(2 points each) Write your answer in the box to the right of the question. 1. A mixture of 1-hexanol and hexanoic acid in diethyl ether is shaken with an aqueous sodium bicarbonate solution. Which line below correctly describes the major organic species in the two resulting immiscible solutions? Ether Sodium bicarbonate solution A) hexanoic acid 1-hexanol B) 1-hexanol hexanoic acid C) sodium hexanoate 1-hexanol D) 1-hexanol sodium hexanoate 2. Which of the following has the largest acid equilibrium constant, Ka? A) C 3 C 2 B) C 2 C 2 C) C 2 C 2 D) C 3 C 2 12. What is the name of the following compound? C 2 C 3 A) 2-chlorohexyl ethanoate C) ethyl 2-chlorohexanoate B) 1-chlorohexyl ethanoate D) ethyl 1-chlorohexanoate 13. Which of the following has the fastest rate of hydrolysis to give acetic acid? 1) C 3 CCC 3 2) C 3 C 3) C 3 CC 2 C 3 4) C 3 C 14. ow are reactions between aldehydes and nucleophiles fundamentally different than reactions between acyl chlorides and nucleophiles? A) Aldehydes are readily oxidized by nucleophiles to carboxylic acids. B) Acyl chlorides have a leaving group, -, whereas aldehydes do not. C) Aldehydes do not form tetrahedral intermediates with nucleophiles. D) Acyl chlorides readily form enol tautomers. 17. What is the relationship between the following two structures? 3 C and 3 C A) resonance forms C) constitutional isomers B) stereoisomers D) tautomers 21. Which of the following compounds, on reaction with aqueous sodium hydroxide, yields sodium butanoate, C 3 C 2 C 2 C 2 Na, at the slowest rate?
rganic Chemistry EXAM 3 Name 1) (C 3 C 2 C 2 C) 2 3) C 3 C 2 C 2 C 2) C 3 C 2 C 2 CC 3 4) C 3 C 2 C 2 C 23. eating butylmalonic acid, C 3 C 2 C 2 C 2 C(C 2 ) 2, to 140 C yields: A) hexanoic acid C) 2-methylpentanoic acid B) pentanoic acid D) 2-hexenoic acid 24. Which one of the following is not a resonance form of the enolate ion formed from ethyl acetoacetate? 1) C 2 C 3 3) C 2 C 3 2) 4) C 2 C 3 C 2 C 3 26. Among the isomeric C 4 11 N amines below, the one with the lowest boiling point is: A) C 3 C 2 C 2 C 2 C) (C 3 ) 2 CNC 3 B) (C 3 C 2 ) 2 N D) (C 3 ) 2 NC 2 C 3 27. Rank the following three compounds in order of decreasing basicity. N 2 A B C A) 1>2>3 C) 3>2>1 B) 2>1>3 D) 3>1>2 30. Which one of the following compounds gives propylamine, C 3 C 2 C 2, upon hydrolysis? 1) C 3 C 2 C N 3)(C 3 C 2 C 2 ) 2 N N 2) C 3 CNC 2 C 2 C 3 4) C 3 C 2 C (3 points each) Write your answer in the box to the right of the question. 25. What is the product of the following reaction sequence? (1) NaEt (xs) 2, + (1) S 2 Et Et (2) 2 C 3 C 2 Br heat (2) N 3 2
rganic Chemistry EXAM 3 Name 1) 2) 3) 4) 22. Which of the following best represents a mechanistic step in the acid catalyzed hydrolysis of acetonitrile? 1) 3 C C N 3) 3 C C N 2) 3 C C N 4) 3 C C N 18. Which one of the following tetrahedral intermediates dissociate to an ester? 1) 3 C C 3) C 3 3 C C 2) 3 C C CC 3 4) 3 C C CC 3 C 3 6. Reaction of acetic acid, C 3 C 2, with isotopically labeled C 3 18 and catalytic sulfuric acid gives: 18 18 1) C 3 CC 3 + 2 3) C 3 CC 3 + 2 2) C 3 C 18 C 3 + 2 4) equal amounts of 1 and 2 8. Identify the lactone formed by the following hydroxy carboxylic acid. 1) 2) 3) 4) 9. Which of the following undergo decarboxylation upon heating? 3
rganic Chemistry EXAM 3 Name C 2 C 2 C 2 C 2 C 2 C 2 A B C D A) 1 and 4 B) 1 and 3 C) 2 and 3 D) 3 and 4 15. The compounds shown below have similar molecular weights but significantly different boiling points. Match the compound with its boiling point. (Boiling points ( C): 28, 57, 100, 141) methyl acetate 2-butanol 2-methylbutane propanoic acid A) 100 141 28 57 B) 57 100 28 141 C) 28 100 57 141 D) 141 57 28 100 16. Which of the following would work best in preparing t-butyl benzoate? A) C 6 5 C 2 plus (C 3 ) 3 C with 2 S 4 catalyst and heat B) C 6 5 C 2 Na plus (C 3 ) 3 CBr and heat C) C 6 5 C plus (C 3 ) 3 C and heat D) C 6 5 C 2 plus S 2 followed by (C 3 ) 3 C with pyridine 28. Which of the following is the product of the reaction shown below? N (1) Na 2 N (2) (C 3 ) 2 CC 2 C 2 Br A) (C 3 ) 2 CC 2 C 2 N C) [(C 3 ) 2 CC 2 C 2 ] 2 N B) (C 3 ) 2 CC 2 C 2 D) (C 3 ) 2 CC 2 C 2 C 29. Which pair of reagents would be used to make the following amine by reductive amination?? +? 2 /Pd C 3 C 2 CC 2 NC 3 C3 A) methylamine and 2-methylbutanoic acid C) ammonia and 3-methyl-2-pentanone B) methylamine and 2-methylbutanal D) dimethylamine and 2-butanone 32. Which one of the following amines gives an N-nitrosoamine on treatment with nitrous acid, N 2? A) 2,4-dimethylaniline C) N,4-dimethylaniline B) 3,5-dimethyaniline D) N,N-dimethylaniline 4
rganic Chemistry EXAM 3 Name 33. What is the product of the following reaction? 3 C C 3 NaN 2, 2, o C 2 warm A) 3,5-dimethyl-4-nitrophenol C) meta-xylene (meta-dimethybenzene) B) 1,3-dimethyl-5-nitrobenzene D) 3,5-dimethylphenol 36. What is the major product of the reaction sequence below? C 3 C 2 C 2 CC 3 C 3 I(xs) (1)Ag 2, 2 (2) heat 1) C 3 C 2 C 2 C=C 2 3) C 3 C 2 C 2 CC 3 2) C 3 C 2 C=CC 3 4) C 3 C 2 C=CC 3 20. Identify the stereochemistries of sec-butyl benzoate and 2-butanol in the following reaction sequence? (Assume that the reaction sequence shown follows the customary mechanisms for bimolecular nucleophilic substitution and nucleophilic acyl substitution.) Br C 6 5 C 2 Na CCC 2 C 3 C 3 sec-butyl benzoate sec-butyl benzoate 2-butanol A) R S B) R R C) R Racemic D) S R E) S S F) S Racemic K, 2 heat C 3 CC 2 C 3 2-butanol (4 points each) Write your answer in the box to the right of the question. 21) (9 points) Choose three of the following. Predict the major organic product of the following reactions. A) (C 3 ) 2 CC 2 (1) LiAl 4 PBr 3 KCN 2, + (2) 2 DMS heat A) (C 3 ) 2 CC 2 C 2 C) (C 3 ) 2 CCBrC 2 B) (C 3 ) 2 C=CC 2 D) (C 3 ) 2 CC 2 C 2 B) 5
rganic Chemistry EXAM 3 Name C 3 NBS, C 4, heat (1) Mg/ether 3 + benzoyl peroxide (2) C 2 C(C 3 ) 3 C 3 C 2 C 3 2 C 1) 2) 3) 4) C 2 C 2 C(C 3 ) 3 C(C 3 ) 3 3 C C C 3 C(C 3 ) 3 C 2 C 2 C) N 2 Br 2 (1) Fe, NaN 2, Cu FeBr 3 (2) Na 2, o C A) meta-bromochlorobenzene C) 1,3-dibromo-5-chlorobenzene B) 1,3,5-tribromobenzene D) mixture of ortho and para -bromochlorobenzene D). What is the product of the reaction series shown below? NaN 2, CuCN (1) C 3 MgBr 2, o C (2) 2, + C 2 C 3 CC 3 CC 3 1) 2) 3) 4) C 2 CN 22) (6 points) Provide the reagents required for each of the following transformations. A) Benzoic acid N,N- dimethylbenzamide B) 1 Bromo 5 pentanol 1 amino 5 pentanol 6
rganic Chemistry EXAM 3 Name 24) (6 points) Choose one of the following. Indicate synthetic route which gives the best yield for the following transformations. A) C 2 Br? C 2 C 3 Br C 2 1) (1) Mg/diethyl ether (2) C 2 (3) 2, + (4) C 3 - Na + 2) (1) Na (2) Mg/diethyl ether (3) C 2 (4) 2, + (5) C 3 I 3) (1) C 3 - Na + (2) Mg/diethyl ether (3) C 2 (4) 2, + 4) (1) C 3 - Na + (2) KCN, DMS (3) 2, 2 S 4, heat B) Benzene to m- bromoaniline. 1) benzene Br 2 N 3 (1) Sn, FeBr 3 2 S 4 (2) Na 2) benzene 3) benzene N 3 (1) Sn, Br 2 2 S 4 (2) Na FeBr 3 N 3 Br 2 (1) Sn, 2 S 4 FeBr 3 (2) Na 4) benzene (1) Sn, N 3 Br 2 (2) Na 2 S 4 FeBr 3 25) (8 points) Propose a mechanism for the following reaction. Benzoyl chloride + acetic acid Acetic benzoic anhydride + hydrogen chloride 26) (8 points) Use the following information to identify compound X. A compound has a molecular mass of 83 and contains nitrogen. Its infrared spectrum contains a moderately strong peak at 2270 cm-1. Its 1 and 13C NMR are shown below. What is the structure of this compound? 7