© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
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
OCH
3
HgO
2
CCF
3
NaBH
4
OCH
3
Hg(O
2
CCF
3
)
2
CH
3
OH
R
R
OH
R
O
HgSO
4
H
3
O
+
enol
ketone
CH
3
CH
3
O
MCPBA
CH
3
CH
3
OH
Br
Br
2
H
2
O
CH
3
BH
3
H
2
O
2
, OH
-
CH
3
H
OH
CH
3
Hg(OAc)
2
CH
3
OH
H
2
O
NaBH
4
1)
2)
CH
3
OsO
4
CH
3
OH
NaHSO
3
OH
1)
2)
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
ELECTROPHILIC SUBSTITUTION REACTIONS
Br
2
FeBr
3
Br
Cl
2
FeCl
3
Cl
I
2
CuI
2
I
HNO
3
H
2
SO
4
NO
2
SO
3
H
2
SO
4
SO
3
H
R-Cl
AlCl
3
R
R
Cl
O
AlCl
3
R
O
O
Br
2
CH
3
CO
2
H
O
Br
Br
2
PBr
3
O
OH
O
OH
1)
2) H
2
O
Br
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
NUCLEOPHILIC ADDITION REACTIONS
Ph
H
O
Ph
H
H
O
CN
H
CN
cyanohydrin
KOH
O
HO
OH
H
2
O
hydrate
+
H
+
or
-
OH
catalyst
O
R-NH
2
H
+
N
R
H
2
O
+
+
imine
O
R
2
NH
H
+
N
R
R
H
2
O
+
+
enamine
O
ROH
H
+
RO
OR
+ 2
an acetal
1,4-addition
O
CH
3
NH
2
O
NHCH
3
1,4-addition
O
O
Ph
1) Ph
2
CuLi
2) H
3
O
+
1,2-addition
O
1) PhMgBr
2) H
3
O
+
HO
Ph
1,2-addition
O
1) PhLi
2) H
3
O
+
HO Ph
R
Cl
O
R
Ph
1) PhMgBr
2) H
3
O
+
HO Ph
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
R
OCH
3
O
R
Ph
1) PhMgBr
2) H
3
O
+
HO Ph
C N
CH
3
1) CH
3
MgBr
2) H
2
O
O
O
+
Ph
3
P CH
2
phosphonium
ylide
CH
2
+
Ph
3
P O
1,2-addition
O
1) NaBH
4
2) H
3
O
+
HO
H
1,2-addition
O
1) LiAlH
4
2) H
3
O
+
HO H
The addition of hydrides to carbonyls is also considered reductions and more examples are listed
under reduction reactions.
O
O
MgBr
OH
O
H
3
O
+
MgBr
O C O
SUBSTITUTION REACTIONS (S
N
1)
CH
3
OH
HCl
CH
3
O
H
H
-H
2
O
Cl
CH
3
CH
3
O
HCl
CH
3
O H
Cl
OH
CH
3
Cl
(regioselective like S
N
1 but stereoselective like S
N
2) (also opens with water to make trans diol)
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
SUBSTITUTION REACTIONS (S
N
2)
S
O
Cl
Cl
OH
H
S
O
O
Cl
Cl
P
Br
Br
Br
OH
H
P
Br
O
Br
Br
S
O
Cl
OH
O
Tos
Tos-Cl
pyridine
Br
OH
Si Cl
CH
3
H
3
C
CH
3
Br
O
Si
CH
3
CH
3
H
3
C
pyridine
trimethylsilyl
chloride (TMS-Cl)
OH
1) NaH
2) CH
3
I
O CH
3
O
HI
O
H
I
O
H
I
+
O
HCl
O
H
Cl
Cl
OH
O
1) PhMgBr
2) H
2
O
Ph
OH
Ph
SH
CH
3
I
Ph
S
CH
3
R
OH
O
NaOH
R
O
O
Na
CH
3
I
R
O
CH
3
O
O
1) LDA
2) CH
3
I
O
CH
3
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
OEt
O
EtO
O
NaOEt, EtOH
R
Br
OEt
O
EtO
O
R
OEt
O
H
3
C
O
NaOEt
EtOH
R
Br
OEt
O
H
3
C
O
R
SUBSTITUTION REACTIONS (Nucleophilic Aromatic and Nucleophilic Acyl)
Cl
NaOH
25 °C
O
2
N
NO
2
NO
2
OH
O
2
N
NO
2
NO
2
NaOH
340 °C
2500 psi
Cl
OH
H
H
benzyne
intermediate
R
OH
O
+
SOCl
2
R
Cl
O
+
SO
2
+
H
Cl
R
OH
O
+
R
O
+
HO
H
R
HO
O
Heat
R
O
O
R
OH
O
HA
R'OH
R
OR'
O
R
Cl
O
+
R
O
+
Na
Cl
R
NaO
O
R
O
O
R
Cl
O
+
H
2
O
R
OH
O
+
H
Cl
R
Cl
O
+
R'OH
R
OR'
O
+
Pyridine-H
Cl
pyridine
R
Cl
O
+
NH
3
R
NH
2
O
+
NH
4
Cl
2
R
Cl
O
R
Ph
O
1)
Ph
2
CuLi
2) H
3
O
+
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
+
H
2
O
O
O
O
OH
O
2
+
ROH
O
O
O
OR
O
+
OH
O
+
NH
3
O
O
O
NH
2
O
+
OH
O
+
R
OCH
3
O
+
H
2
O
R
ONa
O
NaOH (cat)
CH
3
OH
Ph
H
H
O
C N
H
3
O
+
Ph
H
H
O
C
O
OH
R
NH
2
O
+
H
2
O
R
OH
O
HA (cat)
+
NH
4
A
CH
3
O
I
2
, NaOH
O
O
+
CHI
3
iodoform
ELIMINATION REACTIONS
OH
H
3
C
CH
3
H
2
SO
4
E1
OH
POBr
3
pyridine
E2
NH
2
O
Cl
S
Cl
O
C N
O
Br
pyridine
O
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
OXIDATION REACTIONS
R
R
OH
CrO
3
H
3
O
+
R
R
O
R
OH
CrO
3
H
3
O
+
R
OH
O
PCC
R
OH
R
H
O
R
O
CrO
3
H
3
O
+
R
OH
O
H
R
O
R
OH
O
H
Ag
2
O
NH
4
OH
O
KMnO
4
O
OH
O
OH
OH
O
KMnO
4
2
O
H
O
1) O
3
2) Zn, AcOH
+
Ph
SH
Ph
S
Ph
S
I
2
Ph
S
CH
3
H
2
O
2
Ph
S
CH
3
O
Ph
S
CH
3
O
O
H
3
C
O
O
H
O
a sulfoxide
a sulfone
KMnO
4
CH
3
C
O
OH
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
KMnO
4
C
O
OH
KMnO
4
C
O
OH
O
REDUCTION REACTIONS
R
OH
R
H
O
1) NaBH
4
2) H
3
O
+
R
OH
R
H
O
1) LiAlH
4
2) H
3
O
+
R
OH
R
OCH
3
O
1) LiAlH
4
2) H
3
O
+
R
H
R
OCH
3
O
1) DIBAH
2) H
3
O
+
O
R
H
R
C
1) DIBAH
2) H
3
O
+
O
N
1) LiAlH
4
2) H
3
O
+
Ph
H
H
O
C N
Ph
H
H
O
NH
2
R
OH
R
OH
O
1) LiAlH
4
2) H
3
O
+
R
OH
R
OH
O
1) BH
3
2) H
3
O
+
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
R
Cl
O
R
OH
1) LiAlH
4
2) H
3
O
+
R
Cl
O
R
H
O
1) LiAlH(O
t
-Bu)
3
2) H
3
O
+
R
NH
2
R
NH
2
O
1) LiAlH
4
2) H
2
O
O
H
2
N NH
2
KOH
N
NH
2
a hydrazone
H
H
Ph
SH
Ph
S
Ph
S
Zn, H
3
O
+
Pt, 2000 psi
CH
3
or
Rh/C, 15 psi
CH
3
H
2
Pd/C
O
H
2
Pd/C
H
2
NO
2
Pd/C
NH
2
SnCl
2
NO
2
NH
2
H
3
O
+
© Gregory R Cook
page
Chem Exam Reactions
North Dakota State University
OTHER REACTIONS
NBS
peroxides
Br
also benzylic
bromination
EWG
+
EWG
KNH
2
Cl
+
benzyne
intermediate
O
O
H
OH
heat
H
3
O
+
, Heat
HO
O
OEt
O
EtO
O
R
R
+ CO
2
H
3
O
+
, Heat
OEt
O
H
3
C
O
R
H
3
C
O
R
+ CO
2