Eine einfache Methode zur Darstellung wasser‐freier Alkohole

Lund, Hakon; Bjerrum, Jannik

doi:10.1002/cber.19310640204

Cited by 165 publications

(47 citation statements)

References 6 publications

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“…Water-free ethanol was prepared according to Lund& Bjerrum (1931) and sealed in glass capillaries. Single crystals were very difficult to grow: ethanol supercools readily, and when crystallization starts the crystals grow quite fast but with a high degree of disorder.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen bond studies. CXIII. The crystal structure of ethanol at 87 K

Jönsson¹

1976

Acta Crystallogr B Struct Crystallogr Cryst Chem

140

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Section: Introductionmentioning

confidence: 99%

Hydrogen bond studies. CXIII. The crystal structure of ethanol at 87 K

Jönsson¹

1976

Acta Crystallogr B Struct Crystallogr Cryst Chem

140

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“…Nitrate Esters All the nitrate esters and their a-dideuterated analogs were prepared from the reaction of their respective benzyl halides with silver nitrate in acetonitrile using Can (14) and stored under anhydrous conditions. Sodium Ethoxide Sodium ethoxide was prepared by the action of sodium with anhydrous ethanol under strictly anhydrous conditions in a nitrogen atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Isotope Effect Studies on Elimination Reactions. X. The Nature of The Transition State for the E_CO2 Reaction of Para- substituted Benzyl Nitrates with Base in 90% by Volume Ethanol–Water

Smith¹,

Pollock²,

Bourns³

1975

Can. J. Chem.

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Kinetic isotope effects have been determined for the Eco2 reaction of para-substituted benzyl nitrates with ethoxide in 90 vol.% ethanol–water at 20°. The nitrogen isotope effect, (k14/k15−1)100 decreased with increasing electron-withdrawing ability of the para-substituent; i.e. 2.26, 1.95, 1.60, and 0.84 for p-CH3, p-H, p-CF3, and p-NO2, respectively. Furthermore, the primary hydrogen–deuterium isotope effects increased also for electron-withdrawing substituents; i.e. kH/kD = 5.78, 6.06, 6.40, 6.67, and 7.05 for p-CH3, p-H, p-Br, p-CF3, and p-NO2, respectively. The results are discussed in terms of a recent theoretical treatment dealing with the effect of substituents on the nature of the transition state for a concerted E2 process. The conclusion is reached that any structural change which causes one bond (carbon–hydrogen) to be weakened more at the transition state will have a corresponding effect on the other bond (oxygen–nitrogen).

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“…Absolute Ethyl Alcohol This solvent was dried by the method of Lund and Bjerrum (30) and stored under anhydrous conditions. Absolute t-Butyl Alcohol This solvent was dried by refluxing over and distilling from sodium metal.…”

Section: Methodsmentioning

confidence: 99%

Kinetic Isotope Effect Studies on the Reaction of Benzyl Nitrate with Base in Varions Solvents

Pollock¹,

Smith²

1971

Can. J. Chem.

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The role of solvent and base on the nature of the transition state for the concerted one-step carbonyl elimination reaction of benzyl nitrate has been examined using rate and kinetic isotope effect techniques. The primary hydrogen–deuterium isotope effect was found to increase with increasing strength of the abstracting base, kH/kD = 5.94 and 6.41 at 30° for reaction with EtO−/EtOH and t-BuO−/t-BuOH, respectively. The nitrogen isotope effect decreased with increasing strength of the abstracting base, 2.07, 1.82, and 1.54% for reaction with OH−/40 vol % EtOH–H2O, EtO−/EtOH, and t-BuO−/t-BuOH, respectively. The conclusion is reached that an increase in the strength of the abstracting base leads to a more reactant-like transition state with decreased rupture of both the C—H and O—N bonds. The role of solvent on the nature of the transition state was examined by determining rates and nitrogen isotope effects for reaction in various ethanol–water and ethanol–dimethyl sulfoxide mixtures. The nitrogen effect was found to remain essentially constant in solvent mixtures ranging from 65 vol % EtOH–H2O on the one hand to 80 vol% EtOH–DMSO on the other hand where the rate constants differed by a factor of 100 fold. It is concluded that solvent plays only a very minor role in determining transition state structure for the concerted elimination reaction of a neutral substrate with base.

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Eine einfache Methode zur Darstellung wasser‐freier Alkohole

Cited by 165 publications

References 6 publications

Hydrogen bond studies. CXIII. The crystal structure of ethanol at 87 K

Hydrogen bond studies. CXIII. The crystal structure of ethanol at 87 K

Isotope Effect Studies on Elimination Reactions. X. The Nature of The Transition State for the E_CO2 Reaction of Para- substituted Benzyl Nitrates with Base in 90% by Volume Ethanol–Water

Kinetic Isotope Effect Studies on the Reaction of Benzyl Nitrate with Base in Varions Solvents

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Eine einfache Methode zur Darstellung wasser‐freier Alkohole

Cited by 165 publications

References 6 publications

Hydrogen bond studies. CXIII. The crystal structure of ethanol at 87 K

Hydrogen bond studies. CXIII. The crystal structure of ethanol at 87 K

Isotope Effect Studies on Elimination Reactions. X. The Nature of The Transition State for the ECO2 Reaction of Para- substituted Benzyl Nitrates with Base in 90% by Volume Ethanol–Water

Kinetic Isotope Effect Studies on the Reaction of Benzyl Nitrate with Base in Varions Solvents

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Isotope Effect Studies on Elimination Reactions. X. The Nature of The Transition State for the E_CO2 Reaction of Para- substituted Benzyl Nitrates with Base in 90% by Volume Ethanol–Water