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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

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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

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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

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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)

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North Dakota State University
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

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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

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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

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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

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

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Chem  Exam  Reactions
North Dakota State University
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

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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+

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OTHER REACTIONS

NBS Br
peroxides also benzylic
bromination

EWG
EWG
+

Cl KNH2 benzyne
+ intermediate

O O OH
heat

H

O O H3O+, Heat O
R + CO2
EtO OEt HO

R

O O H3 O+, Heat O
+ CO2
H3C OEt H3C R

R

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