Solvent and substrate isotope effects on the enolization and carbon-acid ionization of isobutyrophenone

1996 ◽  
Vol 74 (12) ◽  
pp. 2481-2486 ◽  
Author(s):  
J.R. Keeffe ◽  
A.J. Kresge
Keyword(s):  
Isotope Effect ◽  
Isotope Effects ◽  
Isotopic Fractionation ◽  
Medium Effect ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Solvent Isotope ◽  
Carbon Acid ◽  
Fractionation Factors ◽  
Acid Ionization

Bromine scavenging was used to measure rates of acid-catalyzed enolization of isobutyrophenone in H2O and in D2O solution and of isobutyrophenone-α-d in D2O solution. The results provide the solvent isotope effect kH +/kD + = 0.56 and the substrate isotope effect kH/kD = 6.2 on the enolization reaction, both of which are consistent with the generally accepted mechanism for this process. The present results in combination with literature information also provide the solvent isotope effect on the enolization equilibrium, KE(H2O)/KE(D2O) = 0.92, and the solvent isotope effect on the ionization of isobutyrophenone as a carbon acid, kaK(H2O)/kaK(D2O) = 5.4, as well as the product of isotopic fractionation factor and medium effect, [Formula: see text], for isobutyrophenone enol and the medium effect, Φ = 0.47, for its enolate ion. The isotope effect on KE is the first ever determined for the keto–enol equilibrium of a simple aldehyde or ketone; its near-unit value is consistent with expectation on the basis of fractionation factors for the species involved. Key words: isobutyrophenone, keto–enol equilibrium, carbon-acid ionization, solvent isotope effects, isotopic fractionation factors.

Medium isotope effect for isobutyrophenone in aqueous solution. Solvent isotope effects on carbonyl group hydration

1989 ◽  
Vol 67 (5) ◽  
pp. 792-793 ◽  
Author(s):  
J. R. Keeffe ◽  
A. J. Kresge
Keyword(s):  
Isotope Effect ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Solvent Isotope ◽  
Solvent Isotope Effects ◽  
Fractionation Factors

A medium solvent isotope effect of Φ = 0.827 ± 0.013 was determined for transfer of isobutyrophenone from H2O to D2O. This result, in conjunction with the average solvent isotope effect on hydration of a number of carbonyl compounds, leads to [Formula: see text] as the fractionation factor for the hydroxyl group hydrogens of the hydration reactions' gem-diol products, which is consistent with the expectation that fractionation factors for uncharged hydroxyl groups should be unity. Keywords: isobutyrophenone, fractionation factors, solvent isotope effects, deuterium oxide.

Sauerstoffisotopieeffekte und Hydratstruktur von Alkalihalogenid-Lösungen in H2O und D2O / Oxygen Isotope Effects and Hydrate Structure of Alkali Halide Solutions in H2O and D2O

1973 ◽  
Vol 28 (2) ◽  
pp. 137-141 ◽  
Author(s):  
D. Götz ◽  
K. Heinzinger
Keyword(s):  
Oxygen Isotope ◽  
Oxygen Isotopes ◽  
Alkali Halide ◽  
Isotope Effects ◽  
Bulk Water ◽  
Hydration Water ◽  
Solvent Isotope Effect ◽  
Anion Effect ◽  
Solvent Isotope ◽  
Fractionation Factors

The fractionation of the oxygen isotopes in solutions of LiCl, NaCl. KCl, KBr, KJ and CsCl with H2O and D2O as solvent has been measured at 25 °C by means of the CO2-equilibration technique. As opposed to earlier measurements a slight anion dependence for the potassium halides has been found in H2O. This anion effect is much more pronounced in D2O. It even leads to a change in the directions of the 180 enrichment between cationic hydration water and bulk water for KCl and KBr. The absolute values of the fractionation factors for LiCl and CsCl, which differ in sign in H2O in agreement with positive and negative cationic hydration, respectively, as known from other kinds of measurements, is increased for LiCl and decreased for CsCl in D2O. There is no fractionation of the oxygen isotopes between hydration water and bulk water in both solvents for NaCl.The solvent isotope effect is explained by the stronger anion influence on the structure of the bulk water in D2O as compared with H2O. This stronger influence is expected because of the higher structural order in D2O than in H2O at the same temperature.

Solvent isotope effects in the oxidation of dipeptides by aqueous chlorine

1999 ◽  
Vol 77 (5-6) ◽  
pp. 997-1004 ◽  
Author(s):  
X L Armesto ◽  
M Canle L. ◽  
V García ◽  
J A Santaballa
Keyword(s):  
Isotope Effect ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Second Step ◽  
Solvent Isotope Effect ◽  
General Base ◽  
Peptide Oxidation ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

A kinetic study of the mechanism of oxidation of Ala-Gly and Pro-Gly by aqueous chlorine has been carried out. Among other experimental facts, the deuterium solvent isotope effects were used to clarify the mechanisms involved. In a first stage, N-chlorination takes place, and then the (N-Cl)-dipeptide decomposes through two possible mechanisms, depending on the acidity of the medium. The initial chlorination step shows a small isotope effect. In alkaline medium, two consecutive processes take place: first, the general base-catalyzed formation of an azomethine (β ca. 0.27), which has an inverse deuterium solvent isotope effect (kOH-/kOD- ~ 0.8). In a second step, the hydrolysis of the azomethine intermediate takes place, which is also general base-catalyzed, without deuterium solvent isotope effect, the corresponding uncatalyzed process having a normal deuterium solvent isotope effect (kH2O/kD2O ~ 2). In acid medium, the (N-Cl)-dipeptide undergoes disproportionation to a (N,N)-di-Cl-dipeptide, the very fast decomposition of the latter in deuterium oxide preventing a reliable estimation of the solvent isotope effect.Key words: chlorination, deuterium isotope effects, fractionation factors, peptide oxidation, water treatment.

Deuterium solvent isotope effect on the basicity of methanol. Deuterium fractionation factor for CH3OL2+ in aqueous solution

1986 ◽  
Vol 90 (4) ◽  
pp. 543-545 ◽  
Author(s):  
Joseph L. Kurz ◽  
Stanley L. Hazen ◽  
Linda C. Kurz
Keyword(s):  
Aqueous Solution ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Solvent Isotope

The solvent deuterium isotope effect on the hydroxide-ion-catalyzed conversion of acetaldehyde to its enolate ion

1988 ◽  
Vol 66 (9) ◽  
pp. 2440-2442
Author(s):  
J. R. Keeffe ◽  
A. J. Kresge
Keyword(s):  
Water Molecule ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Deuterium Isotope Effect ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Hydroxide Ion ◽  
Solvent Isotope

Rates of proton transfer from acetaldehyde to the hydroxide ion were measured by iodine scavenging in H2O and in D2O solution at 25 °C; the results give the solvent isotope effect [Formula: see text]. This value is somewhat more consistent with an estimate, made using fractionation factor theory, for hydron transfer directly from the substrate to the hydroxide ion than with another estimate, made similarly, for hydron transfer through an intervening water molecule.

Kinetic Solvent Isotope Effect for the Spontaneous Solvolysis Acetic and Propionic Anhydrides

1971 ◽  
Vol 49 (22) ◽  
pp. 3665-3670 ◽  
Author(s):  
R. E. Robertson ◽  
B. Rossall ◽  
W. A. Redmond
Keyword(s):  
Acetic Anhydride ◽  
Isotope Effect ◽  
Isotope Effects ◽  
Temperature Dependency ◽  
Solvent Isotope Effect ◽  
Propionic Anhydride ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

The large kinetic solvent isotope effects for the neutral hydrolysis of acetic and propionic anhydride show unusual temperature dependency; the former passing through a maximum at about 15°, the latter showing a minimum at 30°. This unusual temperature dependency is the consequence of widely different values of the apparent ΔCp≠ in H2O and D2O: the value for acetic anhydride in H2O being −74 ± 2 cal deg−1 mol−1 but −32 ± 4 in D2O. The corresponding values for propionic anhydride being −31 ± 2 in H2O but −94 ± 10 in D2O. The implications of these differences are discussed.

Studies in Solvolysis. Part IV. Substituent and Solvent Isotope Effects in the Solvolysis of a Series of Benzyl Trifluoroacetates

1972 ◽  
Vol 50 (12) ◽  
pp. 1886-1890 ◽  
Author(s):  
June G. Winter ◽  
J. M. W. Scott
Keyword(s):  
Isotope Effect ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
The Other ◽  
Solvent Isotope Effect ◽  
Other Hand ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

The rates of neutral hydrolysis of a series of 4-substituted benzyl trifluoroacetates 4-X-C6H4CH2OCOCF3, X = NO2, Cl, H, CH3, and OCH3 have been studied in water and deuterium oxide, both solvents containing 0.012 mol fraction of acetone. The alteration of the rates with the nature of the 4-substituent and the kinetic solvent isotope effect (k(H2O)/k(D2O)) are consistent with the proposal that the esters with X = NO2, Cl, H, and CH3 all react by an acyl–oxygen BAc2 mechanism. On the other hand, the same mechanistic criteria indicate that the 4-methoxybenzyl ester reacts by both the BAc2 and the SN1 alkyl–oxygen fission paths in equal amounts.

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