Name: CHM 332 FOURTH EXAMINATION All answers should be written on the exam in the spaces provided. Clearly indicate your answers in the spaces provided; if I have to guess as to what or where your answer is, it is wrong. Where applicable, outline the logic or mystical principle you used to arrive at your answer, as partial credit may be awarded for correct approaches. You may assume that standard work-up conditions (i.e. those required to obtain a stable, neutral product, like aqueous acid as example) follow each reaction on the exam. Clearly indicate stereochemistry where appropriate. Be careful not to show stereochemistry where none exists. This exam is long (as always) for the time allotted. You are strongly advised to read it through completely before you begin. (1)..10 pts...................._____ (2)..24 pts....................._____ (3)..21 pts....................._____ (4)..20 pts....................._____ (5)..16 pts....................._____ (6)..12 pts....................._____ TOTAL (103 pts)......…....._____ Percentage………………_____2 1. [10 pts] Name the following molecules according to IUPAC rules: a. Cl b. Name as an aniline compound: ClNO2H2N 2. [24 pts] Fill in the necessary reagents for each of the following steps (A-H): ICO2HCNNO2NH2N2+FBCDEFGHA1. Mg2. CO2 A: ______________________________ B: ______________________________ C: ______________________________ D: ______________________________ E: ______________________________ F: ______________________________ G: ______________________________ H: ______________________________3 3. [21 pts] Provide the appropriate reagents and conditions, or products for the following transformations, in a single step. a. NO2O2NBrheatNaNH2 b. OH2, Pd/C c. H3CCO2CH3heat d. KMnO4, H2O heat e. BrClOAlCl3 f. Na, NH3HO3SOCH3 g. NO2NH24 4. [20 pts] Propose a reasonable synthetic route to each of the following compounds, starting from benzene. Partial credit will be given for approaches without reagents. Remember: Selectivity is the name of the game-points will be deducted for reactions that result in ortho/para mixtures. a. BrNH2 b. ClH2N OH5 5. [16 pts] The following questions apply to the theoretical and historical aspects of benzene: a. Explain how the monobromination experiment of benzene assisted in the assignment of the structure of benzene, to which the molecular formula of C6H6 had been assigned. What key information did this experiment provide? C6H6 C6H5Br (only one product)Br2, Fe b. Explain how the second bromination experiment of bromobenzene assisted in the assignment of the structure of benzene. What key information was gained from this experiment? C6H5Br C6H4Br2 (three products)Br2, Fe c. Explain why 4n+2 is the perfect number of pi electrons for an aromatic system. d. Explain why every atom in an aromatic system like benzene must be sp2 hybridized.6 6. [12 pts] Short Answer: Answer 3 of the following 5 questions: a. Circle the compound below that will have a higher wavelength (λmax) for ultraviolet absorption. OO b. Propose a logical explanation as to why the first molecule shown below has a larger dipole moment than the second molecule. OPh PhPh PhO c. When HCl is added to 1,3-butadiene at room temperature or higher, the major product is 1-chloro-2-butene. Explain why this forms in preference to 3-chloro-1-butene. d. Predict which of the two following acids is more acidic. Provide an explanation for the differences in acidity utilizing inductive and/or resonance effects in your answer (whatever is most applicable). OHOO2NOHOH3CO7 e. Explain why an acyl group, like that found in acetophenone (shown below), is a meta director. Use resonance forms in your discussion.