| E | 1. The Keq for the interconversion for the two chair forms of methylcyclohexane at 25 °C is 18. What % of the chair conformations feature an axial methyl group? (A) 95 (B) 75 (C) 50 (D) 25 (E) 5 |
| C |  (A) 3,3-dimethyl-1-butanol (B) 3,3-dimethyl-2-butanol
(C) 2,3-dimethyl-2-butanol (D) 2,3-dimethyl-1-butanol
(E) 4-methyl-2-petanol
|
| C |  (A) 2 (B) 4 (C) 6 (D) 8 (E) 0
|
| E | 4. Which of the following statements is (are) true for the Diels-Alder reaction? (A) When the diene is electron-rich, the reaction works best when the dienophile contains one or more electron-withdrawing groups conjugated to its C=C. (B) Substituents which are cis in the dienophile remain cis in the product. (C) Dienes which cannot achieve an s-cis conformation do not react in Diels-Alder reactions. (D) Secondary orbital interactions typically cause the endo product to be favored kinetically over the exo. (E) All of the above. |
| A |  |
| D | 6. Which sequence of reagents works best to convert 3-hexene to 3-hexyne? (A) 1. HCl 2. NaNH2 (B) 1. BH3．THF 2. HO- , H2O2 3. NaNH2 (C) 1. NaNH2 2. HI 3. H3O+ (D) 1. Br2, CH2Cl2 2. NaNH2 (excess) (E) 1. Cl2, CH2Cl2 2. NaCN(excess) |
| E |  (A) NMR (B) IR (C) MS (D) A and B (E) A and C
|
| A |  |
| C |  |
| A |  |
| D |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| A |  |
| C | 13. Which of the following structures is a Fischer projection of (2R,3R,4S)-2,3,4-tribromoheptane?(A) |
| D | 14. Arrange the following substrates in order of their increasing SN2 reactivity with NaCN: (I) 1-bromopentane, (II) 1-chloro-2,2-dimethylpentane, (III) 2-bromo-2-methylpentane, and (IV) 1-chloro-3,3-dimethylpentane. (A) IV < II < I < III (B) III < I < IV < II (C) IV < II < III < I (D) III < II < IV < I (E) None of the above |
| D | 15. Both [E]- and (Z)-hex-3-ene can be treated with D2 in the presence of a platinum catalyst. How are the products from these two reactions related to each other? (A) The [E]- and (Z)-isomers generate the same products but in differing amounts. (B) The [E]- and (Z)-isomers generate the same products in exactly the same amounts. (C) The products of the two isomers are related as constitutional isomers. (D) The products of the two isomers are related as diastereomers. (E) The products of the two isomers are related as enantiomers. |
| A |  (B)  (C)  (D)  (E)  |
| D | 17. In electrophilic aromatic substitution reactions, the hydroxyl group is an o,p-director because: (A) it donates electron density to the ring by induction and destabilizes the meta sigma complex. (B) it donates electron density to the ring by induction and stabilizes the ortho and para sigma complexes. (C) it donates electron density to the ring by resonance and destabilizes the meta sigma complex. (D) it donates electron density to the ring by resonance and stabilizes the ortho and para sigma complexes. (E) None of the above. |
| A | 18. (S)-2-Methylbutanal __________ upon sitting in an acidic or a basic aqueous solution. (A) racemizes (B) esterifies (C) inverts completely to the R configuration (D) hydrolyzes (E) irreversibly forms the hydrate |
| B | 19. When a carbonyl is part of a conjugated π-network, the C=O stretch: (A) has a higher frequency than in a nonconjugated system. (B) has a lower frequency than in a nonconjugated system. (C) always occurs at 1710 cm-1 . (D) occurs around 2700 cm-1 . (E) cannot be distinguished from the C=O stretch in a nonconjugated system. |
| E | 20. When pent-1-ene is treated with mercury(II) acetate in methanol and the resulting product is reacted with NaBH4, what is the primary organic compound which results? (A) 3-ethoxypentane (B) 1-methoxypentane (C) 1-ethoxypentane (D) 2-ethoxypentane (E) 2-methoxypentane |
| A |  (A) I (B) II (C) III (D) IV (E) None of the above.
|
| E | 22. Which of the following terms describes the mechanism of a Claisen rearrangement reaction? (A) Electrophilic addition (B) Nucleophilic addition (C) syn Elimination (D) Radical substitution (E) Pericyclic reaction |
| B |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| B |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| B |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| E |  (A) a lecithin (B) a diterpene (C) a steroid (D) a glyceride (E) a prostaglandin
|
| D |  (A) 1R, 2R only (B) 1S, 2S only (C) 1R, 2S only (D) An equal mixture of 1R, 2R and 1S, 2S
(E) An equal mixture of 1R, 2R and 1R, 2S
|
| D |  (A) It is achiral
(B) It is meso
(C) Its asymmetric center possesses the R configuration
(D) The mirror image of this molecular is its enantiomer
(E) The molecule possesses enantiotopic hydrogens
|
| D | 29. Which of the following m/z values is the base peak for benzyl alcohol? (A) 17 (B) 52 (C) 77 (D) 91 (E) 108 |
| A |  (A) Singlet (B) Doublet (C) Triplet (D) Singlet of singlet (E) Multiplet
|
| A | 31. The Hell-Volhard-Zelinsky reaction involves: (A) α-Bromination of carboxylic acids (B) α-Bromination of ketones (C) Formation of α, β -unsaturated carboxylic acids (D) Formation of β-ketoesters (E) Formation of amines |
| B | 32. Which of the following reagents would reduce carboxylic acids and esters into alcohols? (A) H2/Ranney Ni (B) 1) LiAlH4; 2) H3O+ (C) 1) NaBH4; 2) H3O+ (D) Na/NH3 (E) Zn(Hg)/H+ |
| C |  (A) H2/Ranney Ni (B) 1) LiAlH4; 2) H3O+
(C) 1) NaBH4; 2) H3O+
(D) Na/NH3 (E) Zn(Hg)/H+
|
| B |  (A) 1-Azabicyclo[2,2,1]heptane (B) 2-Azabicyclo[2,2,1]heptane
(C) 1-Azabicyclo[2,2,1]hexane (D) 2-Azabicyclo[2,2,1]hexane
(E) 1-Azabicyclo[2,1,1]hexane
|
| B |  (A) Wittig reaction (B) Michael reaction (C) Dieckmann condensation
(D) Cope reaction (E) Knoevenagel reaction
|
| D | 36. Which of the following lists the correct order of reactivity of the substrates in electrophilic aromatic substitution reactions? (A) Thiophene > pyrrole > furan > benzene (B) Benzene > thiophene > furan > pyrrole (C) Furan > pyrrole > benzene > thiophene (D) Pyrrole > furan > thiophene > benzene (E) Benzene > furan > pyrrole > thiophene |
| B | 37. In the addition of HBr to alkynes in the absence of peroxides, which of the following species is believed to be an intermediate? (A) Vinyl anion (B) Vinyl cation (C) Vinyl radical (D) Carbene (E) Bromonium ion |
| D | 38. Which of the following statements about propene is correct? (A) All of the hydrogen atoms are in the same plane (B) The compound has a cis and trans isomer (C) It generally acts as a Lewis acid (D) There is a total of eight sigma bonds (E) All the carbon atoms are sp2 hybridized |
| E | 39. The t-butoxycarbonyl group (Boc) is a widely used protecting group for primary amine and secondary amine. What reagent is commonly used for deprotection of N-Boc group in the Merrifield solid phase peptide synthesis? (A) OH- (B) Pd/C, H2 (C) Pd(OH)2/C, H2 (D) Acetic acid (E) CF3COOH |
| A |  (A)  (B)  (C)  (D)  (E) None of the above |
| E | 41. The best method for preparation nonhalogenated cyclopropanes is by a process called the _________ reaction. (A) Claisen rearrangement (B) Schmidt (C) Curtius (D) Pauson-Khand (E) Simmon-Smith |
| C |  (A) A (B) B (C) C (D) D (E) E
|
| A |  |
| D |  (A) 1. PhMgBr, ether; 2. H3O+ (B) 1. PhCH2MgBr, ether; 2. H3O+
(C) (C6H5)3P=CHC6H5, THF (D) Li(C6H5)2Cu, ether (E) None of the above
|
| D |  (A) I (B) II (C) III (D) IV (E) None of the above
|
| C | 46. What fragment ion (m/z) is produced from McLafferty rearrangement of 5-methyl-2-hexanone in EI-MS? (A) 114 (B) 43 (C) 58 (D) 108 (E) None of the above |
| B | 47. Select the most reasonable formula for the compounds with the following mass spectral data: M+ at m/z = 136 and M+2 at m/z = 138 of approximately equal intensity. (A) C6H13OCl (B) C4H9Br (C) C10H16 (D) C9H12O (E) None of the above |
| B | 48. If a compound has the –OH, –OCH3, and –CHO groups all attached to a single benzene ring, the IUPAC name of the compound is based on which of the following? (A) Anisole (B) Benzaldehyde (C) Phenol (D) Methylether (E) Phenyl |
| C | 49. Which one of the following would NOT be a suitable solvent for Grignard reagents? (A) Diethyl ether (B) Tetrahydrofuran (THF) (C) Ethanol (D) Hexane (E) They would all be suitable solvents |
| E | 50. (S) (+)-Butanol shows a specific rotation at +13.52o . What is the ratio of (S) (+)-butanol and (R) (-)-butanol when the measured rotation equals to +6.76o ? (A) (S) : (R) = 4 : 1 (B) (S) : (R) = 2 : 1 (C) (S) : (R) = 1 : 2 (D) (S) : (R) = 1 : 2.5 (E) (S) : (R) = 3 : 1 |
| C | 51. Consider the SN1 reaction of tert-butyl chloride with iodide ion: (CH3)3C-Cl + I - → (CH3)3C-I + Cl- If the concentration of iodide ion is doubled, the rate of forming tert-butyl iodide will: (A) Double (B) Increase 4 times (C) Remain the same (D) Decrease (E) Triple |
| B | 52. Which of the following functional groups would NOT show an IR absorbance above 3000 cm-1? (A) An amine (NH2) (B) A carbonyl (C=O) (C) An alcohol (OH) (D) A vinylic carbon-hydrogen bond (=C-H) (E) A methylene hydrogen (-CH2-) |
| A | 53. Which part of the electromagnetic spectrum interacts with the nuclear spins of protons ? (A) Radio Waves (B) X-Ray radiation (C) Visible Light (D) Infrared radiation (E) Ultra violet light |
| B | 54. The pinacol rearrangement proceeds via intermediate. (A) carbanion (B) carbocation (C) radical (D) carbene (E) neutral |
| E |  (A) a (B) b (C) c (D) d (E) e
|
| B |  (A) Ha is coupled to two nonequivalent hydrogens with identical coupling constants.
(B) Ha is coupled to two nonequivalent hydrogens with different coupling constants.
(C) Ha is coupled to three nonequivalent hydrogens with identical coupling constants.
(D) Ha is coupled to three nonequivalent hydrogens with different coupling constants.
(E) Ha is coupled to three equivalent hydrogens with identical coupling constants.
|
| B | 57. Which of the following combinations of reactants would produce a meso compound? (A) Cis-3-hexene and Br2 (B) Trans-3-hexene and Br2 (C) Cis-3-hexene and Br2 in H2O (D) Trans-3-hexene and Br2 in H2O (E) Trans-3-hexene and H2/Pd/C |
| B |  (A) 1,1-Diethylcyclopropane (B) Cis-1,2-diethylcyclopropane
(C) Trans-1,2-diethylcyclopropane (D) Cis and trans-1,1-diiodo-2,3-diethylcyclopropane
(E) Cis-1,2-diethyl-3,3-diiodocyclopropane
|
| B |  |
| C | 60. Which statement is correct for the reaction shown below? 1-chloro-2,4-dinitrobenzene + NaOH → 2,4-dinitrophenol (A) This reaction is an electrophilic aromatic substitution. (B) This reaction is a SN1 substitution. (C) This reaction is a nucleophilic aromatic substitution. (D) Substituted benzyne is the reaction intermediate. (E) None of the above. II. Choose one correct answer for the following questions |
| C | 【單選題】每題 2 分，共計 40 分，答錯一題倒扣 0.5 分，倒扣至本大題零分為止，未作答，不給分亦不扣分。  |
| C |  |
| C |  |
| D | 64. Which of the following compounds is the major organic product generated in the reaction below? Pay particular attention to region- and stereochemical detail.  (A)  (B)  (C)  (D)  (E) None of the above.
|
| D |  (I) NaOH, (II) HCl, (III) PCC, (IV) O3, (V) S(CH3)2, (VI) H2O2, NaOH
(A) II → IV → V (B) III → V → I (C) IV → VI → III (D) IV → V → I (E) None of the above.
|
| D |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| B |  (A) Its C-4 NH2 is strongly basic while the C-1 NH2 is weekly acidic.
(B) Its C-4 NH2 is weekly basic while the C-1 NH2 is strongly acidic.
(C) Its C-4 NH2 is weekly basic while the C-1 NH2 is weekly acidic.
(D) Its C-4 NH2 is strongly basic while the C-1 NH2 is strongly acidic.
(E) Both C-1 NH2 and the C-4 NH2 are weekly basic.
|
| E | 68. Which of the compounds below undergoes solvolysis in aqueous ethanol most rapidly? (A) Cyclohexyl bromide (B) Isopropyl chloride (C) Methyl iodide (D) 3-Chloropentane (E) 3-Iodo-3-methyl pentane |
| E |  (A) AB (B) BC (C) CD (D) AD (E) AC
|
| B |  (A) A (B) B (C) C (D) D(E) None of the above
|
| C |  |
| E | 72. What product would you obtain from Claisen condensation of ethyl propanoate? (A) Ethyl 2-ethyl-3-oxopentanoate (B) Propyl 2-methyl-3-oxopentanoate (C) Ethyl 2-methyl-3-oxohexanoate (D) Propyl 2-methyl-3-oxohexanoate (E) Ethyl 2-methyl-3-oxopentanoate |
| D |  (A) Ethyl benzoate (B) Phenyl propionate (C) Diphenyl ketone (D) Phenyl vinyl ketone
(E) An phenylseleno ketone
|
| D | 74. Which of the following reactions has a mechanism that involves the formation of a cyclic intermediate from acyclic starting materials? (A) Dehydration of an alcohol (B) Addition of HBr to an alkene (C) Chlorination of an alkane (D) Addition of bromine to an alkene (E) Addition of Grignard to ketone |
| B | 75. Which of the following substituents would have the lowest Cahn-Ingold-Prelog priority? (A) -CH2OH (B) -CH2COOH (C) -CH2CH2Cl (D) -CH2NH2 (E) -CH2CH2Br |
| D |  (A) Hg(OCOCF3)2 in MeOH (B) 1. Hg(OAc)2 in THF/H2O2, 2. NaBH4
(C) 1. BH3, 2. NaOH, H2O2 (D) 1. BH3, 2. H2O2, OH-
, 3. NaH, 4. CH3I
(E) H+
, CH3OH
|
| A |  (A) Cyclopentadienyl cation (B) Cyclopentadienyl radical
(C) Cylopentadienyl anion (D) Cyclopentadiene
(E) Cyclopentene anion
|
| B |  |
| C |  (A)  (B)  (C)  (D)  (E) None of the above |
| C |  |
| A | I. Choose one correct answer for the following questions
【單選題】每題 1 分，共計 60 分，答錯 1 題倒扣 0.25 分，倒扣至本大題零分為止，未作答，不給分亦不扣分。 1. What is the carbon nucleophile which attacks molecular bromine in the acid-catalyzed α-bromination of a ketone?
(A) an enol (B) a Grignard reagent (C) an acetylide (D) a carbocation (E) an enolate
|
| A | 2. What species is attacked by the alcohol's hydroxyl in the mechanism of the Swern oxidation? (A) dimethylchlorosulfonium ion (B) dimethylsulfoxide (C) oxalyl chloride (D) oxalinium ion (E) aldehyde or ketone |
| B | 3. When pyridine is treated with a mixture of nitric and sulfuric acids, the major product is . (A) 2-nitropyridine (B) 3-nitropyridine (C) 4-nitropyridine (D) 3-aminopyridine (E) 4-aminopyridine |
| E |  |
| A | 5. When (R)-butan-2-ol is treated with TsCl in pyridine, the product formed is . (A) a single enantiomer (B) a racemic mixture (C) a mixture of diastereomers (D) an achiral compound (E) none of the above |
| D |  (A) a polycarbonate (B) poly(acrylonitrile) (C) a polyester (D) polyurethane (E) a synthetic rubber
|
| B | 7. Which of the following reagents should be used to convert hex-3-yne to {E}-hex-3-ene? (A) H2, Pt (B) Na, NH3 (C) H2, Lindlar's catalyst (D) H2SO4, H2O (E) HgSO4, H2O |
| A | 8. SN1 reaction usually proceed with . (A) slightly more inversion than retention at the center undergoing substitution (B) slightly more retention then inversion at the center undergoing substitution (C) equal amounts of inversion and retention at the center undergoing substitution (D) complete inversion at the center undergoing substitution (E) complete retention at the center undergoing substitution |
| C | 9. Peptide bonds are . (A) ester linkages (B) imido linkages (C) amide linkages (D) ether linkages (E) disulfide linkages |
| E |  |
| D | 11. What compound is produced when (CH3)2CHCH2Br is subjected to the following sequence of steps: 1. Mg, Et2O, 2. CO2, 3. H3O+ ? (A) 2-methylpropanoic acid (B) 3-methylpropanoic acid (C) 2-methylbutanoic acid (D) 3-methylbutanoic acid (E) 2-methylhexanoic acid |
| E |  |
| C |  (A) not isomers (B) conformational isomers (C) structural isomers (D) cis-trans isomers (E) both B and D
|
| A | 14. The Hell-Volhard-Zelinsky reaction involves . (A) the α-bromination of carboxylic acids (B) the α-bromination of ketones (C) the bromination of alcohols (D) the oxidation of aldehydes to acids (E) none of the above |
| B | 15. When indole is treated with bromine in dioxane at 0o C, the major organic product is . (A) 2-bromoindole (B) 3-bromoindole (C) 4-bromoindole (D) 5-bromoindole (E) 6-bromoindole |
| D |  |
| E |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| A |  (A) bridged bicyclic (B) fused bicyclic (C) spiro bicyclic (D) bridged tricyclic (E) fused tricyclic
|
| C |  (A) Li / ND3 (B) (sia)2BD then H2O (C) CH3CH2MgBr then D3O+
(D) (sia)2BD then D2O (E) LiAlD4 then D2O
|
| B | 20. Energy is __________ when bonds are formed and is __________ when bonds are broken; therefore, bond dissociation energies are always __________. (A) released / consumed / exothermic (B) released / consumed / endothermic (C) consumed / released / exothermic (D) consumed / released / endothermic (E) consumed / released / isothermic |
| B |  (A) A only (B) B only (C) C only (D) both B and C (E) A, B, and C
|
| E | 22. Which of the following alkyl chlorides is least likely to undergo rearrangement during a solvolysis reaction? (A) cis-1-chloro-2-ethylcyclohexane (B) trans-1-chloro-2-ethylcyclohexane (C) 2-chloro-4-methylpentane (D) 2-chloro-3-methylpentane (E) 2-chloro-2-methylpentane |
| A | 23. Which of the following descriptions of the nucleoside uridine does not apply to the structure of the molecule? (A) The uracil base is directly bonded to the 1' position of ribofuranose in the α position. (B) The ribofuranose moiety is found in only the D configuration. (C) Nitrogen, at position 1 in the uracil base, is directly bonded to the ribofuranose moiety. (D) The 5' OH group is replaced with phosphate(s) in the nucleotide structure. (E) none of the above |
| E | 24. Which of the following is correct in order of decreasing nucleophilicity toward methyl iodide in methanol? (A) CH3O- > CH3S- > CN- > Br- (B) CH3O- > CN- > CH3S- > Br- (C) CN- > CH3O- > CH3S- > Br- (D) CH3S- > Br- > CH3O- > CN- (E) CH3S- > CN- > CH3O- > Br- |
| D | 25. Which of the following compounds will undergo SN2 reaction most readily? (A) (CH3)3CCH2I (B) (CH3)3CCl (C) (CH3)2CHI (D) (CH3)2CHCH2CH2CH2I (E) (CH3)2CHCH2CH2CH2Cl |
| C | 26. Which of the following carbonyl compounds can be reduced by H2/Raney Ni? (A) acetic acid (B) ethyl acetate (C) acetyl chloride (D) acetamide (E) N-methyl acetamide |
| B |  (A) Step I (B) Step II (C) Step III (D) Step IV (E) Step V
|
| D |  |
| D |  (A) only I (B) only II (C) I and II (D) II and III (E) III and IV
|
| E | 30. Which of the following chemical reactions could be used to distinguish between a polyunsaturated vegetable oil and a petroleum oil containing a mixture of saturated and unsaturated hydrocarbons? (A) addition of bromine in carbon tetrachloride (B) ozonolysis (C) hydrogenation (D) lipidification (E) saponification |
| A | 31. When an alkene is subjected to treatment with Hg(OAc)2 in alcohol followed by reaction with NaBH4, what new class of compound is formed? (A) ether (B) epoxide (C) alkane (D) syn diol (E) alkyne |
| B | 32. Distillation of mixtures of ethanol and water cannot increase the ethanol content of the mixture above 95% because this solution boils at a lower temperature than either pure ethanol or pure water. The term which describes this lower boiling mixture is _____. (A) miscible (B) azeotrope (C) isoniazide (D) epimerization (E) none of these |
| C | 33. The methyl ester of a carboxylic acid can be synthesized by directly using . (A) SOCl2 (B) PCl5 (C) CH2N2 (D) C2O2Cl2 (E) CH3NH2 |
| E |  |
| D |  (A) 1 and 2 (B) 2 and 3 (C) 2 (D) 1 and 3 (E) none are stable
|
| E |  |
| B |  (A) 1. KMnO4 (aq), 2. Hg(OAc)2 (aq), 3. NaBH4/OH-
(B) 1. NaBH4, 2. H3PO4/△ (C) 1. CH3MgBr, 2. H3O+
(D) 1. NaBH4 , 2. HBr(g), 3. Mg/ether, 4. H3O+
(E) 1. Raney nickel, 2. CH3MgBr, 3. H3O+
|
| D | 38. A pure sample of (S)-phenylalanine has a specific rotation of +70o . A mixture of the two enantiomers of phenylalanine gives a specific rotation of -7.0o . What are the percentages of the S and R enantiomers in the mixture? (A) 75 % S, 25 % R (B) 65 % S, 35 % R (C) 55 % S, 45 % R (D) 45 % S, 55 % R (E) 35 % S, 65 % R |
| C |  |
| A | 40. Which of the following compounds would most likely be used in the preparation of isobutylbenzene from benzene? (A) (CH3)2CHCOCl (B) (CH3)2CHCH2Cl (C) (CH3)2CHCH2Br (D) CH3CH2CH2CH2Cl (E) CH3CH2CH2COCl
|
| D |  (A) acetaldehyde (B) acetic acid (C) racemic (2R,3R) and (2S,3S)-2,3-butanediol
(D) meso-2,3-butanediol (E) cis-2,3-epoxybutane
|
| B |  |
| C | 43. Which of the following describes the most stable conformation of trans-1-isopropyl-3-methylcyclohexane? (A) Both groups are equatorial. (B) Both groups are axial. (C) The isopropyl group is equatorial and the methyl group is axial. (D) The isopropyl group is axial and the methyl group is equatorial. (E) none of the above |
| E | 44. Which of the following compounds will react most rapidly with HCl? (A) 5-methyl-1-hexene (B) 4-methyl-1-hexene (C) (E)-5-methyl-2-hexene (D) {E}-2-methyl-3-hexene {E} 2-methyl-2-hexene |
| A |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| B |  |
| E | 47. Which of the following compounds exhibits the pattern of m/z values shown below? 41, 43, 57, 87, 101, 116 (A) n-propylbromide (B) isopropyl bromide (C) 2-hexanol (D) 2-butanone (E) sec-butyl isopropyl ether |
| A | 48. Which of the following statements correctly pertains to a pair of enantiomers? (A) They rotate the plane of polarized light by exactly the same amounts and in opposite directions. (B) They rotate the plane of polarized light by differing amounts and in opposite directions. (C) They rotate the plane of polarized light by differing amounts and in the same directions. (D) They have the same specific rotation, but they have different melting points. (E) They have the same melting points, but they have different boiling points. |
| C |  |
| D |  |
| D |  |
| B | 52. Which of the following compounds has the most signals in the noise-decoupled 13C NMR spectrum? (A) o-dibromobenzene (B) m-dibromobenzene (C) p-dibromobenzene (D) 1,3,5-tribromobenzene (E) 1,2,3,4-tetrabromobenzene |
| C |  (A) I and II (B) II and III (C) I and III (D) III and IV (E) I, III and IV
|
| E | 54. Which of the following compounds has the highest melting point? (A) benzene (B) toluene (C) o-dichlorobenzene (D) m-dichlorobenzene (E) p-dichlorobenzene |
| D |  (A)  (B)  (C)  (D)  (E) none of these
|
| B |  |
| E | 57. A sample of compound X is subjected to elemental analysis and the following percentages by weight are found: 39.97% C, 6.73% H, and 53.30% O. The molecular weight of X is 90. What is the empirical formula of X? (A) C6H8O (B) C2H4O2 (C) C4H10O2 (D) C3H6O3 (E) CH2O |
| E | 58. Which of the following conditions will drive the equilibrium of the Fischer esterification towards ester formation? (A) addition of water (B) removal of water as it is formed (C) addition of an inorganic acid as a catalyst (D) addition of alcohol (E) both B and D |
| B | 59. The Wittig reaction involves . (A) formation of carboxylic acids (B) formation of alkenes (C) formation of α,β-unsaturated carboxylic acids (D) formation of β-ketoesters (E) formation of alcohols |
| C |  (A) chemically equivalent (B) enantiotopic (C) diastereotopic (D) endotopic (E) none of the above
II. Choose one correct answer for the following questions |
| E | 【單選題】每題 2 分，共計 40 分，答錯 1 題倒扣 0.5 分，倒扣至本大題零分為止，未作答，不給分亦不扣分。  |
| A |  |
| C |  |
| B |  |
| D |  |
| E |  |
| C |  |
| C | 68. What is the major organic product resulted from tetrahydrofuran being reacted with excess HBr? (A) 1,2-dibromobutane (B) 1,3-dibromobutane (C) 1,4-dibromobutane (D) 4-bromobutan-1-ol (E) 3-bromobutan-1-ol |
| A |  |
| D |  |
| C |  |
| D |  |
| B |  (A) B < C < A < D < E (B) C < A < B < E < D (C) C < A < E < B < D
(D) E < C < A < B < D (E) none of these
|
| C |  (A)  (B)  (C)  (D)  (E) none of the above
|
| E | 75. Deduce the identity of the compound from the data provided. C8H13Br, 1 H NMR δ(splitting, integral): 3.5 (t, 2H), 1.8 (t, 2H), 0.9 (s, 9H); 13C NMR: 6 signals. (A) 5-bromo-2,2-dimethylhex-3-yne (B) 6-bromo-4,4-dimethylhex-1-yne (C) 3-bromo-1,2-dimethylcyclohexene (D) 4-bromo-1,2,4-trimethylcyclopentene (E) 1-bromo-5,5-dimethylhex-3-yne CO2Me H H O O CH3SOCH2 - Na+ DMSO |
| C |  (A)  (B)  (C)  (D)  (E) none of these
|
| E | 77. Which of the following reactions will result in the formation of a secondary alcohol(s) in good yield? (A) |
| D | 78. Arrange the following reactions in order for preparing 1,4-diaminobutane from cyclohexene. I. NH3 II. KMnO4, H3O+ III. Br2, NaOH/H2O IV. SOCl2 (A) I → IV → II → III (B) II → III → I → IV (C) IV → II → III → I (D) II → IV → I → III (E) none of these |
| A |  |
| B |  |
| A | 1. Which of the following amines gives the correct order of base strengths? (A) aliphatic > ammonia > aromatic (B) aliphatic > aromatic > ammonia (C) aromatic > aliphatic > ammonia (D) aromatic > ammonia > aliphatic (E) ammonia > aromatic > aliphatic |
| D |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| D | 3. What term describes the structural relationship between (2R,3R,4S)-2,3,4-trichloroheptane and (2R,3R,4R)-2,3,4-trichloroheptane? (A) not isomers (B) constitutional isomers (C) enantiomers (D) diastereomers (E) conformers |
| C | 4. Rank the following sets of substituents in order of Cahn-Ingold-Prelog priorities from highest to lowest. Please pick the wrong order set. (A) -Cl, -S, -P, -H (B) -Br, -OH, -CH3, -H (C) -CO2H, CH2OH, -CH2NH2, -CN (D) -CH2OH, -CH=CH2, -CH2CH3, -CH3 (E) -CH2OCH3, -CN, -C≡CH, -CH2CH3 |
| A |  |
| D |  (A) I (B) II (C) III (D) IV (E) V
|
| D | 7. Which of the statements below correctly describes an achiral molecule? (A) the molecule has a nonsuperimposable mirror image (B) the molecule exhibits optical activity when it interacts with plane-polarized light (C) the molecule has an enantiomer (D) the molecule might be a meso form (E) none of the above |
| B |  (A) sec-propyl, sec-butyl, isobutyl (B) isopropyl, isobutyl, sec-butyl (C) sec-propyl, tert-butyl, isobutyl
(D) isopropyl, tert-butyl, isobutyl (E) isopropyl, tert-butyl, sec-butyl
|
| A | 9. What compound is formed when 2,2-dimethyloxirane is treated with ethanol containing a trace of HCl? (A) 2-ethoxy-2-methyl-1-propanol (B) 1-ethoxy-2-methyl-2-propanol (C) 2-ethoxy-2-methyl-2-propanol (D) 2-ethoxy-1-butanol (E) 1-ethoxy-2-butanol |
| C | 10. Which of the following compounds gives a 1 H-NMR spectrum consisting of only two singlets? (A) CH3OCH2CH2OCH2CH3 (B) CH3OCH2CH2CH2CH2OH (C) CH3OC(CH3)2OCH3 (D) CH3OCH2CH(CH3)OCH3 (E) CH3CH2OCH2CH3 |
| E |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 5
|
| D |  (A) m/z = 43 (B) m/z = 57 (C) m/z = 99 (D) m/z = 113 (E) m/z = 43 and m/z = 99
|
| A |  (A) IV, I, V, II, III (B) IV, III, I, V, II (C) I, IV, II, V, III (D) IV, I, II, III, V (E) I, IV, III, II, V
|
| E |  (A) 2 (B) 2 and 5 (C) 3 and 4 (D) 4 (E) 1 and 4
|
| A |  (A) reducing agent, reductive amination (B) reducing agent, decarboxylation
(C) hydrogenation agent, Lindlar’s reaction (D) oxidized agent, transamination
(E) oxidized agent, aldol condensation
|
| A |  (A) SN1-like (B) E2-like (C) E1cB-like (D) E1-like (E) none of the above
|
| C |  |
| D |  (A) (1Z, 3Z, 5Z, 7Z) (B) (1E, 3E, 5Z, 7Z) (C) (1E, 3E, 5E, 7Z) (D) (3E, 5Z) (E) (3Z, 5Z)
|
| B | 19. Which of the following is least likely to undergo a smooth crossed Claisen condensation with methyl pentanoate? (A) (CH3)3CCO2CH3 (B) PhCH2CO2CH3 (C) PhCO2CH3 (D) HCO2CH3 (E) (CH3O)2CO |
| B |  (B)  (C)  (D)  (E)  |
| C | 21. Which is the only one of these compounds which cannot self-condense in the presence of dilute aqueous alkali? (A) phenylethanal (B) propanal (C) 2,2-dimethylpropanal (D) 2-methylpropanal (E) 3-methylpentanal |
| D |  |
| A | 23. Which of the following Wittig reagents would be useful for converting R2C=O into R2CHCHO after hydrolysis? (A) Ph3P=CHOCH3 (B) Ph3P=CHCH3 (C) Ph3P=Cl2 (D) Ph3P=CHCH=CH2 (E) Ph3P=C(OCH3)2 |
| C | 24. Reaction of ethylmagnesium bromide with which of the following compounds yields a tertiary alcohol after quenching with aqueous acid? (A) H2CO (B) CH3CHO (C) (CH3)2CO (D) ethylene oxide (E) n-butyllithium |
| B |  (A) 4-methyl-2-cyclohexen-1-one and 3-butenal (B) 2-methylcyclohexane-1,3-dione and 3-buten-2-one
(C) 2-methyl-2-vinyl-3-cyclohexen-1-one and acetaldehyde (D) 2-methyl-2-cyclohexen-1-one and 1,4-dichlorobutan-2-one
(E) 4-methylcyclohexnone and methyl vinyl ketone |
| C |  |
| B |  |
| E |  |
| D | 29. What compound is produced when (R)-pentan-2-ol is treated with TsCl followed by NaI? (A) sodium (R)-pent-3-oxide (B) sodium (S)-pent-2-oxide (C) (R)-2-iodopentane (D) (S)-2-iodopentane (E) none of the above |
| E | 30. What type of intermediate is present in the SN2 reaction of cyanide with bromoethane? (A) carbocation (B) free radical (C) carbene (D) carbanion (E) This reaction has no intermediate |
| D |  (A) hexane (B) chloroform (C) ethanol (D) water (E) no difference
|
| B |  (A)  (B)  (C)  (D)  (E) none of the above |
| A |  (A) 6 and 7 (B) 7 and 6 (C) 8 and 4 (D) 4 and 8 (E) none
|
| D |  |
| D | 35. When 2-methylcyclohexanone is treated with catalytic base in excess D2O, how many deuterium atoms become incorporated in the organic compound? (A) 0 (B) 1 (C) 2 (D) 3 (E) 5 |
| A |  |
| E |  (A) 4 (B) 1, 2 and 3 (C) 1 (D) 2 (E) 2 and 3
|
| D | 38. LiAl [OC(CH3)3]3H will reduce an acid chloride to an: (A) alcohol (B) alkane (C) acid (D) aldehyde (E) acetal |
| B |  (A) A > C > E > D > B (B) C > A > E > D > B (C) E > C > A > D > B
(D) C > A > B > E > D (E) C > A > D > B > E
|
| E | 40. In the mechanism for the dehydrohalogenation of 3-chloro-3,7-dimethyloctane, what is the dihedral angle between the hydrogen and chlorine atoms that are eliminated? (A) 0 degree (B) 45 degrees (C) 90 degrees (D) 135 degrees (E) 180 degrees |
| B | 41. Which reagent is used to accelerate coupling reactions in both laboratory peptide synthesis and laboratory DNA synthesis? (A) catalytic H (B) dicyclohexylcarbodiimide (C) sodium hydroxide (D) ethyl chloroformate (E) PhS- NH4+ |
| E | 42. What reagent is used to convert pentanamide to 1-pentanamine? (A) POCl3 (B) CuCN (C) MeMgBr (D) SOCl2 (E) LiAlH4 |
| E |  |
| B |  |
| B |  (A) I and II (B) II and III (C) III and IV (D) I and IV (E) III and IV
|
| D |  (A) 7,8-dihydroxynonan-3-one (B) 6,7-dihydroxynonan-3-one (C) 7,8-dihydroxynonan-2-one
(D) 6,7-dihydroxynonan-2-one (E) 6,7-dihydroxynonan-4-one
|
| D |    |
| B | 48. Which of the following alcohols undergoes dehydration upon heating with concentrated H2SO4 without carbocation rearrangement? (A) 2-methylhexan-3-ol (B) 3-methylpentan-3-ol (C) 3,3-dimethylpentan-2-ol (D) 2-methyl-2-phenylpropan-1-ol (E) both A and B |
| E |  |
| D | 50. Alkoxymercuration followed by sodium borohydride reduction would be used to produce (A) alcohol from an alkene (B) aldehyde from alcohol (C) acid from an alkyne (D) ether from an alkene (E) alkene from an aryl halide |
| C |  |
| C | 52. Which reagent(s) can be used to convert bromobenzene to benzoic acid? (A) 1. NaCN; 2. NaOH, H2O (B) KMnO4 (C) 1. Mg; 2. CO2, then H3O+ (D) CrO3, HCl (E) 1. CH3Br; 2. CrO3, H2SO4. |
| C |  |
| A |  (A) EtONa (B) NaH (C) BuLi (D) NaNH2 (E) CH3MgBr
|
| D | 55. What is the major organic product that results when 1-heptyne is treated with 2 equivalents of HBr? (A) 2,3-dibromo-1-heptene (B) 2,3-dibromo-2-heptene (C) 1,2-dibromoheptane (D) 2,2-dibromoheptane (E) 1,1-dibromoheptane |
| A |  (A) 1. NaOH, H2O; 2. LiAlH4 (B) 1. Mg, ether; 2. CO2; 3. LiAlH4
(C) 1. KMnO4; 2. LiAlH4 (D) 1. SOCl2, benzene; 2. LiAlH4
(E) 1. LiAlH4, H2O; 2. NaOH, 3-methyl-2-propylpyridine
|
| A |  (A) NaOI (I2 in NaOH) (B) Br2 in CCl4 (C) CrO3 in H2SO4
(D) NaHCO3 in H2O (E) Ag(NH3)2OH
|
| A |  |
| C |  |
| C |  (A) I only (B) I and II (C) II and III (D) I and III (E) all of them |
| E | 61. Which of the following statement for Diels-Alder reaction is false? (A) Diels-Alder reaction is a pericyclic process. (B) The endo product, rather than exo product, is formed. (C) It is a thermal reaction. (D) It is a suprafacial [4+2]-π-electron cycloaddition. (E) None of the above. |
| D |  (A) The equilibrium in (i) lies to the left. (B) The equilibrium in (ii) lies to the right.
(C) You can prepare propynide salts in NH3 (D) In reaction (ii) ammonia, NH3, acts as a base.
(E) Propyne is a stronger acid than ammonia
|
| A | 63. Which of the following compound does not contain carbonyl group(s) in its structure? (A) dicyclohexylcarbodiimide (B) cycloheptatrienone (C) sulfanilamide (D) benzoyl phosphate (E) dimethyl malonate |
| E | 64. Which comopund has the smallest heat of hydrogenation? (A) 5-methyl-1,2-hexadiene (B) (E)-5-methyl-1,3-hexadiene (C) 5-methyl-1,4-hexadiene (D) 2-methyl-1,5-hexadiene (E) (E)-2-methyl-2,4-hexadiene |
| A | 65. The correct priority of functional groups in IUPAC nomenclature is: (A) acid > ester > amide > ketone (B) amide > acid > ester > ketone (C) amide > ester > acid > ketone (D) ester > amide > ketone > acid (E) ketone > acid > ester > amide |
| C |  (A) I, II, III (B) II, III, IV (C) I, II, IV (D) all of the above (E) none of the above
|
| D | 67. Which of the following reactions of alkenes is not stereospecific? (A) bromohydrin formation (Br2 in H2O) (B) hydrogenation (H2, Pd) (C) bromination (Br2) (D) acid-catalyzed hydration (H2O, H2SO4) (E) dihydroxylation (OsO4, NaHSO3) |
| D | 68. Which system would give the largest ratio of substitution to elimination product(s)? (A) cyclohexanol + acid (B) cyclohexyl iodide + t-BuOK in t-BuOH (C) 1-bromobutane + t-BuOK in DMSO (D) 1-bromobutane + KI in acetone (E) 2-bromobutane + MeONa in DMSO |
| D | 69. Optically pure (S)-monosodium glutamate has a specific rotation of +25o , what percent of (R)-monosodium glutamate in a sample with a specific rotation of -10o ? (A) 10% (B) 30% (C) 40% (D) 70% (E) 50% |
| B | 70. What reagents can be used to convert 1-hexyne into 2-hexanone? (A) 1. Sia2BH; 2. H2O2, NaOH (B) Hg2+, H2SO4, H2O (C) 1. O3; 2. (CH3)2S (D) 1. CH3MgBr; 2. CO2 (E) 1. H2, Ni; 2. Na2Cr2O7, H2SO4 |
| D |   |
| D |  |
| C |  |
| B |  |
| B |  |
| B |  |
| A |  (A) II reacts faster and gives both Y and X (B) II reacts faster and gives only X
(C) I reacts faster and gives both Y and X (D) I reacts faster and gives only Y
(E) I reacts faster and gives only X
|
| C |   |
| D |   |
| D |  |
| E | I. Choose one correct answer for the following questions 【單選題】每題 1 分，共計 60 分，答錯 1 題倒扣 0.25 分，倒扣至本大題零分為止，未作答，不給分亦不扣分。1. According to atomic theory: (A) The nucleus is positively charged (B) The nucleus contains both charged and uncharged particles (C) The electrons contribute very little to the total mass of the atom (D) The electrons are located in the atomic space outside the nucleus (E) All of the above. |
| B | 2. A coenzyme frequently encountered in transamination reactions is (A) Tetrahydrofolate (B) Pyridoxal phosphate (C) Thiamine pyrophosphate (D) Biotin (E) NADH |
| D |  (A) 1 (B) 2 (C) 3 (D) 4 (E) All of the above are the same.
|
| E | 4. Which of the standard amino acids is achiral? (A) Lysine (B) Proline (C) Valine (D) Alanine (E) Glycine |
| C |  (A) 1 (B) 2 (C) 3 (D) 4 (E) both 2 and 3
|
| E |  (A) 1 only (B) 2 only (C) 3 only (D) 1 and 2 (E) 2 and 3
|
| A | 7. In the following structures, the protons pointed by arrow (on C2) which belong to diastereotopic hydrogens. (A) |
| C |  (A) 1,2-Dichlorocyclohexene (B) 2,3-Dichlorocyclohexene (C) 1,6-Dichlorocyclohexene
(D) 1,2-Dichloro-2-cyclohexene (E) None of the above.
|
| C |  (A) 0 (B) −1 (C) +1 (D) −2 (E) +2
|
| E |  (B) MeOH (C) HO  (D) CH3CO2  (E) MeS  |
| C | 11. Which of the following compounds would have a greater dipole moment than you expect? (A) |
| C |   |
| A |  (A) 1 (B) 2 (C) 3 (D) 4 (E) 2 = 3
|
| E |   |
| E |  (A) 0 Hz (B) 3 Hz (C) 7 Hz (D) 10 Hz (E) 15 Hz
|
| D |   |
| E | 17. Which of the following dienes would not react with a dienophile in a Diels-Alder reaction? (A) |
| D |  (A) 2<3<4<1<5 (B) 1<2<4<3<5 (C) 2<4<1<3<5 (D) 2<1<4<3<5 (E) 2<4<1<5<3
|
| D | 19. Which of the following reactions could not produce the desired product? (A) |
| C | 20. Select the most reasonable formula for the compounds with the following mass spectral data: M+ at m/z 101 with a minor M+1 peak. (A) C5H9Cl (B) C5H12N2 (C) C6H15N (D) C9H12O (E) C6H9S |
| E |  (A) CH3CH2MgBr (B) CH3CH2Li (C) (CH3CH2)2Zn (D) CH3CH2B(OH)2 (E) (CH3CH2)2CuLi
|
| D |   |
| A |   |
| C |  (B) H3SO4  (C) H2NO3  (D) HNO2 (E) NO |
| D |  (A) PCC (B) Na2Cr2O7, H2SO4 (C) DMSO, (COCl)2 then Et3N (D) MnO2 (E) H2CrO4
|
| B |  (A)  (B)  (C)  (D)  (E) None of the above.
|
| A |  (A)  (B)  (C)  (D)  (E) None of the above.
|
| D |  (A) m/z = 136 (B) m/z = 121 (C) m/z = 93 (D) m/z = 68 (E) m/z = 49
|
| A |    |
| C |  (A) Atom 1 would produce a peak at 205 ppm and atom 2 would appear as doublet (B) Atom 1 would produce a peak at 175 ppm and atom 2 would appear as a singlet (C) Atom 1 would produce a peak at 205 ppm and atom 2 would appear as a triplet (D) Atom 1 would produce a peak at 175 ppm and atom 2 would appear as a triplet (E) Atom 1 would produce a peak at 175 ppm and atom 2 would appear as a doublet
|
| A |    |
| B |  (A)  (B)  (C)  (D)  (E) None of the above.
|
| D |  (A) 1. (a) NaOH, (b) CH3CH2Br; 2. Na, NH3(l) (B) 1. Na, NH3(l); 2. (a) CH3MgBr, (b) CH3CH2Br (C) 1. (a) NaNH2, (b) CH3CH2Br; 2. H2, Lindlar’s catalyst (D) 1. (a) NaNH2, (b) CH3CH2Br; 2. Na, NH3(l) (E) 1. (a) BuLi, (b) CH3CH2Br; 2. H2, Lindlar’s catalyst
|
| C |  (A) HF (B) CuF (C) HBF4 (D) Bu4NF (E) F2
|
| C |    |
| D |    |
| C |  (A) No reaction  |
| A |  (A) HgCl2, CaCO3, acetone (B) NiCl2, NaBH4, DMF (C) Raney-Ni, EtOH
(D) n-Bu3SnH, AIBN, benzene (E) All of the above work well.
|
| B |  (A)  (B)  (C)  (D)  (E) None of the above.
|
| C |    |
| C |  (A) 1. PhMgBr, ether 2. H3O  (B) PhCH2MgBr, ether 2. H3O  (C) Ph3P=CHPh, THF (D) (PhCH2)2CuLi (E) All of the above work well. |
| A |    |
| A |    |
| A |    |
| A |    |
| C |    |
| D |  (A)  (B)  (C)  (D) Both B and C (E) All of the above.
|
| E |    |
| B |    |
| B |  (A) alkaline Cu2  in H2O (B) Ag  in H2O/NH3 (C) H2, with Ni catalyst
(D) NaNO3 at 0°C (E) NaBH4 in H2O |
| D |    |
| E |    |
| C |    |
| A | 54. Which of the following reaction is called Suzuki-Miyaura coupling reaction? (A) |
| B |    |
| B |  (A)  (B)  (C)  (D)  (E) None of the above.
|
| E |    |
| B |    |
| D |  (A) Carbocation (B) Carbanion (C) Free radical (D) Carbene (E) This reaction has no intermediate.
|
| C |      |
| B |  (A) 2>3>1>4 (B) 4>1>3>2 (C) 2>4>1>3 (D) 3>1>4>2 (E) 4>2>1>3
|
| D |  (A) 2S (B) 5R (C) 6R (D) 6S (E) None of the above.
|
| D |    |
| E |    |
| A |    |
| D |    |
| C |  (A)  (B)  (C)  (D)  (E) None of the above. |
| D |    |
| E |    |
| C |  (A) An example of cycloaddition reaction (B) Bond formation is suprafacial (C) Bond formation is antarafacial
(D) Prefer under thermal conditions (E) All of these apply to this reaction.
|
| E |    |
| E |    |
| A |    |
| C |  (A)  (B)  (C)  (D)  (E) All of the above. |
| E |    |
| B |    |
| A |  (A) Electrocyclic reaction and sigmatropic rearrangement (B) Electrocyclic reaction and ene reaction
(C) Cycloaddition and electrocyclic reactions (D) Cycloaddition reaction and sigmatropic rearrangement
(E) Ene reaction and sigmatropic rearrangement.
|
| C |    |
| D |    |
| D |    |
| C | 1. What is the major product obtained from the following reaction sequence?   (A) I (B) II (C) III (D) IV (E) V
|
| A |   (A) I (B) II (C) III (D) IV (E) V
|
| C |  (A) I (B) II (C) III (D) IV (E) Both I and III
|
| B | 4. The following atoms are commonly encountered in organic molecules. For which is it not possible to isolate enantiomers due to rapid inversion? (A) trivalent phosphorus (B) trivalent nitrogen (C) divalent sulfur (D) trivalent sulfur (E) both B and C |
| E | 5. Which of these alkyl halides can NOT be used to prepare amines using Gabriel synthesis? (A) 1-bromopentane (B) 1-bromo-3-methylbutane (C) 2-bromo-3-methylpentane (D) 1-bromo-2,3-dimethylbutane (E) 2-bromo-2,3-dimethylbutane |
| A |   (A) I (B) II (C) III (D) IV (E) V
|
| B |   (A) I and III (B) II (C) II and V (D) IV (E) I, III and V.
|
| A | 8. Which of the following substituent has the highest priority according to the Cahn-Ingold-Prelog system? (A) –COOH (B) –CHO (C) –CH2OH (D) –CH3 (E) -H
|
| C | 9. What is the IUPAC name of the expected major product formed upon reaction of HCl with 3-methyl-1-butene?(A) 1-Chloro-2-methylbutane (B) 1-Chloro-3-methylbutane (C) 2-Chloro-2-methylbutane (D) 2-Chloro-3-methylbutane (E) 1-Chloropentane |
| D | 
(A) 3 < 2 < 1 (B) 2 < 3 < 1 (C) 2 < 1 < 3
(D) 1 < 3 < 2 (E) 1 < 2 < 3
|
| D | 11. A pure sample of (S)-phenylalanine has a specific rotation of +70o . A mixture of the two enantiomers of phenylalanine gives a specific rotation of -7.0o . What are the percentages of the S and R enantiomers in the mixture? (A) 75 % S, 25 % R (B) 65 % S, 35 % R (C) 55 % S, 45 % R (D) 45 % S, 55 % R (E) 35 % S, 65 % R |
| B | 12. Predict the major product when pyridine is treated with a mixture of nitric acid and sulfuric acid (A) 2-nitropyridine (B) 3-nitropyridine (C) 4-nitropyridine (D) 2,3-dinitropyridine (E) 2,4-dinitropyridine |
| A |  ?  (A) I (B) II (C) III (D) IV (E) V |
| B |  at m/z= 84, relative height=10.0%  at m/z= 85, relative height=0.56% (A) C5H10O (B) C5H8O (C) C5H24 (D) C6H12 (E) C4H6O2
|
| D | 
(A) 3 < 2 < 1 (B) 2 < 3 < 1 (C) 2 < 1 < 3
(D) 1 < 3 < 2 (E) 1 < 2 < 3
. |
| D |  (A) A < B < C (B) B < A < C (C) C < A < B
(D) B < C < A (E) None of above
|
| B |  (A) I (B) II (C) III (D) I and II (E) all of the above
|
| C | 18. Grignard reagents react with oxirane (ethylene oxide) to form 1o
-alcohols but can be prepared in tetrahydrofuran solvent.
Why is this difference in behavior observed? (A) Steric hindrance in the case of tetrahydrofuran precludes reaction with the Grignard. (B) There is a better leaving group in the oxirane molecule.
(C) The oxirane ring is the more highly strained. (D) It is easier to obtain tetrahydrofuran in anhydrous condition. (E) Oxirane is a cyclic ether, while tetrahydrofuran is a hydrocarbon.
|
| B | 19. The regioselectivity and stereospecificity in the oxymercuration-demercuration of an alkene is best described as: (A) Markovnikov orientation with syn-addition (B) Markovnikov orientation with anti-addition (C) anti-Markovnikov orientation with syn-addition (D) anti-Markovnikov orientation with anti-addition (E)Markonikov orientation with both syn- and anti-addition
|
| A |  (A)  (B)  (C)  (D)  (E) None of the above.
|
| C |   (A) I (B) II (C) III (D) IV (E) V
|
| A | 22. Which of the following descriptions of the nucleoside uridine does NOT apply to the structure of the molecule? (A) The uracil base is directly bonded to the 1' position of ribofuranose in the α position. (B) The ribofuranose moiety is found in only the D configuration. (C) Nitrogen, at position 1 in the uracil base, is directly bonded to the ribofuranose moiety. (D) The 5' OH group is replaced with phosphate(s) in the nucleotide structure. (E) None of the above |
| C | 
(A) 3 < 2 < 1 (B) 2 < 3 < 1 (C) 2 < 1 < 3
(D) 1 < 3 < 2 (E) 1 < 2 < 3
|
| A |  (A) 3 < 2 < 1 (B) 2 < 3 < 1 (C) 2 < 1 < 3
(D) 1 < 3 < 2 (E) 1 < 2 < 3
|
| B |   (A) I and II (B) II and IV (C) III and IV (D) III and V (E) IV and V
|
| D |    (A) I (B) II (C) III (D) IV (E) V
|
| C |    (A) I (B) II (C) III (D) IV (E) V
|
| E | 28. Which of the following is the strongest nucleophile? (A) NaOH (B) NaOMe (C) KOH (D) KOMe (E) KSMe |
| A,B | 【已刪除】   (A) I (B) II (C) III (D) IV (E) V (AB)送分 |
| D |  ?   (A) I (B) II (C) III (D) IV (E) V
|
| C |   (A) I (B) II (C) III (D) IV (E) I and II.
|
| B |    (A) I (B) II (C) III (D) IV (E) V
|
| B | 33. Which of the alkynes below, after undergoing an acid-catalyzed hydration, would be expected to produce two different
ketones in nearly equivalent yields? (A) 1-hexyne (B) 2-hexyne (C) 3-hexyne
(D) 3-methyl-1-pentyne (E) 4-methyl-1-pentyne
|
| B |    (A) I, III, and IV (B) II, III, and IV (C) I, III, and V
(D) II, IV, and VI (E) III and IV
|
| D |  (A) a = 5.7, b = 5.2, c = 4.4, d = 1.9 (B) a = 5.2, b = 5.7, c = 1.9, d = 4.4 (C) a = 4.4, b = 5.2, c = 1.9, d = 1.9 (D) a = 5.2, b = 4.4, c = 5.7, d = 1.9 (E) a = 1.9, b = 5.7, c = 5.2, d = 4.4
|
| A | 36. Provide the name of the major alkene product that results when (2R,3R)-2,3-dibromopentane is treated with zinc in acetic acid. (A) (Z)-2-pentene (B) (E)-2-pentene (C) (R)-3-bromo-1-pentene (D) (S)-3-bromo-1-pentene (E) (R)-2-bromo-3-pentene |
| D |  (A) 2,2-Dichloropentane (B) 3,3-Dichloropentane (C) 2,3-Dichloropentane
(D) A and B (E) B and C
|
| B | 38. What is the expected major organic product from treatment of 4-methyl-2-pentyne with hydrogen in the presence of
Lindlar's catalyst? (A) (E)-4-methyl-2-pentene (B) (Z)-4-methyl-2-pentene
(C) (E)-2-methyl-2-pentene (D) (Z)-2-methyl-2-pentene (E) 2-methylpentane
|
| B |  (A) α-L-ribofuranose (B) β-D-ribofuranose (C) α-L-ribopyranose
(D) β-D-ribopyranose (E) None of the above
|
| C | 40. Which of the following best describes the key mechanistic steps in the reaction of an acid chloride and an alcohol to form an ester? (A) elimination followed by addition (B) addition followed by decarboxylation (C) addition followed by elimination (D) substitution followed by addition (E) rearrangement |
| D | 41. Many nucleophilic addition reactions of aldehydes and ketones are catalyzed by acid or base. Bases catalyze hydration by: (A) making the carbonyl group more electrophilic (B) shifting the equilibrium of the reaction (C) making the carbonyl group less electrophilic (D) converting the water to hydroxide ion, a much better nucleophile (E) None of the above |
| E | 42. Which of the following would produce a mixture of products when treated under appropriate conditions with N-bromosuccinimide? (A) oct-4-ene (B) hept-1-ene (C) 4,4-dimethylcyclopentene (D) 4,5-dimethylcyclohexene (E) all produce a mixture of products . |
| C |  (A) contains 6 π electrons and is aromatic (B) contains 6 π electrons and is nonaromatic (C) contains 8 π electrons and is antiaromatic (D) contains 8 π electrons and is aromatic (E) contains 8 π electrons and is nonaromatic
|
| A |    |
| B |   (A) I (B) II (C) III (D) IV (E) V
|
| C | 46. Arrange the following in order of increasing basicity: aniline, p-nitroaniline, p-toluidine, and p-methoxyaniline. (A) p-toluidine < p-methoxyaniline < aniline < p-nitroaniline (B) p-nitroaniline < p-toluidine < aniline < p-methoxyaniline (C) p-nitroaniline < aniline < p-toluidine < p-methoxyaniline (D) p-methoxyaniline < p-nitroaniline < p-toluidine < aniline (E) None of the above |
| D |   |
| D |    (A) I (B) II (C) III (D) IV (E) V
|
| D |    (A) I (B) II (C) III (D) IV (E) None of the above
|
| A |    (A) I (B) II (C) III (D) IV (E) V
|
| B | 51. Which of the following reagents can be used to cleave a tert-butoxycarbonyl (Boc) protecting group from a peptide? (A) H2/Pd (B) CF3CO2H (C) Na2CO3, H2O (D) LiAlH4 (E) None of the above |
| D |  (A)  + enantiomer(B)  + enantiomer (C)  + enantiomer
(D)  + enantiomer (E)  + enantiomer |
| D | 53. What is the best method for the preparation of m-dibromobenzene from benzene? (A) 1). HNO3/H2SO4; 2). Sn/HCl; 3). NaNO2/HCl, 0°C; 4). Br2/FeBr3, twice.
(B) 1). HNO3/H2SO4; 2). Sn/HCl; 3). NaNO2/HCl, 0°C; 4). Br2/FeBr3; 5). H3PO2. (C) 1). HNO3/H2SO4; 2). Sn/HCl; 3). NaNO2/HCl, 0°C; 4). H3PO2; 5). Br2/FeBr3, twice. (D) 1). HNO3/H2SO4; 2). Br2/FeBr3; 3). Sn/HCl; 4). NaNO2/HCl, 0°C; 5). CuBr. (E) Br2/FeBr3, twice.
|
| B | 54. Which is the best method for the synthesis of tert-butyl methyl ether? (A) CH3ONa + (CH3)3CBr → (B) (CH3)3CONa + CH3I → (C) CH3OH + (CH3)3COH + H2SO4 at 140°C → (D) (CH3)3CONa + CH3OCH3 → (E) CH3ONa + (CH3)3COH →
|
| E | 55. Which of the following will result in removal of a benzyl ester protecting group? (A) acid hydrolysis only (B) decarbonylation only (C) catalytic hydrogenation only (D) both acid hydrolysis and decarbonylation (E) both catalytic hydrogenation and acid hydrolysis |
| D | 56. Which of the following ketones will give a positive iodoform test? (A) 3-heptanone (B) 3-hexanone (C) cyclohexanone (D) 2-pentanone (E) 2-methyl-3-hexanone |
| B | 57. Which of the following compounds will display a singlet, a triplet and a quartet in the 1 H NMR spectrum? (A) 1-chloro-2,2-dimethylbutane (B) 3-chloro-3-methylpentane (C) 3-chloropentane (D) 2-chloro-4-methylpentane (E) 3-chloro-2-methylpentane |
| A | 58. Examining the infrared spectrum of a compound allows us to: (A) determine the types of functional groups present in the compound (B) determine the carbon-hydrogen framework of the compound (C) determine the molecular weight of the compound (D) determine the nature of the conjugated pi electron system in the compound (E) None of the above is correct |
| B | 59. Which of these is the least reactive type of organometallic compound? (A) RK (B) R2Hg (C) RLi (D) R2Zn (E) R3Al |
| C |   (A) I (B) II (C) III (D) IV (E) V |
| D | 【單選題】每題 2 分，共計 40 分，答錯 1 題倒扣 0.5 分，倒扣至本大題零分為止，未作答，不給分亦不扣分。 61. A student measured the optical activity of an unknown sugar at two different concentrations. The results of his
measurements are shown below. Given that the sample cell had a path length of 10.0 cm, calculate the specific rotation
for the unknown sugar. concentration observed rotation 2.00 g sugar in 10.0 mL water +159.1° 5.00 g sugar in 10.0 mL water +127.8° (A) -10.5° (B) +25.6° (C) +79.5° (D) -104.5° (E) +256.2°
|
| B |  (I) H2, Pt, (II) B2H6, (III) NaNO2, H3O , (IV) NaCN, HCl, (V) H2O2, NaOH (VI) PCC (A) I → II → V (B) IV → I → III (C) III → VI → V
(D) II → V → III (E) None of the above
|
| A |    (A) I (B) II (C) III (D) IV (E) V |
| D |  (A) 1) HBr; 2) NaCCH; 3) O3; 4) H2O (B) 1) HBr; 2) NaCCH; 3) O3; 4) DMS (C) 1) HBr, ROOR; 2) NaCCH; 3) O3; 4) H2O (D) 1) HBr, ROOR; 2) NaCCH; 3) H2/Ni2B; 4) O3; 5) DMS
(E) 1) NaCCH; 2) H2/Ni2B; 3) O3; 4) DMS |
| B | 65. How many positive and negative peaks appear in the DEPT-135 and in the DEPT-90 spectrum of 2-methylpentane? (A) DEPT-135: two positive and one negative, DEPT-90: one positive (B) DEPT-135: three positive and two negative, DEPT-90: one positive (C) DEPT-135: three positive and two negative, DEPT-90: no signals (D) DEPT-135: two positive and three negative, DEPT-90: two positive (E) None of the above is correct
|
| A |    (A) I (B) II (C) III (D) IV (E) V
|
| B |    (A) I (B) II (C) III (D) IV (E) V
|
| C | 68. Which of the following compounds can adopt a chair conformation in which there are no axial methyl groups? (A) 1,1-dimethylcyclohexane (B) cis-1,2-dimethylcyclohexane (C) trans-1,2-dimethylcyclohexane (D) trans-1,3-dimethylcyclohexane (E) everyone above have no axial methyl group
|
| A |    |
| B | 70. Which of these is NOT a useful method for the synthesis of 1,3-pentadiene? (A) 1,4-pentanediol + H2SO4 at 180o
C (B) 2,4-dibromopentane + (CH3)3COK , (CH3)3COH at 75o
C (C) 2,4-pentanediol + H2SO4 at 180o
C (D) HC=CCH=CHCH3 + H2, Ni2B (P-2) (E) 1,4-dibromopentane + CH3CH2ONa , CH3CH2OH at 75o
C
|
| C |  (I) NaOH, (II) heat, (III) CH3COCH2COOEt, EtONa, (IV) NaOH, heat, then HCl, H2O (A) I → II → III → IV (B) IV → II → I → III (C) III →IV → II → I
(D) II → IV → III → I (E) None of the above
|
| B |  (A) Mixed Aldol condensation (B) Mixed Claisen condensation (C) Mixed Dieckmann condensation
(D) Mixed Michael reaction (E) Mixed Knoevenagel reaction
. |
| B |   |
| D |    (A) I (B) II (C) III (D) IV (E) V
|
| E | 75. The H-bonds formed in the tertiary structure of proteins can be differentiated from those formed in secondary structures.
What is the major distinguishing factor? (A) The H-bonds in 3° structures are significantly stronger than those found in 2° structures. (B) The H-bonds in 3° structures are more random than those formed in 2° structures. (C) The H-bonds in 3° structures are formed by predictable interactions among the peptide backbone α-amine and
α-carboxylate groups. (D) The H-bonds in 3° structures are formed by interactions involving the side chain R-groups. (E) Both B and D are correct.
|
| C |    (A) I (B) II (C) III (D) IV (E) V
|
| B | 77. Which of the following compounds exhibits the pattern of m/z values: 41, 43, 57, 87, 101, 116? (A) n-butyl n-propyl ether (B) sec-butyl iso-propyl ether (C) 2-heptanol
(D) hexanoic acid (E) None of the above
|
| B | 78. How many different β-hydroxyaldehydes and β-hydroxyketones, including constitutional isomers and stereoisomers, are formed upon treatment of a mixture of acetone and acetophenone with base? (A) 4 (B) 6 (C) 9 (D) 10 (E) 12 . |
| D | 79. Deduce the identity of the compound from the data provided. C5H10O2: IR (cm-1): 3380 (br, s). 1
H-NMR (ppm): 1.30 (s, 3H), 3.50 (t, 1H), 3.64 (d, 2H),
4.38 (d, 2H), 4.52 (d, 2H). 13C-NMR (ppm): 20.72 (q), 40.78 (t), 67.59 (t), 79.74 (t).
(A) (2,3-dimethyloxiran-2-yl)methanol (B) 1-(2-methyloxiran-2-yl)ethanol (C) 1-(oxetan-3-yl)ethanol (D) (3-methyloxetan-3-yl)methanol (E) (tetrahydrofuran-2-yl)methanol
|
| C |   (A) I (B) II (C) III (D) IV (E) None of the above
|
(B) 
(C) 
(D) 
(E) None of the above
(B) 
(C) 
(D) 
(E)both（A）and（D）
(B) 
(C) 
(D) 
(E) None of the above.
(B) 
(C) 
(D) 
(E) None of the above.
(B) 
(C) 
(D) 
(E) None of the above.
(B) 
(C) 
(D) 
(E) None of the above.
(B) 
(C) 
(D) 
(E) None of the above.