Carbanion

Mr. Prashant S. Munnolli H.S.K College Of Pharmacy Bagalkot

M.Pharm-1st year Dept. of Ph.Chemistry

 CARBANIONS
A carbanion defined as anion which are electron rich species and carry negative charge. Geometry:.. R C R R

In carbanion, carbon is Sp3 hybridized, three Sp3 orbital form sigma bond and the fourth Sp3 orbital accommodates the unshared electron pair. Hence, the negatively charged carbon in a carbanion has a pyramidal shape similar to that of ammonia. Actually a carbanion and ammonia are isoelectronic species.

 The loss of optical activity is associated with the pyramidal structure due to rapid inversion of configuration during its life time. Carbanion is stabilized by resonance which have planner configuration to accommodate the Sp3 hybridization for their resonance hybrid structure.

R2 R1 C R3

R2 : : C R1 R3

Methods of formation of carbanion :

Carbanions are formed by heterolytic fission of bond. Carbanion are formed by following method: By acid base reaction :
O + NaOH + H - CH2 - C - OH
(Base) (Acid)

O + Na CH2 - C - OH + H2O
carbanion

By removal of proton from hydrocarbons :

+ (C6H5)3 C - H + Na NH2
Tri phenyl methane

Liquid NH3

+ (C6H5)3 C : Na + NH3
carbanion

 By breaking carbon-metal bonds of organometallic compounds :

R - Mg - X - + R + MgX

By adding negative ion to carbon carbon double bond :

O Y: + C = C - C O Y-C-C-C-

By decarboxylation of carboxylic acids :

O R C O R + CO2

Stability of Carbanions :
Inductive effects : The relative order of stabilities of the simple Carbanions is given as follows :
H3C: R - CH2 R R CH R R C R

Due to inductive effect, electron density increase on carbon atom carrying negative charge and it gets destabilized. This destabilities is maximum in case of tertiary carbanion as it has three alkyl groups attached to it and least in case of the methyl carbanion as it has one methyl groups.

 If the electron withdrawing groups are introduced in the alkyl groups, then the stability of carbanion is increased. The negative charge are shared by these groups by I effects.
CF3 C CF3 F F C F H H C H

F3C

S character: The S character of the carbon bearing negative charge affects the stability of a carbanion. Greater the S character of the carbon atom having negative charge, greater will be its stability. The character of hybrid orbital increases in the following order

SP3 < SP2 < SP HC C SP H2C CH SP2 H3C CH2

SP3

Resonance: Carbanions can be stabilized due to resonance when they have double bond or an aromatic ring adjacent to the charged carbon centre. The stabilization by resonance is due to the delocalization of the negative charge which is then distributed over other carbon atom in the hybrid structure. e.g. resonance structure of benzyl carbanion.
CH2 CH2 CH2 CH2 CH2

 The stability of the carbanion is greatly increased if the

negative charge gets conjugated with carbonyl nitro or cyano group. The reason because electronegative atoms such as oxygen and nitrogen can accommodate negative charge better than carbon atoms. The resonating structure of such carbanions as follow :
.. :O: CH3 :CH2 :CH2 C + N CH2 O O N: CH2 CH3 :O: C CH2 O O .. N:

+ N

CH2

Aromatisation : Cyclic carbanions follow the Huckels rule they have (4n + 2) electron for resonance. They are stabilised by aromatisation. e.g. the cyclopentadienyl anion has six electron for resonance (n = 1). Hence it gets aromatic stabilisation.
.. -

Resonance hybrid structure

Reaction of carbanions :
Addition reactions : Carbanions add to the carbonyl group of aldehydes and ketones. e.g. aldol condensations, Perkin and Claisen condensations.
.. :O: R C

O R + C

Substitution reactions : Carbanions take part in nucleophilic substitution reaction at saturated carbon atoms e.g. SN2 reaction. e.g. Reimer - Tiemann reaction, Halogenation of ketones, Wurtz reaction.

R + CH3

CH3 + X

Aldol condensation : Aldehydes containing a -hydrogen atom undergo a reversible self addition in presence of dil. Alkali to give condensation products hydroxy Aldehydes. The hydroxyl aldehyde formed from acetaldehyde is originally called as aldol & the reaction is known as aldol condensation.
O O CH3 - C - H + CH3 - C - H
Acetaldehyde Acetaldehyde OH

OH

CH3 - CH - CH2 - C - H
3-hydroxybutanol (aldol)

 Mechanism :
The enolate ion formation :
O H CH2 C H + OH :CH2 O C H + H2O

Acetaldehyde

Enolate ion (nucleophile)

The enolate ion attacks the carbonyl carbon of another un-ionized aldehyde molecule.
O C CH 3 H O
-

O H

O H

H2C

Acetaldehyde

Enolate ion

The negative oxygen in the product accepts a proton from water to give aldol.

HO

H O O CH2 C H CH3 OH CH O CH2 C + OH H

CH3

CH

3-hydroxybutanol (aldol)

Benzoin condensation :
The self condensation of aromatic aldehydes (with no hydrogen ) in presence of cynide ions as a catalyst to -hydroxy ketone (benzoin) is called benzoin condensation. This reaction is not successfully with aliphatic aldehydes under these condtions.

O C6H5CHO + C6H5CHO
Benzaldehyde Benzaldehyde KCN

OH C H C6H5

C6H5

Benzoin

Mechanism :
The cyanide ion react with benzaldehyde and form carbanion (A).
O O H -CN C6H5 C CN
Benzaldehyde

OH H C6H5 C CN (A)

C6H5

 The carbanion (A) can then react with another benzaldehyde molecule subsequently proton-transfer and loss of the cyanide ion gives benzoin.
OH C6H5 C CN (A) + O C H
Benzaldehyde Proton shift

OH OC6H5 C6H5 C C C6H5

CN H

O C6H5 C

OH C H
Benzoin

C6H5

-CN

O C6H5 C

OH C C6H5

CN H

Cannizzaro reaction :
Aromatic aldehydes ( that do not have -hydrogen atom ) on treatment with conc. Alkali undergo self oxidation and reduction to give alcohol & the salt of the corresponding carboxylic acid. This disproportionation reaction or self oxidation & reduction reaction of aldehydes with lack of -hydrogen is known as cannizzarose reaction. Ortho and para phenolic aldehydes do not give this reaction.

O C6H5CHO + C6H5CHO
Benzaldehyde Benzaldehyde NaOH

C6H5CH2 - OH + C6H5 - C - ONa

Benzyl alcohol Sodium benzoate

 Mechanism : Step 1 : Attack of OH- on the carbonyl carbon

O C6H5 C H + OH C6H5 O C OH (A)
O H C6H5 C6H5CH2O C + OH

Benzaldehyde

Step 2 : Hydride ion transfer.

O C6H5 C OH O H + C6H5 C

Benzaldehyde

Step 3 : Acid base reaction.

O C6H5 C OH + C6H5CH2O + Na+ O C6H5 C ONa + C6H5CH2OH
Benzyl alcohol

Sodium benzoate

Perkin reaction :
Condensation of aromatic aldehydes with an acid anhydride to produce - unsaturated carboxylic acid is called perkin reaction. The reaction of an aliphatic acid anhydride to produce in presence of sodium or potassium salt of the acid corresponding to anhydride to give an ,unsaturated acid is known as perkin reaction. The reaction is carried out by aldehyde and salt of acid with excess amount of aldehyde.

C6H5CHO + (CH3CO)2O
Benzaldehyde Acetic anhydride

CH3COONa

C6H5CH = CH - COOH + CH3COOH

Cinnamic acid Acetic acid

Mechanism : a) Formation of the anion of acetic anhydride (A).

CH3COO + CH2 - CO - O - COCH3 H CH3COOH + :CH2 - CO - O - COCH3 (A)
O + :CH2 - CO - O - COCH3 (A) C6H5 - CH - CH2CO - O - COCH3 (B)

b) Reaction of (A) with benzaldehyde gives (B).

O C6H5 C H

c) Protonation of (B) gives (C).

O C6H5 CH CH2 - CO - O - COCH3
H

OH C6H5 - CH - CH2CO - O - COCH3 (C)

d) Internal proton transfer in (C) followed by elimination of water molecules gives (D).

OH H C6H5 CH CH2 - CO - O - COCH3

- H2O

C6H5 - CH = CH - CO - O - COCH3 (D)

e) Hydrolysis of (D) gives cinnamic acid.

O C6H5 - CH = CH - C - O - CO - CH3
H2O

O C6H5 - CH = CH - C - OH + CH3COOH
Cinnamic acid Acetic acid

Claisen ester condensation :

The base catalysed condensation of an ester containing an -hydrogen atom with a molecule of the same ester or a different ester to give -keto ester is known as claisen condensation of ethyl-acetate in the presence of sodium ethoxide.

O
C2 H5 ONa

O + H

CH3 - C - O C2H5 + CH3 - C - O - C2H5 Ethylaceticacid

CH3 - C - CH2 - C - O - C2H5 + C2H5OH Ethylacetoacetate

Mechanism :

a) Formation of ester anion by reaction with C2H5O-

C2H5O + H - CH2 - COOC2H5

:CH2COOC2H5 + C2H5OH
Ester anion

b) Attack of nucleophile with ester anion.

O CH3 C + :CH2 O C OC2H5 CH3 O C CH2 O C OC2H5

OC2H5

Ester anion

OC2H5

c) Elimination of C2H5OH.
O CH3 C CH2 O C OC2H5
H

+ CH3

O C CH2

O C OC2H5 + C2H5OH

OC2H5

Ethyl acetoacetate

6) Favorskii rearrangement :- Transformation of haloketone into esters in the presence of alkoxide via base catalyzed rearrangement is known as Favorskii rearrangement.

O Cl OR Alkoxide

O C

OR

2-Chlorocycloheptanone

Ester

Mechanism: (I) Abstraction of an proton in order to form carbanions.

O H OR
2-Chlorocycloheptanone

O Cl Cl

R - OH

a (II) Nucleophilic attack on carbanion and rearrangement take place in order to form esters
O Cl Cl O OR O OR

a
O

b
OR C ROH O

c
OR C

OR

+
ester

REFERENCES -:

1) Organic chemistry by Morrison and Boyd. 2) Organic chemistry by Bahl and Bahl. 3) Organic Reaction and Mechanism by Grudeep Chatwal.

4) Reaction mechanism in organic chemistry by S.M.Mukherji and S.P.Singh.

5) organic reaction mechanisms by V.K. ahluwalia, Rakesh Kumar Prashar