Chem 31 Notes
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Evernim OmpacanChem 31 Notes
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Evernim OmpacanALKENES
Electrophilic Addition
Hydrohalogenation 1. Double bond attacks one X of
X2 → halonium ion + X
1. Double bond attacks H of HX
→ cation + halide ion
2. Halide ion attacks carbocation 2. H2O attacks halonium ion →
→ alkyl halide protonated halohydrin
Acid-catalyzed Hydration
3. Protonated halohydrin →
1. Double bond attacks H+ ion of
halohydrin
H2O → carbocation
2. Carbocation + H2O → alcohol
Oxymercuration-Demercuration
Halogenation
1. Double bond attacks one X of
X2 → halonium ion + X
- OH group will attach to the C
with less H atoms
- Hg(OAc)3 will attach to C with
more H atoms
Rearrangement (Hydride or Alkyl
2. Other X attacks ion → Shift)
alkyldihalo compound
- Rarely happens
- Hg-based carbocation
intermediate doesn’t have a
charge that is big enough to go
rearrangement
Mechanism
Halohydrin Formation
1. Hg(OAc)2 dissociates → 3. Alkyl group moves from B to
HgOAc cation + acetate anion adjacent O as OH- leaves
2. Alkene attacks HgOAc → Hg-
bridged carbocation 4. Hydrolysis of Borate Ester:
OH- attacks B → alkoxide
leaves → formation of alcohol
3. H2O attacks C of Hg-bridged
mercurinium ion with less e-
4. Another H2O molecule gets the
H
Hydroboration-Oxidation
Cationic Polymerization
- Same side addition of (BH3)2 → - Addition polymerization initiated by
oxidation with H2O2 and OH- H+ electrophile
- Anti-Markovnikov, no
carbocation intermediate
1. Hydroboration: Formation of
pi complex →
4-atom transition state →
Syn addition of H and B
Polymers – made up of chain/ ring of
linked repeating subunits
Mechanism
Alkene Reduction
2. B accepts e- pair from
hydroperoxide → unstable Catalytic Hydrogenation
intermediate
- Addition of H2 to C=C using a
metal catalyst (Ni, Pd, Pt)
- Syn addition
Ozonolysis
- More vigorous oxidation, cleaves of
C=C double bond
- Higher ∆H, more unstable
- More alkyl group, more stable,
lower ∆H
Alkene Oxidation
ALKADIENE
Hydroxylation
- Unsaturated hydrocarbon with 2
Using cold dilute neutral KMnO4 double bonds
(Baeyer’s reagent) → cis-diol 1. Conjugated dienes – alternate
formation (anti vicinal) single bonds
2. Isolated dienes – separated by at
m-CPBA (meta-chlore peroxybenzoic least 2 single bonds
acid) → trans-diol formation
(syn vicinal)
3. Cumulated dienes – double
bonds with shared C, allenes
Epoxidation
- Reaction of alkene with m- Reaction of Conjugated Alkanes
CPBA using CH2Cl2 →
epoxide
