Answer all four questions (total 5 pages). No notes, books, or smartphone may be consulted during this examination. However, you may use molecular models. All answers should be written in the spaces provided on the pages. Only legible answers can be graded.
I. (30 pts) A. (14 pts) When 1,3-cyclohexadiene is treated with 1 equivalent of HBr (with ROOR and light), two products are formed. (a) Suggest structures of these products. (b) Show the mechanism for their formation. If a series of steps are involved, clearly delineate all steps.
HBr + ROOR hν
B. (6 pts) (a) Predict the major product for photobromination (free radical bromination) of (R)-3-methylhexane. (b) Is the major product a single enantiomer? Or is it a racemic mixture?
C. (10 pts) Phenol is manufactured industrially by oxidation of isopropylbenzene
(cumene) in the following two-step sequence. Show the mechanism for the first step, the formation of cumene hydroperoxide. If a series of steps are involved, clearly show all steps. O2 O initiator R• OOH H3O+ OH +
cumene cumene hydroxperoxide phenol acetone
II. (40 pts)
A. (10 pts) When cis- and trans- 3,3-dimethyl-2-bromocyclohexanols are treated with strong bases (e.g., t-BuOK), they each yield a single product, as shown below. (a) Which product is from cis- and trans- isomers? (b) Explain how each transformation occurs. cis- or trans-3,3-dimethyl-2-bromocyclohexanol
O O t-BuOK t-BuOK
CH3 CH3 CH3 CH3 2 B. (12 pts) An industrial synthesis of glycerol (glycerin) is shown below. Provide structures for all intermediates A–D. Cl2 NaOH heat A H 2O B CH3 C3H5Cl C 3H 6O
propene Cl2 H 2O
OH HCl Ca(OH)2 HO OH H 2O heat D C C3H6O2 C3H7ClO2 1,2,3-propanetriol (glycerol, glycerin)
C. (9 pts) Draw structural formulas for the products formed when each compound is heated at reflux in concentrated HI. (a) (b) (c) O OCH3 O O
D. (9 pts) Show the structures of the major product of the reaction of 2,2,3- trimethyloxirane with each set of reagents. (a) MeOH/MeONa (b) MeOH/H+ (c) Me2NH MeOH MeONa (a) Me Me Me H MeOH, H+ O (b)
Me2NH (c)
III. (20 pts)
A. (10 pts) Predict the product formed by treating each vicinal diol with H2SO4.
OH H2SO4 OH – H2O
OH H2SO4
OH – H2O (racemic) 3 B. (10 pts) For the following epoxide (oxirane) synthesis from cis-2-butene, show structures of the bromohydrin and epoxide products. The stereochemistry must be shown clearly.
Br2 NaOH H H H 2O H 2O H 3C CH3 cis-2-butene a bromohydrin an epoxide
IV. (32 pts) Predict the principal reaction products of the following transformations, and be sure to indicate the stereochemistry, where appropriate. Answer all questions. 1. pyridinium chlorochromate (PCC) 1-hexanol
