Kinetics and tunneling in the proton- and deuteron-transfer reaction between 2,4,6-trinitrotoluene and 1,8-diazabicyclo[5.4.0]undec-7-ene in some aprotic solvents

1982 ◽  
Vol 86 (17) ◽  
pp. 3418-3423 ◽  
Author(s):  
Naoki Sugimoto ◽  
Muneo Sasaki ◽  
Jiro Osugi
Keyword(s):  
Transfer Reaction ◽  
Aprotic Solvents ◽  
Deuteron Transfer

The kinetics of proton and deuteron transfer from 1-(4-nitrophenyl)-1-nitroethane to1,8-diazabicyclo[5.4.0]undec-7-ene in aprotic solvents

1982 ◽  
Vol 60 (13) ◽  
pp. 1692-1695 ◽  
Author(s):  
Kenneth T. Leffek ◽  
Przemyslaw Pruszynski
Keyword(s):  
Energy Barrier ◽  
Reaction Rate ◽  
Significant Contribution ◽  
Transfer Reaction ◽  
Isotope Effects ◽  
Activation Parameters ◽  
Proton Transfer Reaction ◽  
Potential Energy Barrier ◽  
Deuteron Transfer ◽  
Kinetics Of

1-(4-Nitrophenyl)-1-nitroethane reacts with the base1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in both acetonitrile and toluene solvents in a normal second-order proton-transfer reaction, in contrast to its behaviour with the base 2,7-dimethoxy-1,8-bis(dimethylamino)naphthalene in acetonitrile.The primary isotope effect, kHlkD = 12.0 at 25° in toluene is very similar to that observed by other workers for the reaction of 4-nitrophenylnitromethane with DBU under the same conditions. In acetonitrile solvent a kHlkD ratio of 7.8 was found at 25 °C. The isotope effects on the activation parameters for the reaction in both solvents indicate that tunnelling of the proton through the potential energy barrier makes a significant contribution to the reaction rate.

THE ORTON REARRANGEMENT IN APROTIC SOLVENTS: III. THE ACID-CATALYZED CHLORINATION OF ANISOLE BY A SERIES OF 4-SUBSTITUTED N-CHLOROACYLANILIDES

1966 ◽  
Vol 44 (23) ◽  
pp. 2901-2907 ◽  
Author(s):  
John M. W. Scott ◽  
June G. Martin
Keyword(s):  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Transfer Reaction ◽  
Probable Mechanism ◽  
Aprotic Solvents ◽  
Acid Catalyzed ◽  
Reported Data

Anisole has been chlorinated with a sequence of chlorinating agents generated by the reaction of a series of 4-substituted N-chloroacylanilides (4-X-C6H4NClAc (X = Me, H, and CN)) with a series of carboxylic acids (R—COOH (R = CF3, CCl3, CH2Cl, and CH3)). The isomer ratios of the 2- and 4-chloroanisoles produced in these reactions have been measured for each N-chloroacylanilide – carboxylic acid pair, and are found to be dependent on the strength of the catalyzing acid but independent of the structure of the N-chloroacylanilide within the precision of the reported data. These observations are consistent with both the termolecular scheme proposed in part II of this series and the Soper mechanism. However, evidence derived from these and other observations suggests that the termolecular scheme is still the most probable mechanism for the chlorine transfer reaction.

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