SYNTHESIS AND SOLVOLYSIS OF 4,7,7-TRIMETHYL-2-CHLORO-2-AZABICYCLO[2.2.1]HETPANE

4,7,7-Trimethyl-2-chloro-2-azabicyclo[2.2.1]heptane (1) has been prepared via an eight-step synthesis starting with d-camphor, in 43 % overall yield. In methanol at 70˚ 1 solvolyzed with a half-life of ca. 83 min. In the presence of silver perchlorate, 1 solvolyzed in methanol at room temperature with a half-life of less than 1 min demonstrating that silver ion catalysis could account for a rate acceleration of at least 2 x 103. Both the thermal and silver ion catalyzed methanolysis of 1 produced a mixture of exo-2-chloro-3,3,4-trimethyl-l-azabicyclo-[2.2.1]heptane and exo-2-methoxy-3,3,4-trimethyl-1-azabicyclo[2.2.1]heptane with the chlorine-containing product being formed in 77 and 59% yields in the silver ion catalyzed and thermal reactions, respectively. The mechanism of this unprecedented silver ion catalyzed internal return of chlorine is discussed. © 1969, American Chemical Society. All rights reserved.