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H H
H H
Slow + H
+
H H
X H
X C C
H H
H Electrophile Nucleophile (acid) (weak base) Reactivity parallels acid strength. The alkene is a very weak base so you need Order of reactivity = HI > HBr > HCl > HF Why? a very strong acid to get a reaction. Electrophile (acid)
Unsymmetrical alkene
Why?
Sec. 10 - alkenes/alkynes
Markovnikovs Rule
In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion of the adding reagent attaches itself to a carbon atom to the double bond as to yield the more stable carbocation as an intermediate (You already knew this from SN1 reactions. The most stable carbocation intermediate forms) or Hydrogen becomes attached to the carbon atom of the double bond with the greater number of hydrogens
Sec. 10 - alkenes/alkynes
Examples
H3C C H3C C CH3 H
H Br electrophile (acid)
H3C
sp3 H C H CH3
sp2
C H3C sp2
bottom
H H
+
H Br
CH3
CH3
top
CH3
top
Examples
H3C C H3 C CH2 I Cl
H3C C H3 C CH2
Sec. 10 - alkenes/alkynes
Examples
hydration water present H3C C H3 C H O H
+
O O S O OH
CH2
H
dilute H2SO4
O O S O OH
or H
H2O - weak base poor nucleophile but better than HSO4 also in greater concentration
H2O
Sec. 10 - alkenes/alkynes
What is the difference between hydration, elimination of alcohols and substitution reactions with alcohols, they all seem the same? OH H3C C CH3 H3C C H3C H3C C H3C CH2 CH2 CH3 dehydration
cold concentrated H2SO4 dilute H2SO4 heat
concentrated H2SO4
H3C
E1 CH3 -H+
CH2
CH3 HSO4
CH3
CH3
CH3
NaBr
Br C CH3 CH3
6
Dont forget anytime a carbocation is formed rearrangement of the carbon skeleton can occur
Sec. 10 - alkenes/alkynes
Anti-Markovnikov addition
The hydrogen atom becomes attached to the carbon atom with the fewer hydrogen atoms This is a free radical reaction not an ionic reaction. You do not have to memorize the statement above if you understand the mechanism. HBr CH3CH2CH2Br CH3CH=CH2 ROOR Mechanism
a peroxide
RO OR
H3C CH
2 RO
Br H
RO H Br H C 3
Br
ROH + Br
H3C
CH
CH2
CH2
CH2
CH2
Br + Br
propagation
Br
H
H CH3
2
H
H
7
Sec. 10 - alkenes/alkynes
Sec. 10 - alkenes/alkynes
Mechanism
electrophile (acid)
Br
Br + C C R R R R C
Br C R + R
bromonium ion intermediate electrophile (acid)
Br Br
nucleophile (base)
R R
R R C C Br
R R
nucleophile (base)
Br polarized Br
Br + R R R C C R R
Br
R R
Example
+ enantiomer trans-1,2-dibromocyclohexane
Unsymmetrical Alkene
weaker bond + stronger bond
H3C 3 C H3C +
Br C 1
H H
+ Br
H3C
H3C C C
Br H H
Br
Sec. 10 - alkenes/alkynes
10
Bromonium Ion
Sec. 10 - alkenes/alkynes
11
Major product OH
+
Br2 H2O
Na OH H2O Br
Sec. 10 - alkenes/alkynes
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Sec. 10 - alkenes/alkynes
13
OH R CH R
[O] [H]
O R C
Oxidation broad definition a reaction that increases its content of any element more electronegative than carbon
CH3
[O] [H]
CH2Cl
C H
C H
OH
C H
OS = oxidation state
Sec. 10 - alkenes/alkynes
14
Reduction
Sec. 10 - alkenes/alkynes
15
Mechanism
COLD
Sec. 10 - alkenes/alkynes 16
Example
O O OsO4, ether Os O O H
2) Na2SO3
Bond Cleavage
Sec. 10 - alkenes/alkynes
17
Mechanism
O OS = +7 O
Mn
O O H H3C
O
Mn
O O C
OS = +5 cleavage
O C
H3CH2C OS =-1
C(CH3)2 OS = 0
CH3 H OS = +1
OS = 0
OS = +1
Ox
O C CH3
OS = +3
In an acidic solution Mn2+ will be the final manganese product In a basic solution Mn(IV)O2 is formed not MnO3 and is the final manganese product Do not need to know just for interest
HO
no further oxidation
18
Example
1) KMnO4/NaOH heat 2) H3O+ intermediate Ox
Ozonolysis of Alkenes
Ozone is in a class of compounds called 1,3-dipole reagents. They are so called because good neutral resonance forms cannot be written for them.
+ + R2C N N Diazo + RC N O Nitrile oxide + R N N N Azides O + R2C N R Nitrones
Sec. 10 - alkenes/alkynes
19
Ozonolysis of Alkenes
+ O O O O + O O O + O O 1,3-dipolar addition reaction
+
(CH3)C H CH3
O O C CH3 C(CH3)3
CH3 C O O
+ C C(CH3)3
O
C(CH3)3 (CH3)C H O C C O O
1,3-dipolar addition
This form is favoured because of the formation of stronger C-O bonds as opposed to weak O-O bonds
oxidative work up
O
reductive work up
H2O2 Zn, H2O or Zn, CH3COOH
O CH3 C C(CH3)
O (CH3)3C H
(CH3)3C OH +
CH3 C
C(CH3)
an aldehyde
a ketone
Sec. 10 - alkenes/alkynes
20
Examples
H
1) O3, CH2Cl2, -78C 2) Zn/HOAc 1) O3, CH2Cl2, -78C 2) H2O2 Could also use 1) KMnO4/NaOH heat 2) H3O+
What is A?
OO
+
O O
OO H
+
O O
OH
OO OO OH
Sec. 10 - alkenes/alkynes
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Sec. 10 - alkenes/alkynes
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Sec. 10 - alkenes/alkynes
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H 2 O2
Not covered
Not covered
Sec. 10 - alkenes/alkynes
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