Aminolysis reactions. I. Mechanism of aminolysis and amidinolysis of p-nitrophenyl acetate in chlorobenzene

Anderson, Harry L.; Su, Chih-Wu; Watson, Joseph W.

doi:10.1021/ja01030a046

Cited by 23 publications

(13 citation statements)

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“…A third ether function seems to generate a new enhancement of reaction rates although third-order rate constants are decreasing in toluene/DMF mixture (1/1). 4.4. Di(n-dodecyl) Dodecanebis(dithioate) (6) + n-Buty lamine (1) (Table V). Bis(dithioester)s reacting with excess monoamine allow us a priori to observe eventually reactivity differences between the unreacted bis(dithioester) and the first-formed thioamide-dithioester.…”

Section: Resultsmentioning

confidence: 99%

“…It is clear the presence of ether functions in the chain of a bis(dithioester) greatly enhances its reaction rates toward primary amines. As dithioesters are useful reagents for protein modification,14 this result affords a way to Kinetics and Mechanism of Polythioamidation 4737 Table IX Kinetics of Reaction between n-Butylamine (1) and Di(n-dodecyl) l,12-Dodecanebis(dithloate) (6) promote rapid thioacylation reaction as needed for many of these very versatile substrates.…”

Section: Resultsmentioning

confidence: 99%

“…So, we think that third-order reactions are not the consequence of a nucleophilic attack of the first-formed 4 fen was supposed to be identical with fei. 6 Initial slopes, reaction intermediate by any amine doublet.…”

Section: Resultsmentioning

confidence: 99%

“…0.85 (t, 6 ), 1.25 (m, 40 H), 3.22 (t, 8 H), 3.57 (m, 4 H), 310.2 nm (e = 25 400 L-moL'-cm'1); 454.9 nm (< = 53 L-moL'-cm"1).…”

Section: Nmr (Cdci3)mentioning

confidence: 99%

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Kinetics and mechanism of polythioamidation in solution. 1. Reaction of mono- and bis(dithioester)s with excess amine

Deletre¹,

Lévesque²

1990

Macromolecules

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Thioamidation kinetics have been studied for reaction in solution between mono-and bifunctional amines and dithioesters near room temperature (30-50 °C) using large amine excess. We have used aliphatic reagents as well as several ether mono-and diamines and a diether bis(dithioester), which are able to maintain polythioamides in solution throughout the condensation reaction and thus give rise to significant results in polycondensation kinetics for which sufficient solubility is needed. Pseudo-first-order constants (first order relative to dithioesters) were correlated to amine concentrations and allowed to appreciate the values of secondand third-order reaction rate constants. The influences of solvent nature, structure of reagents, and temperature were examined in numerous examples. Added tertiary amines do not have significant influence on reaction rates whereas the primary amine concentration is an important factor of reaction rates. All the collected data are correlated through kinetic analysis with a reaction mechanism involving first a reversible nucleo-

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…0.85 (t, 6 ), 1.25 (m, 40 H), 3.22 (t, 8 H), 3.57 (m, 4 H), 310.2 nm (e = 25 400 L-moL'-cm'1); 454.9 nm (< = 53 L-moL'-cm"1).…”

Section: Nmr (Cdci3)mentioning

confidence: 99%

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Kinetics and mechanism of polythioamidation in solution. 1. Reaction of mono- and bis(dithioester)s with excess amine

Deletre¹,

Lévesque²

1990

Macromolecules

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“…The existence of this dependence is consistent with an aminolysis mechanism proceeding through the formation of a tetrahedral intermediate in non-aqueous solvents. [18][19][20][21][22][23][24] Kinetic data were fitted to an equation of the type: Eqn. ( 2) is formally analogous to eqn.…”

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confidence: 99%

Novel catalytic effects in ester aminolysis in chlorobenzene

et al. 2005

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Basicity of some aliphatic amines in mixed H2O?CH3CN solvents

Khan

Arifin

George

et al. 2000

Int. J. Chem. Kinet.

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The values of pK a ms (K a ms represents ionization constant of conjugate acid of amine base in mixed waterϪacetonitrile solvent) for all amines, except for charged amine bases, show a mild decrease (ca. 0.1-0.4 pK units) with the increase in CH 3 CN content from 2 to ϳ60% v/v. However, the pK a ms values at 70% v/v CH 3 CN become nearly equal or slightly larger (by Յ0.7 pK units) than the corresponding pK a ms at 2% v/v CH 3 CN for all neutral and charged amines. The values of pK a ms for phenol increase from 10.17 to 13.38 with the increase in the content of CH 3 CN from 2 to 70% v/v in mixed aqueous solvent. Taft reaction constants, *, obtained from the plots of pK a ms against ͚* for primary and secondary amines decrease by ca. 0.8 * units with the increase in the CH 3 CN content from 2 to 70% v/v. The values of pK a ms show an empirical linear relationship with the corresponding values of pK a w (where pK a w represents the pK a obtained in aqueous solvent containing 2% v/v CH 3 CN), which allows the estimation of a pK a in mixed H 2 O-CH 3 CN solvents from that in water.

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Aminolysis reactions. I. Mechanism of aminolysis and amidinolysis of p-nitrophenyl acetate in chlorobenzene

Abstract: The kinetics of aminolysis and amidinolysis of p-nitrophenyl acetate (p-NPA) in chlorobenzene at 25.0°w ere investigated. With diamines the pseudo-first-order rate constants fit the equation k¡, obSd = fc2(diamine) + &3(diamine)1

Cited by 23 publications

References 1 publication

Kinetics and mechanism of polythioamidation in solution. 1. Reaction of mono- and bis(dithioester)s with excess amine

Kinetics and mechanism of polythioamidation in solution. 1. Reaction of mono- and bis(dithioester)s with excess amine

Novel catalytic effects in ester aminolysis in chlorobenzene

Basicity of some aliphatic amines in mixed H2O?CH3CN solvents

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