Page 347 - Mechanism and Theory in Organic Chemistry

9. The norbornonium ion is also formed as an intermediate in the solvolysis of a
monocyclic arenesulfonate. This pathway is called the 7-route to the norbornonium ion.
What is the starting material for the 7-route to this ion?
10. Predict the products, and whether each will be chiral or not, from the solvolysis
of (a) optically active 9; (b) optically active 9a. How would you synthesize the sol-
volysis intermediates by the 7-route? (See Problem 9.)

OTs
4 &TS

/-./@, Write mechanisms for Reactions 6 and 7.

>
1 . Treatment of ketone 10, labeled with 14C in the 9-position, with acid gives the
11
hol
alc p with the label equally scrambled between the positions shown. Write a
mechanism for this reaction.

10 11
rite a mechanism for Reaction 8.
0 0 0 OH

(8)
4
CH3 CH3
14. The rearrangement of a-diazoketones to carboxylic acids or esters shown in
Equation 9 is known as the Wolff rearrangement.
0 R
11 - R"OH I
R-C-C-N-N - O=C-C-R' (9)
I + I
R ' OR

Taking into account the following facts, suggest a mechanism for the Wolff rearrange-
ment. (a) The kinetics are clearly first-order in substrate and first-order overall. (b) In