Résonance Magnétique Nucléaire de 17O. Aldéhydes et cétones aliphatiques: additivité des effets de substitution et corrélation avec la 13C-RMN

¹⁷O-NMR. Aliphatic aldehydes and ketones, additivity of substituent effects and correlation with ¹³C-NMR. The ¹⁷O-chemical shifts of 9 aldehydes, 22 aliphatic and 4 alicyclic ketones, in the natural abundance FT.-NMR. spectra followed a good correlation with the ¹³C-chemical shifts of the terminal C-atoms of corresponding methylene compounds. An additivity relation involving 6 parameters represents the ¹⁷O-shifts of 28 of the measured products with a standard deviation of 2.5 ppm. The additivity parameters are discussed with respect to the modifications of the polarity of the carbonyl group induced by the hyperconjugative interaction of π and π* orbitals with the πCH ₃ orbitals of the alkyl substituent groups.     

Determination of the Quadrupolar Coupling Constant and the Asymmetry Parameter of Oxygen-17 in Acetone by 17O- and 1H-NMR in Nematic Phases

Linear relationships between the inverse of the quadrupolar coupling constant, 1/χ and the asymmetry parameter η are obtained for the ⁷O-nucleus of acetone oriented in four different nematic phases, using the information contained in ¹H- and ¹⁷O-NMR spectra. The absence of a unique intersecting point of thee relations shows that the quadrupolar constants differ slightly between polar and apolar nematic phases, while the orientation remains similar. By combination of the experimentally derived relations with predictions from the theory of Townes and Dailey, values for χ = 11.15 MHz and η = 0.47 in polar media and χ = 11.35 Mhz and η = 0.15 in an apolar medium are obtained, which are similar to those found in the gas and solid phases.     

Résonance magnétique nucléaire de 13C et 17O d'éthers aliphatiques. Effets γ entre les atomes d'oxygène et de carbone

The ¹³C- and ¹⁷O-chemical shifts of 31 aliphatic ethers are measured and discussed. The ¹⁷O-chemical shifts of the ethers ROR′ correlate with chemical shifts for the methylene groups of the corresponding alkanes RCH₂R′. The constant of proportionality can be related to the orbital expansion term 〈r^?3〉_2p. The δ_c for carbon atoms can also be correlated with δ_c for the corresponding alkanes. The origin of the correlation is discussed taking into account the conformational modifications resulting from introduction of an oxygen atom in an alkyl chain.     

Etude RMN 13C d'un Dérivé Uniformément Enrichi en 13C. Signe des Valeurs des Constantes de Couplage Observées

The ¹³C NMR parameters of 3-O-acetyl-1,2:5,6-di-O-isopropylidène-α-D-[U-¹³C] glucofuranose, used as a sample for analysis in double labelling biosynthetic experiments, have been measured. Homonuclear double resonance experiments ¹³C? {¹³C} at 62.8 MHz have permitted the determination of all the ¹³C? ¹³C coupling constants. By theoretical computation of spectra, in connection with the second order effects existing at 25.2 MHz and 15.08 MHz, the sign of the coupling constants has been determined. The theoretical computation of spectra took into account all the isotopomers and was calculated with the help of a program (adapted from the LAOCOON program) allowing for the weighted addition of the spectra.     

Spectroscopie RMN du Carbone-13 de Thiocétones Aliphatiques: Propanethione et Dérivés,Thiocétones Bicycliques et α Cyclopropaniques

Carbon-13 NMR spectra of various aliphatic ketones and thioketones were determined and interpreted. As shown by the relation between ¹³C chemical shifts in C=A groups, the C=S is more sensitive to the substituents than the C=O group. Conjugative effects are more pronounced in α-cyclopropyl thioketones than in α-cyclopropyl ketones.     

Etudes stéréochimiques XIV. Adduits de Diels-Alder en série résiniques; action des peracides et ouvertures acido-catalysées d'époxydes

Studies in Stereochemistry XIV. Diels-Alder adducts in the resin series; action of peracids and acid-catalysed ring opening of epoxides The synthesis of Diels-Alder compounds of type 2 with a 17-nor-13(14)-atisène skeleton is described (cf. Schemes 1–3). Depending on the nature and configuration of substituents R¹ and R² on the carbon atoms 15 and 16, an epoxide ( 24–33 ) or a ketone ( 35–38 ) or a mixture of epoxide, ketone and lactone is obtained by the action of p-nitroperbenzoic acid on the double bond of these adducts (cf. Scheme 4). A simplified reaction scheme is suggested to explain the formation of the various products. In an acid-catalysed reaction, the epoxides isomerize mainly into ketones. Nevertherless, in some cases, dienes (e.g. 52 ) or hydroxy-γ-lactones of (13R*, 14S*)-configuration (e.g. 50 ) resulting from the opening of the epoxide ring with retention of configuration were obtained.     

Le mécanisme de la réduction polarographique des dérivés ditosyloxylés et son implication en électrochimie préparative

The cleavage of a single SO₂? O bond occurs during the polarographic reduction of a tosyloxy group (p? CH₃C₆H₄SO₂O = TsO) in aprotic medium and intramolecular cyclisation may ensue when a second TsO group is present on the same molecule. The polarographic behaviour of aliphatic ditosyloxy derivatives is discussed on the assumption that oriented vicinal derivatives at the interface assume a conformation which resembles the geometry of the transition state for an intramolecular elimination with anchimeric assistance of one of the tosyloxy groups. This situation favours the electron transfer, whereas the same geometric requirements hinder the intramolecular interaction of the TsO groups of the oriented non-vicinal derivatives. This interpretation agrees well with the fact that the large scale electrolysis of vicinal ditosyloxy derivatives give much higher yield of cyclic ethers than the higher homologues. It is also shown that intramolecular interaction between TsO groups can occur through an intervening double bond in a non-vicinal derivative.     

Chemische Verschiebungen bei 17O-NMR. und Hydratations geschwindigkeiten von cyclischen Ketonen mit transannularer Wechselwirkung

In 8- and 9-membered cyclic ketones, transannular interactions of an EtN group or an O atom shift considerably the ¹⁷O signal of the carbonyl group to higher fields; S appears to have no such effect. The same ketones show markedly diminished speeds of water addition, compared to simple ketones; this reaction was followed by measuring the rate of oxygen exchange between ¹⁷O-labelled ketones and (unenriched) water. Transannular interaction inhibits completely in N-ethyl-azacyclodecane-6-one the exchange reaction, including labelling attemps.     

Etude par RMN 13C à 62,89 MHz de ramifications longues d'alcanes lourds branchés. Modèles de PEbd et des copolymères éthylène-α oléfines

A series of 12-alkyl tricosanes (four compounds) was examined by use of ¹³C nuclear magnetic resonance at 62,89 MHz as model compounds for isolated short- and long-chain (C₅, C₆, C₇, C₈) branches in low-density polyethylene and ethylene-α olefin copolymers. An array of ¹³C resonances was observed and we note that the ¹³C chemical shifts became insensitive to branch length with octyl and longer branches at this field.     

Nuclear Quadrupole Resonance and Stereochemistry I. α – Chloro ethers

³⁵Cl nuclear quadrupole resonance spectra of cyclic α-chloro ethers of known configuration are presented. The resonance frequencies of chlorine atoms in equatorial positions are in every case some 2.5 MHz higher than those of corresponding chlorine atoms in axial positions. Similar results are obtained for open-chain trichloromethyl ethers and the effect is sufficiently well-defined to distinguish between configurational isomers and establish their conformation. These results may be rationalised in terms of a model in which the lone-pair electrons on the oxygen atom hyperconjugate with the electrons of the C? Cl bond.     

Ultra‐wideline 27Al NMR Investigation of Three‐ and Five‐Coordinate Aluminum Environments

Ultra‐wideline ²⁷Al NMR experiments are conducted on coordination compounds with ²⁷Al nuclei possessing immense quadrupolar interactions that result from exceptionally nonspherical coordination environments. NMR spectra are acquired using a methodology involving frequency‐stepped, piecewise acquisition of NMR spectra with Hahn‐echo or quadrupolar Carr–Purcell Meiboom–Gill (QCPMG) pulse sequences, which is applicable to any half‐integer quadrupolar nucleus with extremely broad NMR powder patterns. Despite the large breadth of these central transition powder patterns, ranging from 250 to 700 kHz, the total experimental times are an order of magnitude less than previously reported experiments on analogous complexes with smaller quadrupolar interactions. The complexes examined feature three‐ or five‐coordinate aluminum sites: trismesitylaluminum (AlMes₃), tris(bis(trimethylsilyl)amino)aluminum (Al(NTMS₂)₃), bis[dimethyl tetrahydrofurfuryloxide aluminum] ([Me₂‐Al(μ‐OTHF)]₂), and bis[diethyl tetrahydrofurfuryloxide aluminum] ([Et₂‐Al(μ‐OTHF)]₂). We report some of the largest ²⁷Al quadrupolar coupling constants measured to date, with values of C_Q(²⁷Al) of 48.2(1), 36.3(1), 19.9(1), and 19.6(2) MHz for AlMes₃ , Al(NTMS₂)₃ , [Me₂‐Al(μ‐OTHF)]₂ , and [Et₂‐Al(μ‐OTHF)]₂ , respectively. X‐ray crystallographic data and theoretical (Hartree–Fock and DFT) calculations of ²⁷Al electric field gradient (EFG) tensors are utilized to examine the relationships between the quadrupolar interactions and molecular structure; in particular, the origin of the immense quadrupolar interaction in the three‐coordinate species is studied via analyses of molecular orbitals.     

Etude par Résonance Magnétique Nucléaire du carbone 13 de complexes du cobalt (III) et de la diméthylglyoxime

From a carbon magnetic resonance study of several alkylcobaloximes RCo(DMG)₂B (DMG = dimethylglyoximate monoanion), it was possible to estimate the α, β and γ effects of the Co(DMG)₂B group on the chemical shifts of the carbon atoms of various alkyl groups R. The chemical shifts of the carbon atoms belonging to the equatorial ligands and to the axial base B are not significantly affected by structural modification of the R groups. Values of δ in benzylcobaloximes XC₆H₄CH₂Co(DMG)₂B agree with a donor effect of the ? CH₂Co(DMG)₂B radical. Values of ¹J(¹³C? H) coupling constants, measured in ¹³C enriched methylcobaloximes, do not vary appreciably when B is changed (J(¹³C? H) = 137 ± 1 Hz) and are close to the value obtained for methylcobalamine.     

17O, 13C and 1H NMR and IR spectral study of crowded ketones: possible intramolecular C—H···O interactions

Unusual behaviour was observed in the study of the ¹⁷O, ¹³C and ¹H NMR and IR spectra of crowded (1‐adamantyl)alkyl ketones. As the size of the alkyl substituent is increased, abnormal upfield chemical shifts in the ¹³C NMR and downfield shifts in the ¹⁷O NMR of the carbonyl group, as well as downfield shifts in the ¹H NMR of the adamantyl γ'‐protons, are found. In the IR spectrum, the ν_C?O stretching frequencies of the ketones with bulky substituents show considerable red shifts. Correlation of the NMR shifts with the number of γ‐carbon atoms of the alkyl substituents and comparison with the IR results indicated that there is an intramolecular through‐space CH···O interaction in crowded ketones. This was supported by the results of ab initio calculations. Copyright © 2002 John Wiley & Sons, Ltd.     

Semi‐analytical description of the S = 9/2 quadrupole nutation NMR experiment: multinuclear application to 113In and 115In in indium phosphide

The density matrix of a spin S = 9/2 excited by a radiofrequency pulse is calculated. The interaction involved during the excitation of the spin system is first‐order quadrupolar. Consequently, the results are valid for any ratio of the quadrupolar coupling ω_Q to the pulse amplitude ω₁. The behavior of the central transition intensities versus the pulse length is discussed. The ¹¹⁵In and ¹¹³In nuclei in a powdered sample of indium phosphide (InP) are used to illustrate the results. It is found that the ratio of the quadrupolar coupling constants determined in this work is in excellent agreement with the ratio of the quadrupole moments of the two nuclei. Copyright © 2015 John Wiley & Sons, Ltd.     

Comparaison des transformations polyreactionnelles induites par les chlorure et bromure de pyridinium : Cas de l'hexanediol-1,6

Pyridinium chloride and bromide react with 1,6-hexanediol through a complex multireactional chain process mostly furnishing unsaturated hydrocarbons, cyclic ethers, unsaturated halides and unsaturated alcohols. The similar transformations undergone by 5-hexene-1-ol and 1-hexanol under the same conditions suggest several hypotheses about the mechanism. Several original assignments from ¹³C NMR data were involved in determining the structures of the products.     

An investigation of the utility of using n.m.r. lanthanide shift reagents for 13C assignments in selected aromatic ethers and ketones. A detailed description of the lanthanide induced shift ratio method for lanthanide shift reagent–substrate geometry analysis

The ¹³C and ¹H spectra of a series of aromatic ketones, ethers and keto-ethers were studied using the lanthanide shift reagent (LSR) Yb(fod)₃ and the data analyzed using the lanthanide induced shift (LIS) ratio method. Studies were carried out on phenalenone, 6-methoxyphenalenone, 1- and 2-methoxynaphthalene, 1-indanone, 5- and 6-methoxy-1-indanone and flavone and the data obtained subjected to LSR-substrate geometry analysis as a means of making ¹³C assignments. The utility and limitations of the LSR method for making ¹³C assignments is discussed and the LIS ratio method for LSR-substrate geometry analysis is described in detail.     

Catalyse heterogene en presence de sels et sans solvant : II. Hydrosilylation d'aldehydes et de cetones satures et α,β ethyleniques

Hydrosilylation of saturated and α,β-unsaturated carbonyl compounds by heterogeneous catalysis without solvent and in the presence of salts (HCO2K, o-Ph(CO₂K)₂, FK, FCs) was carried out with good yields. FCs is a very efficient salt for hydrosilylation of aldehydes and ketones: for instance α-NpSiH₃ reacts quantitatively at room temperature with PhCOPh giving α-NpSi(OCHPh₂)₃. With α,β-unsaturated ketones FCs leads to 1,2-addition. It allows the isomerization of allysilyl ethers in silyl enol ethers, providing that the transferring hydrogen is benzylic.     

Substituted 2-Phenyl- and 2-Cyclohexyl-trans-decalins,New Classes of Nematic Liquid Crystals

Versatile procedures for the preparation of the title compounds are described. Representatives of ketones ( 12 and 27 ), hydrocarbons ( 19 and 28 ), acids ( 13 ), esters ( 15 . and 20 ), ethers ( 22 ) and nitriles ( 18 ) possess wide-range nematic phases, provided their terminal chains R² and R³ contain at least three methylene units.     

Visible-light-driven palladium-catalyzed Dowd–Beckwith ring expansion/C–C bond formation cascade

A visible-light-induced palladium-catalyzed Dowd–Beckwith ring expansion/C–C bond formation cascade is described. A range of six to nine-membered β-alkenylated cyclic ketones possessing a quaternary carbon center were accessed under mild conditions. Besides styrenes, the electron-rich alkenes such as silyl enol ethers and enamides were also compatible, providing the desired β-alkylated cyclic ketones in moderate to good yields.

An intermolecular Dowd–Beckwith ring expansion/C–C bond formation is achieved through light-induced palladium catalysis. Not only styrenes but also the electron-rich alkenes such as silyl enol ethers and enamides were also compatible in this reaction.     

Oxygen-17 and Carbon-13 Nuclear Magnetic Resonance. Chemical shifts of unsaturated carbonyl compounds and acyl derivatives

The ¹⁷O and ¹³C chemical shifts (δ) of 14 α,β-unsaturated aldehydes and ketones and 33 acyl derivatives RXC = O (X = Cl, OH, OMe, OEt, NH₂ and R = H or alkyl) have been measured. In the unsaturated carbonyl series, a correlation exists between δ ¹⁷O and the π electron density at the β-carbon atom. From this correlation, an δ ¹⁷O of 530 ppm was extrapolated for the loss of one electron at the oxygen atom. In the acyl series, the δr ¹⁷O were also sensitive to changes in the polarity of the carbon-oxygen bond. A partial correlation between ¹⁷O-NMR. chemical shifts and the nuclear quadrupole coupling constants exists for aldehydes, ketones, esters and amides but not for acyl chlorides.