312 112

Introduction to Organic Chemistry

: McMurry, M. Organic Chemistry, 3rd ed. Brooks/Cole
Publishing, California, 1992.

e-mail: chapha@kku.ac.th

 (Aromatic Compounds)
Aliphatic = Fatty, Aromatic = Fragrant
O
CH 3

Benzene

Benzaldehyde

Toluene

CH3 O

H
OCH2 C N

H
N
H

CO2H

HO
Estrone

Penicillin V

(Female Steroidal Hormone)

H3CO
CH3
H3C

H3C
O

O
3

N CH3

HO
CH3
Vitamin E

H3CO
Morphine
(Analgesic)

OH

COOH
O

CH3

H3C

O
2-Acetyloxybenzoic acid
(Aspirin, Bayer Aspirin)

2-[4-(2-Methylpropyl)phenyl]propanoic acid
(Ibuprofen)

OH

N-(4-Hydroxyphenyl)acetamide
(Acetaminophen, Tylenol)

HN

C
O

CH3

The Painkillers

 IUPAC

-benzene

alkylbenzene
F

Fluorobenzene

NO2

Nitrobenzene

CH2CH3

Ethylbenzene


CH3

Toluene
CH(CH3)2

Cumene

OH

Phenol

COCH3

Acetophenone

NH2

Aniline

HC

Styrene

CH2

*
phenyl
CH3
CHCH2CH2CH2CH2CH3

A phenyl group

CH2

2-Phenylheptane

CH2
Br

A benzyl group

Benzylbromide

*


ortho- meta- para

X
ortho

ortho

meta

meta

Cl

Cl

ortho-Dichlorobenzene
1,2-Dichlorobenzene

para

O2N

NO2

1
I

4
3

meta-Dinitrobenzene

para-Diiodobenzene

1,3-Dinitrobenzene

1,4-Diiodobenzene

1 CH3
2

H3C

CH3

CH3

2
1

ortho-Iodoaniline

para-Cresol
(p-Cresol)

COOH

NH2
I

4 CH3

HO
meta-Xylene
(m-Xylene)

ortho-Xylene
(o-Xylene)

O2N
meta-Nitrobenzoic acid

CH3
Br
para-Bromotoluene

Br

2
1

CH3

CH3

O2N 4 3 2

4-Bromo-1,2-dimethylbenzene

Br

NO2

4-Bromo-2-ethyl-1-nitrobenzene
1-Bromo-3-ethyl-4-nitrobenzene
(Wrong ???)

Cl

2-Chloro-1,4-dinitrobenzene

NO2
1

2 CH2CH3
1

NO2

Cl

2
3 Br

3-Bromo-5-chloronitrobenzene

O2N 6
5

CH3
1
4
O2N

2
3

NO2

Br 6
5

OH
1
4

2
3

Br

2,6-Dibromophenol

2,4,6-Trinitrotoluene
(TNT)

NH2
1

Br 6
5

2
3

Br

Br
2,4,6-Trbromoaniline

* Polynuclear Aromatic Hydrocarbons

Anthracene

OH

Napthalene

7
6

4 3

2-Napthol (-Naphthol)

SO3H

H2N
6-Amino-2-napthalenesulfonic acid


C6H6
KMnO4/ H2O

COOH
COOH

H3O+

OH

Cyclohexene
HCl
Ether

Cl



KMnO 4/ H 2O

H 3O +

No Oxidation

No Hydration

Benzene
HCl
Ether

No Addition

 1.
Reactant
Cyclohexene
1,3-Cyclohexadiene
Benzene

Product
Cyclohexane
Cyclohexane
Cyclohexane

H2/Metal Catalyst

H0hydrog (kJ/mol)

120
232
208

1.39
1.10

H 1200

C-C 1.54
C=C 1.34

1200
1200

H
H

H
H

1.5 ()

1.5 Bonds on average

H
H

H
H

 (Napthalene)

 (Huckel 4n + 2 Rule)

4n+2

n=0, 2 electrons:
cyclopropenyl cation

n=1, 6 electrons:

n=2, 10 electrons:

 (Anti-Aromatic)

:
Halogenation : X = -F, -Cl, -Br, -I
Nitration : -NO2 / Sulfonation : -SO3H
Alkylation : -R (alkyl group)
Acylation : -COR (acyl group)

H
H

E
H
H

E+X-

H
H
H

E
H+

H
H

1) (Halogenation):

Br

Br

FeBr3

A weak electrophile

Br

Br

FeBr3

Br Br

A strong electrophile

; FeBr3

FeBr3

Br

Br

FeBr3

Br
H

FeBr3Br

Br
H

Br

FeBr3

HBr

Br

Bromobenzene

FeBr3

 (Chlorination)
Cl2

FeCl3

HCl

Cl

(Iododination)
I2

CuCl2

HI

2) (Nitration): nitronium ion

HO N

H OSO3H

Nitric Acid

HO N
O
H

OSO3H

Sulfuric Acid

HO N
O
H
O N O
H

HOH

O N O
Nitronium Ion

NO2
H OSO3H

NO2

3) (Sulfonation)
2H2SO4

O
S

SO3 +

H 3O

+ HSO4

O
S O
O
H

SO3H

H2O, cat. H2SO4, 100 oC

SO3H

HOSO3H

 Benzenesulfonic acids
N
R

SO3Na

SO2NH

H2N

Detergent

Sulfadiazine
(Antimalarial drug)
N

H2N

SO2NH

Sulfathoxazole
(Antibacterial agent)

CH3

4) (Friedel-Craft Alkylation)
*
RH2C X

RH2C

AlX3

AlX3X

XAlX3

H
AlX3

RCH2XAlX3

CH2R

CH2R

AlX3
CH2R

HX

*
X
X
An aryl halide
(ArX)

An vinyl halide

Y
Y = -NO2, -CN, -SO3H,
-COCH3,-COOH,
-COOCH3, -NR3
H3C

CH3
H3C

C
CH3

AlCl3
CH2Cl

CH3
C
CH2CH3

AlCl3

(65%)

Cl

(35%)
H
CH3CH2CHCH2

(Primary (1) Carbocation)

H
CH3CH2CHCH2

(Secondary (2) Carbocation)

5) (Friedel-Craft Acylation)
O
O
R

Cl

O
R

AlCl3

O
Cl

AlCl3

Acylium ion

RC

AlCl3

HCl

Cl

RC

Cl AlHCl3

ClAlCl3

CH3
HNO3/H2SO4

CH3
Cl2/ FeCl3

OH
Bromination



(Reactivity) :

:

ortho-, meta- para-


(Activating Groups) :

ortho- para (Deactivating Groups) :

meta-


(Electron Donating Groups) :

(Electron Accepting Groups) :


100 %
OH

OH

Br2 (xs)

Br

Br
(
No
catalyst
needed)

H2 O

NH2
Br2 (xs)

Br

Br
NH2

(
No
catalyst
needed)

H2O
(xs = excess)

Br

Br

CH3

NO2
(59%)

CH3

CH3
HNO3
H2SO4

(37%)

NO2
CH3
(4%)

NO2


ortho/ para


meta-


ortho/para


meta-


ortho- para- (Steric Effects)

(Electronic Effects)
(Steric Effects)
Electronic Effects

HNO3/H2SO4

NO2

 (Activating Groups)

(Activating Groups)


* (Leaving Groups)



1 4 5 8

 -
Halogenation
CH3

CH2Cl
Cl2
or h

CH2CH3

CHClCH3

CH2CH2Cl

Cl2
or h

Product

Major

Product

Minor

 Oxidation
CH3

HC CHCH
3

C CCH3

1) KMnO4, OH-,
2) H3O+

COOH


NO2

NH2
Zn(Hg), HCl, or H2, Ni, or
Fe, HCl

O
Nitro
(Meta Director)

F 3C

OOH

Amino
(Ortho, Para Director)

CH2R
Zn(Hg), HCl, or
H2/Pd in Ethanol
CrO3, H2SO4, H2O

Alkanoyl
(Meta Director)

Alkyl
(Ortho, Para Director)

 (Alkyl Halides)
CH3

Br

CH3

CH3

CH3

Br

Cl

CH3

Cl

Br
Cl

CH3

CH3

Cl

CH3I
Br

Br

X
C

10%

90%

CH3CH2CH2CH2OH + HBr

(CH3)3COH + HCl

CH3CH2CH2CH2Br + H2O

(CH3)3CCl + H2O

()

()

Halomethane

Dipole Moment, (D)

CH3F

1.82

CH3Cl

1.94

CH3Br

1.79

CH3I

1.64

 SN2

 SN1

Acid
ethanol
water
bicarbonate ion
ammonium ion
carbonic acid
acetic acid
sulfuric acid
hydrogen chloride

pK a
Formula
CH 3 CH 2 OH 15.9
15.7
H2 O
10.33
HCO 3
+

NH 4
H 2 CO 3

9.24
6.36

Conjugate
Base
CH 3 CH 2 O
HO
2-

CO 3
NH 3
HCO 3

CH 3 CO2 H

4.76

H 2 SO 4
HCl

-5.2

HSO 4

-7

Cl

CH 3 CO2
-


1. SN2
RS-, I-, CN-, NH3, Br- tBuO-
E2
2. SN2 E2
3. E1 OH-
OR-