Kinetics and mechanism of the hydrolysis of a (5,6)-spirophosphorane. Thermodynamics of the hydrolysis of cyclic five-membered and six-membered phosphonium ions

1991 ◽  
Vol 69 (12) ◽  
pp. 2064-2074 ◽  
Author(s):  
Glenn H. McGall ◽  
Robert A. McClelland
Keyword(s):  
Free Energy ◽  
Transition State ◽  
Rate Constants ◽  
Strong Acid ◽  
Membered Ring ◽  
Phosphate Esters ◽  
Hydrolysis Rate ◽  
Activation Free Energy ◽  
Stabilizing Effect ◽  
Hydrolysis Of

The cyclic five-membered phosphonium ion 2b (2-(2′-hydroxyethoxy)-2-phenyl-1,3,2-dioxaphospholan-2-ylium) derived from ring-opening of the (5,5)-spirophosphorane 1b (5-phenyl-1,4,6,9-tetraoxa-5-phosphaspiro[4,4]nonane) has been observed in neat CF3SO3H and at >85% H2SO4. The cation undergoes hydrolysis in the latter solutions, and an extrapolation has been carried out to obtain an estimate for reactivity in 100% water. Hydrolysis rate constants for phenyltrialkoxyphosphonium ions in water are 107, 100, and 5 × 10−3 s−1 for cyclic five-membered, cyclic six-membered, and acyclic derivatives respectively; these show an excellent correlation with rate constants for a similar series of phosphate esters. An investigation of the hydrolysis of the (5,6)-spirophosphorane 5 (5-phenyl-8,8-dimethyl-1,4,6,10-tetraoxa-5-phosphaspiro[4,5]decane) provides a clue as to the origins of these rate differences. This phosphorane can in principle hydrolyze via two isomeric cyclic phosphonium ions, the six-membered 14 and the five-membered 15. The former is thermodynamically more stable, being the only cation observed under equilibrating conditions of strong acid. However, the hydrolysis of the spirophosphorane, as well as the hydrolysis of fully formed 14, channels through the cyclic five-membered 15. A thermodynamic breakdown reveals that the 9.5 kcal mol−1 difference in activation free energy for the hydrolysis of five- and six-membered cyclic phosphonium ions is due to a combination of a higher free energy (2.5–4.5 kcal mol−1) for the five-membered cation, and a lower free energy (7–5 kcal mol−1) for the pentacoordinate transition state with the five-membered ring. This analysis also shows that a (5,6)-spirophosphorane is 6–8 kcal mol−1 more stable than a (6,6)-spirophosphorane. Thus, a five-membered ring has a significant stabilizing effect on a pentacoordinated phosphorus structure. The accelerated hydrolysis of cyclic phosphonium ions and phosphate esters with five-membered rings is caused by a combination of this stabilizing effect in the transition state and a destabilizing effect in the ground state associated with ring strain. Key words: phosphorane, hydrolysis, phosphate, phosphonium.

The additivity of methyl groups in electrophilic substitution

1972 ◽  
Vol 25 (11) ◽  
pp. 2369 ◽  
Author(s):  
KE Richards ◽  
AL Wilkinson ◽  
GJ Wright
Keyword(s):  
Free Energy ◽  
Transition State ◽  
Trifluoroacetic Acid ◽  
Rate Constants ◽  
Electrophilic Substitution ◽  
Methyl Groups ◽  
Activation Free Energy ◽  
First Order ◽  
Additivity Principle ◽  
Partial Rate

The rates of detritiation at the ring positions in the polymethylbenzenes have been obtained for exchange at 70�in anhydrous trifluoroacetic acid. The first-order rate constants are analysed in terms of the additivity principle, which is shown not to hold for this system; derived partial rate factors, describing the effect of ortho, meta, and para methyl groups on reactivity, decrease as the reactivity of the ring site increases. Much better agreement between observed and calculated results is obtained if the demand for stabilization made on the methyl groups in the transition state is assumed proportional to the activation free energy. This approach requires no more parameters than the additivity principle, but corrections for ortho-meta and meta-para buttressed methyl groups can give further improvement where required. The application of this "demand-dependent free energy relationship" to other systems, and the origin of the buttressing effects, are discussed.

Solvent effect as a criterion of solvolysis mechanism. Solvolysis of 3-acyl-1,3-diphenyltriazenes

1981 ◽  
Vol 46 (9) ◽  
pp. 2091-2103 ◽  
Author(s):  
Oldřich Pytela ◽  
Petr Svoboda ◽  
Miroslav Večeřa
Keyword(s):  
Transition State ◽  
Solvent Effect ◽  
Mole Fraction ◽  
Rate Constant ◽  
Rate Constants ◽  
Proton Donor ◽  
Hydrolysis Rate ◽  
Solvent Mixtures ◽  
Solvent Dependence ◽  
Hydrolysis Of

Solvent dependence of hydrolysis rate constants of 3-acetyl-1,3-diphenyltriazene (I) and 3-(N-methylcarbamoyl)-1,3-diphenyltriazene (II) has been followed in the solvent mixtures ethanol-water, methanol-water, dioxane-water, and formamide-water within the mole fraction x = 0.0 to 0.5 at 25, 35 and 45 °C. A criterion has been suggested, based on sign of change of logarithm of the observed rate constant in dependence on change of the solvent composition, for evaluation of the reaction molecularity and, hence, participation of water in the hydrolysis mechanism. It has been found that water takes part as a proton donor in the transition state of hydrolysis of the substrates studied.

Hydrolysis of amides. IV. Dilute acid hydrolysis of amides of the type R2CH-CONH2 and R3C-CONH2

1971 ◽  
Vol 24 (3) ◽  
pp. 471 ◽  
Author(s):  
PD Bolton ◽  
GL Jackson
Keyword(s):  
Free Energy ◽  
Hydrogen Bonding ◽  
Acid Hydrolysis ◽  
Rate Constants ◽  
Hydrolysis Rate ◽  
Dilute Acid ◽  
Dilute Acid Hydrolysis ◽  
Reasonable Explanation ◽  
Hydrolysis Of

Enthalpies and entropies of activation have been derived from rate constants measured over a range of temperature for the dilute acid hydrolysis of isobutyramide, diethylacetamide, α-methylbutyramide, cyclohexaneoarboxamide, cyclopentane-carboxamide, and trimethylacetamide. ��� These data, in combination with data for other amides produced earlier, show the hydrolysis rate constants to be dominated by steric influences but with a perturbing effect which is proportional to the number of α-hydrogens present in the substituent. The "α-hydrogen bonding" concept of hyperconjugation appears to offer a reasonable explanation of these perturbations. ��� Controlled steric changes are shown to be non-additive for this reaction and to exert their influence primarily through the enthalpy component of the observed free energy changes.

Kinetics of the hydrolysis of acetic anhydride in concentrated salt solutions

1971 ◽  
Vol 24 (12) ◽  
pp. 2547 ◽  
Author(s):  
DG Oakenfull
Keyword(s):  
Free Energy ◽  
Acetic Anhydride ◽  
Transition State ◽  
Activity Coefficients ◽  
Rate Constants ◽  
Water Structure ◽  
Salt Solutions ◽  
Measured Activity ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of the hydrolysis of acetic anhydride have been investigated in concentrated salt solutions at 20�. Sine salts were used in concentrations of up to 5 mol 1-1; all inhibited the reaction. ��� The salt effect was resolved into its component effects on the reactants and the transition state by use of the Bronsted-Bjerrum equation to calculate transition state activity coefficients from rate constants and measured activity coefficients of acetic anhydride. The effect of a salt on the free energy of the reactants was always significant and in some cases it was the major component of the effect of the salt on the free energy of activation. The enthalpy and entropy of transfer from water to 1 mol l-1 sodium chloride, for both acetic anhydride and the transition state, show the enthalpy-entropy compensation effect which is typical of aqueous solutions. ��� These salt effects are considered to be part of the general phenomenon of the effect of salts on the activity coefficients of non-electrolytes. The inhibition is not caused by formation of a complex between salt and acetic anhydride. Rate constants could not be correlated with dielectric constant and ionic strength, using Gold's equation, and changes in water structure which occur in these salt solutions were shown to have no direct effect on the reaction rate.

Effect of Medium on Reactivity for Alkaline Hydrolysis of p-Nitrophenyl Acetate and S-p-Nitrophenyl Thioacetate in DMSO-H2O Mixtures of Varying Compositions: Ground State and Transition State Contributions

2021 ◽  
Author(s):  
Ik-Hwan Um ◽  
Seungjae Kim
Keyword(s):  
Transition State ◽  
Alkaline Hydrolysis ◽  
Ground State ◽  
Rate Constants ◽  
Kinetic Data ◽  
Reaction Medium ◽  
Stepwise Mechanism ◽  
Rate Determining Step ◽  
Leaving Group ◽  
Hydrolysis Of

Second-order rate constants (kN) for reactions of p-nitrophenyl acetate (1) and S-p-nitrophenyl thioacetate (2) with OH‒ have been measured spectrophotometrically in DMSO-H2O mixtures of varying compositions at 25.0 ± 0.1 oC. The kN value increases from 11.6 to 32,800 M‒1s‒1 for the reactions of 1 and from 5.90 to 190,000 M‒1s‒1 for those of 2 as the reaction medium changes from H2O to 80 mol % DMSO, indicating that the effect of medium on reactivity is more remarkable for the reactions of 2 than for those of 1. Although 2 possesses a better leaving group than 1, the former is less reactive than the latter by a factor of 2 in H2O. This implies that expulsion of the leaving group is not advanced in the rate-determining transition state (TS), i.e., the reactions of 1 and 2 with OH‒ proceed through a stepwise mechanism, in which expulsion of the leaving group from the addition intermediate occurs after the rate-determining step (RDS). Addition of DMSO to H2O would destabilize OH‒ through electronic repulsion between the anion and the negative-dipole end in DMSO. However, destabilization of OH‒ in the ground state (GS) is not solely responsible for the remarkably enhanced reactivity upon addition of DMSO to the medium. The effect of medium on reactivity has been dissected into the GS and TS contributions through combination of the kinetic data with the transfer enthalpies (ΔΔHtr) from H2O to DMSO-H2O mixtures for OH‒ ion.

Hydrolysis of MgH2 in MgCl2 solutions as an effective way for hydrogen generation

2021 ◽  
pp. 38-52
Author(s):  
V. Berezovets ◽  
◽  
A. Kytsya ◽  
Yu. Verbovytskyy ◽  
I. Zavaliy ◽  
...  
Keyword(s):  
Hydrogen Generation ◽  
Strong Acid ◽  
Magnesium Hydride ◽  
Hydrolysis Reaction ◽  
Hydrolysis Rate ◽  
Reaction Yield ◽  
Buffer Solution ◽  
Passivation Film ◽  
Products Of Reaction ◽  
Hydrolysis Of

Magnesium hydride (MgH2) has a high hydrogen storage capacity (7.6 wt%) and the Mg element is abundant on the earth. Due to its strong reduction ability, even at room temperature it can provide the hydrogen yield reaching 15.2 wt% H (1703 mL/g) when interacting with water, which makes it very attractive for the application in supplying hydrogen for autonomous H energy systems. However, the hydrolysis reaction is rapidly inhibited by the Mg(OH)2 passivation layer formed on the surface of MgH2. In order to remove the passivation film and improve the efficiency of the MgH2 hydrolysis process, several methods including alloying, ball milling, changing the aqueous solution, have been successfully utilized. In this paper the process of hydrolysis of magnesium hydride in aqueous solutions of MgCl2 used as a promotor of the interaction has been studied in detail. It was found that the initial hydrolysis rate, pH of the reaction mixture, and overall reaction yield are all linearly dependent of the logarithm of MgCl2 concentration. It has been shown that pH of the reaction mixture in the presence of MgCl2 is well described by considering a system “weak base and its salt with strong acid” type buffer solution. Reference data for this hydrolysis reaction were also carefully analyzed. The mechanism and the kinetic model of the process of MgH2 hydrolysis in water solutions involved passivation of the MgH2 surface by the formed Mg(OH)2 precipitate followed by its repassivation have been proposed. The obtained after the hydrolysis reactions precipitates were studied using XRD and EDS. It was found also that the final products of reaction consist of Mg(OH)2 (brucsite type) and remaining MgH2. This fact shows that the formation of solid species such as MgCl2 xMgO yH2O at the studied conditions is unlikely and decreasing of pH the reaction mixture has a different nature.

Elucidating the role of solvents in acid catalyzed dehydration of biorenewable hydroxy-lactones

2020 ◽  
Vol 5 (4) ◽  
pp. 651-662 ◽  
Author(s):  
Gourav Shrivastav ◽  
Tuhin S. Khan ◽  
Manish Agarwal ◽  
M. Ali Haider
Keyword(s):  
Free Energy ◽  
Transition State ◽  
Energy Barrier ◽  
Free Energy Barrier ◽  
Activation Free Energy ◽  
Acid Catalyzed

Utilizing the differential stabilization of reactant and transition state in the polar and apolar solvents to lower the activation free energy barrier for acid-catalyzed dehydration of hydroxy lactones.

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