Reactions For Final Exam

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 NaBH 4
CH3 OH
HgO 2CCF3
HgSO4 OH O
H3O+
R R R
enol ketone
CH3 MCPBA CH3

O
Br2
CH3 H2O CH3
OH
Br
BH3
CH3 H2 O2, OH- CH3
H
OH
CH3 1) Hg(OAc)2 H2O CH3

2) NaBH4 OH
CH3 1) OsO 4 CH3

2) NaHSO3 OH
OH
© Gregory R Cook page Chem Exam Reactions

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
Br2 Br
CH3CO2H
O 1) Br2 PBr3 O
OH 2) H2O OH
Br

NUCLEOPHILIC ADDITION REACTIONS
O HCN HO CN
Ph H Ph H
KOH
cyanohydrin
H+ or - OH
O catalyst HO OH
+ H2O
hydrate
H+ R
O N
+ R-NH2 + H2O
imine
R R
O H+ N
+ R2NH + H2O
enamine
RO OR
O
H+
+ 2 ROH
an acetal
O O
CH3 NH2
1,4-addition
NHCH3
O 1) Ph2CuLi O
2) H3O+
1,4-addition
Ph
O 1) PhMgBr Ph
HO
2) H3O+
1,2-addition
O 1) PhLi Ph
HO
2) H3O+
1,2-addition
1) PhMgBr HO
O Ph
2) H3O+
R Ph
R Cl

1) PhMgBr HO
O Ph
2) H3O +
R Ph
R OCH3
O
1) CH3MgBr
C N 2) H2O CH3
O CH2
+ Ph3P CH2 + Ph3P O
phosphonium
ylide
O 1) NaBH4
HO H
2) H3O+
1,2-addition
O 1) LiAlH 4
HO H
2) H3O+
1,2-addition
The addition of hydrides to carbonyls is also considered reductions and more examples are listed
under reduction reactions.
O C O O O
MgBr H3 O+
O MgBr OH
SUBSTITUTION REACTIONS (SN1)
CH3 CH3 H CH3

HCl -H 2O
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)

SUBSTITUTION REACTIONS (SN2)
O O
S H S
OH Cl Cl O Cl Cl
Br Br
P H P
OH Br Br O Br Br
O Tos-Cl
S
Cl Tos
OH O
pyridine
CH3 trimethylsilyl
H 3C Si Cl chloride (TMS-Cl)
CH3
Br OH Br O CH3
Si
pyridine H 3C CH3
1) NaH
OH O CH3
2) CH3I
HI H I H
O O O
+ I
H OH
O HCl O Cl
Cl
OH
O 1) PhMgBr
Ph
2) H2O
CH3 I CH3
Ph SH Ph S
O O CH3 I O
NaOH
R OH R O Na R OCH3
O 1) LDA O
2) CH3I CH3

O O NaOEt, EtOH O O
EtO OEt EtO OEt

R Br
R
O O NaOEt 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 NaOH OH
benzyne
340 °C intermediate
H 2500 psi H
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 pyridine O
+ R'OH + Pyridine-HCl
R Cl R OR'
O O
+ 2 NH3 + NH4Cl
R Cl R NH2
1) Ph2CuLi
O 2) H3O+ O
R Cl R Ph

O O O
+ H2O 2
O OH
O O O O
+ ROH +
O OR OH
O O O O
+ NH3 +
O NH2 OH
O NaOH (cat) O
+ H2O + CH3OH
R OCH3 R ONa
O
H3O+
HO C N HO C OH
Ph H Ph H
O HA (cat) O
+ H2O + NH4A
R NH2 R OH
O O
I2, NaOH
CH3 O + CHI3
iodoform
ELIMINATION REACTIONS
H3C
OH H2 SO 4 CH3
E1
POBr3
OH pyridine
E2
O
O S
Cl Cl C N
NH2
O O
Br pyridine

OXIDATION REACTIONS
OH CrO3 O
R R R R
H3O+
OH CrO3 O
R R OH
H3O+
OH O
PCC
R R H
O CrO3 O
R H R OH
H3O+
Ag2O
O O
NH4OH
R H R OH
O O
KMnO4
OH
OH
O
KMnO4 2
OH
1) O3
2) Zn, AcOH O O
+
H
I2
Ph SH Ph S S Ph
O
O O
H2O2 H 3C O H O O
S S S
Ph CH3 Ph CH3 Ph CH3
a sulfoxide a sulfone
O
CH3 KMnO4 C
OH
© Gregory R Cook page

Chem Exam Reactions
O
KMnO4 C
OH
O O
KMnO4 C
OH
REDUCTION REACTIONS
1) NaBH4
O 2) H3O+
R H R OH
1) LiAlH 4
O 2) H3O+
R H R OH
1) LiAlH 4
O 2) H3O+
R OH
R OCH3
1) DIBAH
O
O 2) H3O+
R H
R OCH3
1) DIBAH
2) H3O+ O
C N R H
R
1) LiAlH 4
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

1) LiAlH4
O 2) H3O+
R OH
R Cl
1) LiAlH(Ot-Bu)3
O 2) H3O+ O
R Cl R H
1) LiAlH4
O 2) H2O
R NH2 R NH2
NH2
O H2N NH2 N H H
KOH
a hydrazone
Zn, H3 O+
Ph S S Ph Ph SH
CH3 CH3
Pt, 2000 psi
or
Rh/C, 15 psi
O
H2
Pd/C
H2
Pd/C
H2
NO 2 NH2
Pd/C
SnCl2
NO2 NH2
H3O+

OTHER REACTIONS
NBS Br
peroxides also benzylic
bromination
EWG
EWG
+
Cl KNH2 benzyne
+ intermediate
O O OH
heat
O O H3O+, Heat O
R + CO2
EtO OEt HO
O O H3 O+, Heat O
+ CO2
H3C OEt H3C R


Reactions For Final Exam

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REACTIONS

For Final Exam