课程名称︰有机化学一 课程性质︰化学系系必修 课程教师︰杨吉水 开课学院：理学院 开课系所︰化学系 考试日期（年月日）︰ 97 / 12 / 04 考试时限（分钟）： 10 : 20 ~ 12 : 30 , 130 分钟 是否需发放奖励金：是 试题 : 注：试题中所有图片以[PicXX]表示者， 　　请自 http://0rz.tw/e2594 下载图片。（下载按钮在网页左下角） A. 单一选择题（每题三分，选十题作答，共三十分） 1. Which of the following reactions would give cyclohexylmethanol as the major product? (A) Methylenecyclohexane + borane in THF, followed by basic hydrogen peroxide. (B) Methylenecyclohexane + concentrate potassium permanganate in hot condition. (C) Methylenecyclohexane + mercuric acetate in methanol, followed by sodium borohydride. (D) Methylenecyclohexane + ozone, then dimethyl sulfide. (E) Methylenecyclohexane + MMPP in water. 2. Which of the following is not the possible product of the reaction shown below? [Pic01] (A) [Pic02] (B) [Pic03] (C) [Pic04] (D) [Pic05] (E) [Pic06] 3. Which of the following names of structures in INCORRECT? (A) [Pic07] 3-bromo-(3Z,5E)-octa-3,5-diene (B) [Pic08] trans-cyclodecene (C) [Pic09] (Z)-4-tert-butyl-5-methyloct-4-ene (D) [Pic10] 4,4-dichloro-5-cyclopropyl-1-iodoheptane (E) [Pic11] (2S,3S)-2,3-dibromobutane 4. Which of the following statements is/are INCORRECT? (1) The following reaction gives the Markovnikov product: [Pic12] + HBr (2) Free radical addition of HCl to unsymmetrical alkene gives anti-Markovnikov product. (3) Hydroboration of alkene is an example of stereospecific reaction. (4) Oxymercuration-demercuration is a method for converting alkenes to alcohol with anti-Markovnikov orientation. (5) In elimination reactions if the most substituted alkene predominates, it follows the principle of the Zaitsev's rule. (A) 2 and 4 (B) 1,3, and 5 (C) 2 and 3 (D) 3 only (E) 2 only 5. Which of the following is the Least Possible product of the reaction shown below? (3R,4S)-3-bromo-3,4-dimethylhexane + Sodium methoxide. (A) [Pic13] (B) [Pic14] (C) [Pic15] (D) [Pic16] (E) [Pic17] 6. For each of the following compounds, how many structures is/are optically active? (1) [Pic18] (2) [Pic19] (3) [Pic20] (4) [Pic21] (5) [Pic22] (A) 1 (B) 2 (C) 3 (D) 4 (E) 5 7. How many Z-alkenes are shown below? (1) [Pic23] (2) [Pic24] (3) [Pic25] (4) [Pic26] (5) [Pic27] (A) 1 (B) 2 (C) 3 (D) 4 (E) 5 8. Which stereogenic center of the followings is in R-configuration? (A) [Pic28] (B) [Pic29] (C) [Pic30] (D) [Pic31] (E) [Pic32] 9. For SN2 reactions, which of the following statements is CORRECT? (A) An SN2 reaction usually proceeds faster in polar protic than in polar aprotic solvents. (B) The following reaction will give a product of S-configuration. [Pic33] (C) (S)-CH3CH2CHDI will be obtained as the major product from the reaction of (R)-CH3CH2CHDI and NaI in acetone. (D) According to (CH3)3COH pKa = 18 and CH3OH pKa = 15.5 in water, (CH3)3CO- should give a higher rate than CH3O- toward a secondary alkyl bromide. (E) H3CS- is a better nucleophile than H3CO-. 10. For the SN1/E1 reactions of a specific alkyl halide, which of the following statements is INCORRECT? (A) The rate-determine step is the dissociation of the carbon-halogen bond that gives a carbocation intermediate. (B) The SN1/E1 reactions proceed through the same carbocation intermediate. (C) [Pic34] will give a racemic product. (D) Rearranged products are always formed. (E) Tertiary halides react faster than primary halides. 11. For E2 reactions, which of the following statements or results is CORRECT? (A) (R,R)-2,3-dibromoburane gives an E-alkane. (B) [Pic35] (C) Dehalogenation of 1,2-dihalides with I- has an E2-like transition state. For the following two substrates A and B, A undergoes dehalogenations with I- faster than B. ( A = [Pic36], B = [Pic37] ) (D) The nature of leaving group is unimportant in the reaction rate of E2 reaction. (E) KOH would be a better base than KO(tBu). 12. Ozonolysis of an unknown compound give CH2=O, CH3CHO and CH3COCHO. What are possible structures for the unknown compound? (1) [Pic38] (2) [Pic39] (3) [Pic40] (4) [Pic41] (A) 1 and 4 (B) 1 and 2 (C) 2 and 4 (D) 2 and 3 (E) 1 and 3 B. 简答题（每大题十分，选七大题作答，共七十分） 1. One of the constituents of turpentine is α-pinene, formula C10H16. The following scheme gives some reactions of α-pinene. Determine the reaction reagents and products A through J. [Pic42] Br2 A α-pinene C10H16 ─────→ C10H16Br2 CCl4 MCPBA B H3O+ C α-pinene C10H16 ─────→ C10H16O ────→ C10H18O2 D [Pic43] H2SO4 E(major) F(minor) α-pinene C10H16 ─────→ C10H17BrO ────→ C10H15Br (racemic) heat G [Pic44] α-pinene C10H16 ─────→ C10H18O2 (racemic) (1) O3 H α-pinene C10H16 ─────→ C10H16O2 (2) (CH3)2S KMnO4, OH- I α-pinene C10H16 ─────→ C10H16O3 (warm, concd.) Pt, H2 J α-pinene C10H16 ─────→ C10H18 2. (a) Explain why the following reaction gives only one product and two other alkenes are not observed. (4%) NaOCH3 [Pic45] ───→ [Pic46] ( [Pic47][Pic48] not observed ) (b) When pure (2S,3R)-3-iodo-2,3-diphenylpentane reacts with NaOCH3 in methanol, the products are two alkenes: A (pure isomer) and B (cis + trans mixture). Upon catalytic hydrogenation, alkenes A and B gives alkanes C. Draw all the possible structures of A, B, and C. (6%) 3. Propose a reasonable mechanism with curved arrows to account for all the products shown in the following reactions. ((a):3%; (b):3%; (c):4%) H3O+ (a) [Pic49] ────→ [Pic50] HBr (b) [Pic51] ────→ [Pic52] (CH3COO)2 H+ (c) [Pic53] ────→ [Pic54] 4. Propose a mechanism with curved arrows for the following reaction. ((a):4%; (b):3%; (c):3%) Br2 (a) [Pic55] ────→ [Pic56] [Pic58] (b) [Pic57] ────→ [Pic59] Br2 (c) [Pic60] ────→ [Pic61] 5. Show how you would synthesize each compound, starting with alkenes or cycloalkenes that contain no more than six carbon atoms. You may use any additional reagents you need. (a) [Pic62] (b) [Pic63] 6. Provide products (include all stereoisomers) for the following reactions. Indicate if the products are achiral/ optically inactive (A) racemic/ optically inactive (R) meso/ optically inactive (M) or chiral/ optically active (C). 1. Hg(OAc)2, MeOH MCPBA (a) [Pic64] ────────→ (b) [Pic65] ────────→ 2. NaBH4 1. O3 1. BH3, THF (c) [Pic66] ────────→ (d) [Pic67] ────────→ 2. (CH3)2S 2. H2O2, NaOH CHCl3, KOH (e) [Pic68] ────────→ 7. Label each pair as enantiomers, diastereomers, and same molecule. (a) [Pic69] and [Pic70] (b) [Pic71] and [Pic72] (c) [Pic73] and [Pic74] (d) [Pic75] and [Pic76] (e) [Pic77] and [Pic78] 8. (a) The specific rotation of (R)-mandelic acid is -158°. A solution that contains a mixture of enantiomeric acid (0.10 g/mL) has an observed rotation of +6.32° when placed in a polarmeter tube of 20cm long. What is the percentage of each enantiomer in the solution? (5%) (b) When (S)-2-bromobutane is heated in slightly basic aqueous solution, 2-butanol is formed. If the SN2 substitution proceeds double as fast as the SN1, calculate the e.e. and the observed rotation expected for the product (5%). (The specific of (S)-2-butanol is +12°). 9. Consider the following reactions and use the letters (A-J) to answer the following questions. NaNH2 KBr A [Pic79] ──────→ B [Pic80] ──────→ NH3(l) acetone H2O NaI C [Pic81] ──────→ D [Pic82] ──────→ nitromethane KOH NaSH E [Pic83] ──────→ F [Pic84] ──────→ ethanol ethanol NaI NaOCH3 G [Pic85] ──────→ H [Pic86] ──────→ acetone H+ H2SO4 I [Pic87] ──────→ J [Pic88] ──────→ ethanol (a) Reactions that proceed mainly through the SN2 mechanism. (b) Reactions that proceed mainly through the E2 mechanism. (c) Reactions that proceed mainly through the SN1 mechanism. (d) Reactions that proceed mainly through the E1 mechanism. (e) Reactions that do not undergo either one of the above reactions. Over, Good Luck! --

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