Tentative Lecture Schedule
| Date |
Topics |
Chapter |
Book Problems |
|
|
1 |
1/11 | Synthesis tools. Review of reactions
from Chem 350 |
11.1 | 11.11-11.12 |
|
2 |
1/12 | Multistep synthesis.
Retrosynthetic analysis. Green chemistry. |
11.2-11.7 | 11.15,
11.18, 11.21, 11.22 |
|
3 |
1/14 | Alcohols and Phenols.
Physical properties and acidity. Reactions
with strong acids. |
12.1-2 |
12.27-12.31 |
|
4 |
1/19 | Other reagents for halogenation of
alcohols. Oxidation of alcohols |
12.9, 12.10 |
12.20-21,
12.32a-e,g,i |
|
5 |
1/21 | Methods for alcohol
preparation. Hydride reduction of ketones,
aldehydes. Grignard synthesis of alcohols. |
12.3-12.6 |
12.34-12.37,
12.42, 12.44 |
|
6 |
1/24 | Grignard synthesis;
generality and incompatible groups. Planning a
Grignard synthesis. Intro to ether reactions and
preparation. |
12.6, 13.5-13.6 |
12.54,
12.57 |
|
7 |
1/26 | Ethers - Preparation, and Reactions. Silyl ethers as protecting groups. Multistep syntheses requiring protected alcohols. | 12.7, 13.3, 13.5-13.6 | 13.27,
13.68, 12.16, 12.65 |
|
8 |
1/28 | Cyclic Ethers - Nomenclature and Reactions. Regiochemistry of reactions of unsymmetrical epoxides. Use of epoxides in the Grignard synthesis. | 13.5, 13.6-13.10 | 13.33,
13.38c,d, 13.39, 13.44, 13.51c,d,f,n,o |
|
9 |
1/31 |
Bromohydrin route to epoxides. Asymmetric epoxidation. Crown Ethers. Sulfur compounds. | 13.4, 13.8-13.11 | 13.20,
13.21a,b, 13.35, 13.67 |
|
10 |
2/2 |
Autooxidation of ethers. Oxidation of Sulfides. |
13.6,
13.11 |
13.21 |
| 2/4 | Exam 1 | 11-13, 14 (MS) |
||
| 11 | 2/7 | Dienes.
Electrophilic addition to conjugated dienes.
Thermodynamic vs kinetic control. |
16.1, 16.2, 16.4, 16.5 |
16.30-31,
16.33-16.38 |
| 12 | 2/9 | 1,2 and 1,4 Addition in reactions that
do not involve allylic carbocations. Huckel
Molecular Orbital Theory. Linear polyenes. |
16.4, 16.3 |
16.5 |
| 13 | 2/11 | Benzene and Aromaticity.
Cyclobutadiene and cyclooctatetraene. MO theory and
the Huckel Rule. |
17.1-17.5 | |
|
14 |
2/14 | Theoretical criteria and
experimental hallmarks of aromaticity. The
annulenes. Aromatic ions. Heteroaromatic rings. |
17.5 | 17.30,
17.32-17.36 |
|
15 |
2/16 | Electrophilic
aromatic substitution - general mechanism.
Friedel-Crafts reactions. Rearrangements in F.C.
alkylation. F.C. acylation followed by reduction of
the C=O to CH2. Benzene nomenclature. |
18.1, 18.5-18.6, 17.2 |
17.24-17.26,
18.45, 18.48, 18.49d, 18.50, 18.52b |
|
16 |
2/18 | Benzene Halogenation, Nitration, and
Sulfonation. Substituent effects in SEAr
reactions. |
18.2-18.4, 18.7-18.10 | 18.39-18.43 |
| 17 | 2/21 | Substituent
Effects in SEAr Reactions (cont) . SEAr
reactions on disubstituted rings. |
18.7-18.11 |
18.16-18.17,
18.46, 18.55, 18.64 |
| 18 | 2/23 |
Friedel-Crafts limitations and
synthetic implications. Reduction of aromatic nitro
groups. Side chain reactions. |
18.4, 18.12, 17.6 | 17.42,18.52-18.54,
18.71, 18.63c |
|
19 |
2/25 |
Synthesis of subsituted benzene
rings using retrosynthetic analysis. |
18.12 |
18.26,
18.53, 18.63, 18.67 |
| 20 | 2/28 | Nucleophilic substitution on benzene rings. The SNAr and Benzyne mechanisms. Benzenediazonium salts. | 18.13-18.14, 22.11 | 18.30-18.34,
18.56, 18.87, 22.26, 22.44d,e, 22.95 |
| 21 | 3/2 |
Birch Reduction. Aldehyde/Ketone properties and reactions. Nucleophilic addition of hydride and Grignard reagents. | 17.7 19.3-4, 19.9-19.10 |
|
| |
3/4 | Exam 2 | 16.1-16.5, 17-18, 22.11 |
|
| 22 |
3/14 |
Aldehyde/Ketone reactions. The
Wittig reaction. Acid catalyzed AN
reactions. Hydration. Acetal formation. |
19.4-19.5, 19.10 | 19.49-19.52,
19.57a-b, 19.69a, 19.73b |
|
23 |
3/16 |
Acetals as protecting groups.
Reactions of aldehydes and ketones with amines.
Solid derivatives. |
19.5-19.7 |
19.54a-f,
59-61, 63b, 64a,e, 70, 73e,g |
|
24 |
3/18 | Hydrazine reduction mechanism. Hydrolysis of imines and enamines. Thioacetals. Baeyer-Villiger Oxidation. | 19.7-19.12 |
19.23,
19.26-27, 19.61-62, 19.63b, 19.54h-i, 19.70 |
|
25 |
3/21 |
Baeyer-Villiger Oxidation. Carboxylic
Acids. Naming, properties, and reactions. |
19.11, 20.1-20.5 | 20.35,
20.37-39, 20.43, 20.45a-c, 20.46a, 20.49a-b, 20.50c |
| 26 | 3/23 |
Reactivity of Carboxylic Acids and Carboxylic Acid Derivatives. Interconversions of CADs. Hydrolysis of CADs. Saponification. | 20.6-20.12 | 20.44a,c,d,e,f,
20.46b,d,f,g,h, 20.50b,d, 20.51a,c, 20.59 |
|
27 |
3/25 | More examples of CAD reactions: Fisher esterification. Cyclic anhydrides, esters, amides. Hydrolysis of nitriles. Nitrile synthesis of carboxylic acids. | 20.9-20.13 |
20.45d,
20.46c, 20.47, 20.49b-f, 20.54, 20.56, 20.61a-c |
| 28 | 3/28 |
Reactions of esters and acid
chlorides with hydride donors and organometallics.
Reduction of amides to amines. Reactions of nitriles
with Grignard reagents. |
20.8, 20.11-13, 12.4, 12.6 | 20.44b,g,h,
20.46e, 20.48, 20.51b,d, 20.53, 20.55, 20.57, 20.61e |
| 29 | 3/30 |
LAH reduction of nitriles. SN2 route to esters. CAD Nomenclature. | 20.6, 20.11, 20.13 | |
| 30 |
4/1 | Enolate chemistry. Epimerization and halogenation of the alpha carbon. The haloform reaction. alpha-Alkylation. | 21.1-21.2 | 21.47,
21.51, 21.53, 21.55-56, 21.59, 21.74a-b, |
| 4/4 | Exam 3 | 12.4, 12.6, 19-20 |
||
| 31 | 4/6 | Kinetic vs Thermodynamic Enolates. The aldol condensation. Crossed aldols and directed aldols. | 21.5, 21.3 |
21.53,
21.61-21.64, 21.66, 21.72, 21.76d, 21.78a,g |
| 32 | 4/8 |
The acetoacetic ester and malonic ester syntheses. Intramolecular aldols. | 21.5, 21.3 |
21.49-50,
21.68-69, 21.71, 21.84a-c,e,g |
| 33 | 4/11 |
Reactions of Esters; the Claisen
condensation. Intramolecular Claisen. Aldol and
Claisen variations involving highly stabilized
enolates and enolate relatives. |
21.4-21.6 |
21.67,
21.76a,b, 21.77a, 21.80-82 |
33 |
4/13 |
Conjugate (Michael) addition vs direct addition to conjugated aldehydes/ketones. Stork enamine synthesis. Robinson annulation. | 21.4,
21.6-21.7 |
21.73,
21.76c, 21.77c, 21.78b-f, 21.83, 21.84d, 21.85-86 |
| 34 |
4/18 |
Other pericyclic
reactions - electrocyclic ring closure, sigmatropic
shifts. Frontier MO theory and the Wooward-Hoffmann
rules. |
16.8-16.10 |
16.13,
16.17, 16.21-22, 16.25, 16.42-16.43, 16.52-56 |
| 35 |
4/22 |
The Diels-Alder reaction. Stereochemistry, regiochemistry, and substituent effects. | 16.6-16.7 |
16.39-40,
16.42-46, 16.57-58, 16.66, 16.71 |
| 36 |
4/25 |
Amines | 22 |
|
| 37 |
4/27 |
Amines |
22 |
|
| 38 |
4/29 |
Exam 4 |
16.6-16.10, 21-22 |
|
| 5/2 |
Final Exam | 1-22 |