Substituent and temperature controlled tautomerism: Multinuclear magnetic resonance, X-ray, and theoretical studies on 2-phenacylquinolines

Proton-transfer equilibria in chloroform solution of twelve 2-phenacylquinolines were studied by 1H, 13C and 15N NMR spectroscopies. The (Z)-enaminone form stabilized by an intramolecular hydrogen bond was found to prevail in all cases. Electron-donating substituents in the phenacyl part of the molecule lead to an increase of the ketimine form (to 33% for p-NMe2). Variable temperature 1H NMR measurements show that higher temperatures have the same effect. The negative logarithm values of the equilibrium constant, pKT, were found to be linearly dependent on Hammett σ substituent constants. The pKTvs. temperature correlation also has a linear character. In general, strong electron-withdrawing…

ortho-Substituent effects inN-arylacetamides. NMR and molecular mechanics investigation

1H, 13C, 15N and 17O NMR spectra of N-phenylacetamide (acetanilide) and 21 ortho-substituted acetanilides were measured and assigned. The observed NMR parameters are related to the Hammett substituent parameters and conformational characteristics of the acetamido moiety estimated by molecular mechanics calculations. Significant relationships were found for the 13C NMR chemical shifts of C-5 (para to substituent) and the direct spin–spin coupling constant, 1J(C, H), of C-3 (ortho to substituent) with Hammett substituent parameters. For 15N NMR chemical shifts of the amido nitrogen, no general correlation with the Hammett substituent parameters was found. The interactions between functionalit…

Structural study of ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates: conformation and transmission of substituent effects across the diazabicycloheptene ring

Nine new ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates were prepared by a [4 + 2] cycloaddition and their FTIR, 1H, 13C and 15N NMR spectra were measured and assigned. Single crystals were grown for five compounds and their X-ray data were obtained. The electronic structure and the conformations were calculated by the semi-empirical AM1 method. Using correlations between the spectral, empirical and theoretical structural data, the transmission of substituent effects and the preferential conformation connected with the consecutive double nitrogen inversion and regarding the mutual orientation of NH and CO bonds were investigated. The results are compared with those f…

?-Phenylsulfonyl-N-arylacetamides (?-phenylsulfonylacetanilides):1H,13C and15N NMR spectral characterization

119Sn-NMR Study on Bis(Tri-Butyltin)oxide Derivatives of Phenolic Compounds

Abstract 119Sn-NMR spectroscopy has been utilized in the characterization of various phenolics as their bis(tri-butyltin)oxide, TBTO, derivatives. The present method has been applied both for determination of simple model compounds and for characterization of complex biopolymeric material originating from spent bleach liquor fractionated by an ultrafiltration technique. Based on the large range of 119Sn-NMR chemical shifts of TBTO derivatives of the phenolic compounds and the similar relaxation properties of 119Sn nuclei located in those derivatives, both qualitative and quantitative analytical conclusions can be drawn.

1H, 13C and 17O NMR spectral study of chlorinated 3,4-dihydroxybenzaldehydes (protocatechualdehydes)

Abstract Chlorinated 3,4-dihydroxybenzaldehydes have been studied by means of 1 H, 13 C and 17 O NMR spectroscopy. The 1 H and 13 C NMR spectral assignments are based on 2-dimensional 13 C- 1 H chemical shift correlation spectroscopy (COSY). The 17 O NMR measurements at natural isotope content in organic solvents are problematic owing to the poor solubility of the compounds and/or broadness of the resonance lines. In aqueous alkaline solutions, however, all protocatechualdehydes exhibit “easy-to-detect” 17 O NMR spectral characteristics. The 17 O NMR chemical shifts in the range of 140–480 p.p.m. are interpreted as arising from the different canonical structures of formyl substituted phenol…

1H,13C,17O and19F NMR spectroscopic study of isomeric ring-substituted monofluoro-(E)-3-phenylpropenals

Isomeric ring substituted monofluoro-(E)-3-phenylpropenals (cinnamaldehydes) were synthesized in order to provide, with the NMR-active 19F nucleus, an insight into the influence of substituents and the transmission of electronic effects between the aromatic ring and the side-chain. Their 1H, 13C and 17O NMR chemical shifts and their nJ(H,H), nJ(H,F), nJ(C,H) and nJ(C,F) values were determined. Generally, the nJ(C,F) coupling constants correlate with the length of the coupling route and thus simplify the assignments of the 13C NMR spectra. Only the side-chain carbons C-2 and C-3 in the ortho-substituted compounds showed an exception to this rule. Many long-range nJ(H,F) (n = 4–7) values were…

Predominance of inductive over resonance substituent effect on33S NMR chemical shifts of 4-substituted phenyl-4′-methylphenacyl sulfones

33S NMR chemical shifts have been determined for the first time for a series of 10 substituted phenacyl sulfones. Electron-withdrawing and electron-releasing substituents in 4-substituted phenyl-4′-methylphenacyl sulfones, p-MeC6H4COCH2SO2C6H4R-p, cause a ‘reverse’ substituent effect on the 33S NMR resonance. Dual-substituent parameter (DSP) analysis of δ(33S) values revealed that the inductive effect of the substituent predominates over its resonance effect. This finding shows that the 33S NMR chemical shifts are of importance in estimating the electronic properties of sulfur-containing compounds. The 13C and 17O NMR chemical shifts of the title compounds are also discussed. Copyright © 19…

Multinuclear magnetic resonance study of 1,3,3-trimethylbicyclo [2.2.1]heptan-2-one (fenchone) oxime, its five monochloro derivatives and a dehydrochlorination product

Fenchone oxime, 5-exo-chlorofenchone oxime, 6-exo-chlorofenchone oxime, 7-anti-chlorofenchone oxime, 8-chlorofenchone oxime, 9-chlorofenchone oxime and a dehydrochlorination product of 10-chlorofenchone oxime were synthesized from fenchone and the corresponding chlorofenchones. The 1H, 13C and 17O NMR spectra of the oximes and the dehydrochlorination product were recorded. The NMR data were compared with the corresponding parameters obtained earlier for fenchone and monochlorofenchones in order to determine the differences between the carbonyl and oxime substituents from the NMR spectroscopic point of view, and to assign the stereochemistry of the oxime group. This stereochemistry could not…

NMR spectroscopy in environmental chemistry:1H and13C NMR chemical shift assignments of chlorinated dibenzothiophenes based on two-dimensional NMR techniques andab initio MO and DFT/GIAO calculations

Methods for the Identification of Tainting Terpenoids and other Compounds from Algae

Off-flavour compounds produced by algae in freshwater ecosystems were studied for their structure using integrated sensory and spectroscopic methods: mass spectrometry (MS), nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR). Both solvent extraction and thermal desorption were used to isolate and to introduce the compounds into gas chromatography/mass spectrometry (GC/MS) and gas chromatography/Fourier transform infrared (GC/FTIR) systems. Ten ng of a terpenoid compound gave a readable IR spectrum. For 1H NMR studies the compounds were collected directly into NMR solvent by preparative gas chromatography. About 5 µg of a monoterpenoid compound was needed for a reliable 1…

Predominance of 2-arylhydrazones of 1,3-diphenylpropane-1,2,3-trione over its proton-transfer products

2-Phenylhydrazones of 1,3-diphenyl-1,2,3-trione are the dominant tautomeric form detected in chloroform solution by 15N NMR chemical shifts. The substituent in the phenylhydrazone moiety does not affect this tautomeric preference. The substituent effect is transmitted effectively only to the hydrazone nitrogen and hydrogen atoms. Ab initio calculations show that the ketohydrazone tautomer is really very much favoured over its proton-transfer products in chloroform solution. The same tautomer was also detected in the crystal state by X-ray crystallography. Copyright © 2001 John Wiley & Sons, Ltd.

The identification of vicinally substituted cyclohexane isomers in their mixtures by 1H and 13C NMR spectroscopy.

The radical addition reactions of organobromine compounds, XBr (X = CH2COOMe, PhCH2, CHBr2 and CCl3) with cyclohexene afforded mixtures of cis/trans isomer pairs of 1-X-2-Br-cyclohexanes. In addition to benzyl benzoyloxy derivatives are formed also, when benzoyl peroxide is used as an initiator. Owing to the great difficulties in separating these cis/trans isomer pairs, they are identified directly in their mixtures by NMR spectroscopy. In addition to one-dimensional (ID) 1H, proton decoupled 13C and DEPT-135, also two-dimensional (2D) 13C-13C INADEQUATE as well as 1H-13C HMQC experiments have been used in assigning the signals of each compound in their mixtures. The identification of each …

Multinuclear NMR study of 1,3,3-trimethylbicyclo[2.2.1]heptan-2-one (fenchone) and its six monochlorinated derivatives

1H, 13C and 17O NMR spectra of fenchone and six monochlorofenchones have been recorded. The second-order 1H NMR spectra were analysed by an iterative computer program. The 1H and 13C chlorine-induced substituent chemical shifts (SCS) were calculated. The vicinal coupling constants proved to be essential in the assignment of the chemical shifts of the geminal methyls. No clear correlation was observed between the chemical shifts of the carbonyl oxygen and the carbonyl carbon. All monochlorofenchones were previously unknown compounds and were synthesized for this work.

Multinuclear magnetic resonance, electrospray ionization time-of-flight mass spectral and molecular modelling characterization of lithocholic acid amide esters with various nitrogen heterocycles

1H, 13C and 15N NMR and electrospray ionization time-of-flight mass spectrometric characterizations of five lithocholate esters of piperazine diamides are described. Two of them are cholaphane-type cyclic structures esterified with 2,2′-bipyridine-4,4 ′ - and pyridine-2,6-dicarboxylic acid and the other three esters are open structures comprising two or four lithocholyl residues. The conformational preferences of the dimeric congeners were examined by using molecular modelling and variable-temperature 1H NMR techniques. Copyright © 2003 John Wiley & Sons, Ltd.

Predominance of resonance over polar effects on1H,13C and15N NMR substituent chemical shifts inN-arylglycines

N,N-Di-n-octyl-N,N-dimethyl and N,N-di-n-nonyl-N,N-dimethyl ammonium cholates: 13C and 15N CPMAS NMR, powder X-ray diffraction and thermoanalytical characterization

Abstract N,N-Di-n-octyl-N,N-dimethyl cholate (1) and N,N-di-n-nonyl-N,N-dimethyl ammonium cholate (2) have been prepared by crystallization from equimolar mixtures of sodium cholate and quaternary N,N-di-n-alkyl-N,N-dimethyl (n-octyl or n-nonyl) ammonium bromides. The formed crystalline materials have been structurally characterized by 13C and 15N cross polarization magic angle spinning (CPMAS) NMR, powder X-ray diffraction (PXRD) and thermoanalytical (TGA/DTA and DSC) methods and compared with each other. Powder X-ray diffraction patterns of 1 and 2 reveal clear similarities. Combined with the thermoanalytical data of these structures an existence of two hydrated polymorphs (most probably …

trans-4-tert-Butyl-1-methylcyclohexanol hemihydrate

The title compound, C11H22O·0.5H2O, is a hemihydrate of trans-4-tert-butyl-1-methyl­cyclo­hexa­nol, containing one water and two organic mol­ecules in the asymmetric unit. Crystals were obtained from an NMR sample by very slow evaporation of the solvent. In the solid state, the title compound forms a double-layered structure with the organic and water mol­ecules connected by O—H⋯O hydrogen bonds.

Nitramino, NRNO2 (R = H, CH3), as a substituent.13C and15N NMR spectroscopic study of nitraminobenzenes and -pyridines

In order to clarify the special properties of the aryl-bound nitramino substituent NRNO 2 (R=H, CH 3 ), 13 C and 15 N NMR spectra of six nitraminobenzenes and nine nitraminopyridines were measured in DMSO-d 6 and their chemical shifts assigned. 1 H NMr chemical shifts and spin-spin coupling constants of all the compounds were also determined. In contrast to the behaviour of nitropyridines or -benzenes studied previously, most of the present compounds gave very broad 17 O NMR lines even at elevated temperatures and their 17 O NMR data were not useful for any reliable conclusions

Substituted methyl 5β-cholan-24-oates II.13C NMR spectral assignment

The 13C NMR spectra were recorded and assigned for nine derivatives of methyl 5β-cholan-24-oates (esters of bile acids) including hydroxy, oxo and/or acetyloxy groups. Assignments were based on the empirical substituent-induced chemical shifts (SCS), spectral comparison with compounds of similar structure, distortionless enhancement by polarization transfer (DEPT) and proton coupled 13C NMR measurements.

Structural, Thermoanalytical and Molecular Modeling Studies on N-(3-hydroxypropyl) 3a,12a-Dihydroxy-5b-cholan-24-amide and Its Monohydrates

The synthetic method for preparing N-(3-hydroxypropyl) 3 alpha,12 alpha-dihydroxy-5 beta-cholan-24-amide can lead to formation of at least three different crystal forms - an anhydrous compound and two monohydrates. The structural and thermal properties of these forms have been characterized by 13C-CP/MAS-NMR and IR spectroscopy, thermo- gravimetry, differential scanning calorimetry and by powder and single crystal x-ray crystallography. In addition, theoretical 13C-NMR chemical shift calculations were also performed for the anhydrous compound and for the first monohydrate, starting from single crystal structures and the structures of these species have now been verified. The first monohydra…

Multinuclear 1H, 13C and 15N NMR study of some substituted 2-amino-4-nitropyridines and their N-oxides.

1H, 13C and 15N NMR chemical shift assignments based on pulsed field gradient selected PFG 1H,X (X = 15C and 15N) HMQC and HMBC experiments are reported for three 4-nitropyridine N-oxides and four 4-nitropyridines. It was found that an ortho effect of a methyl group inhibits the deshielding effect of the 4-nitro group and that this effect and the so-called back donation is influenced by electronegativity and position of substituents in the multisubstituted pyridine N-oxides. The shielding effect of N-oxide group is most pronounced in the 15N NMR chemical shifts of the studied compounds. This effect is further modified by methylamino, methylnitramino, 5- or 3-methyl and 4-nitro groups. Among…

Self-Organization of 2-Acylaminopyridines in the Solid State and in Solution

Aggregation of 2-acylaminopyridines and their 6-methyl derivatives in chloroform solution was studied by (1)H, (13)C, and (15)N NMR spectroscopies. The results were compared with (13)C and (15)N CPMAS NMR and IR spectral as well as with X-ray structural data. Intermolecular interactions in solution and in solid state were found to have a similar nature. Relatively strong N(amide)-H···N(pyridine) intermolecular hydrogen bonds enable dimerization to take place. Steric interactions in N-pivaloyl- and N-1-adamantylcarbonyl as well as that caused by the 6-methyl group hinder formation of the dimeric aggregates stabilized by the N(amide)-H···N(pyridine) intermolecular hydrogen bonds. In general, …

Influence of Bond Fixation in Benzo-Annulated N-Salicylideneanilines and Their ortho-C(O)X Derivatives (X = CH3, NH2, OCH3) on Tautomeric Equilibria in Solution

1H, 13C, and 15N NMR spectra show that an ortho-C(=O)X group present in the molecules of N-salicylideneanthranilamide (X = NH2), methyl N-salicylideneanthranilate (X = OCH3), N-salicylidene-o-aminoacetophenone (X = CH3), and their benzo analogues have only a minor effect on the tautomeric OH/NH-equilibrium in solution. Only two of three possible tautomers were detected. Lability of the absent form was proved by theoretical calculations. Calculated energies show that the enolimino form (OH) is less stable than the enaminone (NH) form only for dibenzo-annulated N-salicylideneanilines. The population of each species in the tautomeric mixture was found to be inversely proportional to its energy…

1H,13C and17O NMR spectroscopic study of four bicyclo [3.1.1]heptenes (derivatives of α-pinene) and four bicyclo[3.1.1]heptanes (derivatives of β-pinene)

Four derivatives of 2, 6, 6-trimethylbicyclo[3.1.1]hept-2-ene (α-pinene) and four derivatives of 2-methylene-6, 6-dimethylbicyclo[3.1.1]heptane (β-pinene) were synthesized and their 1H, 13C and 17O NMR spectra were measured, analysed and assigned. The 1H NMR spectral parameters were obtained by computer-aided analyses of the very complex multi-spin, second-order spectra. Some of the 13C NMR chemical shift assignments of these compounds reported in the literature should be changed, based on these accurate 1H NMR spectral analyses and carbon-proton chemical shift correlated spectra (COSY). The new assignments are supported by the 1J(C, H) values, which show a strong dependence on the bond ang…

NMR spectroscopy in environmental chemistry:1H and13C NMR parameters of tricyclic polychlorinated C10 hydrocarbons and their oxy derivatives based on two-dimensional NMR techniques

Two-dimensional homo- and heteronuclear NMR chemical shift correlation techniques were applied in the characterization of five tricyclic polychlorinated C10 hydrocarbons, chlordene (1), heptachlor (2), trans-nonachlor (3), α-chlordene (4) and γ-chlordene (5), which are spread globally in the environment owing to their use as insecticides. Approximate and partly contradictory 1H and 13C NMR chemical shifts reported in the literature were corrected in this work. The chemical shift assignments of 1–5 were based on DQF COSY, HMQC and HMBC experiments. In addition, an INADEQUATE experiment was needed to ascertain the 13C chemical shifts assignment of 2. The nJ(H,H)s of 1–5 were solved by compute…

Long-range substituent and temperature effect on prototropic tautomerism in 2-(acylmethyl)quinolines

Tautomeric equilibria between 2-(cinnamoylmethyl)quinoline, (Z)-1,2-dihydro-2-(cinnamoylmethylene)quinoline and (Z)-4-phenyl-1-(2-quinolyl)-1,3-butadien-2-ol were studied by 1H, 13C and 15N NMR methods. The —CHCH— fragment conjugated with phenyl and a strong electron donor p-(1-pyrrolidine) substituent were found to favour the enolimine tautomer. This undergoes fast exchange (on the NMR time-scale) with the enaminone form. The amount of the latter tautomer was found to increase at low temperatures. Copyright © 2001 John Wiley & Sons, Ltd.

Solid-State NMR, X-ray Diffraction, and Thermoanalytical Studies Towards the Identification, Isolation, and Structural Characterization of Polymorphs in Natural Bile Acids

Combined solid-state NMR, powder, and single crystal X-ray diffraction, as well as thermoanalytical studies were performed towards the identification, isolation, and structural characterization of ...

Macrocycles prepared from lithocholic acid, piperazine and isomeric pyridine dicarboxylic acids and their selective affinities towards sodium and potassium

Abstract Two novel macrocycles prepared from lithocholic acid, piperazine and pyridine dicarboxylic acids (2,6- and 3,5-isomers), have been characterized by 13C NMR and ESI–MS techniques. In case of the pyridine-2,6-dicarboxylate derivative, the molecular formula of the cycle was C59H87O6N3 (I), while the pyridine-3,5-dicarboxylate derivative (II) was a trimeric structure by molecular mass when compared with I. Furthermore, cycle I showed a special affinity towards potassium cation, while II possessed significant proton and sodium cation recognition properties.

NMR and quantum chemical studies on association of 2,6-bis(acylamino)pyridines with selected imides and 2,2′-dipyridylamine

Association constants of 2,6-bis(alkylcarbonylamino)pyridines (alkyl = methyl or ethyl) and their perfluoroalkyl analogues with succin- and maleimide as well as with 2,2′-dipyridylamine (complementary DAD and ADA hydrogen bonding motifs are responsible for formation of the associates) have been determined by NMR titrations and quantum chemical calculations. Interactions of 2,6-bis(alkylcarbonylamino)pyridines with imides differ by character from these of perfluoroalkyl analogues. Such large difference was not observed for the 2,2′-dipyridylamine associates. Since fluorine atoms cause carbonylamino groups to be stronger hydrogen bond donors, perfluorinated species of this type were found to …

Secondary interactions as driving force in heterocomplex formation of 2,7-disubstituted-1,8-naphthyridines: Quantum chemical, NMR and mass spectral investigations

Abstract Tautomerism and dimerization of 2,7-disubstituted-1,8-naphtyridines has been studied theoretically by quantum chemical methods and experimentally by liquid and solid state NMR and ESI-TOF mass spectral techniques. The heterocomplex formation has been proven in solution by variable temperature 1H NMR and in solid state by 13C CPMAS NMR spectra of a grinded mixture of two congeners. Secondary interactions have been proposed as driving forces in the heterocomplex formation. The energy differences between homo- and heterocomplexes were calculated with recently developed DFT + D methods. The energy data obtained by the quantum chemical methods are in agreement with the concept of second…

13C NMR spectroscopic study of diphenyl ether and 28 of its polychlorinated derivatives

The 13 C NMR chemical shifts and coupling constants for diphenyl ether and 28 environmentally interesting polychlorinated diphenyl ethers were measured and analysed

1H,13C,17O NMR and IR spectroscopic study of all methyl chloropropanoates

1 H, 13 C and 17 O NMR chemical shifts, n J(H,H) and n J(C,H) spin-spin coupling constants and IR absorption maxima and intensities for the most characteristic bands of methyl propanoate and all eleven chloropropanoic acid methyl esters are reported

Substituent and temperature controlled tautomerism of 2-phenacylpyridine: the hydrogen bond as a configurational lock of (Z )-2-(2-hydroxy-2-phenylvinyl)pyridine

2-Phenacylpyridines substituted in the benzene ring are in equilibrium with (Z)-2-(2-hydroxy-2-phenylvinyl)pyridines when dissolved in chloroform. The substituent affects significantly the tautomeric equilibrium [the amount of the enolimine form stabilized by the intramolecular hydrogen bond is 1 and 92% for R = p-N(CH2)4 and p-NO2, respectively]. The negative logarithm of the tautomeric equilibrium constant, KT, is linearly dependent on the Hammett σ substituent constants. The dependence of KTvs. temperature is exponential in character: the more electron-withdrawing is the substituent, the more distinct is the influence of temperature. Unexpectedly, the tautomer present in the crystalline …

ChemInform Abstract: Ortho-Substituent Effects in N-Arylacetamides. NMR and Molecular Mechanics Investigation.

1H, 13C, 15N and 17O NMR spectra of N-phenylacetamide (acetanilide) and 21 ortho-substituted acetanilides were measured and assigned. The observed NMR parameters are related to the Hammett substituent parameters and conformational characteristics of the acetamido moiety estimated by molecular mechanics calculations. Significant relationships were found for the 13C NMR chemical shifts of C-5 (para to substituent) and the direct spin–spin coupling constant, 1J(C, H), of C-3 (ortho to substituent) with Hammett substituent parameters. For 15N NMR chemical shifts of the amido nitrogen, no general correlation with the Hammett substituent parameters was found. The interactions between functionalit…

Tuning the hydrogen bonding strength in 2,6-bis(cycloalkylcarbonylamino)pyridine assemblies by variable flexibility. Association constants measured by hydrogen bonded vs. non-hydrogen bonded protons

International audience; The association of 2,6-bis(cycloalkylcarbonyloamino)pyridines with rigid and non-rigid counterparts was studied in chloroform solution by 1H NMR and computational methods. The angles within the cycloalkyl ring and rotation of these substituents determine the strength of the association via triple hydrogen-bonding. The dimerization and methyl-methyl repulsion have been addressed as mechanisms restricting heterocomplexation of diacetamide. The association constants obtained by the shift changes of hydrogen-bonded protons are in agreement with those of methine protons. This "dual shift" method was proposed as an additional verification of association constants obtained …

Substituted methyl 5β-cholan-24-oates. I—17O NMR spectral characterization

Methyl esters of four common bile acids, 3α-hydroxy-5-β-cholan-24-oic (lithocholic) acid, 3α, 7α-dihydroxy-5β-cholan-24-oic (chenodeoxycholic) acid, 3α,12α-dihydroxy-5β-cholan-24-oic (deoxycholic) acid and 3α,7α,12α-trihydroxy-5β-cholan-24-oic (cholic) acid, and 14 acetylated, trifluoroacetylated, mesylated and oxo derivatives of methyl 5β-cholan-24-oates were prepared and their 17O NMR spectra recorded. In spite of their relatively high molecular masses and the rigid molecular structure of the steroid skeleton, most of the oxygens included in these structures gave well resolved 17O NMR resonance lines at natural abundance in 0.25–0.5 M acetonitrile solutions at 75°C. In agreement with the …