Conformational Effects and Hydrogen Bonding in 1,4-Diols

Kuhn, Lester P.; Schleyer, Paul von Ragué; Baitinger, William F.; Eberson, Lennart

doi:10.1021/ja01058a022

Cited by 65 publications

(24 citation statements)

References 8 publications

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“…These substances are chosen for a comparison with the hydrate because they geometrically resemble more or less our hydrate structure. However, one must realize that intramolecular hydrogen bonding depends strongly on geometrical factors [20,22] and that the agreement we find for the enthalpies of formation might be fortuitous.…”

Section: Alterations At Low Temperaturesmentioning

confidence: 60%

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A study of the hydration of polyoxyethylene at low temperatures by differential scanning calorimetry

Vringer

Joosten

Junginger

1986

Colloid & Polymer Sci

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Abstract:As a part of a study of the colloidal structures present in nonionic ointments, the interaction between polyoxyethylene and water is investigated. A series of mixtures of polyoxyethylene 1550 and water is studied using differential scanning calorimetry. Heating as well as cooling experiments are performed. The effects of the heat of mixing, supercooling and melting point depression on the measured enthalpy changes are discussed. From the non-freezing water fraction it is concluded that 2 water molecules per oxyethylene unit are tightly bound to the polymer chain. The observed differences between the cooling and the heating curves lead to a possible explanation for the alterations in the samples occurring at low temperatures. A hydrate structure of polyoxyethylene at low temperatures is proposed. Finally, comment is made on the phase diagram of the system polyoxyethylene/water.

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Section: Alterations At Low Temperaturesmentioning

confidence: 60%

“…The hydrogen bonds are linked forming a helix around the polymer chain. The hydrogen bonds are chosen to be linear because this is the most favourable form and indeed, in crystals most hydrogen bonds are linear [19,20]. The bond length we chose lies within [20].…”

Section: Alterations At Low Temperaturesmentioning

confidence: 99%

A study of the hydration of polyoxyethylene at low temperatures by differential scanning calorimetry

Vringer

Joosten

Junginger

1986

Colloid & Polymer Sci

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“…2) The magnitude of the difference in frequency between the absorptions of the free (ν f ) and of the bonded (ν i ) maxima is customarily taken as a measure of the strength of the H bond [60] [61] and is denominated as ∆ν OH . The value of ∆ν OH depends on a number of factors.…”

Section: H Nmr and Ft-ir Datamentioning

confidence: 99%

Carbohydrate Hydrogen-Bonding Cooperativity − Intramolecular Hydrogen Bonds and Their Cooperative Effect on Intermolecular Processes − Binding to a Hydrogen-Bond Acceptor Molecule

et al. 2002

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The high hydroxy (OH) group content in carbohydrates makes the study of carbohydrate OH···XH and OH···X Hbond energetics fundamental to understanding of carbohydrate recognition. There is, however, a relative lack of knowledge concerning the factors that allow a carbohydrate to participate in recognition events stabilised by intermolecular H bonds. We therefore present here a systematic study on the factors that determine the formation of a well-defined intramolecular H-bonding network between carbohydrate hydroxy groups, and its cooperative or anti-cooperative influence on selected intermolecular processes mediated by H bonds. With this in mind, we first determined the H-bonding networks of a series of carbohydrate derivatives − monoalcohols, 1,2-and 1,3-diols and amidoalcohols − by 1 H NMR and FT-IR spectroscopy. The hydroxy groups of these compounds showed different abilities to form intramolecular H bonds, depending on their relative positions and configurations on

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“…Le spectre ir, effectuC en solution 5 X molaire dans CC14 montre une raie fine a 3625 cm-' et une bande large a 3460 cm-', l'aspect du spectre Ctant tout a fait analogue a celui des y-diols saturks dkja dkcrits (25 …”

Section: Les Structures De Ces Lactones Sont Ctablies Par Rmn Du Protunclassified

Étude d'α-bromo-butyrolactones; application à la préparation du méthyl-3 phényl-4 Δ² buténolide et du méthyl-2 phényl-1 butène-2 diol-1,4 de configuration Z

Gharbi-Benarous¹,

Morales‐Ríos²,

Dana³

1985

Can. J. Chem.

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R e p le 12 septembre 1984 JOSYANE GHARBI-BENAROUS, MARTHA S. MORALES-RIOS et GILBERT DANA. Can. J. Chem. 63, 2384 (1985.A partir de dtrivCs dihydro-2,3 furanniques, on prtpare successivement les bromhydrines et les bromobutyrolactones correspondantes. Une mtthode d'tquilibration de ces dernikres par solvolyse dans le DMF est dtcrite. Les divers sttrCoisomtres sont sCparts et CtudiCs a I'ttat pur. Une rtaction d'tlimination catalyske par les bases faibles (LiBr) conduit au buttnolide correspondant avec un excellent rendement lorsqhe la lactone comporte un substituant en CP. La rtaction se produit quelle que soit la configuration de l'isomkre de dtpart. Une application de la reaction est dCcrite avec la synthkse stCrtostlective du y-diol du titre avec un rendement total supCrieur a 85%.JOSYANE GHARBI-BENAROUS, MARTHA S. MORALES-RIOS, and GILBERT DANA. Can. J. Chem. 63, 2384 (1985).Starting from 2,3-dihydrofuranic compounds, we prepare the corresponding a-bromohydrines and a-bromo-butyrolactones.A solvolytic method of equilibration of these bromolactones in DMF is described. All the stereoisomers are separated and studied. With a CP substituant, the elimination promoted by a weak base (LiBr) gives the A2 butenolide in good yield, whatever the starting isomer configuration may be. An application is given with the stereoselective synthesis of a trisubstitued ethylenic y-diol with a Z configuration.Au cours de nos ttudes concernant la dtshydratation des a-diols tthyltniques, nous avons montrt que les diols du type 1 peuvent conduire de f a~o n quasi-exclusive (1) a des composts dihydro-2,5 furanniques 2. Rtcemment, nous avons mis en tvidence l'existence d'un intermtdiaire rtactionnel, l'a-diol tthyltnique 3 de configuration E, isomkre de 1 (2) dont la formation semble nkcessiter le passage par un y-diol insaturt, de type 4,Z ou 4,E.Suivant sa configuration, ce diol 4 pourrait &tre un prtcurseur direct de 2 (isomkre 2 ) ou un prtcurseur de 3 qui Cvolue ensuite en 2 (2). Dans le present memoire nous dtcrivons une synthbe stlective et aiste du mtthyl-2 phtnyl-1 butkne-2 diol-1,4 (4, Ar = C6H5) de configuration Z.Cette synthkse consiste principalement a prtparer, i partir des deux dtrivts dihydro-2,3 furanniques 5 et 6 (3, 4), le buttnolide 7 (schtma 1): on forme d'abord les bromhydrines correspondant aux dtrivQ dihydrofuranniques 5 et 6; par oxydation ces bromhydrines donnent acces h des butyrolactones ( a-bromtes dont la dtbromhydratation en A'-butholide s'est avtrte facile. La rtduction de ce buttnolide en diol4 de confi-I guration 2 , a t t t rtaliste par action de LiAlH4.Nous discuterons la sttrtochimie des difftrentes &apes de ' Auteur a qui adresser la correspondance. LiBrLiAIH.-4,z

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Conformational Effects and Hydrogen Bonding in 1,4-Diols

Cited by 65 publications

References 8 publications

A study of the hydration of polyoxyethylene at low temperatures by differential scanning calorimetry

A study of the hydration of polyoxyethylene at low temperatures by differential scanning calorimetry

Carbohydrate Hydrogen-Bonding Cooperativity − Intramolecular Hydrogen Bonds and Their Cooperative Effect on Intermolecular Processes − Binding to a Hydrogen-Bond Acceptor Molecule

Étude d'α-bromo-butyrolactones; application à la préparation du méthyl-3 phényl-4 Δ² buténolide et du méthyl-2 phényl-1 butène-2 diol-1,4 de configuration Z

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Conformational Effects and Hydrogen Bonding in 1,4-Diols

Cited by 65 publications

References 8 publications

A study of the hydration of polyoxyethylene at low temperatures by differential scanning calorimetry

A study of the hydration of polyoxyethylene at low temperatures by differential scanning calorimetry

Carbohydrate Hydrogen-Bonding Cooperativity − Intramolecular Hydrogen Bonds and Their Cooperative Effect on Intermolecular Processes − Binding to a Hydrogen-Bond Acceptor Molecule

Étude d'α-bromo-butyrolactones; application à la préparation du méthyl-3 phényl-4 Δ2 buténolide et du méthyl-2 phényl-1 butène-2 diol-1,4 de configuration Z

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Étude d'α-bromo-butyrolactones; application à la préparation du méthyl-3 phényl-4 Δ² buténolide et du méthyl-2 phényl-1 butène-2 diol-1,4 de configuration Z