推 srwff :化學系已收 09/12 11:28
課程名稱︰有機化學二
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）︰2009.06.18
考試時限（分鐘）：10:20~12:30，130分鐘
是否需發放獎勵金：是
（如未明確表示，則不予發放）
試題 :
備註：內容中含有[FigXX]者請下載圖片。http://0rz.tw/CwxEW
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A. 單一選擇題（每題三分，選十題作答，共三十分）
1. Rank the following compounds in an order of decreasing acidity?
CH2COOH CH2COOH CH2COOH CH3COOH CH2COOH
| | | |
CN Cl NO2 OH
A. B. C. D. E.
(A) C>B>A>D>E (B) C>A>B>E>D (C) D>E>B>A>C
(D) D>B>C>A>E (E) E>A>C>B>D
2. Which of the following compounds is the strongest Bronsted Base?
(A) [Fig01] (B) [Fig02] (C) [Fig03] (D) [Fig04] (E) [Fig05]
3. Which of the following reaction(s) will give rise to amines as the major
product?
NH2OH H2 NH2Ph H3O+
[Fig06] ───→ ────→ A [Fig07] ───→ ────→ B
H+ Ni H+
NH3 1)LiAlH4 NH3 Cl2, NaOH
[Fig08] ───→ ────→ C [Fig09] ───→ ────→ D
2)H2O H2O
NaCN H3O+
[Fig10] ───→ ────→ E
(A) All of above. (B) A, C, D, and E. (C) A, C, and D
(D) B and D (E) A, B, C, and E
4. In the following reactions, which one does not show the major product?
1. LAH Na(CH3COO)3BH
(A) [Fig11] ────→ [Fig12] (B) [Fig13] ───────→ [Fig14]
2. H2O
1. H2O2 1. excess CH3I
(B) [Fig15] ────→ [Fig16] (D) [Fig17] ───────→ [Fig18]
2. Heat 2. Ag2O3, Heat
H3PO2
(E) [Fig19] ────→ [Fig20]
5. Which of the following amines cannot be resolved into enantiomers?
(A) ethylmethylamine
(B) 2-butanamine
(C) 1,2,2-trimethylaziridine
(D) 2-methylcyclohexanamine
(E) methylethylpropylisopropylammonium iodide
6. Which of the following pairs is the best one for the preperation of
compound X by aldol condensation?
X: [Fig21]
(A) [Fig22]+[Fig23] (B) [Fig24]+[Fig25] (C) [Fig26]+[Fig27]
(D) [Fig28]+[Fig29] (E) [Fig30]+[Fig31]
7. A catalytic amount of sulfuric acid was added to a mixture of 1 mole acetic
acid and 1 mole of 18O labeled methanol. After a short period, which is the
correct isotopically labeled product?
CH3-18OH
[Fig32] ────→
H2SO4
(A) [Fig33] + H2-18O (B) [Fig34] + H2O (C) [Fig35] + H2O
(D) [Fig36] + H2O (E) [Fig37] + H2-18O
8. What is the product in the following reaction?
CH3MgI H3O+
[Fig38] ───→ ──→
Et2O
(A) [Fig39] (B) [Fig40] (C) [Fig41] (D) [Fig42] (E) [Fig43]
9. Which of the following statements is INCORRECT?
(A) An enamine is a stronger nucleophile than an enol.
(B) The alpha carbon refers to the carbon next to a carbonyl group.
(C) The pKa of a typical ketone is about 20.
(D) The Michael reaction is a nucleophilic addition to ketones or
aldehydes.
(E) Dialkylcuprates are good Michael donors.
10. Rank the following compounds in an order of decreasing boiling point.
A: ethanenitrile B: 1-propanol C: acetamide
D: methyl formate E: ethanoic acid
(A) C>E>B>A>D (B) C>A>B>E>D (C) E>B>C>A>D
(D) C>B>E>D>A (E) E>C>A>B>D
11. Rank the reactivity of the following acid derivatives toward nucleophilic
attack:
(i) propanyl chloride (ii) benzyl 2-methylpropanoate
(iii) ammonium butanoate (iv) 6-aminohexanoic acid lactam
(v) phthalic anhydride
(A) (iii)>(ii)>(i)>(v)>(iv)
(B) (i)>(v)>(iv)>(ii)>(iii)
(C) (v)>(i)>(iv)>(iii)>(ii)
(D) (i)>(v)>(ii)>(iv)>(iii)
(E) (v)>(ii)>(i)>(iv)>(iii)
12. Which of the following statements is INCORRECT?
(A) To convert acetophenone to α-bromoacetophenone by reacting with
bromine, it is better to carry out under acidic condition rather than
basic condition.
(B) To make α-acetylcyclohexanone, pyrrolidine enamine of cyclohexanone
is a better nucleophile than cyclohexanone enolate to react with
acetyl chloride.
(C) Phosgene is a good starting material for the preparation of
isocyanates.
(D) Basic hydrolysis of an ester generally gives a better yield than the
corresponding acidic hydrolysis, beacuse the nucleophilic attack by
hydroxide (OH-) is faster than that by water.
(E) Quaternary ammonium salts can work as phase-transfer catalysis to move
ionic reagents into organic solvents in which they would not otherwise
dissolve.
B. 簡答題 （每大題十分，選七大題作答，共七十分）
Attention: When you are asked to propose a reation mechanism, curved arrows
are always allowed.
1. When the (S,S) isomer of the amine shown below is treated with an excess of
methyl iodidem then silver oxide, and then heated, the major product is
Hofmann product but Zaitsev product is also formed.
[Fig44]
(A) Draw the structure of the Hofmann product and explain the observation
by Newman projection. (5%)
(B) When the amine is treated with H2O2 and heat, the Zaitsev product has
the (Z) configuration. Draw the transition state to explain the
stereochemistry. (5%)
2. Propose a mechanism for the following reaction [Robinson annulation]. (10%)
NaOCH3
[Fig45] + [Fig46] ───→ [Fig47]
3. Give the proper reagents and reaction intermediates for the following
synthesis. (5% for each)
(a) [Fig48] ─→ [Fig49]
(b) CH3CHCHCOOC2H5 ─→ [Fig50]
4. Provide the reagents for the following transformations. More than one step
may be required. (5% for each)
(a) [Fig51] ─→ [Fig52] (b) [Fig52] ─→ [Fig53]
5. Provide an appropriate synthesis for the target compounds. All of the
carbon atoms should be derived from the allowed starting materials. You may
use any common reagents. (5% for each)
Target (a) [Fig54] (b) [Fig55]
Allowed Starting Materials [Fig56] [Fig57] CH3OH CO2
6. Predict the organic products of the following reactions. (2% for each)
1.HOCH2CH2OH, H+
1.[Fig59] 2.Mg/ ether
(a) [Fig58] ─────→ (b) [Fig60] ────────→
2.NH2-NH2 3.CO2
4.H+, H2O
1.NaCN, H+
(c) CH3-N=C=O + [Fig61] ─→ (d) [Fig62] ─────→
2.HCl, H2O
1.AlCl3
(e) [Fig63] + [Fig64] ────→
2.H2O
7. Provide the reagents or products in the following reactions. (1% for each)
H2N-OH 1.LAH
[Fig65] ───→ [(A)] ───→ [(B)]
cat.H+ 2.H2O
[(C)] H3O+
[Fig66] ───→ nBu-CN ──→ [(D)]
H2O
[(E)] [(F)]
[Fig67] ───→ [Fig68] ───→ [Fig69]
excess I2
[Fig70] ──────→ [(G)] + [(H)]
excess NaOH
1.cat.NaOH
[Fig71] ──────→ [(I)]
2.NaOH, heat
Cl2, OH-
[Fig72] ────→ [(J)]
H2O
8. Define the following terms by giving an example: (2% for each)
(a) the Sandmeyer reaction (b) a sulfamide (c) a 2°amine
(d) lactone (e) thioester
9. The hydrolysis of a nitrile (A) to a carboxylic acid (C) involves initial
foundation of a primary amide (B). Provide a detailed mechanism for each
the following transformation.
H+, H2O
(A)[Fig73] ←───→ (B)[Fig75]
H+, H2O
(B)[Fig75] ←───→ (C)[Fig74]
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