REACTIONS
For Final Exam
Reactions for Final Exam
Although you don t need to know all of the mechanisms for these reactions, knowing them
makes it easier to understand the reactions and to figure out a reaction if you forget it. Consult the
lecture notes for more details on the mechanisms and issues of stereo- and regioselectivity.
ELECTROPHILIC ADDITION REACTIONS
HX
+
X X
OCH3 OCH3
Hg(O2CCF3)2
NaBH4
CH3OH
HgO2CCF3
HgSO4
OH O
H3O+
R
R R
enol ketone
CH3 MCPBA CH3
O
Br2
CH3
CH3 H2O
OH
Br
BH3
CH3
H2O2, OH-
CH3
H
OH
CH3
CH3 1) Hg(OAc)2 H2O
2)
NaBH4
OH
CH3
CH3 1) OsO4
2)
NaHSO3 OH
OH
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North Dakota State University
ELECTROPHILIC SUBSTITUTION REACTIONS
Br2
FeBr3 Br
Cl2
FeCl3 Cl
I2
CuI2 I
HNO3
H2SO4 NO2
SO3
H2SO4 SO3H
R-Cl
AlCl3 R
O
O
R Cl
AlCl3
R
O O
Br
Br2
CH3CO2H
O 1) Br2 PBr3 O
OH OH
2) H2O
Br
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North Dakota State University
NUCLEOPHILIC ADDITION REACTIONS
O
HO CN
HCN
Ph H
Ph H
KOH
cyanohydrin
H+ or -OH
O
catalyst
HO OH
+
H2O
hydrate
R
H+
O N
R-NH2 H2O
++
imine
R R
H+
O N
R2NH H2O
++
enamine
RO OR
O
H+
2 ROH
+
an acetal
O O
CH3NH2
1,4-addition
NHCH3
1) Ph2CuLi
OO
2) H3O+
1,4-addition
Ph
1) PhMgBr
O
Ph
HO
2) H3O+
1,2-addition
1) PhLi
O
Ph
HO
2) H3O+
1,2-addition
1) PhMgBr
HO
Ph
O
2) H3O+
R Ph
R Cl
© Gregory R Cook page Chem Exam Reactions
North Dakota State University
1) PhMgBr
HO
Ph
O
2) H3O+
R Ph
R OCH3
O
1) CH3MgBr
C N
2) H2O
CH3
O CH2 Ph3P
Ph3P CH2 O
+ +
phosphonium
ylide
1) NaBH4
O
H
HO
2) H3O+
1,2-addition
1) LiAlH4
O
H
HO
2) H3O+
1,2-addition
The addition of hydrides to carbonyls is also considered reductions and more examples are listed
under reduction reactions.
O
O C O O
H3O+
MgBr
OH
O MgBr
SUBSTITUTION REACTIONS (SN1)
CH3 CH3 H CH3
HCl
-H2O
OH O Cl
H
CH3
CH3 CH3
Cl
Cl
HCl
O
O H
OH
(regioselective like SN1 but stereoselective like SN2) (also opens with water to make trans diol)
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North Dakota State University
SUBSTITUTION REACTIONS (SN2)
O
O
H S
S
O Cl Cl
OH Cl Cl
Br
Br
H P
P
O Br Br
OH Br Br
O
Tos-Cl
S
Cl
Tos
OH O
pyridine
CH3 trimethylsilyl
H3C Si Cl chloride (TMS-Cl)
CH3
Br OH Br O CH3
Si
pyridine CH3
H3C
1) NaH
OH O CH3
2) CH3I
H H
I
HI
O O O
+
I
H
OH
HCl
O O
Cl
Cl
OH
1) PhMgBr
O
Ph
2) H2O
CH3I
CH3
Ph SH Ph S
CH3I
O O O
NaOH
R OH R O R OCH3
Na
O O
1) LDA
CH3
2) CH3I
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North Dakota State University
O O NaOEt, EtOH O O
EtO OEt EtO OEt
R Br
R
NaOEt
O O O O
EtOH
H3C OEt H3C OEt
R Br
R
SUBSTITUTION REACTIONS (Nucleophilic Aromatic and Nucleophilic Acyl)
Cl OH
O2N NO2 O2N NO2
NaOH
25 °C
NO2 NO2
Cl OH
NaOH
benzyne
intermediate
340 °C
H H
2500 psi
O O
+ SOCl2 + SO2 + HCl
R OH R Cl
O O Heat O O
+ + HOH
R OH HO R R O R
O
HA
O
R OH
R OR'
R'OH
O O O O
+
+
NaCl
R Cl NaO R R O R
O O
+ H2O + HCl
R Cl R OH
O O
pyridine
+ R'OH + Pyridine-HCl
R Cl R OR'
O O
+ NH3 + NH4Cl
2
R Cl R NH2
1) Ph2CuLi
O O
2) H3O+
R Cl R Ph
© Gregory R Cook page Chem Exam Reactions
North Dakota State University
O O O
H2O
+ 2
O OH
O O O O
ROH +
+
O OR OH
O O O O
NH3 +
+
O NH2 OH
NaOH (cat)
O O
+
CH3OH
+ H2O
R OCH3 R ONa
O
H3O+
HO C N HO C
OH
Ph H Ph H
HA (cat)
O O
+ H2O +
NH4A
R NH2 R OH
O O
I2, NaOH
CH3 O
+ CHI3
iodoform
ELIMINATION REACTIONS
H3C
H2SO4
OH CH3
E1
POBr3
pyridine
OH
E2
O
O
S
Cl Cl C N
NH2
O O
Br pyridine
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North Dakota State University
OXIDATION REACTIONS
O
OH
CrO3
R R R R
H3O+
O
OH
CrO3
R R OH
H3O+
O
OH
PCC
R R H
O
O
CrO3
H
R R OH
H3O+
Ag2O
O
O
NH4OH
H
R R OH
O O
KMnO4
OH
OH
O
O
KMnO4 2
OH
1) O3
O O
2) Zn, AcOH
+
H
I2
Ph SH Ph S S Ph
O
O
O
O O
H2O2
H3C O H
S S S
Ph CH3 Ph CH3 Ph CH3
a sulfoxide a sulfone
O
CH3 C
KMnO4
OH
© Gregory R Cook page Chem Exam Reactions
North Dakota State University
O
C
KMnO4
OH
O O
C
KMnO4
OH
REDUCTION REACTIONS
1) NaBH4
O
2) H3O+
R OH
R H
1) LiAlH4
O
2) H3O+
R OH
R H
1) LiAlH4
O
2) H3O+
R OH
R OCH3
1) DIBAH
O
O
2) H3O+
R H
R OCH3
1) DIBAH
O
2) H3O+
C N
R H
R
1) LiAlH4
2) H3O+
HO C N HO
NH2
Ph H Ph H
1) LiAlH4
O 2) H3O+
R OH
R OH
1) BH3
O 2) H3O+
R OH
R OH
© Gregory R Cook page Chem Exam Reactions
North Dakota State University
1) LiAlH4
O
2) H3O+
R OH
R Cl
1) LiAlH(Ot-Bu)3
O O
2) H3O+
R Cl R H
1) LiAlH4
2) H2O
O
R NH2
R NH2
NH2
O N
H2N NH2
H H
KOH
a hydrazone
Zn, H3O+
Ph S S Ph Ph SH
CH3 Pt, 2000 psi CH3
or
Rh/C, 15 psi
O
H2
Pd/C
H2
Pd/C
H2
NO2 NH2
Pd/C
SnCl2
NO2 NH2
H3O+
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North Dakota State University
OTHER REACTIONS
NBS
Br
peroxides also benzylic
bromination
EWG
EWG
+
Cl KNH2
benzyne
+
intermediate
O
O OH
heat
H
O O H3O+, Heat O
+ CO2
R
EtO OEt HO
R
O O H3O+, Heat O
+ CO2
H3C OEt H3C R
R
© Gregory R Cook page Chem Exam Reactions
North Dakota State University