課程名稱︰有機化學一 課程性質︰化學系必修 課程教師︰羅禮強 開課學院：理學院 開課系所︰化學系 考試日期（年月日）︰2012/11/22 考試時限（分鐘）：110 min (延長至 130 min) 是否需發放獎勵金：是 （如未明確表示，則不予發放） 試題 : ***以下以紅色表示凸出紙面，以黃色表示沒入紙面*** 1. Define an aprotic solvent and give two examples (name and structural formu- la). (5 points) 2. Write an equation to show the reaction between C2H5OH and CH3Li. Draw all nonbounding electrons and show electron flow with curved arrows. (4 points) 3. Draw the most stable conformation of the folloing substance: (4 points) (a) trans-1-bromo-3-(sec-butyl)cyclohexane (b) trans-1-bromo-2-fluorocyclohexane. 4. (a) Draw the Newman projection formula for the most stable conformation of the C2-C3 bond in 3-methylpentane; (b) Draw the Newman projection formula for the gauche conformation of the C2-C3 bond in pentane. (4 points) 5. Write a bond-line formula for each of the following compounds: (6 points) (a) 2,2-dicyclobutyl-5-ethyloctane (b) bicyclo[2.2.1]heptane (c) 3,7-diethyl-2,2-dimethyl-4-isopropylnonane. 6. Draw Fischer projection for the following compounds and use (R,S) system to assign the stereogenic centers. (7 points) (a) (b) OEt O ▕ ▕ ▕ || ／＼／＼ ／＼／＼ ∣ ▕ OH OH NH2 7. When the optical activity for a solution of compound A, prepared from 3 grams of A in 50 mL of EtOH, was measured, we observed a rotation of -8.1 degrees. The experimental data was recorded with a 20 cm sample cell mea- sured at 589.6 nm (the sodium D line) and 25 degC. Please calculate the spe- cific rotation for compound A and express it in a correct format. (6 points) 8. The following two alkyl halides both undergo nucleophilic substitution re- actions with NaCN (0.01 M) in EtOH. However, in equation (1), cyanide ion acts as the major incoming nucleophile, whereas in equation (2), EtOH acts as the major incoming nucleophile. Please provide explanation for this re- sult. (6 points) Cl NaCN (0.01 M) CN ＼／＼／ ----------------> ＼／＼／ ---(1) EtOH │ NaCN (0.01 M) │ ─ ----------------> ─ ---(2) ／＼ EtOH ／＼ Cl OEt 9. Which major product(s) would you expect to obtain from each of the following reactions? Please also indicate the mechanism (SN1, SN2, E1, or E2) by which the major product is formed. (8 points) (a) (b) EtONa KOH, MeOH ／＼／＼ ---------> (S)-2-Bromobutane ------------> Br EtOH 50 degC (c) 25 degC (R)-3-Bromo-e-methylhexane --------> MeOH (d) ＿ Cl MeOH D＿／ ＼／ ------> ＼＿／＼ H2O CH3 10. Predict the product(s) for the following reaction sequence. (4 points) (a) OTf (i) NaI, acetone ▕ ------------------> ＼／＼／＼ (ii) NaCN, DMF (b) Cl ＼／＼／ (i) NaI, acetone ▕ ▕ -----------------------> ＼／ (ii) CH3CO2Na, CH3CO2H 11. Compound B with the molecular formula C10H16 is known not to contain any triple bonds. When treated with excess hydrogen and a platinum catalyst, compound B is converted to 2,6-dimethyloctane. Ozonolysis of compound B fo- llowed by treatment with dimethyl sulfide yields 2 mol of HCHO, 1 mol of CH3COCH3, and a third compound C (C5H6O3). (a) What is the IHD of compound B? (1 point) (b) How many rings does compound B contain? (1 point) (c) How many double bonds does compound B have? (1 point) (d) What is the structure of compound B? (2 points) (e) What is the structure of compound C? (1 point) 12. Write a reasonable and detailed mechamism for the following transformations : (13 points) O (a) ∥ ▕ OH I2, NaHCO3 ／＼ ∥＼／＼／ ------------> ▕ O || ＼／ I O ▕＼／ (b) ＼／ ／＼ concd H2SO4 ／＼／＼／ ▕ || ＼／ -------------> ▕ || ▕ ＼／＼／＼／＼ heat ＼／＼／ ▕ OH (c) Br NaOEt, EtOH Ph ▕ -------------> Ph ＼／＼ heat ＼∥＼ ▕ Ph ▕ Ph 13. Give the major product(s) in each of the following reactions. (10 points) (a) ▕ ／＼／＼ (i) NaOEt, EtOH ▕ ▕ -----------------> ／＼／ (ii) D2, Pd/C Br (b) ▕ NaOEt, EtOH ＼／＼／ -------------> ▕ heat Br (c) Br2, CCl4 ／＼∥＼／ ------------> (d) Li, liq. NH3 H3C—C≡C—CH3 ---------------> (e) (i) Hg(OAc)2, H2O ＼＿ -------------------> ＿／─＼ (ii) NaBH4 14. Propose a reasonable synthetic strategy for the synthesis of trans-6-methyl-3-heptene from 4-methyl-1-pentyne. (6 points) 15. Perform retrosynthetic analysis for the following compound. You may use any compounds containing four carbons or fewer as the starting material. Pro- vide reagents for each step in your synthetic route. (7 points) OH ▕ ＼／＼／＼ ▕ OH 16. Starting with 2-methylpropene and using any other neede reagents, outline a synthesis of each of the following: (4 points) (a) (b) ▕ OH ＼│ Cl ／＼／ ／＼／ HO --

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