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）︰2011/12/01 考試時限（分鐘）：110 是否需發放獎勵金：是 （如未明確表示，則不予發放） 試題 : 一.Multiple choice Identify the choice that best completes the statement or answers the question. 1.What is wrong with the following mechanism? + - H2O ←┐ Br Br │─┘　　　↑　　　　 ｜ ＼／＼ ──┼──→ ＼／＼ │ │ └─────┘ A.There is no leaving group, so there should be no arrows. B.The arrow should be removing a proton from the H2O group. C.An arrow is also needed to indicate the loss of the leaving group. D.The arrow indicating the formation of C-Br bond (nulceophilic attack) should start at the bromide anion. 2.Identify the nucleophilic and electrophilic sites in the following reaction. O O 　　　║　 ║ ／＼／＼ HOMe ／＼／＼ │○│ Cl ─────→│○│　 OMe ＼／　　　　　　　 ＼／ A.Nucleophilic site: carbonyl O; Electrophilic site: carbonyl C B.Nucleophilic site: O of methanol; Electrophilic site: carbonyl C C.Nucleophilic site: benzene ring; Electrophilic site: Cl D.Nucleophilic site: O of methanol; Electrophilic site: carbinyl O 3.Which of the following reaction is the LEAST likely to occur? 　　　　　Br NaI　　　　　　I A.＼／＼／ ────→＼／＼／ 　OH OTs ／＼O │ ｜ pyr　　│ │ B. ＼／＼／ ────→ ＼／ Br NaOCH3 OCH3 C.＼／＼／ ────→＼／＼／ /\ /\ D D D D 　　 Br NaH H D.＼／＼／ ────→＼／＼／ /\ /\ D D D D ／＼／＼ ／＼／＼ │○│ Cl　H2O │○│ OH E.＼／ ────→＼／ 4.For a reversible reaction with ΔG°=2.72kcal/mol, what is the most possible value for the equilibrium constant K at 297K? A.0.1 B.0.01 C.0.001 D.10 E.100 5.Which of the following is the rate-determining step for the following dehydration? OH |/ H2SO4 │ ／＼ ─────→／〝 \＿/ \＿/ ..─┐ + OH │┌┐ OH2 |/ ↓│↓ |/ ／＼ H－SO3H ／＼ A.\＿/─────→\＿/ + OH2 |/_↖ +｜ ／＼￣ ／＼ B.\＿/─────→\＿/ 　+｜↙\H ｜ ／＼／ ／〝 C.\＿/─────→\＿/ /↘+ \_ OH2 　 |/↙\H　　　　 ｜ ／＼／ ／〝 D.\＿/─────→\＿/ 6.How many of the following compounds have (E) configuration? I II III OCH3 　　　　〃 F ／ ｜ Cl ｜ ｜ ／＼〃＼／ ＼〃＼ ／＼〃＼ F3C ｜　｜ ｜ Br Br ｜ CN 　 NH2 Cl F IV V VI OH Cl Cl ｜ Cl Br ｜ ／＼／ ／＼／ ＼〃＼ \╴/ 　　 ｜ ║ ｜ H O╴／￣＼__O ／＼／＼／＼ Cl ￣＼ / \ NH2 O__／ A.1 B.2 C.3 D.4 E.5 7.How many of the following indicated atoms have empty 2p orbitals? I II III IV V + + +| + Br← H-O ← ＼／ －N－ |＿OH2 / \ ║ ｜↖ |↖ ／\ ↖ ／/￣ ／＼ A.1 B.2 C.3 D.4 E.5 8.How many of the following compounds have tertiary carbon(s)? I ＿ II III IV V O / \ ／＼ O＼／O HC==＿ ｜＿F CHCl3 ｜ ｜ ◢￥ 　￣　＼ ／\ ＼／ H CH3 HN A.1 B.2 C.3 D.4 E.5 9.Which of the following route can be applied ro synthesize compound BB from AA (regardless of stereoisomers)? Br OH ｜ ｜ ? │ │ ╱╲╱╲ ─────→ ／＼／＼ ｜ │ 　　AA BB A.NaOMe; then MCPBA B.t-BuOK; then BH3; then H2O2, NaOH C.NaOMe; then BH3; then H2O2, NaOH D.NaOMe; then Hg(OAc)2; then NaBH4 E.t-BuOK; then MCPBA 10.How many of the following compounds are the expected major product(s) of HCl addition to the alkene shown below? Br ▼　 HCl 〃＼／＼ ────→ ? I II III IV V Cl Br Br Br Cl Cl Br Br ▼ ▼ Cl ▼ ￥ ▼ ￥ ￥ ￥ ／＼／＼ ＼／＼／＼ ／＼／＼ ／＼／＼ ／＼／＼ ｜ Cl A.1 B.2 C.3 D.4 E.5 11.How many of the following statements about SN2 mechanisms are FALSE? Assume the substrates undergo nucleophilic attack only once during the course of reaction. I.The rate equation must be second-order. II.The stereogenic carbon subjected to nucleophilic attack must proceeds with inversion of configuration. III.If the configuration of the stereogenic carbon subjected to nucleophilic attack is originally (R), it must be converted into (S) after the reaction, and vice versa. IV.The reaction proceeds without any intermediates. V.All the anions with negative charges on O atom are poor leaving groups. A.1 B.2 C.3 D.4 E.5 12.Which of the following cycloalkene, CC and DD, is more stable? / / _/| _/| ／/ ＼ ／/ ＼ ￣ ︾／ ￣ ＼〃 CC DD A.CC B.DD C.same D.additional information is required 13.Predict the major product and the pathway of the following reaction Br 　 ｜ |/ ／/＼ ／＼ O- K+ ｜ ｜───────→ ? ＼／ A. O＿/_ 　 \/ \ ／＼ │ │ ＼／ via SN2 mechanism B. O＿/_ \/ \ ／＼ │ │ ＼／ via SN1 mechanism C. │ 〃＼ ｜ ｜ ＼／　　via E2 mechanism D. ║ ／＼ ｜ ｜ 　　＼／ via E1 mechanism E. ║ ／＼ ｜　｜ ＼／　　via E2 mechanism 14.What is the expected major product of the following reaction sequence? Br ▼ 1.NaOEt, EtOH, 70℃ ／＼／＼ ｜　｜ ｜ ───────────→ ＼／＼／ 2a.O3, CH2Cl2, -78℃ ￥ H 2b.DMS A. ＿ O ／　＼〃 / \ \ / 〃＼＿／ O B. OH ▼ ／＼／＼ ｜　｜　｜ ＼／＼／ ▲ OH C. O ║ ／＼／＼ ｜　　　｜ 〃＼／＼／ O D. O═CH ｜ ／＼／＼ ｜　　　｜ ＼／＼／ ｜ HC═O E. O O 〃 ／＼〃 ／＼ ｜　｜　｜ H ＼／＼／ 15.Rank the following compounds according to the rate for undergoing SN1 mechanism. I II Br III IV ＼〃＼ ｜ Br Br ｜ Br ／＼／＼／＼ 〃＼／ ｜ ｜○｜ ｜○｜ ｜ ／＼ ＼／　　＼／ A.IV>II>III>I B.II>III>I>IV C.III>II>IV>I D.I>II>III>IV E.II>III>IV>I 16.How many of the following compounds are NOT able to undergo E2 process? I II ￥ III IV V / ／＼◢Br ｜ ｜ Br _/| CH3Br ｜　｜ ＼／/＼ ／/＼／ ／/ ＼ ◢＼／￥ Br ￣/＼／ t-Bu Br A.1 B.2 C.3 D.4 E.5 17.Which of the following reaction does NOT give a diol as product? A. ／＼／〝 1)MCPBA ｜○｜ ─────→ ＼／ 2)OH- B. ／＼／〝 1)MCPBA ｜○｜ ─────→ ＼／ 2)H3O+ C. ／＼／〝 H3O+ ｜○｜ ─────→ ＼／　 H2O D. ／＼／〝 1)OsO4,NMO ｜○｜ ─────→ ＼／ 2)NaHSO3,H2O 18.How many of the following reactions give the correct product? I II D2 D CH3 H Ph m-CPBA H　 O H ／〝／ ─→ ＼▲￥ +enantiomer ╴／ ───→ ￥／ ＼￥ Pt ￥　 ／￣ ◢￣￣ ◣ H CH3 D Ph Ph Ph III CH3 CH3 IV H ▼ ▼ ￥ ￥ ／＼◢Br NaOCH3 ／＼ ／＼／ 1)BH3 ／＼▲ ／＼▲H ｜　｜ ───→ ｜ ║ ｜　║ ───→ ｜　｜ + ｜　｜ t-Bu◤＼／￥ t-Bu◤＼／＼ ＼／＼ 2)H2O2,OH- ＼／▼D ＼／▼OH 　 CH3 CH3 D ￥ ￥ OH D V HO OH ╴ 1)OsO4,NMO ＼＿／ ／￣＼ ────→ ◢￥￥◣ Ph Ph 2)NaHSO3,H2O Ph H H Ph A.1 B.2 C.3 D.4 E.5 19.Which of the following statements concerning SN2 reactions is TRUE? A.H3CO- is a better nucleophile than H3CS- B.HO- is a better leaving group than H2O C.H2N- is a poorer nucleophile than HO- D.I- is a good nucleophile and a good leaving group E.The alkyl substituent at the β-position of an alkyl halide is too remote from the reaction center and, hence, does not affect the rate of the reaction. R-CH2CH2-X β α 20.Which of the following statements about carbocation is TRUE? A.Carbocation are Lewis acids. B.A carbocation has a half-filled p orbital. C.Carbocations are electron-rich species and thus are nucleophilic. D.The formation of carbocation is usually exothermic. E.Carbocations cannot be stabilized by adjacent geteroatoms such as N, O due to the electron-negativities of the heteroatoms. --

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