Mechanism and catalysis of 2-methyl-3-thiosemicarbazone formation. Second change in rate-determining step and evidence for a stepwise mechanism for proton transfer in a simple carbonyl addition reaction

1973 ◽  
Vol 95 (17) ◽  
pp. 5637-5649 ◽  
Author(s):  
J. M. Sayer ◽  
W. P. Jencks
Keyword(s):  
Proton Transfer ◽  
Addition Reaction ◽  
Stepwise Mechanism ◽  
Rate Determining Step ◽  
Carbonyl Addition

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.

Nonenforced catalysis of the bisulfite carbonyl addition reaction by hydrogen bonding

1977 ◽  
Vol 99 (4) ◽  
pp. 1206-1214 ◽  
Author(s):  
P. R. Young ◽  
W. P. Jencks
Keyword(s):  
Hydrogen Bonding ◽  
Addition Reaction ◽  
Carbonyl Addition

Preparation of pyridine nucleotide analogs by the carbonyl addition reaction

1957 ◽  
Vol 70 (1) ◽  
pp. 87-106 ◽  
Author(s):  
Robert Main Burton ◽  
Anthony San Pietro ◽  
Nathan O. Kaplan
Keyword(s):  
Addition Reaction ◽  
Pyridine Nucleotide ◽  
Nucleotide Analogs ◽  
Carbonyl Addition

Proton transfer from imidazole, benzimidazole, and their 1-alkyl derivatives. FMO analysis of the effect of methyl and benzo substitution

1986 ◽  
Vol 64 (6) ◽  
pp. 1240-1245 ◽  
Author(s):  
Erwin Buncel ◽  
Helen A. Joly ◽  
John R. Jones
Keyword(s):  
Proton Transfer ◽  
Reaction Scheme ◽  
Frontier Molecular Orbital ◽  
Neutral Species ◽  
Ph Profile ◽  
Hydroxide Ion ◽  
Methyl Substitution ◽  
Rate Determining Step ◽  
Alkyl Derivatives ◽  
Conjugate Acid

The rate–pH profile for detritiation from the C-2 position of 1-methylimidazole has been determined in aqueous solution at 85 °C. The profile is consistent with a mechanism involving attack by hydroxide ion on the conjugate acid of the substrate to give an ylid intermediate in the rate-determining step. At higher pH, hydroxide-catalyzed exchange of the neutral species becomes increasingly important. Comparison of the second-order rate constants derived from the rate–pH profiles of imidazole, 1-methylimidazole, benzimidazole, and 1-methylbenzimidazole showed that methyl substitution caused the rate to increase by 2-to 3-fold while benzo annelation increased the rate by 10- to 20-fold. Frontier molecular orbital (FMO) analysis of the reaction scheme for proton transfer from imidazole, benzimidazole, and their 1-alkyl derivatives has been used to explain the rate-accelerating effect of methyl substitution and benzo annelation in these processes.

Mechanistic studies in strong acids. VIII. Hydrolysis mechanisms for some thiobenzoic acids and esters in aqueous sulfuric acid, determined using the excess acidity method

1982 ◽  
Vol 60 (24) ◽  
pp. 3061-3070 ◽  
Author(s):  
Robin A. Cox ◽  
Keith Yates
Keyword(s):  
Sulfuric Acid ◽  
Proton Transfer ◽  
Strong Acid ◽  
Weak Acid ◽  
Medium Composition ◽  
Hydrolysis Rate ◽  
Water Molecules ◽  
Aqueous Sulfuric Acid ◽  
Ion Formation ◽  
Rate Determining Step

The excess acidity method has been applied to hydrolysis rate data, obtained as a function of medium composition, for four thiobenzoic acids, thioacetic acid, eight ethyl thiolbenzoates, and eight ethyl thionbenzoates in aqueous sulfuric acid. The mechanistic behaviour thus revealed has both similarities to and differences from that of a typical ester like ethyl benzoate, which gives benzoic acid by an A-2 reaction involving two water molecules in weak acid, and by A-1 acylium ion formation in strong acid. The thioacids follow this behaviour, except that the A-2 process involves three water molecules, and that the mechanistic changeover occurs in 60% rather than 80% acid. The A-2 process for the ethyl thiolbenzoates is slow; the major hydrolysis mechanism is acylium ion formation, not in an A-1 reaction but by a concerted A-SE2 process involving both proton transfer to sulfur and carbon–sulfur bond breaking. The major proton transfer agent is the undissociated sulfuric acid molecule. The thionbenzoate esters, in contrast, undergo very fast A-2 hydrolysis; so fast, in fact, that the initial protonation of sulfur is the rate-determining step in acids more dilute than about 62% w/w. It appears that proton transfer to sulfur is a comparatively slow process.

scholarly journals Ultrafast Proton Transfer Reaction in Phenol–(Ammonia)n Clusters: An Ab-Initio Molecular Dynamics Investigation.

2021 ◽  
Author(s):  
Rakesh Pant ◽  
Reman Kumar Singh ◽  
G Naresh Patwari
Keyword(s):  
Proton Transfer ◽  
Ab Initio ◽  
Transfer Process ◽  
Md Simulations ◽  
Proton Transfer Reaction ◽  
Ab Initio Molecular Dynamics ◽  
Transfer Event ◽  
Rate Determining Step ◽  
Out Of Plane ◽  
Proton Transfer Process

The ability of phenol to transfer the proton to surrounding ammonia molecules in a phenol-(ammonia)n cluster will depend on the relative orientation of the ammonia molecules and a critical field of about 285 MV cm-1 is essential along the O–H bond for the transfer process. Ab-initio MD simulations reveal that for a spontaneous proton transfer process, the phenol molecule must be embedded in a cluster consisting of at least eight ammonia molecules, even though several local minima with proton transferred can be observed for clusters consisting of 5-7 ammonia molecules. Further, phenol solvated in large clusters of ammonia, the proton transfer is spontaneous with the proton transfer event being instantaneous (about 20-120 fs). These simulations indicate that the rate-determining step for the proton transfer process is the organization of the solvent around the OH group and the proton transfer process in phenol-(ammonia)n clusters follows a curvilinear path which includes the O–H bond elongation and out-of-plane movement of the proton and can be referred to as a “Bend-to-Break” process.

Sign in / Sign up

Export Citation Format

Share Document