4-isopropylpyridine hydroperoxide crystals resulting from the aerobic oxidation of a 4-isopropylpyridine/4-propylpyridine mixture.
We model the interaction of side-chain and end-chain groups of poly(4-vinylpyridine) by a 5:1 molar ratio mixture of 4-isopropylpyridine (side-chain model) and 4-propylpyridine (end-chain model). We find that the 4-isopropylpyridine in the mixture is oxidized in a slow air flow to produce 4-isopropylpyridine hydroperoxide which in turn precipitates as lamellar crystals with monoclinic structure. The fact that the peroxide group is exchanged for the hydrogen of the tertiary carbon demonstrates the high activity of the latter and gives strong support for its involvement in the self-protonation mechanism proposed earlier for the poly(4-vinylpyridine)/pyridine gel.
Vaganova
Evgenia
E
Department of Organic Chemistry and the Farkas Center for Light-Induced Processes, The Hebrew University of Jerusalem, 91904, Jerusalem, Israel. gv@cc.huji.ac.il
Wachtel
Ellen
E
Leitus
Gregory
G
Danovich
David
D
Yitzchaik
Shlomo
S
D003198:Computer Simulation; D018360:Crystallography, X-Ray; D008956:Models, Chemical; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
C541143:4-isopropylpyridine hydroperoxide; D010545:Peroxides; D011725:Pyridines; C541145:4-propylpyridine; C541144:4-isopropylpyridine; D010100:Oxygen