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Alkyl Halider
Alkyl Halider
Alkyl Halider
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
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
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 ()
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
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
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
H
CH3CH2CHCH2
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) :
meta-
(Electron Donating 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
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-