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）︰ 98 / 01 / 15
考試時限（分鐘）： 10 : 20 ~ 13 : 10 ， 共 130 分鐘
是否需發放獎勵金：是
註：試題中所有圖片以[Pic**], [Mass*], [IR*]表示者，
請自 http://0rz.tw/56OZi 下載圖片。（下載按鈕在網頁左下角）
試題 :
A.單一選擇題（每題三分，選十題作答，共三十分）
1. About Benzyl alcohol, which of the following description is not
appropriate?
(a) It can be oxidized to benzaldehyde by PCC.
(b) It can be obtained from the reduction of methyl benzoate by LiAlH4.
(c) In the presence of H2SO4, benzyl alcohol can react with ethyl bromide
to produce benzylethyl ether.
(d) It can be obtained from the reduction of benzaldehyde by NaBH4.
(e) Its IR spectrum shows strong peaks at 690 and 750 cm^-1.
2. How could the following synthesis be accomplished?
[Pic01] ─→ [Pic02]
(a) (i) SOCl2, (ii) Mg, ether, (iii) acetaldehyde, then H+
(b) (i) SOCl2, (ii) Li, ether, (iii) (CH3CH2)2CuLi, (iv) KMnO4, OH-
(c) (i) PBr3, (ii) Mg, ether, (iii) ethylene oxide, then H+, (iv) PCC,
CH2Cl2
(d) (i) PCl3, (ii) Li, ether, (iii) acetaldehyde, then H+, (iv) PCC, CH2CL2
(e) (i) NBS, (ii) CuI, ether, (iii) acetaldehyde, then H+
3. The mass spectrum of an organic halide compound that contains both Br and
Cl is shown below. Predict the Br/Cl ratio with the mass spectrum.
[Mass1]
(a) 1 (b) 2 (c) 0.5 (d) 0.33 (e) 3
4. Which type of compounds is more likely to give the strongest intensity for
the parent ion in mass spectrum?
(a) conjugated olefins (b) branched alkanes (c) alcohols
(d) aliphatic ethers (e) acids
5. Choose the best reagents to carry out the following reaction:
[Pic03] ─→ [Pic04]
(a) D2, Pd/C (b) 1. Mg, ether; 2. D2O (c) D2SO4, D2O, Δ
(d) DONa, Δ (e) BD3
6. How many of the following reactions give Ketone(s) as the major product
after normal work up procedure?
HgSO4 1. O3
i. [Pic05] ───→ ii. [Pic06] ─────→
H3O+ 2. (CH3)2S
KMnO4 CH3MgBr
iii. [Pic07] ───→ iv. [Pic08] ────→
H3O+ excess
(a) 0 (b) 1 (c) 2 (d) 3 (e) 4
7. How many cis-compound(s) could be obtained when
(1R,3S)-3-methylcyclohexanol reacts with the reagent I - V ?
I. SOCl2 II. PCl3 III. HCl IV. TsCl/ Pyridine then NaCl
V. Lucas reagent
(a) 1 (b) 2 (c) 3 (d) 4 (e) 5
8. Concerning the reactions of alcohols, which of the following statements is
NOT TRUE?
(a) Phenol is more acidic then cyclohexanol because of resonance effect.
(b) Lucas reagent can be used to distinguish 1°butanol from 3°butanol.
(c) Pinacol rearrangement is formally a dehydration reaction.
(d) The reaction of 2,3-dimethyl-2,3-butanediol reacts with sulfuric acid
at 100℃ give 3,3-dimethyl-2-butanone.
(e) Most enols are stable because of the resonance effect.
9. Concerning the major products in the reaction sequence shown below, which
of the following statements is NOT TRUE?
1. NaNH2 Na 1. MCPBA
[Pic09]────→ A ───→ B ─────→ C
2. EtBr NH3(l) 2. H+, H2O
(a) The product A must be hex-3-yne.
(b) The product B must be trans-hex-3-ene.
(c) The product C has broad IR absorption around 3300cm^-1.
(d) The product C undergo pinacol rearrangement in the acid condition.
(e) The product C must be optically active.
10. Concerning the reaction of X with O3, which of the following statement is
not true?
1. O3
X ────────→ [Pic10] + [Pic11] + [Pic12]
2. (CH3)2S, H2O
(a) X has sharp IR absorption around 3100cm-1.
(b) X shows IR absorption around 2150cm-1.
(c) The molecular weight of X is 150.
H2 / Lindlar's Reagent
(d) X ───────────→ diene
excess HBr
(e) X ─────→ tetra-halogen-substituted alkane
11. Which of the following absorption frequencies are more likely to appear
with significant intensities in the IR spectrum of CH3－C≡C－Ph?
(a) 3300, 2700, 1600 cm^-1 (b) 2900, 1710, 1380 cm^-1
(c) 2150, 1650, 990, 910 cm^-1 (d) 2900, 2150, 1380 cm^-1
(e) 2700, 2150, 1460 cm^-1
12. Which of the following statements about the Grignard reagents is NOT TRUE?
(a) The reagents are prepared from the reaction between alkyl or aryl
halides and Mg.
(b) The halides may be chlorides, bromides, or iodides.
(c) Primary, secondary, and tertiary halides may all used to prepare the
reagents.
(d) The solvent can be THF or ether.
(e) The reagent reacts as nucleophiles but not bases.
B. 簡答題（每大題十分，選七大題作答，共七十分）
1. (a) Determine the structire of compounds A-D. (8%)
(b) Give two characteristic IR peaks for compound D. (2%)
PBr3 1. Mg, ether [Pic14]
[Pic13] ──→ A ───────→ C ────→ D + HCl
2. compound B
3. H3O+
CrO3
[Pic13] ───→ B
H2SO4
2. Show how you might carry out the following transformations from the
indicated starting materials. You might use any reagent containing six or
fewer carbon atoms and any necessary solvents and inorganic reagents.
(a:6% and b:4%)
(a) [Pic15] ─→ [Pic16]
(b) [Pic17] ─→ [Pic18]
3. (a) Predict the products you would expect from the reaction of the
following compound with LAH, NaBH4, and Raney nickel, respectively.
(6%) [Pic19]
(b) Draw the structures of compounds A-D in the following two-step
synthesis. (4%)
A 1. C
[Pic20] ─→ B ──→ [Pic21]
2. D
4. A molecule with the molecular formula C7H7Br displays the following mass
spectrum. [Mass2]
(a) What is the structure of the molecule? (2%)
(b) What is the fragment of the base peak at m/e 91? (2%)
(c) Explain why the two peaks at m/e 170 and 172 are of nearly equal
intensity? (3%)
(d) What characteristic peaks do you expect to see in the IR spectrum of
this molecule? (3%)
5. Regarding the following synthetic stragegies, point out the errors and
correct them (5% for each.)
NaBH4, CH3CH2OH LDA 1. [Pic25]
(a) [Pic22] ────────→ [Pic23] ──→ [Pic24] ─────→ [Pic26]
2. H+
thionyl chloride
────────→ [Pic27]
1. KH PBr3, ether Mg, DMSO
(b) [Pic28] ───→ [Pic29] ──────→ [Pic30] ────→ [Pic31]
2. H+
1. [Pic32] H3PO4
─────→ [Pic33] ───→ [Pic34]
2. H+
6. Propose a reasonable mechanism with curved arrows for each of the following
reactions.
(a) Swern oxidation
(CH3CH2)3N
[Pic35] + [Pic36] + [Pic37] ─────→ [Pic38] + (CH3)2S + CO2 + CO + 2HCl
CH2Cl2
H2SO4
(b) [Pic39] ───→ [Pic40] + [Pic41]
heat
7. Write the major organic products A-J in the following reactions.
1. HCl (1 eq)
[Pic42] ─────────────→ A
2. HBr (1 eq)
HgSO4
[Pic42] ─────────────→ B
H2SO4, H2O
excess Cl2
[Pic42] ─────────────→ C
1. NaNH2
[Pic42] ─────────────→ D
2. 1-bromo-2-methylpropane
H2
[Pic42] ─────────────→ E
Lindlar's Catalyst
KMnO4, H2O
[Pic42] ─────────────→ F
neutral
H2
[Pic42] ─────────────→ G
Pd/C
1. Sia2BH, H2O
[Pic42] ─────────────→ H
2. H2O2, NaOH
1. O3
[Pic42] ─────────────→ I + J
2. H2O
8. Define the following terms (2% for each.)
(a) mercaptans
(b) Gilman reagent
(c) Fischer esterification
(d) tautomerism
(e) an IR-inactive vibration
9. The infrared spectra of three compounds A-C are shown below.
[IR1] [IR2] [IR3]
(a) Predict the functional groups present in each compound. (6%)
(b) Assign all the vibrational modes a-h. (4%)
Over, Good Luck and Happy New Year!
--
※ 發信站: 批踢踢實業坊(ptt.cc)
◆ From: 118.166.8.111