ORGANIC CH 4 HOMEWORK 1. The free radical monochlorination of ethane can yield two products as shown in the reactions below. The first reaction occurs but the second does not. CHsCHs + Cle > CHsCH2Cl + HCI CHaCHs + Cl, — 2 CH3Cl a. Givea step-by-step mechanism for each of the reactions. Show only the initiation and propagation steps. b. Using BDE’s, calculate the AHS for the propagation steps. Why does the second reaction not occur? ¢. Draw a potential energy diagram for both reactions propagation steps. Label reactants (R), products (P), intermediates (1), E,, AH’s and transition states (TS). 2. The monochlorination of ethane can be run using hydrogen peroxide (HOOH) as the free radical initiator. Give a step-by-step mechanism for the initiation and propagation steps for the reaction. (Hint: BDE's might help you decide which bond get homolytically cleaved in HOOH). Would this be a better method to use for the monochlorination of ethane? Explain. 3. When butane reacts with Br2 in the presence of Cl, both brominated and chlorinated products are obtained. Under such conditions, the usual selectivity of bromination is not observed. In other words, the ratio of 2-bromobutane to 1-bromobutane is very similar to the ratio of 2-chlorobutane and 1-chlorobutane. Give an explanation as to why we do not observe the normal selectivity expected for bromination. 4, AIBN is an azo compound (a compound with a N=N ) that is often used as a radical initiator. Upon heating, AIBN liberates nitrogen gas to produce two identical radicals: = a. Give two reasons why these radicals are so stable. b. Would the following azo compound also make a good radical initiator? Why or why not? at /5. Consider the following reaction and its possible products: of & ot af a. draw the free radical from which each is formed and give the BDE required to form each radical. b. Rank the products from highest % yield expected to lowest % yield expected. Explain. ¢. Givea step-by-step mechanism (including initiation and propagation) for the product formed in the highest % yield. Calculate the AH for each step and for the reaction overall. d. Draw the transition state for the RDS in part c. Use Hammond's postulate to explain what you have drawn.