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CH3 CH
Cl
CH
Tetrachloromethane
or carbon tetrachloride
CH3 CH
CH3
Cl
Cl
CH3
CH2 CH2
Cl
Br
2-Chloro-3-methylbutane
3-Bromo-1-chlorobutane
CH2CH3
Br
F
1-Bromobutane
1-Ethyl-2-fluorocyclohexane
Cl
Cl
C
Cl
Cl
Trichlorofluoromethane
(Freon-11)
Cl
C
Cl
2-Chloropropane or
Isopropyl chloride
F
Dichlorodifluoromethane
1,1,1, 2-Tetrafluoroethane
(Freon-12)
Halothane (Fluothane)
Physical Properties of
Alkyl Halides
Most alkyl halides are liquids at room
temperature.
Liquid alkyl halides are insoluble in water
and more dense than water.
alkyl halide
substrate
product
:X
R-X
: :
nucleophile
: :
Nu:
halide ion
Nu: R +
::
bond heterolysis
:X : :
: :
Nu:- + R X
electron pair
from nucleophile
Cl:
CH3CH2-I + Cl
: :
+ CH3CH2- Cl:
: : : :
: :
I
CH3-OH
: :
: :
+ CH3-Cl:
: :
HO:
: : : :
: :
Nucleophiles
A nucleophile has an unshared pair of electrons available
for bonding to a positive center.
Nucleophiles may be negatively charged:
NH2
: : ::
: :
: :
or neutral:
- -
: :
: :
: :
HO , CH3O , I ,
Halide ion
is the leaving
group.
electropositive center.
Examples
H
(1)
HO
nucleophile
C
Cl
H
H3C
substrate
H
(2) H
H+
nucleophile
C
Cl
H
H3C
substrate
H
H
H3C
OH
product
Cl
leaving group
H
C O H
H
H3C
H
ethyloxonium ion
Cl
leaving group
H2O
H
H
H3C
product
OH + H3O
Leaving Groups
The halogen is only one of many leaving groups, "L". A more general
description of nucleophilic substitution is :
Nu:
R-Nu
R-L
+
L:leaving group
H-A
strong acid
+ H2O
+
H3O
A:-
anion
very stable
A good
leaving group
in R-A .
Hydroxide ion is a
poor leaving group
because it is the anion
of a weak acid, H2O.
CH3OH
H2SO4
+
CH3OH +
H
HSO4
+
CH3OH
H
+
CH3OCH3
H
H2O
leaving group
10
10
11
11
12
12
OH-
H
H
C
H
Cl
HO
H
C
HH
TS
Cl
H
HO
+ Cl
13
13
SN2 reaction
All SN2 reactions proceed with
backside attack of the
nucleophile, resulting in
inversion of configuration at
the stereogenic center.
14
14
15
15
+ HO-
H2O
acetone
CH3
CH3-C-OH
CH3
+ Cl-
16
16
SN1 reaction
The key features
1. The mechanism has two steps.
2. Carbocations are formed as
reactive intermediates.
3. Reactions proceed with
racemization at a single
stereogenic center.
Relative stabilities of carbocations
R
R C+
R
3o
most stable
>
R
R C+
H
2o
>
H
R C+
H
1o
>
H
H C+
H
methyl
least stable
17
17
alcohols
R'O-
R-OR'
ethers
HS-
R-SH
thiols
-:CN
R-CN
nitriles
R'C
C:-
O
R'-C-O-
CR' alkynes
O
R-O-C-R' esters
R'3N:
R-NR'3
ammonium
ion
N3-
R-N3
azides
RC
R-X
for R= CH3, 1o, 2o
X = Cl,Br, I
R-OH
18
18
H3C
CH3
H
H3CH2C
Br
(R)-2-bromobutane
C H
CH2CH3
(S)-2-methylbutanenitrile
19
19
C C
X Y
C C
(-XY)
C C
X H
(-HX)
alkyl halide
C C
alkene
CH2=C
CH3
CH3
isobutene
+ HOCH2CH3
+ Na+ Br20
20
CH3
position H
(-HBr)
Br
CH3
or
CH2 C
CH3 position
2
CH2
CH3
1 CH3
C
CH3
NaOEt
KOBu-t
21
21
22
22
H CH3
H
H
C
H
CH3CH2O
C
Br
Br + CH3CH2OH
C
H
C
Br
H
C
H CH3
C
CH3
23
23
The E1 Reaction
The reaction of tert-butyl chloride in the mixed solvent of 80%
ethanol-20% water at 25o C yields a product mixture from two
competing reaction paths: substitution and elimination.
substitution
CH3
CH3CCl
CH3
83%
17%
elimination
CH3
CH3C-OR R = H, CH3CH2CH3
CH3
CH2=C
CH3
24
24
bond heterolysis
CH3
RDS
CH3CCl
slow step
CH3
CH3
CH3C + +
CH3
Cl-
tert-butyl carbocation
: :
CH3
CH3C + + R-O-H
CH4 ethanol
or water
SN1
fast
E1
CH3
CH3C-OR ROH as
CH3
nucleophile
CH2=C
CH3
CH3
ROH as
base
25
25
: :
CH3
CH3C + ROH
CH3
fast
nucleophile
fast
(-H+)
CH3
CH3COR
CH3
substitution product
R-O
H
:
H
H C
+
C
CH3
CH3
fast
ROH2
H
H
CH3
CH3
26
26
Summary of Reactions
27
27
Summary of Reactions
28
28
ALCOHOLS
29
29
Alcohols
Alcohols can be regarded as derivatives of water in which
one or two of the H atoms has been replaced by an alkyl
group
Water, H2O
H
0.96 A
104.5
Methanol, CH3OH
0.96 Ao
H C
o
H H
H
1.43 Ao
108.5o
30
30
Methanol
- I (net dipole)
O +
H
H3C
Electronegativity of oxygen causes an
unsymmetrical distribution of charge
31
31
Ethanol content
Beer, 3-9%
Wine, 11-13%
Whisky, 40-45%
Vanilla Extracts, 35%
Listerine, 25%
32
32
Classification of Alcohols
H
H3C C OH
H
CH3
H3C C OH
H
CH3
H3C C OH
CH3
o
Secondary
(2
) Alcohol
Primary (1o) Alcohol
Tertiary (3o) Alcohol
33
33
Acidity of Alcohols
Alcohols are very weak Acids
H
R O H
+ +
Alcohol
H
+
R O
O H
H O H
Alkoxide
2 CH3CH2OH + 2 Na
2 CH3CH2
Vigorous Reaction
C C H > RH
Na
+ H2
sodium ethoxide
34
34
Preparations of Alcohols
35
35
Hydration of Alkenes
Hydroboration-oxidation
Oxymercuration-reduction
36
36
Prepare 1,2-diols
Hydroxyration
37
38
38
39
39
40
40
Ester reaction
41
41
Reactions of Alcohols
42
42
43
43
Dehydration in Acid
44
44
45
45
46
46
47
47
48
48
Conversion of Alcohol to
Alkyl Halides with HX
49
49
Mechanism
50
50
Problem
51
51
Solution
52
52
Conversion of Alcohol to
Alkyl Halides with SOCl2 and PBr3
1o and 2o alcohols can be converted to alkyl halides using SOCl2 and PBr3
Phosphorus
tribromide
53
53
Mechanism
54
54
Mechanism
55
55
Oxidation of Alcohols
56
57
57
58
58
59
59
Mechanism
60
60
61
61
Breathalyzer Tests
When the Breathalyzer test is used for
suspected drunk drivers, the driver
exhales a volume of breath into a solution
containing the orange Cr6+ ion. If there is
ethyl alcohol present in the exhaled air,
the alcohol is oxidized, and the Cr6+ is
reduced to give a green solution of Cr3+
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62
ETHERS
63
63
Acyclic Ethers
Water, H2O
H
0.96 Ao
H C
O CH2CH3
Diethyl Ether
C H
H H H H
104.5o
CH3CH2
1.43 Ao
109.5o
H 3C O
CH3CH2
1.10 Ao
111.7o
Methoxy group
Ethoxy group
64
64
H3CO
Diethyl Ether
OCH3
1-Propoxypropane
Methoxybenzene anisole
Non-Flammable Anaesthetics
Cl F
H C C O C H
F
F F
Enflurane
C C O C H
F
F Cl
Isoflurane
Cyclic Ethers
65
65
Reaction of Ether
Williamson Ether Synthesis
66
66
Examples
67
67
68
68
69
69
Cyclic Ethers
O
Furan
O
Tetrahydrofuran (THF)
Pyran
Cyclic ethers are one of the main components of epoxy glues. Such a glue is strong,
70
but also lightweight. It is used as a component of the Stealth bomber.
70
Preparation of Epoxides
Mechanism
One step
Without intermediates
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71