Carroll, pp 543 - 547: # 1, 2, 4, 5, 9, 10, 11, 12, 15, 16, 18
1. Predict the final position(s) of the 14C label after acetolysis of the compound shown below. It does rearrange.
2. Consider a solvolysis reaction that can be intercepted with an added nucleophile (NaN3):
RX ---(NaN3, H2O)---> RN3 + ROH
Describe the conditions under which both of the following relationships hold.
Product ratio = [RN3] / [ROH] = kN [N3-] / kw [H2O]
Rate acceleration (R.A.) = ( kN [N3-] + kw [H2O] )/ kw [H2O]
When both of those relationships hold, show that the following is also true:
1 - (R.A.)-1 = % RN3 / 100
Which of the two data sets below fits the description above?
RX = 2-Propyl-OTs RX = 2-Adamantyl-OTs
[N3-] , M R.A. % RN3 R.A. % RN3
0.00 0 0 0 0
0.02 1.44 31 1.08 0.1
0.04 2.18 54 1.12 0.4
0.06 2.94 65 1.16 0.7
Describe the different behavior of these two reactions in terms of the nature of the R groups and the different mechanisms involved.
