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O 18 M
H O S O H
O expanded octet
representation
H O
+ - -
H O H O O S O
H H O
water hydronium ion sulfate ion
ADDITION OF
SULFURIC ACID AND WATER
ADDITION OF WATER AND SULFURIC ACID TO ALKENES
THREE DIFFERENT REACTIONS
cold,
1) Alkyl hydrogen sulfates concentrated,
large amount
18M
(stoichiometric)
conc. OSO3H
0o C
C C + H2SO4
C C
H
2) Hydration to alcohol
2-6M
H2 SO4
OH
C C + H2O C C
H
NOTE DIFFERENT
CONDITIONS FOR dilute, aqueous
EACH REACTION
HERE AND ON THE
6M
NEXT SLIDE continued
warm,
concentrated, 18 M
smaller amount, small amt.
(not stoichiometric)
3) Polymerization
conc
H2SO4 H
C C
C C
C C
C C
excess n
OSO3H
polymer
monomer A
Alkene molecules add
together to make long
Sections 8.9 and 8.14
( discussed later … )
chains or polymers
A-A-A-A-A-A-A-A-A
REACTION CONDITIONS
ARE IMPORTANT !
CONCENTRATED SULFURIC
Formation of Alcohols
sulfate is a
MECHANISM poor nucleophile
dilute higher conc.
H2SO4 ADDITION OF WATER than SO42-
(HYDRATION)
alkene H
H + O H
O H
O H
H2SO4 H
C C C C C C
H2O oxocation
+
H H (oxonium ion)
+
H O H
used the catalyst is
H not used up H
FOLLOWS THE O +
MARKOVNIKOFF C C + H O H
RULE
H H
SAME MECHANISM regenerated
AS HCl ADDITION alcohol
MARKOVNIKOFF ADDITION
( HYDRATION REACTIONS, H2SO4 + H2O )
CH3 CH3
H2SO4
+ H2O OH
CH2 CH3
H2SO4 OH
+ H2O
H2SO4
CH CH2 CH CH3
+ H2O OH
DIFFERENT WAYS OF WRITING REACTIONS
Reactants specifically shown with a “+” sign,
catalyst written over arrow.
H2SO4
+ H2O OH
H2SO4
H2O OH
H2O
Chemists
+ HCl Cl use all of
these!
STEREOCHEMISTRY
HX and H2O
H+ could add H
to either side O H
left or right
+
CH3 H2O CH3 CH3
H2SO4
H
H3C add to left
H
H+ side bottom O H
CH3 OH
CH3 CH3
+ + enantiomer
+ enantiomer OH CH3
H H
syn addition DIASTEREOMERS anti addition
EFFECT OF POLARITY OF THE SOLVENT
100%
CAUTION anti
CH3 HBr (g) CH3 Br
The addition to + addition
pentane to top
both sides of
the C+ ion is H CH3 H CH3 side only
common in H2O conc. HBr
solutions, but The typical result in
(in H2O)
if you change a non-polar solvent.
to a non-polar
solvent, this
may not happen.
CH3 Br + CH3 CH3
anti + syn
This will be addition to
explained later H CH3 H Br
both sides
50/50
A “bridged” rather The typical result in a
than an “open” cation
polar solvent like H2O.
is involved.
ADDITION POLYMERS
ADDITION POLYMERS
A + A + A + A A A A A
monomers polymer
+ + +
+ + +
concentrated,
smaller amount,
not cold
Polymerization
conc
H2SO4 H
C C
C C
C C
C C
excess n
OSO3H
repeating
unit polymer
+
resonance
stabilized
(Markovnikoff)
H2SO4 (+) (+)
(+)
H H
+ + etc.
Polystyrene
+ Another way is to
lose a hydrogen
and form a double
bond (ghosted).
This method will be
discussed in the
next chapter.
POLYSTYRENE
starting
proton
addition of OSO3H-
completes the end
H
of the chain
OSO3H
CH2 CH
repeating
unit
=
C C
There is only a small
amount of HOSO - 3
and a large amount
C C of alkene.
+
H