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Special Topics for Final Exam: Topics that Frequently Appear on ACS or
Standardized Tests, But That I Didn’t Cover in Class This Year
1. Epoxides as Electrophiles (Section 14.12-15. Representative Problems: 14.25-28)
OR CH3 CH3
H+, HOR Z , Z-H
CH3 O OH
Acid Catalyzed Attack Anion Nucleophile Z
OH SN2 Attack
by Weak, Neutral Nucleophile
Inversion of Stereochemistry Inversion of Stereochemistry
Attack on *More* Subbed End Attack on *Less* Subbed End
• Because of ring strain, epoxides are relatively reactive toward nucleophilic substitution,
in which one of the C-O bonds breaks.
• Two different substitution profiles:
o Strong, anionic nucleophiles
SN2 mechanism, followed by a protonation step
Types of nucleophiles:
Carbon anions: Grignards, enolates, alkyne anions
Oxygen anions
Stereochemistry: Inversion (if stereochemistry matters).
Site of Attack: If Epoxide is unsymmetric, nucleophile attacks the less
hindered end
o Acid-catalyzed addition of weak, neutral nucleophiles
Types of nucleophiles: normally water or alcohol
Stereochemistry: Inversion (if stereochemistry matters)
Site of Attack: if epoxide is unsymmetric, nucleophile adds to the
more hindered end.
H3CH2CO Me H+ Me NaOCH2CH3
OH O Me OH
OCH2CH3
EtOH ethanol
OH
Ph
1. PhMgBr
2. H+
OMe H+ O NaOMe OH
OH OMe
MeOH MeOH
1. Ph C CNa
2. H+
OH Ph
Chem 360 Jasperse Ch. 20, 21 In-Class Problems. 2
Details
• Acidity
o The Ka value for acetylenes is about 10-23, (comparable to a ketone).
o Why? Acidity follows hybridization: sp > sp2 > sp3
o Why? The more s character, the closer the electrons are gripped by the
positive nucleus. (Reverse of amine basicity…)
• Base Requirements:
o Complete deprotonation is required
o Therefore, strong bases are required.
o Oxygen anion bases (NaOH, NaOMe…) are too weak.
o Nitrogen bases are good: NaNH2 or LDA
o Carbon bases are good: BuLi
• 3 Electrophiles:
• Carbonyls (aldehydes and ketones, just as for Grignard and aldol reactions…)
• Alkyl halides (SN2 reactions)
• Epoxides
1. NaNH2
Ph C C H Ph C C CH2CH2CH3
2. Br
1. BuLi
2. acetone
OH
H
3. H+
1. NaNH2
H 3C C C H
2. OH
O
3. H+
Chem 360 Jasperse Ch. 20, 21 In-Class Problems. 3
OCH3 Cl NHCH2CH3
NO2 NO2 CH3CH2NH2 (excess) NO2
NaOCH3
O2N NO2
NO2 NO2 NO2 E
D
A B C
Common Question formats:
A. What is product? B. Rank reactivity (or, which is fastest? Or slowest?)
C. Which would be an intermediate or the resonance structure of an intermediate in the
following reaction?
Chem 360 Jasperse Ch. 20, 21 In-Class Problems. 4
B B A D D A E B B E
A D = A C D = = = =
E B B E A D D A
E E
B, D, E, F, G
A and C.
Addition Polymers
• No change in atoms, you simply add all the atoms in the reactants together to make long
polymer strings. The repeat unit in the polymer must have the same atoms as the monomer.
• Precursors: Alkenes or Conjugated Dienes
• Polymer has one fewer double bond than monomer: monoalkene none; diene one.
• For a conjugated diene, the two middle carbons end up double-bonded in the polymer
• Initiation/recognition: Usually radical/peroxides. Sometimes acid or Lewis acid catalyzed.
• Skills: Given monomer, draw polymer
• Skills: Given polymer, recognize monomer.
• Skills: Use and understand shorthand
Ex:
peroxide H2 H2 H2 H2 H2 Polystyrene
Ph C C C C C etc
etc CH CH CH CH CH CH2CHPh
styrene heat
Ph Ph Ph Ph Ph
shorthand
peroxide H H2 H H2 H H2 "PCBD"
etc C C C C C C
C C C C C C etc CH2CH=CClCH2
Cl heat H2 H2 H2
Cl Cl Cl shorthand
2-chloro
butadiene
Cl
Cl Cl H2 Cl
C CH2 peroxide H2 H2
H 2C C etc C C C C C C
C C C C C C etc CH2CCl=CPhCH2
Ph heat H2 H2 H2
monomer Ph Ph Ph
shorthand
Draw the polymer from the following monomer, both shorthand and longstretch
H2 H2 H2 H2 H2
C C C C C etc
CH3 etc CH CH CH CH CH CH2CH(CH3)
"propylene" CH3 CH3 CH3 CH3 CH3
shorthand
H H2 H H2 H H2
etc C C C C C C CH2CH=C(CO2Me)CH2
C C C C C C etc
CO2Me H2 H2 H
monomer CO2Me CO2Me 2 CO2Me
shorthand
Chem 360 Jasperse Ch. 20, 21 In-Class Problems. 7
O O Shorthand:
-H2O H H
OH etc N N etc
H2N N N N
O H H H
O O O
O O Shorthand:
Cl etc O O etc
HO O O O * OCH2CH(O)
O O O O
O O O O
H H
NH2 N N etc
Cl Cl + H2N etc N N
H H
O O
6. Miscellaneous
3. Br2/Fe = FeBr3
O
"Ethyl acetate" =
5. O
O
"OTs" = O S CH3 Outstanding leaving group. (Anion is
comparable to sulfuric acid anion)
O
SN2/E2 candidate
R OTs is like R Br SN1/E1 candidate
6.