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Unformatted text preview: problem set 8; Chem. 127/227, fall quarter 2007 1. In parts a-c, specify whether a primary or a secondary KIE is anticipated. What is the basis for each response? Formulate a transition structure for each transformation. (a) CH 2 H/D CHO HO CH 3 /CH 2 D CHO HO [i] Draw a transition structure for the process shown above. [ii] The product corresponds to a radical that is stabilized by both an electron withdrawing and an electron donating group. There is a special term that describes radicals stabilized in this manner. What is it? (b) (D)H R O + NC R H(D) O CN (c) O D/H H/D H/D H/D + CO 2. Ammonium formate is occasionally used as a reducing agent. When the deuterated form is used and the relative rates measured, one finds a substantial primary KIE. (a) Use this information to formulate a mechanism for the transformation. (b) Draw a reasonable transition structure for the process. NH 4 OCH(D)O R 1 R 2 O + ammonium formate R 1 R 2 ONH 4 H(D) + CO 2 3. (a) When heated, allyl alkyl sulfones loose sulfur dioxide. One example is shown below. Suggest a 3....
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- Fall '09