Hydroxyl proton magnetic resonance study of aliphatic alcohols

Rader, Charles P.

doi:10.1021/ja01040a027

Cited by 34 publications

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“…Hence the low value of this coupling is due to steric effects and not to any intramolecular hydrogen bonds. Note that the value of this coupling in cis-4-tert-butylcyclohexanol is even lower (3.0 Hz), 6 presumably reflecting the increased rigidity of this cyclohexane ring. In contrast, the CH-OH couplings for the axial C(4,6)OH groups in 1,3,5-methylidene-myo-inositol (28) are larger than average (5.8 Hz,) implying a favoured trans orientation of the OH groups, and this supports the proposed existence of a 1,3-diaxial intramolecular H-bond in this compound.…”

Section: Dmso Solvent Effectsmentioning

confidence: 97%

“…In DMSO-d 6 solution all the signals are resolved and the OH protons couple with the adjacent CH proton. The assignment follows that in D 2 O solution and the individual OH signals were assigned by a COSY plot.…”

Section: Myo-inositol (27)mentioning

confidence: 99%

“…The remaining five resonances could not be assigned unambiguously. The assignment was resolved when the spectrum was acquired in DMSO-d 6 . In DMSO one multiplet pattern (3.10 ppm) does not have an additional coupling and this is clearly H-2, the only ring proton with no geminal OH group.…”

Section: Quebrachitol (30): 2-o-methyl-chiro-inositolmentioning

confidence: 99%

“…6,52,53 However, in contrast to the CH-CH couplings, the CH-OH coupling has an intrinsic solvent 6 and temperature 52 In myo-inositol (27), only the C(2)(OH) is axial and the CH-OH coupling for this OH group is low (3.4 Hz, Table 4). This implies a favoured gauche orientation which is immediately understandable as the trans arrangement of the HC-OH moiety would result in the OH hydrogen facing into the ring producing steric repulsions with the axial C4,6 hydrogens.…”

Section: Dmso Solvent Effectsmentioning

confidence: 99%

“…The value of the CH-OH coupling in alcohols in solution shows that the OH proton is usually not in a single orientation but may have a preferred conformation. 6 However, it is very difficult to estimate accurately the populations of the different OH conformers, especially in D 2 O solution. These considerations plus the very considerable problems of modelling solvation in these systems by quantum mechanics 7 mean that the very useful GIAO calculations 8 are impractical at this stage for these systems.…”

Section: Introductionmentioning

confidence: 99%

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1H chemical shifts in NMR: Part 22—Prediction of the1H chemical shifts of alcohols, diols and inositols in solution, a conformational and solvation investigation

et al. 2005

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The (1)H NMR spectra of a number of alcohols, diols and inositols are reported and assigned in CDCl(3), D(2)O and DMSO-d(6) (henceforth DMSO) solutions. These data were used to investigate the effects of the OH group on the (1)H chemical shifts in these molecules and also the effect of changing the solvent. Inspection of the (1)H chemical shifts of those alcohols which were soluble in both CDCl(3) and D(2)O shows that there is no difference in the chemical shifts in the two solvents, provided that the molecules exist in the same conformation in the two solvents. In contrast, DMSO gives rise to significant and specific solvation shifts. The (1)H chemical shifts of these compounds in the three solvents were analysed using the CHARGE model. This model incorporates the electric field, magnetic anisotropy and steric effects of the functional group for long-range protons together with functions for the calculation of the two- and three-bond effects. The long-range effect of the OH group was quantitatively explained without the inclusion of either the C--O bond anisotropy or the C--OH electric field. Differential beta and gamma effects for the 1,2-diol group needed to be included to obtain accurate chemical shift predictions. For DMSO solution the differential solvent shifts were calculated in CHARGE on the basis of a similar model, incorporating two-bond, three-bond and long-range effects. The analyses of the (1)H spectra of the inositols and their derivatives in D(2)O and DMSO solution also gave the ring (1)H,(1)H coupling constants and for DMSO solution the CH--OH couplings and OH chemical shifts. The (1)H,(1)H coupling constants were calculated in the CHARGE program by an extension of the cos(2)phi equation to include the orientation effects of electronegative atoms and the CH--OH couplings by a simple cos(2)phi equation. Comparison of the observed and calculated couplings confirmed the proposed conformations of myo-inositol, chiro-inositol, quebrachitol and allo-inositol. The OH chemical shifts were also calculated in the CHARGE program. Comparison of the observed and calculated OH chemical shifts and CH.OH couplings suggested the existence of intramolecular hydrogen bonding in a myo-inositol derivative.

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Section: Dmso Solvent Effectsmentioning

confidence: 97%

Section: Myo-inositol (27)mentioning

confidence: 99%

Section: Quebrachitol (30): 2-o-methyl-chiro-inositolmentioning

confidence: 99%

Section: Dmso Solvent Effectsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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1H chemical shifts in NMR: Part 22—Prediction of the1H chemical shifts of alcohols, diols and inositols in solution, a conformational and solvation investigation

et al. 2005

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Ein Boraadamantan‐Ringsystem mit B,N‐Betain‐Struktur

Kliegel

Ahlenstiel

1976

Chem. Ber.

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Die Bisalkylierung primarer Amine rnit Diepoxiden (10) fiihrt zu I-Alkyl-3,5-piperidindiolen (ll), die zu N-Oxiden (12) oxidiert werden. Durch Reaktion von 12 mit Arylboronsauren erhalt man Bor-Stickstoff-Betaine rnit adamantoidem (8) oder bicyclischem (16) Ringsystem.A Boraadamantane Ringsystem with B,N-Betaine Structure Bisalkylation of primary amines with diepoxides (10) leads to l-alkyl-3,5-piperidinediols (1 I) which are oxidized to N-oxides (12). These react with areneboronic acids to give boron-nitrogenbetaines with an adamantoid (8) or bicyclic (16) ringsystem. Vor 20 Jahren berichteten Angyal und McHugh'.'' iiber die Ionophorese von Cyclitolen in Natriumtetraborat-Losung und erklarten die Beweglichkeit bestimmter Polyole rnit der Bildung von adamantoiden Borat-Komplexen 1, denen bin Struktur-Vorschlag von J. A. Mills zugrunde lag 'I, Ahnliche Trioxaboraadamantan-Ringsysteme wurden in der darauf folgenden Z i t f i r eine Reihe von Borsaureester-Komplexen cyclischer Polyole postuliert und teilweise auch spektroskopisch nachgewiesen 3-9).Bei den Borat-Komplexen von Inosaminen (2) kann auch die Aminogruppe in das heterocyclische System einbezogen sein lo). Ausschlielllich mit Bor-und Sauerstoff-Atomen ist das Hexaoxatetraboraadamantan-Geriist 3 aufgebaut, das als Struktur fur die kristallinen Hydrate von Natriummetaborat vorgeschlagen wurde"). Die 1-und 2-Boraadamantane, 4"' und 5 12), mit Bor als einzigem Heteroatom, wurden in jiingerer Zeit zuganglich, ebenso die Hexaboraadamantane 6 mit B-Methyl-I") bzw. B-Halogen-Substituenten 14'. I ) S. J . Angyal und D.

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Recherches dans la série des cyclitols XXXIX RMN. de protons d'hydroxyles de cyclopentane‐ et de cyclopentène‐polyols

Cocu

Wolczunowicz

Bors

et al. 1970

Helvetica Chimica Acta

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VI 70)Suinmary. Several mono-, di-, and tr-hydroxy d-rivatives of cyclopentanc and cyclopentene have been studied by NMR. spectroscopy. The chemical shifts and thc coupling constants of the OH groups have been correlated with their position, with their configuration and, in some cases, with their conformation. do, est constant pour des concentrations infkrieures B 0,12M; chaque OH est alors associC uniquement avec le solvant. La valeur de 6, pour un hydroxyle donnC, dCpend de la force de la liaison OH . . . DMSO : grosso modo, plus cette liaison est forte, plus la rCsonance du proton OH est dCplacCe vers des champs faibles. Si la molCcule contient 1)Adresse pern-anente : DBpartement de Chimie organique de l'Universit6 de Bucarest.

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Hydroxyl proton magnetic resonance study of aliphatic alcohols

Cited by 34 publications

References 0 publications

1H chemical shifts in NMR: Part 22—Prediction of the1H chemical shifts of alcohols, diols and inositols in solution, a conformational and solvation investigation

1H chemical shifts in NMR: Part 22—Prediction of the1H chemical shifts of alcohols, diols and inositols in solution, a conformational and solvation investigation

Ein Boraadamantan‐Ringsystem mit B,N‐Betain‐Struktur

Recherches dans la série des cyclitols XXXIX RMN. de protons d'hydroxyles de cyclopentane‐ et de cyclopentène‐polyols

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