Rate Data and Isomer Distribution in the Reactions of the Halobenzenes with Mercuric Acetate in Acetic Acid. Partial Rate Factors for the Mercuration Reaction1-3

1962 ◽  
Vol 84 (9) ◽  
pp. 1650-1654 ◽  
Author(s):  
Herbert C. Brown ◽  
Gordon. Goldman
Keyword(s):  
Acetic Acid ◽  
Mercuric Acetate ◽  
Rate Data ◽  
Isomer Distribution ◽  
Partial Rate

STUDIES ON THE FORMATION OF HEXAMINE

1952 ◽  
Vol 30 (9) ◽  
pp. 687-693 ◽  
Author(s):  
T. R. Ingraham ◽  
C. A. Winkler
Keyword(s):  
Activation Energy ◽  
Acetic Acid ◽  
Acid Solution ◽  
Induction Period ◽  
Ammonium Nitrate ◽  
Sodium Acetate ◽  
Glacial Acetic Acid ◽  
Initial Rate ◽  
Acetic Acid Solution ◽  
Rate Data

Rate curves have been determined for the reaction of ammonium nitrate with formaldehyde in glacial acetic acid solution at 25 °C., 35 °C., 45 °C., and 55 °C. over a range of Initial mole ratios (formaldehyde: ammonia) of 0.75:1 to 9.0:1. Data obtained at 25 °C. show a definite induction period in the formation of hexamine. The length of the induction period is not changed by increasing ammonium nitrate concentrations above the theoretical (1.5:1), but may be appreciably shortened by initial additions of excess formaldehyde or of sodium acetate. From 35 °C. upward, the induction period is not apparent. The order of the reaction with respect to formaldehyde has been determined from initial rate data, and an activation energy calculated. The reactions in general appear analogous to those found in slightly acid aqueous systems.

SOME OXIDATION REACTIONS OF DELCOSINE

1957 ◽  
Vol 35 (4) ◽  
pp. 397-408 ◽  
Author(s):  
Ragini Anet ◽  
D. W. Clayton ◽  
Léo Marion
Keyword(s):  
Acetic Acid ◽  
Silver Oxide ◽  
Chromic Acid ◽  
Mercuric Acetate ◽  
Membered Ring ◽  
Oxidation Reactions ◽  
Ethyl Group ◽  
Compound C ◽  
Ring Oxidation ◽  
Group B

The alkaloid delcosine was oxidized by chromic acid in acetic acid, and also by the Oppenauer reaction, to dehydrodelcosine in which the carbonyl was shown by infrared absorption to be in a pentatomic ring. Oxidation of the alkaloid with silver oxide gave two products: (a) N-desethyldelcosine, which could be N-acetylated or converted back to the original base by ethylation, thus proving the presence of an N-ethyl group; (b) a compound, C24H37O7N, the properties of which agreed best with those of an internal ether, i.e., anhydrohydroxydelcosine. The action of N-bromosuccinimide on the alkaloid produced the same two compounds as silver oxide, plus a derivative, C22H33O7N, that proved to be N-desethyl-anhydrohydroxydelcosine. Potassium permanganate oxidized delcosine to a product, C22H31O7N, that had lost the N-ethyl group, contained the internal ether, and also a carbonyl in a five-membered ring. This same product was obtained on similar oxidation of N-desethyl-anhydrohydroxydelcosine. Oxidation of delcosine with mercuric acetate gave N-desethyldelcosine and N-desethyl-anhydrohydroxydelcosine, together with a compound that was very soluble in water and proved to be the carbinolamine formed by hydroxylation of the methylene in the N-ethyl group. These results are discussed in terms of a structure that is tentatively advanced for delcosine.

Notizen: Effect of Ortho Substitution on the Aminolysis of Active Esters in Aprotic Solvents

1977 ◽  
Vol 32 (11) ◽  
pp. 1359-1360 ◽  
Author(s):  
T. Kómives ◽  
A. F. Márton ◽  
F. Dutka ◽  
M. Lów ◽  
L. Kisfaludy
Keyword(s):  
Acetic Acid ◽  
Aprotic Solvents ◽  
Rate Data ◽  
Intramolecular Catalysis ◽  
Active Esters ◽  
Kinetics Of

Kinetics of the piperidinolysis of active esters of acetic acid in acetonitrile and chlorobenzene was investigated. The rate data show intramolecular catalysis for the aminolysis of 2-nitro- and 2-cyanophenyl esters, while reactions of 2,6-disubstituted compounds are hindered by steric inhibition.

Sign in / Sign up

Export Citation Format

Share Document