課程名稱︰有機化學一
課程性質︰化學系系必修
課程教師︰楊吉水
開課學院：理學院
開課系所︰化學系
考試日期（年月日）︰ 97 / 12 / 04
考試時限（分鐘）： 10 : 20 ~ 12 : 30 , 130 分鐘
是否需發放獎勵金：是
試題 :
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請自 http://0rz.tw/e2594 下載圖片。（下載按鈕在網頁左下角）
A. 單一選擇題（每題三分，選十題作答，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. 簡答題（每大題十分，選七大題作答，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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