課程名稱︰有機化學 課程性質︰必帶 課程教師︰楊吉水 開課學院：工學院 開課系所︰化工系 考試日期（年月日）︰2012/01/12 考試時限（分鐘）：130 是否需發放獎勵金：是 （如未明確表示，則不予發放） 試題 : 16.Which of the following reactions gives aldehydes as the product? A) Br ｜ ｜ 1)xs NaNH2 3)9-BBN ／＼／＼ ───→ ───→ Br 2)H3O+ 4)NaOH,H2O2 B) 1)H2,Pt ＿==＿／ ───→ ￣ 2)O3 3)DMS C) O LiAlH4 ＼＿〃 ───→ ／ ＼ OCH3 D) ／＼ 1)Br2,H2O ｜　║ ────→ ＼／ 2)PCC E) Na2Cr2O7 ︽／＼ ───→ OH H2SO4,H2O 17.Considering the following statements about phenol (left) and cyclohexanol (right), which of them is TRUE? OH ／＼／ /＼／/＼ ｜○｜ / / OH ＼／ /／＼/ A)Both possess non-planar geometry. B)Upon treatment with concentrated H2SO4, both may undergo dehyhration. C)Both can be deprotonated by sodium amide. D)Both hydroxyl groups can be replaced by Br upon treatment with PBr3. 18.Which of the following conversions is the best choice for the reaction shown below to proceed? ┌┐ 1)└┘ ／＼／＼ ───→ ／＼／＼ OH 2)NaBr Br A)TMSCl,pyr. B)TsCl,pyr. C)NaH, then CH3I D)NaI E)H2SO4 19.Predict the product for the following reaction: 1)H2,Lindlar's catalyst 3-hexyne ───────→ 2)OsO4,NMO 3)NaHSO3,H2O H OH OH H HO OH ◥￥ ◥￥ ◥￥ ／＼／＼／　／＼／＼／ ／＼／＼／ ◢￥ ◢￥ ◢￥ OH H OH H H H I II III A)I B)II C)III D)I and II E)None of these 20.Rank the following phenol derivatives in the order of decreasing acidity. I) OH II) OH III) OH IV) OH ／＼／ ／＼／ ／＼／ ／＼／ ｜○｜ ｜○｜ ｜○｜ ｜○｜ ／＼／ ＼／ ／＼／ ／＼／ Br O2N A)I>IV>II>III B)IV>I>II>III C)IV>II>III>I D)III>II>I>IV E)I>II>III>IV 21.Which of the labeled C-H bonds is the weakest? Hc＿ Hd \／ ／＼╴／￣ Ha /￣\ ＼／＼ ｜ He Hb A)Ha B)Hb C)Hc D)Hd E)He 22.How many of the following reagents are NOT suitable for converting 1-butanol into 1-bromobutane? I)Br2 II)PBr3 III)1)conc.H2SO4;2)HBr IV)1)TsCl,pyr;2)NaBr V)HBr,ROOR A)1 B)2 C)3 D)4 E)5 23.Which of the following statements is NOT true in terms of the free-radical halogenation reactions of alkanes? A)Bromination has a better regioselectivity than chlorination. B)Fluorine is more reactive rhan iodine. C)The reaction mechanism is a chain reaction. D)The initiation step is always endothermic. E)Brominations are faster than chlorinations. 24.Which of the following comparisons between Grignard reagent and LAH is TRUE? A)Both are strong nucleophiles. B)Both reduce esters into tertiary alcohols. C)Water is commonly used as solvents when manipulating the two reagents. D)Upon treating with esters, the expulsion of alkoxides proceeds through SN2 mechanism. 25.Compound A has molecular formula C9H20. Compound A produces three constitutional isomers upon chlorination, and one constitutional isomer upon bromination. Which of the following is the possible structure of compound A? A) ／ ／ ｜　｜ ＼／ /\ B) ｜ \/ ／＼／＼ ｜ C) ＼／＼／＼ ｜ ｜ ｜ D) ｜ ｜ ／＼／＼ /\ E) ＼ ＼ ｜ ｜ ／＼／ ｜ 二.Essay Questions 1.Draw the mechanism (by using curve arrows) for each step of the following reaction. Remember to show all the intermediates and the final product. Br Br 1)xs NaNH2 \／ 2)xs EtOTs ／＼／￣ ─────→ ｜　｜﹋ 3)Na,NH3 ＼／ 2.Triphenylmethane readily undergoes autooxidation to produce a hydroperioxide: ／＼ ｜○｜ ＼／ ｜ ／＼／＼／＼ ｜○｜ ｜○｜ ＼／ ＼／ a)Draw the mechanism of autooxidation process and the corresponding hydroperoxide. b)In the presence of phenol, triphenylmethane undergoes autooxidation at a much slower rate. Explain this observation. c)When two trityl radicals, whose structures are shown below, react together, compound BB instead of hexaphenylethane is formed. Draw the mechanism for the formation of BB. Ph Ph Ph ＼▲￥ ￥▼＼ ／＼ ↗ Ph Ph Ph ｜○｜ ／ ＼／　　 ／ hexaphenylethane, not observed ｜　　　＼　 ／＼／＼／＼　 ＼ Ph H ╴ Ph ｜○｜ ｜○｜　　↘ ＼ \／￣＼╴／ ＼／ ＼／ ￥▼＼╴／￣＼ Ph Ph ￣ Ph BB, observed d)Explain why hexaohenylethane is NOT formed in the above reaction. 3.The following reaction does not produce the desired product CC, but does produce a product DD, which is a constitutional isomer of the desired product. Answer the following questions. OH OH ／＼/╴== 1)NaNH2 ／＼/＿==＿ ｜　｜ ￣ ───→ ｜　｜ ￣ ＼／ 2)MeI ＼／ CC a)Draw product DD and propose a mechanism to account for its formation. b)Starting from the same precursor, design a proper synthetic route to obtain CC. You don't have to write down any mechanisms, but make sure you put the reagents in the correct order and write down all the isolable intermediates. 4.Start from cyclohexane and acetophenone EE, write a synthetic route to synthesize compound GG within 10 steps. You don't need to write down any mechanism, but you have to write down the reagents required and isolable intermediates. Stereoisomers can be neglected. O ／＼CHO ║ ｜ ／＼／＼ ／＼／＼／＼ ｜○｜ ｜　｜　｜○｜ ＼／ ＼／　　＼／ EE GG 5.Start with acetylene and any other compounds that contain two carbon atoms or fewer as your carbon source, show a way to prepare the following products. You don't have to write down any mechanisms, but you have to draw all the isolable intermediates and put the reagents in the correct order. Neglect stereoisomers. a) (3S,4R)-3,4-dyhydroxyhexane and its enantiomer. b) O ／ ＼ ｜ ｜ ＼ ／ 　　　O (Hint: use acetylene as the only carbon source) 6.Propose a plausible synthesis for the following transformation in maximum steps of three. You don't have to show mechanisms, but you have to write down all the isolable intermediates and put all the reagents in the correct order. 〃 ／＼ ┌┤ ───→ ┌┤ Cl └┘ └┘ --

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