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.

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.

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.

Effect of Preferential Solvation on the Kinetics and Thermodynamics of Oxidation of Anilines by Nicotinium Dichromate

2005 ◽  
Vol 60 (10) ◽  
pp. 1105-1111 ◽  
Author(s):  
Durvas S. Bhuvaneshwari ◽  
Kuppanagounder P. Elango
Keyword(s):  
Free Energy ◽  
Preferential Solvation ◽  
Zero Order ◽  
Substituted Anilines ◽  
Isokinetic Relationship ◽  
Solvent Interactions ◽  
Activation Free Energy ◽  
First Order ◽  
Linear Free Energy ◽  
Energy Relationships

The nicotinium dichromate (NDC) oxidation of anilines, in varying mole fractions of benzene/2- methylpropan-2-ol mixtures, in the presence of p-toluenesulfonic acid (TsOH) is first order in NDC and TsOH and zero order with respect to anilines in the concentration range investigated. The NDC oxidation of 15 meta- and para-substituted anilines complies with the isokinetic relationship but not to any of the linear free energy relationships. The activation free energy data failed to correlate with macroscopic solvent parameters such as εr and ENT. Correlation of ΔG# with Kamlet-Taft solvatochromic parameters (α, β , π*) suggests that the specific solute-solvent-solvent interactions play a major role in governing the reactivity.

Aminolysis of naphthyl acetates catalyzed by cyclodextrins

1999 ◽  
Vol 77 (5-6) ◽  
pp. 950-959 ◽  
Author(s):  
Oswald S Tee ◽  
Michael J Boyd
Keyword(s):  
Aqueous Solution ◽  
Transition State ◽  
Rate Constants ◽  
Nucleophilic Attack ◽  
Reactivity Ratios ◽  
Aryl Group ◽  
First Order ◽  
Free Amine ◽  
Transition State Stabilization ◽  
Pseudo First Order

The effects of cyclodextrins (CDs) on the rate of nucleophilic attack on 1- and 2-naphthyl acetates (1-NA and 2-NA) in aqueous solution have been investigated. Analysis of the variation of the pseudo-first-order rate constants with [nucleophile] and [CD] affords rate constants for reaction of the nucleophiles with free ester (kN) and with ester bound to the CD (kcN). The reaction of 1-NA and 2-NA with the trifluoroethoxide anion is slowed down by β-CD as the ratios kcN/kN are 0.11 and 0.30, respectively. For reaction with the anion of 2-mercaptoethanol in the presence of α-CD, β-CD, "hydroxypropyl-β-CD" (hp-β-CD) and γ-CD, the reactivity ratios kcN/kN vary between 0.04 and 2.4, ranging from strong retardation to modest catalysis; the retardations arise with β-CD and hp-β-CD, which bind the esters strongly. By contrast, the attack of primary alkylamines is generally accelerated, and in many cases substantially so. For the aminolysis of 1-NA in the presence of β-CD, values of kcN/kN range from 7 to 460, assuming that free amine reacts with CD-bound ester. Alternatively, if the CD-catalyzed reaction involves free ester reacting with CD-bound amine, with rate constant kNc, the ratios kNc/kN vary from 43 to 140. Either way, there is appreciable catalysis of the aminolysis of 1-NA by β-CD. For the aminolysis of 2-NA, the effects are less dramatic: the ratios kcN/kN range from 0.19 to 17, and values of kNc/kN vary from 17 to 110. The reaction of 1-NA with n-hexylamine is also catalyzed by γ-CD. The variations of kinetic parameters with alkylamine chain length suggest that the CD-catalyzed aminolysis basically takes place by the attack of CD-bound amine on the free ester. However, there must be some stabilizing interactions between the aryl group of the ester and the CD during the reaction, since the transition state stabilization is different for 1-NA and 2-NA, as well for other esters.Key words: aminolysis, catalysis, cyclodextrin, ester cleavage, kinetics.

Rate constants, timescales, and free energy barriers

2016 ◽  
Vol 41 (1) ◽  
Author(s):  
Peter Salamon ◽  
David Wales ◽  
Anca Segall ◽  
Yi-An Lai ◽  
J. Christian Schön ◽  
...  
Keyword(s):  
Free Energy ◽  
Transition State ◽  
Rate Constants ◽  
Transition State Theory ◽  
State Theory ◽  
Energy Landscapes ◽  
Energy Barriers ◽  
Free Energy Landscapes

AbstractThe traditional connection between rate constants and free energy landscapes is extended to define effective free energy landscapes relevant on any chosen timescale. Although the Eyring–Polanyi transition state theory specifies a fixed timescale of

Pyrolysis of aryl azides. III. Steric and electronic effects upon reaction rate

1975 ◽  
Vol 28 (10) ◽  
pp. 2147 ◽  
Author(s):  
LK Dyall
Keyword(s):  
Transition State ◽  
Rate Constants ◽  
Reaction Rate ◽  
Steric Effects ◽  
Electronic Effects ◽  
Aryl Azides ◽  
Phenyl Azide ◽  
Methyl Group ◽  
First Order ◽  
Ortho Substituent

First-order rate constants have been measured for the pyrolysis of 15 phenyl azides in decalin solution. The rate for phenyl azide is increased only slightly by all para and many ortho substituents; in these cases Eact and ΔSact values are related linearly. ��� The very large rate increases when the ortho substituent is phenylazo, nitro, acetyl or benzoyl cannot be from steric or normal electronic effects and therefore identify a specific involvement of these groups in the transition state. This rate enhancement is reduced to scarcely significant levels by a 6-chloro or 6-methyl group in 2- nitrophenyl azide, but not by a 6-nitro group. These results raise doubts about recent claims1 to establish mechanism by measuring polar effects on rates of pyrolysis of azides in which steric effects might also operate.

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.

Hydrolysis of Monothio-β-diketones. II. Hydrolysis of three fluorinated Monothio-β-diketones

1974 ◽  
Vol 27 (11) ◽  
pp. 2357 ◽  
Author(s):  
M Leban ◽  
J Fresco ◽  
M Das ◽  
SE Livingstone
Keyword(s):  
Acid Solution ◽  
Hydrogen Sulphide ◽  
Trifluoroacetic Acid ◽  
Rate Constants ◽  
The Other ◽  
Hydrolytic Cleavage ◽  
First Order ◽  
Rapid Decomposition ◽  
Pseudo First Order ◽  
Hydrolysis Of

The rapid decomposition of the fluorinated monothio-β-diketones RC(SH)=CHCOCF3, 4-(3?-bromophenyl)-1,1,1-trifluoro-4-mercaptobut-3-en-2- one (R = m-BrC6H4), 4-(4?-bromophenyl)-1,1,1-trifluoro-4-mercaptobut-3- en-2-one (R = p-BrC6H4) and 1,1,1-trifluoro-4-mercaptopent-3-en-2-one(R = Me), in acid solution has been shown to occur by hydrolytic cleavage to yield the ketone RCOCH3, hydrogen sulphide and probably trifluoroacetic acid. The pseudo first-order rate constants for these compounds are (8.0�0.3)x 10-3, min-1, (6.0 � 0.6) x 10-3 min-1 and 0.12�0.01 min-1, respectively. The greater vulnerability of 1,1,1- trifluoro-4-mercaptopent-3-en-2-one, compared to the other two monothio-β-diketones, towards hydrolytic cleavage is related to the nature of the R substituent in that conjugation involving the terminal aromatic ring stabilizes the monothio-β-diketone.

Sign in / Sign up

Export Citation Format

Share Document