CARBON ACIDS

CARBON ACIDS
• A carbon acid is an organic substance that, when
treated with a suitable base, donates a proton to that
base by fission of a carbon-hydrogen bond
 The acidity of protons
A hydrogen on an alkane is not at all acidic – its pKapKa is somewhere on the order of 50, about as
non-acidic as it gets in the organic chemistry world. The reason for this is that if the hydrogen were to
be abstracted, the electrons from the broken bond would be localized on a single carbon atom

Because carbon is not electronegative and is terrible at holding a negative charge, such
carbanion species are extremely unstable.

An acid becomes stronger if the conjugate base (carbanion) is stabilized

CARBANION
STABILISATION
• The main features that serve to
stabilise carbanions are:
(a) increase in s character at the
carbanion carbon
. (b) electron-withdrawing
inductive effects,
(c) conjugation of the carbanion
lone pair with a polarised
multiple bond,
(d) aromatisation
 (a) Increase in s character at the carbanion
carbon
• Increasing acidity of the hydrogen atoms is in the sequence:

CH3-CH3 < CH2=CH2 < HC≡CH.

pka : (45). ( 37). (25)

• s character increases in the order

Sp3 < sp2 < sp.

The electron pair in an sp orbital is held closer to, and more tightly by, the carbon atom than an electron
pair in an sp2 or sp3 orbital. This serves not only to make the H atom more easily lost without its electron
pair, i.e. more acidic, but also to stabilise the resultant carbanion.
 (b) Electron-withdrawing inductive effects

pKa-43 pKa-28 pKa-11

• The powerful electron-withdrawing inductive effect of the fluorine atoms making the H atom more acidic, and
also stabilising the resultant carbanions
(c) Conjugation of the carbanion lone pair with a
multiple bond

• Conjunction of lone pairs with double bond incresese the stability of conjugate base.
• An active methylene is a
carbon in the α position
relative to two carbonyl
groups rather than just
one. Protons on active
methylene carbons are
more acidic than other a-
protons, because the
charge on the conjugate
base can be localized to
two different oxygen
atoms, not just one. This
keto-ester compound, for
example, has a pKa of
approximately 11
(d) Aromatisation.
• pKa of cyclopentadiene is 16

• This is due to the resultant carbanion, the cyclopentadienyl anion being a 6π electron delocalised system,
(i.e. a 4n + 2 Hiickel system where n = l) is stable

• The 6π electrons can be accommodated in three stabilised π molecular orbitals

• It is stabilised by aromatisation
Kinetic and thermodynamic acidity
Kinetic Acidity

• Kinetic acidity pertains to the rates at which acids donate protons to bases.

• Protons that dissociates fastly have hight greater kinetic acidity.

LDA
a b a

• Consider the above enolate formation.Hb deprotonated by the base rapidly.So H b has higher kinetic acidity than
Ha ,due to its less steric environment the bulky base LDA can easily abstract the proton.
• The product formed is thermodynamically less stable due to less substituted double bond.

• The above reaction is kinetically controlled.

Thermodynamic acidity

To form a thermodynamically stable product ( having highly subsitituted double bond), H a has to be deprotonated using a different
base( RO-/ROH). So we can say that Ha has more thermodynamic acidity than Hb, since it’s deprotonation leads to a more
thermodynamically stable product. The reaction is kinetically slow compared to the first reaction due to steric hindrance of R groups.