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Autumn 2004
A direct relationship was found between these processes for a specific set ! of compounds, the p- and m-substituted benzoic acids (R=Ar).
Autumn 2004
Autumn 2004
The term (pKa(H) - pKa) is given the symbol !m or !p for meta and para-substituted benzoic ! acids and is known as the substitution constant. This can be calculated for any substituted benzoic acid for which we can find (or measure) pKa.
Autumn 2004
a
!
logk/ko or log K/Ko
benzene 25 C
a b
"= -2.69
"= 2.51
b c
EtI
CH2COOH
c d
0.47 -0.99
COOEt
d
X
-1
0 sigma
0.2
0.4
0.6
0.8
Autumn 2004
or
" = reaction constant Proportionality constant between log of k (or K) values and !
A measure of the total polar effect exerted by substituent X (relative to no substituent) on the reaction centre. recall: ! = -(pKa # pKa(H)) #ve = electron-donating +ve = electron-withdrawing
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Autumn 2004
Electron-withdrawing m-NO2 (! = +0.71) increases stability of tetrahedral intermediate compared to electrondonating m-CH3 (! = -0.07).
Methoxy substituent can be electron-withdrawing due to inductive effects (meta, ! = +0.12) , or electron-donating (para, ! = -0.27) due to mesomeric effects.
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Autumn 2004
Autumn 2004
Significance of "
Lets consider again two of the reaction examples we looked at previously:
NH2 O + X Cl k O N H X
benzene 25 C
a
logk/ko or log K/Ko
"= -2.69
"= 2.51
b
COOEt COO! OH! k EtOH/H2O 25 C X
d
d
+ X
-1
0 sigma
0.2
0.4
0.6
0.8
electrondonating
electronwithdrawing
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Autumn 2004
OH + H2 O X
O!
+ H3 O+ X
When electron-withdrawing due to to mesomeric effects can be extended to the reaction centre via through conjugation, the result is an even more stabilized species.
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Autumn 2004
!#
Scale
We can develop new ! values for these substrates by separating out these through-conjugation effects from inductive effects. Develop line with " value based on m-substituents only, which cannot exhibit mesomeric effects. The amount by which certain substituents deviate from the line can be added to their ! values to produce a new scale of !# value.
Autumn 2004
p-OCH3 and p-CH3 are above the line; through-conjugation enhances their electron-donating ability.
!+ scale:
substituent C6H5 Me MeO NH2 NMe2 !p -0.01 -0.17 -0.27 -0.66 -0.83 !p+ -0.18 -0.31 -0.78 -1.30 -1.70
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Autumn 2004
Autumn 2004
H O
OH2
O OMe Ar
slow
O
+
O Ar OH H+ Ar
OMe H+
Ar H2 O
OH
OH2
H2 O
Autumn 2004
O OCH2 Me Ar O H+
slow
O Ar OH
CH2 Me
CH2 Me
OH2
For electron-withdrawing substituents: Positive charge at reaction centre is decreased during rate-limiting step.
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Autumn 2004
ln k
sigma
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Autumn 2004
Positive " for electrondonating X,Z substituents Negative " for electronwithdrawing X,Z substituents
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Autumn 2004
a)
+
! H2 O C Ar OH2 Ar C+ Ar
Ar
b)
C+ Ar Ar Ar
C+ Ar
+
H
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Autumn 2004
b) r.l.s. a) r.l.s.
a)
+
! H2 O C Ar OH2 Ar C+ Ar
Ar
b)
C+ Ar Ar Ar
C+ Ar
+
H
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Autumn 2004
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Autumn 2004
log(k/kH)
Equilibrium constant:
! $ K ' o o o o "2.303RT # log& ) = (*H " *H x ) " T (*S " *Sx ) %KH (
RCOO" + H 2O
log(K/KH)
RCOOH + OH " #K $ # %# #
!
!
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Autumn 2004
Rate constant:
Equilibrium constant: !