Rubber Chemicals from Cyclic Amines. V. Thiocarbamyl Sulfenamide Accelerators Derived from 3-Azabicyclo(3.2.2)Nonane

1971 ◽  
Vol 44 (4) ◽  
pp. 889-897 ◽  
Author(s):  
J. J. D'Amico ◽  
E. Morita
Keyword(s):  
Crosslink Density ◽  
Major Part ◽  
Order Reaction ◽  
Second Order ◽  
Crosslinking Reaction ◽  
Second Order Reaction ◽  
Amino Groups ◽  
First Order ◽  
Cyclic Amines ◽  
Order Rate

Abstract Evaluation of thiocarbamyl sulfenamides (I) prepared from 3-azabicyclo-(3.2.2) nonane and other amines indicates that the curing properties of stocks accelerated by (I) are influenced by the amino groups which constitute the thiocarbamyl and sulfenamide moieties, R and R′, respectively, and also vary with the formulation of the rubber stocks. The fastest cures are obtained when R is pyrrolidinyl or dimethyl and slowest cure when R′ is N-tert-butyl or N-morpholino. The lowest maximum crosslink density is obtained with morpholino- or piperidinothiocarbonyl sulfenamide. In a non-extended SBR black stock the crosslinking reaction generally proceeds as a second order reaction. The major part of the crosslinking reaction of the slower curing stocks proceeds by a fast first order rate followed by a slower first order rate.

Nucleophilic decomposition of α-disulfones

1969 ◽  
Vol 47 (6) ◽  
pp. 873-877 ◽  
Author(s):  
Paul Allen Jr. ◽  
Patrick J. Conway
Keyword(s):  
Activation Energy ◽  
Order Reaction ◽  
Second Order ◽  
Hammett Equation ◽  
Second Order Reaction ◽  
Kcal Mole ◽  
Arrhenius Activation Energy ◽  
Hydroxide Ion ◽  
First Order ◽  
Sulfur Bond

The sulfur–sulfur bond of α-disulfones is attacked by hydroxide ion in alcohol to yield sulfinate and sulfonate ion by a second-order reaction, first order in each of the reactants. With aromatic disulfones the ρ value of the Hammett equation is 0.2. The Arrhenius activation energy of the reaction of p-tolyl disulfone is 7.95 kcal/mole.

Kinetics and mechanism of nucleophilic displacements with heterocycles as leaving groups. Part 23. Studies at the borderlines between reactions proceeding (i) via free carbocations, (ii) via rate-determining formation of ion–molecule pairs, and (iii) via rate-determining nucleophilic attack on ion–molecule pairs

1986 ◽  
Vol 64 (6) ◽  
pp. 1161-1169 ◽  
Author(s):  
Alan R. Katritzky ◽  
Bogumil Brycki
Keyword(s):  
Order Reaction ◽  
Second Order ◽  
Kinetics And Mechanism ◽  
First Order Reaction ◽  
Nucleophilic Attack ◽  
First Order ◽  
Order Rate ◽  
Leaving Groups ◽  
Nucleophilic Trapping

Evidence is presented to demonstrate that at the borderline between first-order reaction via nucleophilic trapping of intimate ion–molecule pairs and first-order reaction via the formation of free carbocations, both mechanisms proceed independently, without merging. Similarly at the borderline between first-order (rate-determining formation) and second-order (rate-determining nucleophilic attack) reactions of intimate ion–molecule pairs, both reactions again proceed independently.

KINETIC LAWS FOR SURFACE REACTIONS IN FLOW SYSTEMS

1958 ◽  
Vol 36 (7) ◽  
pp. 1081-1088 ◽  
Author(s):  
K. J. Laidler
Keyword(s):  
Catalyst Surface ◽  
Order Reaction ◽  
Second Order ◽  
Graphical Form ◽  
Second Order Reaction ◽  
First Order ◽  
General Differential Equation ◽  
Special Cases ◽  
Reaction Proceeds ◽  
Set Up

A general differential equation is set up for the flow of reactant gases through a catalytic reactor, account being taken of changes in volume as the reaction proceeds and of the possibility that the catalyst surface is not completely available. Integrated solutions are given for three special cases and are presented in graphical form: (1) first-order reaction, the result being applicable whether the surface is completely available or not (Fig. 1); (2) second-order reaction with the surface completely available (Fig. 2); (3) second-order reaction with only a small fraction of the surface available (Fig. 3). The treatment is related to previous treatments of Hulburt, Thiele, and Wheeler.

Stability of radical anions derived from substituted 5-nitrofurans investigated by ESR spectroscopy

1985 ◽  
Vol 50 (7) ◽  
pp. 1594-1601 ◽  
Author(s):  
Jiří Klíma ◽  
Larisa Baumane ◽  
Janis Stradinš ◽  
Jiří Volke ◽  
Romualds Gavars
Keyword(s):  
Radical Anion ◽  
High Stability ◽  
Esr Spectroscopy ◽  
Reaction Path ◽  
Order Reaction ◽  
Second Order ◽  
Radical Anions ◽  
Second Order Reaction ◽  
Unpaired Electron Density ◽  
The Stability

It has been found that the decay in dimethylformamide and dimethylformamide-water mixtures of radical anions in five of the investigated 5-nitrofurans is governed by a second-order reaction. Only the decay of the radical anion generated from 5-nitro-2-furfural III may be described by an equation including parallel first- and second-order reactions; this behaviour is evidently caused by the relatively high stability of the corresponding dianion, this being an intermediate in the reaction path. The presence of a larger conjugated system in the substituent in position 2 results in a decrease of the unpaired electron density in the nitro group and, consequently, an increase in the stability of the corresponding radical anions.

Kinetics of the reaction between hexamethylenediisocyanate and 1-pentanol

1983 ◽  
Vol 48 (11) ◽  
pp. 3279-3286
Author(s):  
Slavko Hudeček ◽  
Miloslav Bohdanecký ◽  
Ivana Hudečková ◽  
Pavel Špaček ◽  
Pavel Čefelín
Keyword(s):  
Liquid Chromatography ◽  
Rate Constants ◽  
Reversed Phase ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction ◽  
Reversed Phase Liquid Chromatography ◽  
Consecutive Reactions ◽  
Phase Liquid ◽  
Kinetics Of

The reaction between hexamethylenediisocyanate and 1-pentanol in toluene was studied by means of reversed-phase liquid chromatography. By employing this method, it was possible to determine all components of the reaction mixture including both products, i.e. N-(6-isocyanate hexyl)pentylcarbamate and N,N'-bis(pentyloxycarbonyl)hexamethylenediamine. Relations for the calculation of kinetic constants were derived assuming a competitive consecutive second-order reaction. It was demonstrated that the reaction involved in this case is indeed a second-order reaction, and the rate constants of the first and second consecutive reactions were determined.

Analytical resolution of a parallel second-order reaction mechanism

2003 ◽  
Vol 35 (6) ◽  
pp. 246-251
Author(s):  
A. E. Croce ◽  
L. V. Mogni ◽  
C. Vicente Irrazábal
Keyword(s):  
Reaction Mechanism ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction ◽  
Analytical Resolution
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