in 0.1 m [NBu₄][ClO₄]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV.     

The effect of the internal reference on ASIS correlations: 2—The intrinsic ASIS of TMS protons in aromatic hydrocarbon solvents

A method is developed to calculate the intrinsic ASIS of TMS protons used as internal reference, based on linear correlation of the ASIS of a group of sensor protons in two fixed aromatic solvents. Several solute systems (p-X-benzaldehydes, camphor, α-Br-camphor, 5-X-furfurals, p-X-acetophenones and methyl ketones) are used to calculate a series of intrinsic ASIS values of TMS in 12 aromatic hydrocarbon solvents. The Δ^α _TMS values are used, in turn, to calculate the intrinsic ASIS of CHO protons in dimethylformamide and diphenylformamide, and of the CH₃ protons in diethyl ether and diisopropyl ether.     

Proton magnetic shielding in malonic acid by multiple pulse techniques

The proton NMR in single crystals of malonic acid has been studied by multiple pulse line narrowing techniques. The nuclear magnetic shielding tensors σ⁽ⁱ⁾ of all protons in malonic acid could be determined from the spectra. There are two magnetically distinct carboxyl protons. The principal components of their shielding tensors are found to be σ⁽¹⁾_ZZ= ?0.8 ppm, σ⁽¹⁾_YY = ?19.2 ppm, σ⁽¹⁾_XX = ?21.8 ppm, and σ⁽²⁾_ZZ = ?1.0 ppm, σ⁽²⁾_ZZ = ?21.3 ppm relative to adamantane. The error limits are estimated to be ± 1 ppm. The most shielded directions lie along the hydrogen bond directions to within 8 degrees. The least shielded directions are essentially perpendicular to the plane of the carboxyl groups. Within experimental accuracy the shielding of the aliphatic protons is axially symmetric about the CH bond axes. The anisotropy Δσ = σ_? ? σ_⊥ is (4 ± 1) ppm. The gross features of the anisotropy of the carboxyl protons are shown to be governed by the diamagnetic effect.     

Anisochrony of the O-methylene protons of the C-2-ethyl ester function in triethyl meso,cis-1,3-dimethylcyclohexane-1,2,3-tricarboxylate—Atropisomerism of an ester group

The methylene protons of the ethyl ester function at C-2 in triethyl meso, cis-1,3-dimethylcyclohexane-1,2,3-tricarboxylate (A) are anisochronous, despite the apparent symmetry of structure A. The necessary diastereotopy is thought to be engendered by the central ester being stabilized in a rotamerization in which the O:C·O plane is held parallel to the general plane of the 6-membered ring while fast exchanges take place among rotamers about the alkyl–oxygen bond; other rotamers about the ester axis are thought to encounter high order repulsive steric/polar interactions with the flanking ester functions and C-methyl groups. Evidence for the axial orientation of the C-1 and C-2 ester functions in A, based on comparisons of its ¹H NMR spectral characteristics with those of its RS-cis, trans and meso, trans analogues, is presented. The role of ion-pairing in the stereoselectivity of methylation of precursor enolates, leading to the formation of these three systems, is briefly discussed. A comment on the appropriateness, or otherwise, of drawing conformational conclusions from the magnitudes of the anisochrony in comparable systems is included. Triester A is thought to be the first instance where atropisomerism about an sp³? sp² bond involving an ordinary ester function has been detected employing a prochiral sensor group.     

1H NMR spectra part 31: 1H chemical shifts of amides in DMSO solvent

The ¹H chemical shifts of 48 amides in DMSO solvent are assigned and presented. The solvent shifts Δδ (DMSO‐CDCl₃) are large (1–2 ppm) for the NH protons but smaller and negative (?0.1 to ?0.2 ppm) for close range protons. A selection of the observed solvent shifts is compared with calculated shifts from the present model and from GIAO calculations. Those for the NH protons agree with both calculations, but other solvent shifts such as Δδ(CHO) are not well reproduced by the GIAO calculations. The ¹H chemical shifts of the amides in DMSO were analysed using a functional approach for near ( ≤ 3 bonds removed) protons and the electric field, magnetic anisotropy and steric effect of the amide group for more distant protons. The chemical shifts of the NH protons of acetanilide and benzamide vary linearly with the π density on the αN and βC atoms, respectively. The C=O anisotropy and steric effect are in general little changed from the values in CDCl₃. The effects of substituents F, Cl, Me on the NH proton shifts are reproduced. The electric field coefficient for the protons in DMSO is 90% of that in CDCl₃. There is no steric effect of the C=O oxygen on the NH proton in an NH…O=C hydrogen bond. The observed deshielding is due to the electric field effect. The calculated chemical shifts agree well with the observed shifts (RMS error of 0.106 ppm for the data set of 257 entries). Copyright © 2014 John Wiley & Sons, Ltd.     

The routine determination of boron,carbon, nitrogen and oxygen by charged-particle activation analysis

Normalized parameters for the determination of boron, carbon, nitrogen and oxygen are given. The irradiations are performed with 9 MeV protons or 7.5 MeV deutons. The beam current is measured with a Faraday cup and beam current fluctuations are corrected for by a computer calculation. The samples are automatically counted on a time schedule based upon the half-lives. Counting data are evaluated by means of computerized least squares decay analysis. Absolute sensitivity factors with the dimension dpm⁻¹ μA⁻¹(g/cm²)⁻¹ are determined.     

1H endor investigations in tris-sarcosine-calcium chloride doped with manganese

¹H ENDOR spectra of the ferroelectric tris-sarcosine-calcium chloride doped with Mn²⁺ are reported. All identified protons are located in CH₃ groups of sarcosine molecules. From the ENDOR data, the distances of the CH₃ protons from the manganese ion were determined.     

Structural Studies of Antarctic Fish Antifreeze Glycoproteins by One- and Two-Dimensional NMR Spectroscopy

Abstract

The solution structure of antifreeze glycoproteins (AFGP's) of the polar fish Tetramatomus borchgrevinki has been investigated by 2D ¹ H NMR spectroscopy as well as molecular modeling calculations (MM2). The simple glycotripeptide repeating structure in the shorter AFGP's (fractions 7 & 8) makes the structural analysis amenable. The resonance assignments of AFGP's 7 & 8 were determined by two-dimensional NMR techniques (COSY, Relayed-COSY, Phase Sensitive DQCOSY, NOESY). Information about the protein secondary structure was obtained by the coupling constants between the back-bone amide and α-carbon protons (obtained by phase sensitive COSY). Additional three dimensional constraints were obtained from NOESY through-space connectivities. The three dimensional solution structures of several AFGP's glycotripeptide fragments were based on MM2 calculations. The model structure was compared with the experimental data. Exchange rates of amide protons measured by dynamical spectroscopy show that the threonine and some of the alanine amide protons have two different and distinct exchange rates. GalNAc and the C-terminal Ala' amide protons appear to show relatively slow exchznge rates. The results suggets that the amide protons are not involved in any strong intramolecular hydrogen bonding.