O-Chem Day 3: Alkene/Alkyne Rxns, Halogenation and EAS

Electrophilic Addition Reactions

Reagents What’s Regioselectivity Stereose Intermediate Rearrange
added lectivity ments
HBr (or HCl, HI) H and Br-
+
Markovnikov - carbocation Possible
H3O+ H+ and OH- Markovnikov - carbocation Possible
H+, ROH H+ and OR- Markovnikov - carbocation Possible
Br2/CCl4 (or Cl2) Br+ and Br- - Anti bromonium ion Not possible
Br2/H2O Br+ and OH- Markovnikov Anti bromonium ion Not possible
Cl2/H2O Cl+ and OH-
Br2/ROH Br+ and OR- Markovnikov Anti bromonium ion Not possible
Cl2/ROH Cl+ and OR-
(1) Hg(OAc)2, H2O H+ and OH- Markovnikov Anti mercurinium Not possible
(2) NaBH4 ion
(1) Hg(OAc)2, ROH H+ and OR- Markovnikov Anti mercurinium Not possible
(2) NaBH4 ion
(1) BH3.THF H+ and OH- Anti- Syn Not possible
-
(2) H2O2, OH , H2O Markovnikov
H2/catalyst H and H - Syn Not possible
(Catalyst = Pt/C, Pd/C, or Ni)
HBr/ROOR (peroxide) H. and Br. Anti- - radical Not possible
Markovnikov
(1) RCO3H OH and OH - Anti Not possible
+
(2) H3O
(1) OsO4 OH and OH - Syn Not possible
(2) H2O2
KMnO4 (cold, dilute)/ OH- OH and OH - Syn Not possible
Alkynes
Reduction (Addition of Hydrogen)
H2 H2
Pd/C Pd/C

H2 Na
Lindlar's NH3(l)
catalyst
Addition of H2O
OH O
H2SO4 tautomerization +
+
OH O
Terminal alkynes require HgSO4 as a catalyst (Markovnikov)
O
HgSO4
tautomerization
H2SO4
OH
Hydroboration oxidation with a terminal alkyne produces an aldehyde (anti-Markovnikov)
HO
1. (Sia) BH THF
2 tautomerization H
2. H2O2, OH-, H2O O
Nucleophilic Addition of Acetylide Ions
NaNH2
C
A strong nucleophile

An acetylide ion has 3 typical electrophiles:

1) an alkyl halide

C +
Br + Br

2) a carbonyl (C=O)
O H3O+
O
C + HO

3) an epoxide (adds to least substituted side)

O OH
H3O+
O
C +

Organometallic Reactions
Formed by combining an alkyl halide with Li or Mg
Mg
R X + 2Li R Li + LiX R X R MgX
ether

1) an allylic or benzylic halide

MgBr Br + MgBr2

2) a carbonyl (C=O)

O H3O+
MgBr + MgBr+ O HO

3) an epoxide (adds to the least substituted side)

O H3O+
MgBr + + Mg(OH)Br

O MgBr+ OH
Oxidative Cleavage of Alkenes
Reducing conditions
B. (1) O3, -78°C (2) Zn/H2O or (CH3)2S
Oxidizing conditions
A. KMnO4 (hot, concentrated)/OH- (or with H3O+)
B. (1) O3 (2) H2O2
Free Radical Halogenation
1) Initiation
2) Propagation
3) Termination

Selectivity and stability of radicals (chlorination vs. bromination)

Criteria for Aromatic Compounds

1) cyclic and containing conjugated pi bonds
2) each atom in the ring must have an unhybridized p orbital
3) planar structure
4) delocalization of the pi electrons must lower the electronic energy (4N+2 π electrons)

Antiaromatic compounds satisfy the first 3 rules above but delocalization of the pi electrons increases
the electronic energy (4N π electrons)

Nonaromatic compounds are those that don't satisfy one or more of the first 3 rules above

Side-Chain Reactions of Benzenes

Permanganate Oxidation
O

Chromic acid
-
1. KMnO4, OH , boil OH (Na2Cr2O7 / H2SO4)
2. H3O+ achieves the same
HO
reaction

O
Side-chain Reduction
Clemmenson Reduction – reduces ketones and aldehydes to alkanes
O

Wolff Kishner
Zn (Hg) Reduction does the
HCl, H2O same thing with
H2NNH2, OH-, heat
Electrophilic Aromatic Substitution
+ E E E
C H
H H
E+ + +
C C

Activating Deactivating

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