| Date |
Topics |
Chapter |
Book Problems |
|
|
1 |
1/8 | Synthesis tools. Review of reactions
from Chem 350. Some standard "moves" |
10-13 |
|
|
2 |
1/10 | More advanced
synthesis problems. Retrosynthetic analysis. |
10-13 |
see
pset 1 posted on D2L |
| 1/12 |
Class canceled |
|||
|
3 |
1/17 | Radicals, structure,
stability and elementary reactions. |
27.1-27.3 |
27.3,5-9,12-13 |
|
4 |
1/19 | Radical halogenation.
NBS for allylic bromination |
27.4 | 27.15-19 |
|
5 |
1/22 | Radical addition of HBr. Air
oxidation of ethers. Lipid
peroxidation. |
27.5 |
27.14,27-30,42 |
|
6 |
1/24 | Stereochemistry of
radical reactions. Allylic rearrangement in NBS
reactions. Dissolving metal reductions. |
27.6, 27.7 |
27.21,
35-37 |
|
7 |
1/26 | Radical polymerization. | 28.1 | 28.1-3,6-7 |
|
8 |
1/29 | Benzene structure. Huckel's rule. Conjugation. Allylic systems and conjugated dienes looked at using MO theory. | 14.1-14.5 | 14.2-3,5,8 |
|
9 |
1/31 | Linear polyene MOs.
The HOMO and LUMO. MOs of benzene vs
cyclobutadiene and cyclooctatetraene. 10-Annulene. |
14.5-14.8 | 14.8,19,21,24 |
|
10 |
2/2 |
Predicting the aromaticity of annulenes, heterocycles, and ions. | 14.7 | 14.10-18 |
| 2/5 | Exam 1 | 27, 28.1, 14 and
synthesis |
||
| 12 | 2/7 | Electrophilic aromatic substitution
(SEAr). General mechanism. Halogenation
and Friedel-Crafts alkylation. |
24.1-24.3 |
24.1-5,
7, 9-10 |
| 13 | 2/9 | F-C acylation.
Reduction of acyl benzenes to primary alkylbenzenes.
Nitration. Sulfonation. |
24.4-24.8 |
24.16-17, 19, 24 |
|
14 |
2/12 | Subsituent effects in SEAr
reactions: regiochemistry and reactivity. |
25.1-25.3 | 25.1a,
2-4, 6-7, 9-10 |
|
15 |
2/14 | Theory
of subsitutent effects continued. Synthesis using SEAr reactions. Using SO3H as a blocking group. |
25.1-25.3, | 25.11-25.13 |
|
16 |
2/16 | FC limitations and amine
substituents. Nitro group reduction. Alkyl group
oxidation. |
25.2-25.5, 24.9 | 24.21-23,
24.25, 25.23 |
| 17 | 2/19 | SEAr reactions on: (1) di- and tri-substituted benzenes (2) on nonbenzene aromatics | 25.6-25.7 | 25.22,
25.24, 25.27-29 |
| 18 | 2/21 |
Nucleophilc aromatic substitution
mechanisms. SNAr and PEEK polymer.
Benzyne and Diels-Alder trapping. Diazonium
chemistry. |
24.9, 25.9 | 25.44-49,
24.26-27 |
|
19 |
2/23 |
Diels-Alder cycloaddition. Substituent effects - MO description | 26.1-26.7 |
26.1-7,10-11,
12a, 14-17, 19, 26, 34 |
| 20 | 2/26 | Birch reduction. Synthesis problems. |
27.7b, 25.10-25.11,
26.10 |
27.39-40 |
| 21 | 2/28 |
Diels-Alder-based
polymers |
||
| |
3/1 | Exam 2 | 24-26, 27.7b (except
25.8, 25.12, 26.8-9) |
|
| 22 |
3/11 |
Nucleophilic addition to aldehydes
and ketones. General mechanism and reactivity.
Hydride nucleophiles. Organolithiums and Grignards. |
18.1-18.4 |
18.9.11,13, 15,17,19,21 |
|
23 |
3/13 |
The Grignard synthesis of alcohols. |
18.4-18.5, 20.6 |
18.1,
21, 22, 24 |
|
24 |
3/15 | Grignard
reactions with imines and nitriles. The Wittig
synthesis of alkenes. |
18.3-18.7 |
18.7,
10, 12, 14, 20, 23, 25-28 |
|
25 |
3/18 |
Addition of neutral nucleophiles; water and alcohols. Acid and base catalysis. Acetals. | 19.1-19.2 | 19.1,
5-6, 12-14, 16a,b,d |
| 26 | 3/20 |
Nitrogen nucleophles. imines, and enamines. | 19.4 |
19.15,19 |
|
27 |
3/22 | Nitrile hydrolysis. Reductive amination. Wolff-Kishner reduction. | 19.5-19.7 | 19.16b,
21-23 |
| 28 | 3/25 |
Enolate nucleophiles; aldol
reactions. |
19.8-19.11 | 19.24-19.28 |
| 29 | 3/27 |
Lithium dialkycuprates and conjugate addition reactions. Synthesis. | 18.8-18.11, 19.3 | 18.31-34 |
| 30 |
3/29 |
More aldol chemistry. Knoevenagel
condensations. Stork enamine synthesis. Robinson
annulation. |
19.11-19.14 |
19.27,
29, 38-40 |
| 4/1 | Exam 3 | 18-19 |
||
| 31 | 4/3 | Oxidation
of alcohols and aldehydes |
20.5 |
20.17-20.19 |
| 32 | 4/5 |
Nucleophilic
acyl substitution reactions (SNacyl).
Overview. Basic hydrolysis of esters and
amides.Gabriel synthesis of primary amines.The
haloform reaction. |
22.1-22.5 |
22.1-22.6 |
| 33 | 4/8 |
SNacyl with hydride sources. SNacyl of organometallics and enolates. | 22.7-22.8, 23.9 |
22.18-22.24 |
| 33 | 4/10 | Reactivity of carboxylic acid derivatives. SNacyl with weak nucleophiles. Acid catalyzed hydrolysis. Synthesis of carboxylic acid derivatives and acid halides. |
23.1-23.4 |
23.2-23.6 |
| 34 |
4/15 |
Synthesis
of carboxylic acid derivatives and acid halides.Two
methods for esters. Fischer esterification. |
23.4,
23.7 |
23.11-12,
23.19, 23.21, 23.23 |
| 35 |
4/17 |
Cyclic
anhydrides. Amides from carboxylic acids. Polyesters
and polyamides.Baeyer-Villiger oxidation. |
23.4,
28.5, 23.8 |
23.9,
23,26-27; 28.22-26 |
| 36 |
4/19 |
Nomenclature
of ketones, aldehydes, carboxylic acids, and
carboxylic acid derivatives. |
D.3-5 |
D.11-28 |
| 37 |
4/22 |
The
Claisen condensation and related reactions. The
acetoacetic ester synthesis. |
23.9-23.10 |
23.29-32, 23.35 |
| 38 |
4/24 |
The
malonic ester synthesis. alpha-Halogenation of
carboxylic acids. Synthesis problems. |
23.10,
23.5 |
|
| 39 |
4/26 |
Exam 4 |
20.5, 22-23, 28.5,
D.3-5 |
|
| 4/30 |
Final Exam |