110b Exam 4 Review Sheet- Spring Semester 2012
Review Session: Monday, April 9, 7:00 PM, SN Aud
Exam 4: Wednesday, April 11, SN Aud
Chapter 20 Goals:
1.
Nomenclature: be familiar with the examples on pp. 912-913 10E pp. 900-901 9E, including
pyridine and sulfanilamide (know a bit of the history behind this drug, see p. 945 10E p. 930-931
9E). Become familiar with the structure and properties of one biologically important amine, p.
922 10E p. 910-911 9E.
2.
Properties of amines: review lecture notes concerning structural and conformational features.
Basicity: you should be prepared to explain trends in basicity among alkyl and arylamines.
Know the “ballpark” pKa’s for these two classes of amines (as the protonated forms). 913-918
10E, 903-907 9E
3.
Preparation of amines: Gabriel primary amine synthesis, mechanism of reaction/deprotection.
925-926 10E, 913-914 9E
4.
Amines via alkylation of amines, reduction of alkyl azides, nitro groups. 924-927 10E, 912-914
9E
5.
Reductive amination as a means for 1°, 2°, and 3° amine synthesis. Mechanism of reaction for
each case. 927-929 10E, 914-916 9E
6.
Reduction of amides, oximes, and nitriles as a means for synthesizing amines. 929-930 10E, 916917 9E
7.
The Hofmann and Curtius rearrangement as methods for amine synthesis. Reaction mechanism.
931-933 10E, 917-919 9E
8.
Reactions of secondary alkylamines and primary arylamines with HONO: prep of Nnitrosoamines and aryldiazonium ions. Mechanism of formation, properties of the
products. 935-937 10E, 921-923 9E
9.
Reactions of aryldiazonium salts: The Sandmeyer reaction (replacement with Cl, H, Br, F, CN,
OH) and its utility in direct preparation and/or blocking strategies. Coupling reactions with
aryldiazonium salts (dye syntheses) mechanism of reaction. 937-943 10E, 923-929 9E
10.
Review the Hinsberg test for structural assignment of 1°, 2°, or 3° amine. 943-947 10E, 929-934
9E
11.
Analysis of amines: spectroscopic signatures. 947-949 10E, 934-935 9E
12.
Elimination reactions involving ammonium compounds: the Hoffmann and Cope elimination
reactions. 949-950 10E, 935-937 9E
13.
Be prepared to apply any reactions discussed in Chapter 20 (and assigned end of chapter
problems) in predict-the-product and synthetic proposals.
Chapter 21 Goals:
1.
Nomenclature: be familiar with the examples on 965 10E, 955 9E.
2.
Properties of phenols: be prepared to explain the trends in acidity for substituted phenols.
Solubility as an indicator for phenol vs alcohol vs carboxylic acid. 966, 969-971 10E, 957, 961963 9E.
3.
Laboratory synthesis (hydrolysis of a diazonium salt) vs industrial syntheses (Dow process,
Cumene process) of phenol. Mechanisms of these reactions. 967-969 10e, 957-961 9e
4.
EAS reactions of phenols: bromination, nitration, sulfonation, the Kolbe reaction and utility in
aspirin synthesis. 973-975 10e, 964-966 9e
5.
The mechanism and utility of the Claisen rearrangement. Be familiar with the historical method
used to provide evidence for a concerted mechanism. How would you do it today, without resort
to radioactive materials? 977-978 10e, 967-968 9e.
6.
Quinones: synthesis, reactions, and biological utility in redox systems. 978-980 10e, 968-969 9e.
7.
NAS reactions via the addition-elimination SNAr mechanism. The Meisenheimer complex.
Aromatic substituents that promote the reaction, substituents that act as leaving groups.
Thyroxine synthesis. [Learning Group Problem 1, p. 997 10e, 984 9e] 980-983 10e, 969-972 9e.
8.
NAS reactions via the elimination-addition (benzyne) mechanism. Evidence for this mechanistic
intermediate. Roberts’ historical experiment with 14C. Propose an alternative experiment,
without resorting to 14C, to provide evidence for the intermediacy of a benzyne intermediate.
984-988 10e, 973-977 9e.
9.
Spectroscopic signatures of phenols and aryl halides. 988 10e, 977 9e.
10.
DDT, Agent Orange, and PCBs: know their stories and their chemistry. 989 10e, 992-994 9e.
11.
Work the text problems, be prepared to predict the products, propose syntheses, and address
issues outlined above.
Suggested problems for Chapter 20. 10E: 19, 22, 24, 27, 29, 31, 33, 34, 36, 38, 42, 45, 47, 49. 9E: 21-47
odd only. Suggested problems for Chapter 21. 10E: 14, 23, 26, 28, 30, 33, 35, 37, 38, 39 9E: 17-35 odd
only.