Assignment of the 1H and 13C NMR Chemical Shifts of (3,4-Dihydro-2H-pyran-5-yl)-oxo-acetic Acid Methyl Ester Using the Two Dimensional HMBC Technique

The identification of (3, 4-dihydro-2H-pyran-5-yl)-oxo-acetic acid methyl ester has been realized by combination of two dimensional HETCOR and HMBC techniques. ¹³C and ¹H chemical shifts asignements are described.     

Determination of the Stereochemistry of Substituted 5-Methylenehydantoins and Thiohydantoins by 13C NMR and Homonuclear NOE Experiments

Basically the aim of this work is to define the accurate configuration of the exocyclic double bond of substituted 5-methylenehydantoins and thiohydantoins which have been conceived as potential Aldose Reductase inhibitors. A previsional survey based upon the chemical shifts analysis from ¹H and decoupled ¹³C NMR spectra discloses, for a part of the family of compounds, the assignment of the Zconfiguration for unsubstituted (2,3) and N-3 substituted (6,7,9) derivatives, and the E-configuration for the N-1 substituted (8,11) ones. The qualitative study with Homonuclear NOE (8,11) and the coupling constant measuring ^{3 J}C4-C=C-H6 from coupled ¹³C NMR (1–11), lead to the assignment of the accurate configuration of the whole family's compounds in agreement with the previsional study.     

A 15N NMR Study of Some Imidazolidine-2,4-Dichalcogen Derivatives

The ¹⁵N NMR chemical shifts and ¹(¹⁵N-¹H) coupling constants of a series of imidazolidine-2,4-dichalcogen (O, S) derivatives are reported.The ¹⁵N NMR chemical shifts show a linear correlatlon wlth the vNH stretchlng vlbratlons. The influence of the substitution of the oxygen at C₂ and/or C₄ with the sulphur, and of the hydrogen at C₅ wlth the methyls and phenyls has been considered. The ¹J(¹⁵N-¹H)'s found In thls serles of molecules agrees well with the expected values.     

13C NMR Chemical Shifts of Heterocycles: Empirical Substituent Effects in 5-Halomethylisoxazoles

Evaluation by empirically derived equations for the Substituent effect (α, β, γ, δ) on the ¹³C NMR chemical shifts for C-3, C-4. C-5 and halomethyl-substituent carbon (C-6) in isoxazoles 1-5 [where C-3 substituent (R¹) = H, alkyl or phenyl, C-4 Substituent (R²) = H, alkyl, and C-5 substituent (R³) = di-or trihalomethyl, methyl and H], taking as reference the compound la, is reported. From the calculated values for the α, β, γ, δ effects for each substituent it was possible to estimate the chemical shift of each carbon of the compounds 1–5. The ¹³ C chemical shifts of the C-3, C-4, C-5, C-6 of these compounds, can be estimated with good precision: 94% of the calculated chemical shifts are found to be within ±1.0ppm, and 100% are found to be within ±1.5ppm.     

Synthesis,Spectroscopic Characterization and Redox Reactivity of Some New N-(2,6-Di-Tert-Butyl-L-Hydroxyphenyl) Salicylaldimines

New substituted N- (2,6-Di-tert-butyl-l-hydroxyphenyl) Salicylaldimines (L_xH) were prepared by the condensation of various hydroxy and methoxy salicylaldehyde derivatives and 2,6-Di-tert-butyl-4-aminophenol and characterized by elemental analysis, IR, UV-Vis, ¹H NMR spectroscopy, as well as ESR studies of the oxidation products of L_xH. It was found that L_xH, unlike analogous electron-withdrawing C1, Br, NO₂ bearing derivatives, in the solid state exist both in associated and non-associated forms. UV-Vis and ¹H, NMR studies show that L_xH in solutions exists both in phenolimine and ketoamine tautomer forms. In addition, alcohol solutions of L_xH exhibited a new band in the region of 630-675 run. The ESR studies of one -electron oxidation of L_xH, in the condition of THF, CHC1₃ and toluene solutions at 300 K, indicate the formation of corresponding primary or secondary phenoxyl radicals. It was found that the stability and conversion pathway of the primary phenoxyl radicals are dependent upon both kind and position of the substituents in salicylaldehyde moiety of L_xH. For some L_xH without observation of primary phenoxyl radicals, the secondary Coppinger's type radical was detected. The ESR parameters of all radical intermediates have been determined.     

13C NMR Chemical Shift of β-Alkoxyvinylketones: II. Empirical Substituent Effects in β-Aryl-β-Methoxyvinyltrihalomethylketones

Evaluation by empirically derived equations for the substituent effect (α,β,γ,δ) on the ¹³C NMR chemical shifts for C-1, C-2, C-3 and C-4 in β-aryl-β-methoxyvinylhalomethylketones 1a-g to 2a-g [R³C(O)-CH=C(Ar)-OMe, where R³ = CCl₃, CF₃ and Ar = p-YC₆H₄ (Y = H, Me, MeO, F, Cl, Br, NO₂)], taking as reference the β-ethoxyvinyltrichloromethylketone (3), is reported. From the calculated values for the α,β,γ,δ effects for each substituent it was possible to estimate the chemical shift of each carbon of the compounds 1,2. The ¹³C chemical shifts of the C-1, C-2, C-3, C-4 of these compounds, can be estimated with good to rasoable precision: 84% of the calculated chemical shifts are found to be within ±1.0ppm, and 100% are found to be within ±1.5ppm. The Y-Effects on C-3 and C-4 are compared with carbon charge densities (qr).     

IR Evidences for N-9 and N-7 Regioisomers of the Acyclic Purine Nucleoside Analogues

The IR spectra have been recorded in the solid state for the parent molecule, 6-(N-pyrrolyl)purine (1) and its N-9-and N-7-substituted derivatives: 9-and 7-(2-hydroxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (2 and 3), 9-and 7-(2-acetoxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (4 and 5), 9-and 7-(2,3-dihydroxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (6 and 7) as well as 9-and 7-(2,3-diacetoxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (8 and 9). Analysis of the characteristic bands has proved to be useful in differentiating between N-9 and N-7 regioisomers.     

1H and 13C NMR Spectra of Alditolyl Derivatives of 3-Hydrazino-5-Methyl[1,2,4]triazino[5,6-b]indole and Their Cyclized Products.

The ¹H and ¹³C NMR spectra of sugar (5-methyl [1, 2, 4]-triazino [5, 6-b] indol-3-yl) hydrazones (1), per-0-acetyl aldehydo sugar 1-acetyl-1-(5-methyl [1, 2, 4] triazino [5, 6-b]-indol-3-yl) hydrazones (2), l- (penta-0-acetyl-pentitol-1-yl)-10-methyl [l, 2, 4] triazolo [3′, 4′:3, 4] [l, 2, 4] triazino [5, 6-b]-indoles (3) have been investigated. The 2 D NMR (H, C COSY) spectrum of 2a has been studied.     

13C NMR Chemical Shifts of β-Alkoxyvinyl Ketones: III✠-Empirical Substituent Effects in 1-Alkylamino-6-Ethoxy-1,5-Hexadien-3,4-Diones and 1,6-bis(Alkylamino)-1,5-Hexadien-3,4-diones

Evaluation by empirically derived equations for the substituent effect (E_Xn and E_Yn, n = 1 to 6) on the ¹³C NMR chemical shifts for C-1, C-2, C-3, C-4, C-5 and C-6 in 1-alkylamino-6-ethoxy-1,5-hexadien-3,4-diones 1a-f and 1,6-bis(alkylamino)-1,5-hexadien-3,4-diones 2a-f [XCH=CHC(O)-C(O)CH=CHY, where X, Y = OEt, NH₂, PhCH₂NH, n-BuNH, i-PrNH, cyclo-C₆H₁₁NH, t-BuNH], taking as reference the 1,6-diethoxy-1,5-hexadien-3,4-dione (3), is reported. From the calculated values for the E_Xn and E_Yn effects for each substituent it was possible to estimate the chemical shift of each carbon of the compounds 1,2 with excellent precision: 100% of the calculated chemical shifts are found to be within ±0.5ppm. The carbon-13 chemical shifts of C-1, C-2 and C-3 of compounds 1a,2a,3 led a good correlation with carbon charge densities (qr).     

NMR Study of Pentafluoroaniline - Hydrogen Bonding and Proton Exchange

The temperature and concentration dependence of ¹H NMR chemical shifts of pentafluoroaniline and aniline in acetone (Ac), dimethylsulphoxide (DMSO) and hexamethylphosphortriamide (HMPA) indicate that the effect of hydrogen bond formation, δ = δ_obs - δ_A' is similar for both anilines. The analysis of ¹H NMR spectra showed, that proton exchange of t-butyl alcohol (tBA) and 2,6-di-t-butylphenol (DTBPh) with pentafluoroaniline is slower than that with aniline.     

1H and 13C NMR Spectral Study of Some 2r-Aryl-6c-phenylthian-4-ones,Their 1-Oxides and 1,1-Dioxides

ABSTRACT

Four 2r-aryl-6c-phenylthian-4-ones 1b?1e and their 1-oxides 2b?2e and 1,1-dioxides 3b?3e have been newly synthesized. ¹H and ¹³C NMR spectra have been recorded for all these compounds and 2r,6c-diphenylthian-4-one 1-oxide 2a. ¹³C NMR spectrum has been recorded for the sulfone 3a of 1a. For selected compounds ¹H-¹H COSY, HSQC, HMBC, and NOESY spectra have been recorded. The vicinal proton–proton coupling constants suggest that in all these compounds, the heterocyclic ring adopts chair conformation with equatorial orientations of the aryl and phenyl groups. Proton and carbon chemical shifts suggest that in the sulfoxides, the S=O bond is axial and enhances the J _aa value by some special effect. The S = O bond causes a significant upfield shift even on carbons without hydrogens. Significant solvent shifts also were observed.     

The Influence on NMR Parameters of Silicon Penta Coordination in Silatranes

¹H, ¹³C, ¹⁹F and ²⁹Si NMR chemical shifts and coupling constants for Si-substituted silatranes, XSi(OCH₂CH₂)₃N, and triethoxysilanes, XSi(OCH₂CH₃)₃, where X = H, CH₃, and F have been studied. Expansion of the coordination numbers of silicon and tin leads to similar changes in the NMR parameters.     

Intermolecular Hydrogen Bonding and Dimeric Structures in Bilirubin Esters from 1H-NMR Spectroscopy

Analysis of the N-H ¹H-NMR chemical shifts of various bilirubin dimethyl esters indicates intermolecularly H-bonded dimers in CDCl₃ solution with pairwise pyrromethenone associations. The presence of an exo (C-2 or C-18) vinyl or ethyl group on the lactam ring leads to relatively weaker H-bonding as compared with an endo (C-3 or C-17) vinyl or ethyl group. Consequently, in a non-symmetric bilirubin, e.g. IXα, the endo-vinylpyrromethenone to endo-vinylpyrromethenone intermolecular H-bonding becomes much stronger (with more deshielded N-H proton chemical shifts) than in corresponding symmetric isomers, e.g. XIIIα or IIIα.     

Spectral and Computational Studies on Benzil Mono-(2-Pyridyl)Hydrazone

In the present study, structural properties of Mono-(2-Pyridyl) Hydrazone were studied extensively utilizing density functional theory (DFT) employing B3LYP exchange correlation. The Fourier transform infrared (solid phase) was recorded. The vibrational frequencies in the ground state were calculated by using density functional method (B3LYP) with 6-31G* and 6-311G** as basis sets. The spectral studies revealed that the title compound exists in Keto form. Spectral techniques that we employed include ¹H and ¹³C NMR, electronic, thermal techniques. Correlation between experimental chemical shifts and GIAO/B3LYP/6-311G**-calculated isotropic shielding constants, δ_exp = a + bσ_calc, are reported. Good linear regressions between experimental and theoretical results for ¹H and ¹³C were obtained.     

13C NMR Chemical Shifts of Heterocycles: 3∗. Empirical Substituent Effects in 2-Halomethyl-2-hydroxy-tetrahydrofurans and -5,6-tetrahydro-4H-pyrans

Abstract

Evaluation by empirically derived equations for the Substituent effect (α, β, γ, δ) on the ¹³C NMR chemical shifts for C-2, C-3, C-4, C-5, C-6, the halomethyl-substituted carbon (C-7) and the cyano or oxymic carbon (C-8) in 2-halomethyl-2-hydroxy-tetrahydrofurans 1a-c, 2, 3a, b, 4a and -5,6-tetrahydro-4H-pyrans 5a-c, 6a [with C-2-substituents (R²): CF₃, CCl₃ or CHCl₂, C-3-substituents (R³): CN, C(Me)=NOH, CH=NOMe, C(Me)=NOMe or CH=NOH], taking as reference the 2-trifluoromethyl-2-hydroxy-tetrahydrofuran (la), is reported. From the additivity properties of the α-, β-, γ-, δ-and ?-effects for each Substituent it is possible to predict the chemical shift of each carbon of the compounds 1–6.

     

Al and Si MAS NMR investigations of cordierite glass, μ- and α-cordierite

²⁷Al and ²⁹Si Magic-Angle Spinning NMR results are reported for conventionally prepared glass of cordierite stoichiometry (2MgO · 2Al₂O₃ · 5SiO₂), the metastable high-quartz solid solution (μ-cordierite) and the high-temperature polymorph of cordierite (α-cordierite). Both, ²⁷Al two-dimensional (2D) quadrupole nutation experiments and ²⁷Al satellite transition spectroscopy (SATRAS) have been applied to identify two different tetrahedrally-coordinated aluminium sites (AlO₄). SATRAS has been used to extract the quadrupole interaction parameters and their distribution, the isotropic chemical shifts and the relative populations of the different Al sites. Both, the ²⁷Al and ²⁹Si NMR results, lead to the conclusion that a perfect Si/Al disorder does not exist in these investigated cordierite samples.     

Natural Abundance 17O NMR Studies on Methyl N-Arylcarbamates: Torsion Angle and Electronic Effects

Natural abundance ¹⁷O NMR data for 14 substituted methyl N-arylcarbamates obtained in acetonitrile solution at 75°C are reported. The ¹⁷O NMR chemical shifts of hindered ortho N-arylcarbamates are shielded relative to unhindered ones; a quantitative relationship is observed between the carbonyl ¹⁷O NMR chemical shifts and molecular mechanics (MM2) predicted torsion angles. The carbonyl ¹⁷O NMR chemical shifts of meta and para substituted N-arylcarbamates are correlated with Hammett sigma constants.     

Solid-state NMR investigations of Si-29 and N-15 enriched silicon nitride

We compare ²⁹Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra from the two modifications of silicon nitride, α-Si₃N₄ and β-Si₃N₄, with that of a fully (²⁹Si, ¹⁵N)-enriched sample ²⁹Si₃¹⁵N₄, as well as ¹⁵N NMR spectra of Si₃¹⁵N₄ (having ²⁹Si at natural abundance) and ²⁹Si₃¹⁵N₄. We show that the ¹⁵N NMR peak-widths from the latter are dominated by J(²⁹Si–¹⁵N) through-bond interactions, leading to significantly broader NMR signals compared to those of Si₃¹⁵N₄. By fitting calculated ²⁹Si NMR spectra to experimental ones, we obtained an estimated coupling constant J(²⁹Si–¹⁵N) of 20 Hz. We provide ²⁹Si spin-lattice (T₁) relaxation data for the ²⁹Si₃¹⁵N₄ sample and chemical shift anisotropy results for the ²⁹Si site of β-Si₃N₄. Various factors potentially contributing to the ²⁹Si and ¹⁵N NMR peak-widths of the various silicon nitride specimens are discussed. We also provide powder X-ray diffraction (XRD) and mass spectrometry data of the samples.     

1H and C-13 Nuclear Magnetic Resonance of Tiaprofenic Acid

¹H-NMR spectrum of tiaprofenic acid in CDCI3 was obtained and proton chemical shifts from tetramethylsilane were assigned to each proton and set of equivalent protons of the molecule. The hydroxy proton of the carboxylic acid group was confirmed by deuterium exchange. The natural abundance C-13 nuclear magnetic resonance spectrum of the compound in CDCI3 was recorded using Fourier transorm technique. The chemical shifts of carbon resonances have been assigned on the basis of the chemical shift additivity theory and the signal multiplicity observed in the single frequency off-resonance decoupled (SFORD) spectrum. Also comparison with carbon chemical shifts of model compounds were useful.     

Structural Assignment of Stilbenethiols and Chalconethiols and Differentiation of Their Isomeric Derivatives by Means of 1H‐ and 13C‐NMR Spectroscopy

Abstract

The ¹H‐ and ¹³C‐NMR spectra of some substituted stilbenes and chalcones were assigned unambiguously on the basis of a combination of homo‐ (COSY) and heteronuclear (HETCOR) two‐dimensional methods, the chemical shifts, as well as spin‐coupling constants. The A_ik empirical parameters of the –O–C(S)–N(CH₃)₂, –S–C(O)–N(CH₃)₂, and –SH group were calculated to help predict the chemical shifts of substituted stilbenes, 4′‐nitrostilbenes, and chalcones. The ¹H‐ and ¹³C‐NMR spectra have been shown to be able to differentiate between the isomers of O‐stilbenyl (4, 5) and S‐stilbenyl N,N‐dimethylthiocarbamates (7, 8) as well as O‐chalconyl (6) and S‐chalconyl N,N‐dimethylthiocarbamates (9).