Pseudophase Approach to Reactivity in Microemulsions:  Quantitative Explanation of the Kinetics of the Nitroso Group Transfer Reactions betweenN-methyl-N-nitroso-p- toluenesulfonamide and Secondary Alkylamines in Water/AOT/Isooctane Microemulsions

2003 ◽  
Vol 42 (22) ◽  
pp. 5450-5456 ◽  
Author(s):  
L. García-Río ◽  
P. Hervés ◽  
J. C. Mejuto ◽  
J. Pérez-Juste ◽  
P. Rodríguez-Dafonte
Keyword(s):  
Transfer Reactions ◽  
Nitroso Group ◽  
Group Transfer ◽  
Quantitative Explanation ◽  
Kinetics Of

Nitroso Group Transfer Reactions between N-Methyl-N-Nitroso-P-Toluene Sulfonamide and N-Alkylamines in CTACL Micellar Aggregates

2006 ◽  
Vol 31 (3) ◽  
pp. 129-138 ◽  
Author(s):  
L. García-Río ◽  
J.C. Mejuto ◽  
M. Pérez-Lorenzo ◽  
P. Rodríguez-Dafonte
Keyword(s):  
Binding Constant ◽  
Transfer Reactions ◽  
Micellar Media ◽  
Cetyltrimethylammonium Chloride ◽  
Nitroso Group ◽  
Micellar Phase ◽  
Group Transfer ◽  
Pseudophase Model ◽  
Micellar Aggregates ◽  
Intrinsic Reactivity

The influence of micellar media upon the transnitrosation reaction between N-methyl-N-nitroso-p-toluensulfonamide (MNTS) and three linear alkylamines (n-octylamine (OA), N-methyl-n-octylamine (MOA) and N,N-dimethyl-n-octylamine (DMOA)) in micelles of Cetyltrimethylammonium Chloride (CTACl) has been studied. The rate constants were obtained and the pseudophase model allowed us to obtain the intrinsic reactivity constants in the aqueous pseudophase and in the micellar pseudophase (ki2 and kw2) and the binding constant of the amines to the micellar phase (Ka).

Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4′-bipyridine cocrystal with their crystal structures

2014 ◽  
Vol 70 (11) ◽  
pp. 1040-1045 ◽  
Author(s):  
Majid I. Tamboli ◽  
Vir Bahadur ◽  
Rajesh G. Gonnade ◽  
Mysore S. Shashidhar
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Transfer Reaction ◽  
Acyl Transfer ◽  
Transfer Reactions ◽  
Group Transfer ◽  
Hydrogen Bonding Interactions ◽  
Benzoyl Group ◽  
The Stability ◽  
Group Migration

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8,(1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2,(1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In(1), molecules are assembled around the crystallographic twofold screw axis (baxis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal(1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

Termination and Transfer Reactions in the Group Transfer Polymerizations of Acrylates Catalyzed by Mononuclear Early d-Block and f-Block Metallocenes:  A DFT Study

2007 ◽  
Vol 26 (9) ◽  
pp. 2157-2166 ◽  
Author(s):  
Simone Tomasi ◽  
Horst Weiss ◽  
Tom Ziegler
Keyword(s):  
Dft Study ◽  
Transfer Reactions ◽  
Group Transfer
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