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ORGANIC CHEMISTRY
CHEM 243

Course goals and objectives: This is an introductory course to organic chemistry. Detailed mechanisms of several reactions will be covered. Course requirements are CHEM 241 and CHEM 242.

Textbook: Wade (Organic Chemistry, Ed. 5) is recommended.

Grading:
2 1.5-hour exams 2 x 100
final 200
total 400

Course Information: An FAQ for the class is maintained on this blog and is updated periodically. E-mail the instructor if your question is not addressed in the FAQ.external image cholesterol.jpg

Make-up test policy: Tests, quizzes and exam will be available on WebCT. Location and times of testing are specified in this wiki. Quizzes will be available for each chapter but will not count towards the final grade. Make-up tests will be available on WebCT but will consist of additional questions without additional time. The better score between the test and make-up will be used.

Lecture archives: This class can be taken fully online. The class archives are made available by screencasting as streaming audio/video as well as podcast by audio with pdfs to follow along. Students attending the class fully online are encouraged to contact the instructor by e-mail to ask questions or to schedule phone or physical appointments to go over any material that requires further explanation.

Grading Policy:
A+ 97-100
A 93-96
A- 90-92
B+ 87-89
B 83-86
B- 80-82
C+ 75-79
C 70-74
C- 65-69
D+ 60-64
D 55-59
D- 50-54
F 0-49

Material Covered


Aromatic compounds
Electrophilic Aromatic Substitution
Mechanism: sigma complex, electrophile
-bromination of benzene with Br2 and FeBr3
-chlorination of benzene with Cl2 and AlCl3
-iodination of benzene with I2 and HNO3
-nitration of benzene with HNO3 and H2SO4
-sulfonation of benzene with SO3 and H2SO4
-Friedel-Crafts alkylation with R-X and AlCl3 or FeBr3
-Friedel-Crafts alkylation with alkenes or alcohols and acids
-Friedel-Crafts acylation with RCOCl and AlCl3 (acylium ion)

Ortho/Para directors
-Ortho directors: R, X, OR, OH, NH2, NHCOR
-Meta directors: COR, CO2H, CO2R, SO3H, CN, NO2, N+R3
-Mechanism of ortho/para direction: Resonance

Reactions at side chains
-Clemmensen reduction of Ar-COR with Zn(Hg)/HCl(aq.)
-free radical halogenation
-permanganate oxidation of ArR to ArCO2H
-SN1 substitution at benzylic halides

Other reactions
-The Benzyne mechanism: reaction of p-bromotoluene with NH2-
-Catalytic hydrogenation of aromatic ring


Ketones and Aldehydes
Carbonyl compounds:
-ketones, aldehydes, carboxylic acids, acid chlorides, esters, amides
-dipole moment
-nomenclature: formaldehyde, acetaldehyde, acetone, benzaldehyde, methyl ethyl ketone, benzophenone, acetophenone, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid
-hydrogen bonding with alcohols
-infrared spectra: ketones and aldehydes 1710 cm-1

Preparation:
-secondary alcohols to ketones with Na2Cr2O7/H2SO4
-primary alcohols to acids with Na2Cr2O7/H2SO4
-primary alcohols to aldehydes with PCC
-ozonolysis of alkenes to aldehydes and ketones
-phenyl ketones from Friedel-Crafts reaction
-hydration of alkynes to ketones with Hg2+/H2SO4/H2O (Markovnikov addition)
-hydroboration-oxidation of alkynes to aldehydes with Sia2BH/H2O2, NaOH
-alkylation of 1,3-dithiane followed by hydrolysis with HgCl2 to ketones and aldehydes
-Grignard reagents and nitriles to ketones and aldehydes
-acid chlorides to aldehydes with LiAlH(O-t-Bu)3
-acid chlorides to ketones with R2CuLi

Reactions:
-nucleophilic addition of:
-Grignard reagents to alcohols
-Wittig reaction to alkenes
-hydrates and acetals – use as protecting group
-cyanohydrins then to a-hydroxy acid
-imines
-oximes and hydrazones
-oxidation of aldehydes to acids with Na2Cr2O7/H2SO4
-reduction of ketones and aldehydes with NaBH4 or LiAlH4 to alcohols

Amines
Nomenclature
-primary, secondary, tertiary, quaternary
-aniline, N,N-diethylaniline, 3-ethylaniline, p-toluidine, pyrrole, pyrrolidine, imidazole, pyridine, piperidine

Reactions
-alkylation
-acylation
-imine formation
-diazotation
-Hofmann elimination

Synthesis
-reductive amination
-acylation then reduction
-reduction of nitro compounds
-reduction of azides
-reduction of nitriles (b-hydroxy amines)
-Hofmann rearrangement

TEST 1 ------------


Carboxylic Acids and derivatives
Nomenclature
-formic, acetic, propionic, butyric, valeric acids, cyclohexanecarboxylica acid, benzoic acid, phthalic acids, alpha and beta
-effect of substituents on acidity

Synthesis
-from primary alcohols with KMnO4
-from alkenes or alkynes with KMnO4
-carboxylation of Grignard reagents
-hydrolysis of nitriles
Nucleophilic Acyl Substitution
-acyl halides, anhydrides, esters, amides; reactivity and preparation
-acid catalyzed and base catalyzed mechanisms for the hydrolysis of esters (tetrahedral intemediate)

Reactions
-reduction of acids and esters to primary alcohols with LiAlH4
-reduction of amides to amines with LiAlH4
-reduction of acid chlorides to aldehydes using LiAlH(O-t-Bu)3
-formation of amides from amines and acid chlorides
-formation of esters from alcohols and acid chlorides
-formation of acids from water and acid chlorides
-formation of anhydrides from acids and acid chlorides
-formation of ketones from organocuprates and acid chlorides (Grignards give alcohols)

Enols and Enolate Ions
-Mechanism of alpha substitution (base and acid catalyzed)
-the haloform reaction
-aldol condensation (base and acid catalyzed)
-dehydration of aldol products
-aldol cyclizations
-Claisen condensation
-malonic ester synthesis
-acetoacetic ester synthesis
-Michael addition