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）︰2009.05.07 考試時限（分鐘）：10:10~12:30 (130) 是否需發放獎勵金：是 試題 : 試題中有[Fig**]者，請至http://tinyurl.com/ls49cg下載圖片(有機分子結構) A. 單一選擇題（每題三分，選十題作答，共三十分） 1. How many of the following molecules would be considered as aromatic compounds under the Huckel Rule? [Fig01][Fig02][Fig03][Fig04][Fig05][Fig06][Fig07][Fig08][Fig09] (A) 6 (B) 5 (C) 4 (D) 3 (E) 2 2. Which of the following statements is incorrect? (A) The Wolff-Kishner reduction is a chemical reduction that reduces a ketone (or aldehyde) to an alkane. (B) The Clemmenson reduction is a reduction of ketones (or aldehydes) to alkanes using AlCl3 / CuCl catalyst and hydrochloric acid . (C) The Wittig reaction converts an aldehyde or ketone to an alkene. (D) The Diels-Alder Reaction is a converted reaction and forms two new C-C bonds. (E) The Friedel-Crafts reactions are examples of electrophilic aromatic substitution reactions. 3. Rank the following acyl derivatives based on their reactivity as electrophiles toward hydroxide ion. 1) [Fig10] 2) [Fig11] 3) [Fig12] 4) [Fig13] 5) [Fig14] (A) 3>2>5>1>4 (B) 3>2>1>5>4 (C) 2>3>1>5>4 (D) 2>3>5>1>4 (E) 4>3>1>2>5 4. What is the major product labeled Z in the reaction sequence shown below? OH- KMnO4 H3O+ [Fig15] ──→ X ───→ Y ──→ Z heat I [Fig16] II [Fig17] III [Fig18] IV [Fig19] (A) only I (B) only II (C) I and II (D) only III (E) only IV 5. Rank the following molecules in order of decreasing reactivity for electrophilic aromatic substitution reactions. 1) [Fig20] 2) [Fig21] 3) [Fig22] 4) [Fig23] 5) [Fig24] 6) [Fig25] 7) [Fig26] (A) 6>3>2>5>4>1>7 (B) 6>2>3>5>4>1>7 (C) 3>6>2>5>4>7>1 (D) 3>2>6>5>7>4>1 (E) 2>6>3>5>4>7>1 6. Which of the follwing series are arranged correctively in order of functional groups of the following structures? i. [Fig27] ii. [Fig28] iii. [Fig29] iv. [Fig30] v. [Fig31] (A) Semicarbazone, oxime, acetal, imine, hydrazone. (B) Oxime, semicarbazone, hemiacetal, amine, hydrazone. (C) Semicarbazone, hydrazone, acetal, enamine, oxime. (D) Carbazone, oxime, hemiacetal, enamine, hydrazone. (E) Amide, acetal, oxime, imine, hydrazone. 7. What of the following compounds will give a POSITIVE Tollen's test? (A) [Fig32] (B) [Fig33] (C) [Fig34] (D) [Fig35] (E) [Fig36] 8. Rank the following carbonyl compounds in order of increasing equilibrium constant for hydration. 1) CH3COCH2Cl 2) ClCH2CHO 3) CH2O 4) CH3COCH3 5) CH3CHO (A) 4>1>2>5>3 (B) 2>5>3>4>1 (C) 2>1>3>5>4 (D) 3>2>5>1>4 (E) 3>1>2>5>4 9. Which of the nitrogen atoms in purine is(are) basic? purine[Fig37] (A) 1,2,3,4. (B) 1,2,3. (C) Only 4. (D) 1,4. (E) 2,3. 10. What would be the final product of the following reaction? [Fig39] [Fig40] H3O+ [Fig38] ────→ ────→ ──→ product H+ (A) [Fig41] (B) [Fig42] (C) [Fig43] (D) [Fig44] (E) [Fig45] 11. Which of the following compounds is imidazole? (A) [Fig46] (B) [Fig47] (C) [Fig48] (D) [Fig49] (E) [Fig50] 12. Which of the following dienes undergoes most efficiently in Diels-Alder reactions with methyl ethyl ketone? (A) [Fig51] (B) [Fig52] (C) [Fig53] (D) [Fig54] (E) [Fig55] B. 簡答題（每大題十分，選七大題作答，共七十分） 1. (a) Propose a mechanism for the forward reaction (to the right) of the following equilibrium. (5%) H+, H2O [Fig56] + H3C-NH2 ←───→ [Fig57] (b) When benzene and propenal are mixed together, no appreciable reaction occurs (reaction I). However, when AlCl3 is added, the reaction (reaction II) proceeds well. Propose a mechanism for the reaction II. reaction I : [Fig58] + [Fig59] ───→ No reaction AlCl3 reaction II: [Fig58] + [Fig59] ───→ [Fig60] + AlCl3 2. (a) Reaction of cis-2,3-epoxybutane and triphenylphosphine generates 2-butene. Propose a mechanism for this reaction. (7%) (b) What is the stereochemistry of the double bond in the product (cis or trans)? (3%) 3. Show how you would accomplish the following syntheses. You can use any necessary reagents. (a) [Fig61] to [Fig62] (b) [Fig63] to [Fig64] (c) [Fig65] to [Fig66] 4. The [4+4] cycloaddition reaction between two 1,3-butadiene molecules is thermally forbidden but photochemically allowed, which gives product A. In contrast, the corresponding [4+2] cycloaddition reaction is thermally allowed, which gives product B. (a) Draw the structures of A and B. (2%) (b) Draw the HOMO and LUMO of 1,3-butadiene in the ground state. (4%) (c) Use MO theory to explain why A is photochemically allowed but thermally forbidden. (4%) 5. Provide the necessary reagents for the following synthetic schemes. (1% for each and 10% total) (A) (B) (C) 1) [Fig67] ──→ [Fig68] ──→ [Fig69] ──→ [Fig70] (D) (E) (F) 2) [Fig67] ──→ [Fig71] ──→ [Fig72] ──→ [Fig73] (G) (H) (I) (J) 3) [Fig67] ──→ [Fig74] ──→ [Fig75] ──→ [Fig76] ──→ [Fig77] 6. Give a name (common name or IUPAC nomenclature) for the following compounds. (10%) (a) [Fig78] (b) [Fig79] (c) [Fig80] (d) [Fig81] (e) [Fig82] 7. When a Friedel-Crafts reaction is performed on furan, two products are obtained. (a) Provide a mechanism for the formation of each product. For full credit, be sure to draw any resonance structures and charges that occur during the mechanism. (6%) (b) Circle the major product. (2%) (c) Briefly explain why one product is favored over the other. 8. (a) Draw the orbitals (by shading the lobes appropriately) at each energy level for 1,3,5-hexatriene. (6%) (b) Write the number of nodes in the box to the left of each orbital array. (c) For the ground state of 1,3,5-hexatriene, draw the electron population for each orbital in the line to the right of each orbital array. For each electron, clarify indicate whether it is "spin up" or "spin down". If there are no electrons in a given orbital, leave it blank. (2%) [Fig87] 9. (a) A graduate student tried to make o-fluorophenylmagnesium bromide by adding magnesium to an ether solution of o-fluorobromobenzene, but the THF solvent she used was contaminated with furan. She isolated the compound C shown below. Propose a mechanism for its formation. (6%) Mg [Fig88] ────────→ [Fig91] [Fig89], [Fig90] (b) Draw the structure of compound D and E in the following reaction. (4%) Br2 heat [Fig92] ──→ compound D ────→ compound E CCl4 acetone Over, Good Luck! --

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