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.     

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).     

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).     

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.     

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.     

Assignment of 13C Resonances in the Phencyclone-Norbornadiene Adduct Via 2D NMR. 13C Evidence for Hindered Rotation of Unsubstituted Bridgehead Phenyl Rings

¹³C NMR chemical shift assignments were obtained for the Diels-Alder adduct of phencyclone with norbornadiene in CD₂Cl₂ and in CDCl₃ solution. The ¹³C spectrum at 50.3 MHz, as well as the ¹H spectrum at 200.1 MHz, show evidence for hindered rotation of the two unsubstituted bridgehead phenyl rings of the adduct at ambient temperatures. In CD₂Cl₂ solution, all 19 of the unique ¹³C nuclei of this molecule give rise to individual ¹³C resonances. The ¹H assignments which were made earlier, together with one-bond and long-range 2D heteronuclear correlation experiments, allowed the assignment of all ¹³C chemical shifts in the molecule.     

Analysis of 1H and 13C{1H} NMR Spectral Parameters and Geometries of Three Isomeric Diphenylbicyclo[2.2.1]Hept-5-Ene-2,3-Dicarboxylic Anhydrides

Diels-Alder adducts of 1,4-diphenyl-1,3-cyclopentadiene and maleic anhydride were investigated by recording the ¹H and ¹³C{¹H} NMR spectra of three isomeric diphenylbicyclo[2.2.1]hept-5-ene endo and exo 2,3-dianhydrides. the spectra were recorded in CD₂Cl₂ and analysed completely. the effect of the endo and exo configuration of the anhydride ring on the chemical shifts of the bridgehead phenyl protons is discussed. the ortho protons of the exo isomers resonate at higher field than those of the endo isomer, and the resonance pattern of the aromatic protons is narrower in the exo than the endo anhydride. the aromatic regions of the spectra are compared with the same regions of the ¹H NMR spectra of the earlier investigated addition products of 1,4-di-p-tolyl-1,3-cyclopentadiene and 1-phenyl-4-p-tolyl-1,3-cyclopentadiene with maleic anhydride. Chemical shifts of the bridge protons are explained on the basis of X-ray data of the compounds and MacroModel calculations on the minimum energy conformations.     

GIAO Calculations of Chemical Shifts in Ethene‐1,1,2,2‐tetrayltetramethylene tetrathiocyanate

Geometric optimization and gauge including atomic orbital (GIAO). ¹H and ¹³C NMR chemical shift calculations with Hartree–Fock (HF) method and density functional method (B3LYP), using the 6‐31G(d) and 6‐31+G(d) basis sets, are proposed as a tool to be applied in the structural characterization of ethene‐1,1,2,2‐tetrayltetramethylene tetrathiocyanate, thus providing useful support in the interpretation of experimental NMR data. Parameters related to linear correlation plot of computed versus experimental ¹³C NMR chemical shifts in DMSO‐d₆ are provided.     

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.     

13C NMR Chemical Shifts Substituent Effects of (E)- and (Z)-N-ethyl-N-Methylamides

Carbon-13 NMR chemical shifts of a series of (E)- and (Z)-N-ethyl-N-methylamides [RC(O)NEtMe, R=H, Me, Et, i-Pr, t-Bu, CF₃, ClCH₂, Cl₂CH, Cl₃C, BrCH₂, Br₂CH, Br₃C and ICH₂] are reported. The α-carbon and carbonyl carbon chemical shifts are correlated with the empirical α-substituent effect and Charton's electrical parameter ([sgrave]_I), respectively. The N-alkyl carbon resonances were attributed mainly to the γ- and δ-effects of R.     

Substituent effect study on δc values of the bridge group carbons in disubstituted cinnamyl aniline series

The ¹³C nuclear magnetic resonance (NMR) chemical shifts δ_c of bridge group carbons (C‐β, C‐α, and C═N) were measured in this work for a wide set of substituted cinnamyl anilines p‐XC₆H₄CH═CHCH═NC₆H₄Y‐p (X = NO₂, Cl, H, Me, MeO, or NMe₂; Y = NO₂, CN, CO₂Et, Cl, F, H, Me, MeO, or NMe₂) and were used to study the substituent effect. In the study on ¹³C NMR chemical shifts of the titled compounds with single substituent changed, for every bridge carbon δ_c, the effect of cinnamyl substituent X is opposite to that of aniline substituent Y. That is, the action of the same substituent on different aromatic rings is different from the ¹³C NMR chemical shifts, and for C‐β, C‐α, and C═N, the choice of correlation equation depends on the ratio ρ_F(Y)/ρ_R(Y). When the ratio ρ_F(Y)/ρ_R(Y) is close to 1, the chemical shifts of bridge carbons can be well correlated with the single‐parameter equation; otherwise, it is better to adopt the dual‐parameter equation for correlation, and the further the values of ρ_F(Y)/ρ_R(Y) stray from 1, the more suitable the corresponding δ_c values are to be correlated with the dual‐parameter equation. In the study on δ_c of model compounds with simultaneous variations of substituents X and Y, for δ_c(C═N), a multi‐parameter correlation equation is obtained, and the substituent cross‐interaction item Δσ² is suitable to scale the interaction between substituents; however, for δ_c(C‐α and C‐β), the substituent cross‐interaction item Δσ² is perhaps too small to be observed. The multi‐parameter correlation equations can be recommended to predict well the corresponding δ_c values of disubstituted cinnamyl anilines. Copyright © 2012 John Wiley & Sons, Ltd.     

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).     

CHHC and H–H magnetization exchange: Analysis by experimental solid-state NMR and 11-spin density-matrix simulations

A protocol is presented for correcting the effect of non-specific cross-polarization in CHHC solid-state MAS NMR experiments, thus allowing the recovery of the ¹H–¹H magnetization exchange functions from the mixing-time dependent buildup of experimental CHHC peak intensity. The presented protocol also incorporates a scaling procedure to take into account the effect of multiplicity of a CH₂ or CH₃ moiety. Experimental CHHC buildup curves are presented for l-tyrosine·HCl samples where either all or only one in 10 molecules are U–¹³C labeled. Good agreement between experiment and 11-spin SPINEVOLUTION simulation (including only isotropic ¹H chemical shifts) is demonstrated for the initial buildup (t_mix < 100 μs) of CHHC peak intensity corresponding to an intramolecular close (2.5 Å) H–H proximity. Differences in the initial CHHC buildup are observed between the one in 10 dilute and 100% samples for cases where there is a close intermolecular H–H proximity in addition to a close intramolecular H–H proximity. For the dilute sample, CHHC cross-peak intensities tended to significantly lower values for long mixing times (500 μs) as compared to the 100% sample. This difference is explained as being due to the dependence of the limiting total magnetization on the ratio N_obs/N_tot between the number of protons that are directly attached to a ¹³C nucleus and hence contribute significantly to the observed ¹³C CHHC NMR signal, and the total number of ¹H spins into the system. ¹H–¹H magnetization exchange curves extracted from CHHC spectra for the 100% l-tyrosine·HCl sample exhibit a clear sensitivity to the root sum squared dipolar coupling, with fast buildup being observed for the shortest intramolecular distances (2.5 Å) and slower, yet observable buildup for the longer intermolecular distances (up to 5 Å).     

C-13 and H-1 NMR Assignments of the Chamigrenes Prepacifenol and Dehydroxyprepacifenol Epoxioes

A complete assignment of the signals in the ¹H and ¹³C NMR spectra and the stereostructural analysis of the compounds prepacifenol epoxide and the new dehydroxyprepacifenol epoxide are presented. These compounds were extracted from the marine mollusc Aplysia dactylomela and represent the first occurrence of chamigrenes found in Brazilian waters. The NMR analyses are supported by NOE difference and COSY experiments and also by gradient selected HMBC, HSQC-TOCSY and HSQC-DE. ¹H spectra simulations were done for the final fitting of the chemical shifts and coupling constants.     

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.     

On the significant relativistic heavy atom effect on 13C NMR chemical shifts of β- and γ-carbons in seleno- and telluroketones

Unexpectedly large ‘Heavy Atom on Light Atom’ (HALA) effects have been found in ¹³C NMR (Nuclear Magnetic Resonance) chemical shifts of β- and γ-carbons of seleno- and telluroketones established by means of the high-accuracy calculations of ¹³C NMR chemical shifts in three representative real-life compounds, 2,2,5,5-tetramethyl-3-cyclopentene-1-selone, selenofenchone and 1,1,3,3-tetramethyl-1,3-dihydro-2H-indene-2-tellurone. The proposed computational scheme consists of the combination of accurately correlated coupled-cluster singles and doubles model approach for the non-relativistic calculations of shielding constants taking into account the solvent, vibrational and relativistic corrections, the latter obtained within the 4-component fully relativistic gauge-including atomic orbitals KT2 approach resulting in a very good agreement of the performed calculations with the experiment. The stereochemical dependence of the ‘long-range’ γ-HALA effect on the dihedral angle has been established in the model seleno- and telluroketones providing the largest shielding effect in the orthogonal orientation of the X=C_α–C_β–C_γ (X=Se, Te) moiety.     

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.     

Deuterium Nuclear Spin–Lattice Relaxation Times and Quadrupolar Coupling Constants in Isotopically Labeled Saccharides

¹³C and ²H spin–lattice relaxation times have been determined by inversion recovery in a range of site-specific ¹³C- and ²H-labeled saccharides under identical solution conditions, and the data were used to calculate deuterium nuclear quadrupolar coupling constants (²H NQCC) at specific sites within cyclic and acyclic forms in solution. ¹³C T₁ values ranged from 0.6 to 8.2 s, and ²H T₁ values ranged from 79 to 450 ms, depending on molecular structure (0.4 M sugar in 5 mM EDTA (disodium salt) in ²H₂O-depleted H₂O, pH 4.8, 30°C). In addition to providing new information on ¹³C and ²H relaxation behavior of saccharides in solution, the resulting ²H1 NQCC values reveal a dependency on anomeric configuration within aldopyranose rings, whereas ²H NQCC values at other ring sites appear less sensitive to configuration at C1. In contrast, ²H NQCC values at both anomeric and nonanomeric sites within aldofuranose rings appear to be influenced by anomeric configuration. These experimental observations were confirmed by density functional theory (DFT) calculations of ²H NQCC values in model aldopyranosyl and aldofuranosyl rings.     

13C-Nmr Spectroscopy of β-Nitrostyrenes. II. Mono-, Bi- and Tri-Methoxy Phenyl-Substitutions and Long Distance Electronic Effects

By means of ¹³C-NMR spectroscopy and AM1 molecular orbital calculations of mono-, bi- and tri-methoxy-β-nitrostyrenes at the meta and para positions, we have characterized a long distance electronic charge transfer pattern on the ethylenic bridge (CH=CH) and on the aromatic ring (Ph) carbon centers, determined by the electron-donor nature of the methoxy-substituent groups.

After a complete spectral assignment of the ¹³C-NMR signals, we have found a functional dependence of the chemical shifts on the C₁ and C_β centers respect to the C₄ and C₃ methoxy subtitution sites on the aromatic ring, while in the same molecular series C_alfa-chemical shifts are practically constants. on the other hand, the ¹³C-NMR chemical shifts of the C₃ and C₄ centers plus the analysis of the AM1 electronic charge density have permitted us determine the long distance charge transfer effect induced by the C₄ methoxy substitutions as well as the attenuation of this effect due to the C₃ methoxy substitutions.     

Proton Dynamics in Letovicite, (NH4)3H(SO4)2: A H and N NMR Spectroscopic Study

The improper ferroelastic phase letovicite (NH₄)₃H(SO₄)₂ has been studied by ¹H MAS NMR as well as by static ¹⁴N NMR experiments in the temperature range of 296–425 K. The ¹H MAS NMR resonance from ammonium protons can be well distinguished from that of acidic protons. A third resonance appears just below the phase transition temperature which is due to the acidic protons in the paraelastic phase. The lowering of the second moment M₂ for the ammonium protons takes place in the same temperature range as the formation of domain boundaries, while the signals of the acidic protons suffer a line narrowing in the area of T_c. The static ¹⁴N NMR spectra confirm the temperature of the motional changes of the ammonium tetrahedra. Two-dimensional ¹H NOESY spectra indicate a chemical exchange between ammonium protons and the acidic protons of the paraphase.