The acid-catalyzed demetalation of 1-(tri-n-butylstannyl)-2-phenylethyne. A surprisingly small β-stannyl effect

1996 ◽  
Vol 74 (7) ◽  
pp. 1366-1368 ◽  
Author(s):  
I. Egle ◽  
V. Gabelica ◽  
A.J. Kresge ◽  
T.T. Tidwell
Keyword(s):  
Key Words ◽  
Isotope Effect ◽  
Acid Concentration ◽  
Rate Constant ◽  
Perchloric Acid ◽  
Hydronium Ion ◽  
Stabilizing Effect ◽  
Aromatic Product ◽  
Acid Catalyzed ◽  
The Difference

Rates of conversion of 1-(tri-n-butylstannyl)-2-phenylethyne to phenylethyne in H2O and D2O solutions of perchloric acid were found to be proportional to acid concentration, giving the hydronium ion rate constant [Formula: see text] and the isotope effect [Formula: see text]. The magnitude of this isotope effect suggests that the reaction occurs by rate-determining hydron transfer to the substrate, producing a vinyl carbocation; this carbocation then loses its tributylstannyl group, giving phenylacetylene as the only detectable aromatic product. The hydronium ion rate constant, when compared to the rates of protonation of phenylethyne and 1-(trimethylsilyl)-2-phenylethyne, gives a β-stannyl stabilizing effect of δΔG≠ = 6.6 kcal mol−1 and a differential β-stannyl/β-silyl effect of δΔG≠ = 3.2 kcal mol−1. These stabilizations are very much smaller than previously reported β-stannyl effects. Possible reasons for the difference are suggested. Key words: β-stannyl effect, β-silyl effect, carbocation stabilization, protodemetalation.

scholarly journals THE RATE CONSTANT OF THE REACTION BETWEEN FERROUS IONS AND HYDROGEN PEROXIDE IN ACID SOLUTION

1957 ◽  
Vol 35 (5) ◽  
pp. 428-436 ◽  
Author(s):  
T. J. Hardwick
Keyword(s):  
Hydrogen Peroxide ◽  
Acid Solution ◽  
Sulphuric Acid ◽  
Acid Concentration ◽  
Rate Constant ◽  
Perchloric Acid ◽  
Ferrous Ion ◽  
Ferrous Ions ◽  
Bimolecular Rate Constant

Identical values of the bimolecular rate constant of the ferrous ion – hydrogen peroxide reaction were obtained from intercomparisons of the methods previously used in following this reaction. In perchloric acid the bimolecular rate constant is unaffected by acid concentration; in sulphuric acid it increases slightly in acid concentrations above 10−2N. The results agree with and explain the differences between those obtained by Baxendale and by Dainton, but are only in marginal agreement with those recently reported by Weiss.

The hydrolysis of thioacetic, thiobenzoic, and three substituted thiobenzoic acids in perchloric and sulfuric acids

1978 ◽  
Vol 56 (7) ◽  
pp. 935-940 ◽  
Author(s):  
John T. Edward ◽  
Graeme Welch ◽  
Sin Cheong Wong
Keyword(s):  
Sulfuric Acid ◽  
Activity Coefficients ◽  
Acid Concentration ◽  
Perchloric Acid ◽  
Transition States ◽  
Sulfuric Acid Concentration ◽  
Thiobenzoic Acid ◽  
The Difference ◽  
Different Response ◽  
Hydrolysis Of

The rates of hydrolysis of thioacetic, thiobenzoic, and three substituted thiobenzoic acids increase with concentration of solvent sulfuric or perchloric acid to a maximum in 30–40% acid and then decrease. Yates–McClelland r, Bunnett–Olsen [Formula: see text], and Hammett ρ parameters, and entropies of activation indicate an AAC2 mechanism over this range of acid concentrations. In acid concentrations above 50–60% the rates increase sharply and the same mechanistic criteria now indicate an AAc1 mechanism. The difference between the rate–acidity profile of thiobenzoic acid and that of ethyl thiolbenzoate can be explained by the different response of the activity coefficients of their transition states to increase in sulfuric acid concentration.

The 4,4'-dimethoxytrityl carbenium ion by ionization of 4,4'-dimethoxytrityl alcohol in acetonitrile - aqueous perchloric and nitric acids containing electrolytes: kinetics, equilibria, and ion-pair formation

1999 ◽  
Vol 77 (5-6) ◽  
pp. 530-536 ◽  
Author(s):  
Juan Crugeiras ◽  
Howard Maskill
Keyword(s):  
Rate Constant ◽  
Perchloric Acid ◽  
Reaction Rate ◽  
Reaction Rate Constant ◽  
Ion Pair ◽  
Ion Concentration ◽  
Forward Rate ◽  
First Order ◽  
Hydronium Ion ◽  
Carbenium Ion

We have studied the equilibration shown in eq. [3] of 4,4prime-dimethoxytrityl alcohol in aqueous perchloric and nitric acids containing low proportions of acetonitrile using stopped-flow kinetics techniques. The rate constants for the overall progress to equilibrium, kobs, have been resolved into forward and reverse components using the equilibrium UV absorbance and a value for the molar absorptivity of the 4,4prime-dimethoxytrityl carbenium ion determined in concentrated aqueous perchloric acid. The forward reaction (rate constant kf) is first order in both the alcohol and the acid concentrations; the reverse reaction (rate constant kr) is pseudo first order with respect to the carbocation. At constant hydronium ion concentration, the forward rate constant increases linearly with the concentration of electrolyte, whereas the reverse rate constant decreases. These effects depend upon the nature of the anion, but not the cation, and are not ionic strength effects. At constant anion concentrations, kf in both acids, and kr in perchloric acid, are independent of hydronium ion concentration; however, kr decreases with increasing hydronium ion concentration at constant nitrate concentration. At nonconstant ionic strength, changes in kf and kr observed in increasing concentrations of perchloric acid are attributable wholly to changes in perchlorate concentration. A mechanism is proposed which involves pre-equilibrium protonation of the alcohol, heterolysis of the protonated alcohol to give a 4,4prime-dimethoxytrityl carbenium ion - water ion-molecule pair, then conversion of this into a dissociated carbenium ion in equilibrium with ion pairs. To account for the strong effects of perchlorate and nitrate upon the forward rate constants, it is proposed that these anions provide additional reaction channels from the ion-molecule pair. However, we find no evidence of acid catalysis in the reaction of the ion-molecule pair (in contrast to our finding for the reaction of the corresponding ion-molecule pair formed from dimethoxytritylamine in acidic media). Some of the elementary rate and equilibrium constants of the proposed mechanism have been evaluated.Key words: trityl, carbenium ion, stopped-flow, ion pair, ion-molecule pair.

Kinetics of acid-catalyzed hydration in aqueous solution of 1-methoxy- and 1-methylthio-2-phenylethyne and some related acetylenes

1987 ◽  
Vol 65 (2) ◽  
pp. 441-444 ◽  
Author(s):  
N. Banait ◽  
M. Hojatti ◽  
P. Findlay ◽  
A. J. Kresge
Keyword(s):  
Aqueous Solution ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Rate Constants ◽  
Acid Catalysis ◽  
The Other ◽  
Buffer Solutions ◽  
Hydronium Ion ◽  
Acid Catalyzed ◽  
Kinetics Of

The rates of conversion of C6H5C≡COCH3 to C6H5CH2CO2CH3 were measured in dilute HClO4/H2O, DCIO4/D2O, and H3PO4–H2PO2−/H2O buffer solutions, and the rates of conversion of C6H5C≡CSCH3 to C6H5CH2COSCH3, C6H5C≡CH to C6H5COCH3, 2,4,6-(CH3)3C6H2C≡CH to 2,4,6-(CH3)3C6H2COCH3, and p-CH3OC6H4C≡CCH3 to p-CH3OC6H4COCH2CH3 were measured in concentrated HClO4/H2O solutions, all at 25 °C. The reaction of C6H5C≡COCH3 showed general acid catalysis and gave the isotope effect [Formula: see text], which indicates that it proceeds through rate-determining proton transfer from catalyst to substrate. The hydronium ion catalytic coefficient for this reaction is [Formula: see text], and those for the other four, in the order given above, are [Formula: see text], and 8.5 × 10−6 M−1 s−1. Relative reactivities based on these rate constants are discussed.

scholarly journals Vinyl ether hydrolysis. XXIII. Solvent isotope effect on the reaction of divinyl ether catalyzed by the hydronium ion

1990 ◽  
Vol 68 (12) ◽  
pp. 2129-2130 ◽  
Author(s):  
A. J. Kresge ◽  
M. Leibovitch
Keyword(s):  
Vinyl Ether ◽  
Isotope Effect ◽  
Perchloric Acid ◽  
Divinyl Ether ◽  
Solvent Isotope Effect ◽  
Hydronium Ion ◽  
Solvent Isotope ◽  
Hydrolysis Of

Rates of hydrolysis of divinyl ether (CH2=CHOCH=CH2), measured in dilute H2O and D2O solutions of perchloric acid at 25 °C, provide the catalytic coefficients kH+ = 0.0084 M−1 s−1 and kD+ = 0.0028 M−1 s−1, and these lead to the isotope effect kH/kD = 3.0. The magnitude of this isotope effect indicates that this reaction occurs by rate-determining hydron transfer from catalyst to substrate and thus follows the conventional mechanism for vinyl ether hydrolysis. Keywords: divinyl ether, vinyl ether hydrolysis, solvent isotope effect.

Some Kinetic and Equilibrium Isotope Effects in the Isobutylphenone Eno land Enolate Ion System

1989 ◽  
Vol 44 (5) ◽  
pp. 406-412 ◽  
Author(s):  
Y. Chiang ◽  
A. J. Kresge ◽  
P. A. Walsh
Keyword(s):  
Acetic Acid ◽  
Isotope Effect ◽  
Acid Catalysis ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Free Energies ◽  
Kinetic Isotope ◽  
Hydronium Ion ◽  
Acid Catalyzed ◽  
Water Catalysis

The following kinetic isotope effects were determined for acid-catalyzed ketonization of isobutyrophenone enol and enolate ion through rate-determining hydron transfer from catalyst to substrate: enol, kH/kD = 3.30±0.07 (hydronium ion catalysis), kH/kD = 4.0 + 2.8 (acetic acid catalysis); enolate ion, kH/kD= 1.00 + 0.21 (hydronium ion catalysis), kH/kD = 3A \ +0.20 (acetic acid catalysis), kH/kD = 7.48±0.23 (water catalysis). The magnitude of these isotope effects, when assessed in terms of the free energies of reaction for the processes in which they occur, are consistent with Melander-Westheimer- Bigeleisen theory. An equilibrium isotope effect of KH/KD = 5.88±0.32 was also determined for the ionization of isobutyrophenone enol as an oxygen acid.

Participation of 19-ester groups in the cleavage of 2α,3α- and 5α,6α-steroid epoxides. A case of competition between participation and external nucleophile attack

1979 ◽  
Vol 44 (5) ◽  
pp. 1496-1509 ◽  
Author(s):  
Pavel Kočovský ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Hydrobromic Acid ◽  
Ester Group ◽  
Carbonyl Oxygen ◽  
Cyclic Carbonate ◽  
Cyclic Ether ◽  
Normal Reaction ◽  
Neighboring Group ◽  
Ether Oxygen ◽  
The Difference

Acid cleavage of the acetoxy epoxide IIIa with aqueous perchloric acid or hydrobromic acid gave two types of products, i.e. the diol Va or the bromohydrin VIa, and the cyclic ether VIII. The latter compound arises by participation of ether oxygen of the ester group. On reaction with perchloric acid the epoxide IVa gave the diol XIIIa as a product of a normal reaction and the isomeric diol Xa as a product arising by intramolecular participation of the carbonyl oxygen of the 19-acetoxy group. Participation of the 19-ester group is confirmed by the formation of the cyclic carbonate XI when the 19-carbonate IVb is treated analogously. On reaction with hydrobromic acid, the epoxide IVa gave solely the bromohydrin XIVa as a product of the normal reaction course. Discussed is the similarity of these reactions with electrophilic additions to the related 19-acetoxy olefins I and II, the mechanism, the difference in behavior of both epoxides III and IV, the dependence of the product ratio on the nucleophility of the attacking species, and the competition between participation of an ambident neighboring group and an external nucleophile attack.

Participation of 19-substituents in electrophilic additions to 6,7-unsaturated 5α-cholestane and B-homo 5α-cholestane derivatives; A case of competition between the participation of an ambident neighboring group and external nucleophile attack

1980 ◽  
Vol 45 (2) ◽  
pp. 559-583 ◽  
Author(s):  
Pavel Kočovský ◽  
Ladislav Kohout ◽  
Václav Černý
Keyword(s):  
Perchloric Acid ◽  
Hydrobromic Acid ◽  
Cyclic Ether ◽  
Cyclic Ethers ◽  
Neighboring Group ◽  
Acid Cleavage ◽  
Neighbouring Group Participation ◽  
Aqueous Perchloric Acid ◽  
The Difference ◽  
Electrophilic Additions

Hypobromous acid action upon the 6,7-unsaturated 19-substituted 5α-cholestans Va-Vc results in the formation of two types of products, the cyclic ethers IX as products of 5(O)n participation of the 19-substituent, and the bromohydrins X. All these compounds are formed from the 6α,7α-bromonium ions Va'-Vc'. Under the same conditions the B-homo-5α-cholestane derivatives VIIa-VIIc afforded solely the cyclic ethers XIV as products of 5(O)n participation of the 19-substituent in the cleavage of the bromonium ions VIIa'-VIIc'. Acid cleavage of the 6α,7α-epoxides VIb and VIc with aqueous perchloric acid or hydrobromic acid gave two types of products, i.e. the cyclic ethers XI and the diols XII or bromohydrines XIII. The cyclic ethers XI arise by 5(O)n participation of the 19-substituent. The B-homo-6α, 7α-epoxide VIIIc on cleavage with aqueous perchloric acid have solely the cyclic ether XVc and by treatment with hydrobromic acid VIIIc afforded the mixture of XVc, as the main product, and of the bromohydrin XVIc. Discussed is the similarity of the bromonium ion cleavage with the fission of the corresponding epoxides, the mechanism of these reactions and the difference in the behaviour of the isomeric olefins Ia-c, IIIa-c, Va-c and VIIa-c and epoxides IIb,c, IVb,c, VIb,c and VIIIb,c. The competition between ambident neighbouring group participation and external nucleophile attack is discussed as well as the dependence of the products ratio on the nucleophilicity of the attacking species.

Perchloric acid catalyzed acylation of anisole

1976 ◽  
Vol 10 (3) ◽  
pp. 363-364
Author(s):  
B. M. Savin ◽  
S. A. Kesler
Keyword(s):  
Perchloric Acid ◽  
Acid Catalyzed

scholarly journals Alkylation of glyceraldehyde-3-phosphate dehydrogenase with haloacetylphosphonates. An unusual pH-dependence

1991 ◽  
Vol 275 (3) ◽  
pp. 767-773 ◽  
Author(s):  
Y K Li ◽  
J Boggaram ◽  
L D Byers
Keyword(s):  
Isotope Effect ◽  
Rate Constant ◽  
Ph Dependence ◽  
Thiol Group ◽  
Order Rate Constant ◽  
Acidic Group ◽  
Irreversible Inhibitors ◽  
Effects Of Ph ◽  
Solvent Isotope ◽  
Bell Shaped Curve

Two new alkylating reagents, chloro- and bromo-acetylphosphonate, were found to be very effective thiol-blocking reagents. The pH-dependence of the reaction of BAP with 2,4-dinitrothiophenol (25 degrees C, I 0.5) shows a tailing bell-shaped curve (with a plateau at high pH) characteristic of two ionizing groups: the thiol group (pKa 3.2) and the phosphonate group (pKa2 4.6). The rate constant for the reaction of the monoanionic inhibitor with dinitrothiophenolate (k2 = 7 M-1.s-1) is 120 times larger than that of the dianionic species. The haloacetylphosphonates were found to be irreversible inhibitors of glyceraldehyde-3-phosphate dehydrogenase from a variety of sources. They react with the active-site thiol group (Cys-149) and are half-site reagents with yeast glyceraldehyde-3-phosphate dehydrogenase. Thus, when two of the identical four subunits are modified the enzyme is catalytically inactive. The effects of pH (7-10), 2H2O and NAD+ on the reaction with the yeast enzyme were examined in detail. NAD+ enhances the alkylation rates. The second-order rate constant does not show a simple sigmoidal dependence on pH but rather a tailing bell-shaped curve (pKa 7.0 and 8.4) qualitatively similar to that obtained with dinitrothiophenol. There is no significant solvent isotope effect on the limiting rate constants and a normal isotope effect on the two pKa values. The results are consistent with the more reactive enzyme species containing a thiolate and an acidic group that may either donate a proton to the dianionic haloacetylphosphonate or orient the inhibitor.

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