CARBANION

As a reactive intermediate

Carbanion
Carbanions are units that contain a negative charge

on a carbon atom In many reactions bond breaks heterolytically and negative charge comes on Carbon that trivalent carbon having negative charge is called Carbanion

Geometry of Carbanion
Structurally, carbanions have a tetrahedral molecular

geometry if the lone pair is counted. This means that carbon, the central atom, is symmetrically surrounded by the electron orbitals in the shape of a tetrahedron.

Geometry of Carbanion
TRIGONAL PYRAMIDAL

If only the three bonds are included in the

geometry, the molecule is trigonal pyramidal, with the carbon atom at the apex of the pyramid, the three bonded atoms forming the base, and the lone pair floating on top.

Sources of carbanion
Organolithium reagents

n-BuLi, PhLi, MeLi commercially available

t-BuLi > sec-BuLi> n-BuLi in base strength Bu-Br + 2 Li c o l d Bu-Li + LiBr ether or hexane
H3CH2C Li
H3C CH2

Li

2. Carbon Acids

3. Enolization

Factors Effecting Carbanion Stability

1. Hybridization More s character, more acidic is the molecule

S character pulls the charge towards nucleus. S

orbitals are closer to the nucleus than corresponding p orbitals , and they are at a lower energy level. The electron pair in sp orbital is held closer to, and more tightly by the carbon atom than an electron pair in sp2 and sp3 orbital. This serves not only to make H atom lose more easily without its electron pair I,e., more acidic, but also to stabilize the resultant Carbanion.

2. Inductive Effects
Electron-withdrawing substituents will inductively

stabilize negative charge on nearby carbons.

3. Conjugation - Delocalization

Delocalization of negative charge, especially onto electronegative atoms, provides potent stabilizations of carbanionic centers. Since almost all conjugating substituents are also more electronegative than H or CH3, there is usually a significant inductive contribution to the stabilization.

4. Second and Third Row Element Effects ("d-orbital" effects)

All measures of acidity show that there is an unusual

level of carbanion stabilization for all second row elements (Cl, S, P, Si, as well as higher elements) when these are bonded to a carbanion center.

5. Lone Pair Effects

For the first row elements N, O, F, and

perhaps also for higher elements, the presence of lone pairs has a strong destabilizing effect on a directly bonded carbanion center.

Reactions of Carbanion

1.Aldol condensation
CH3CH=O acetaldehyde OH CH2CH=O + CH3CH O
dil. NaOH

OH CH3CHCH2CH O 3-hydroxybutanal O CH3CHCH2CH O + H2O

+ H2O

Ketones
H3C O C dil. NaOH CH3 H3C O C OH CH3 C C CH3 H2 + H2O O C O C O CH3 C C CH3 H2

OH

H3C

O C

CH2

H3C

CH3

H3C

+ H2O

Cyclic compounds
O dil. OHOH OH O

O O O + HOH

Acidic Medium
O O dil. H+ + H2O

With dilute acid the final product is the ,-unsaturated carbonyl compound!
dil NaOH CH2 CH O phenylacetaldehyde OH CH2 C CH CH=O H

dilute H+ CH2 C C CH=O H

H2O

note: double bond is conjugated with the carbonyl group!

 In general, in these reactions the concentration of

base has to be controlled. With higher concentration, dehydration of aldol products occurs rather readily due to the formation of stable conjugated unsaturated carbonyl compounds.

2. Claisian condensation

3. Substitution reactions

Malonate synthesis of carboxylic acids.

1. Diethyl malonate has acidic alpha-hydrogens

CO2CH2CH3 CH2 CO2CH2CH3

2. When reacted with sodium metal, the ester is converted into its conjugate base (an enolate anion)
CO2CH2CH3 CH2 CO2CH2CH3 Na CO2CH2CH3 + Na+ + H2 CH CO2CH2CH3

3. The enolate can be used as the nucleophile in an

SN2 reaction with a 1o or CH3 alkyl halide.

CO2Et SN2 + R-X CH CO2Et CO2Et R CH CO2Et

4. Upon hydrolysis, the substituted malonic acid will decarboxylate when heated.
CO2H CO2Et H O, H+ - CO2 2 R CH R CH heat heat CO2H CO2Et R CH2CO2H

5.

Product is a carboxylic acid derived from acetic acid.

O C OEt CH2 C OEt O

Na

O C OEt Na CH C OEt O

RX

O C OEt R CH C OEt O

H+,H2O heat

O C OH R CH C OH O heat -CO2 R CH2COOH

diethyl malonate

Na

O C OEt R'X R C C OEt O

O C OEt R C R' C OEt O

H+,H2O heat

O C OH R C R' C OH O

-CO2 heat

R CHCOOH R'

4. Michael addition reaction

5. Organomettalic compounds
1. With Formaldehyde: product is 1o alcohol

2. With Aldehydes R'CHO: product is a 2o alcohol with R and

R' on the a-C.

 3. With Ketones R'COR": product is a 3o alcohol

4. With Esters: product is a 3o alcohol with 2 identical asubstituents.

6. Wurtz reaction
One electron from the metal is transferred to the halogen

to produce a metal halide and an alkyl radical. R-X + M R + M+X The alkyl radical then accepts an electron from another metal atom to form an alkyl anion and the metal becomes cationic. This intermediate has been isolated in a several cases. R + M RM+ The nucleophilic carbon of the alkyl anion then displaces the halide in an SN2 reaction, forming a new carboncarbon covalent bond. RM+ + R-X R-R + M+X
Limitations

The Wurtz reaction is limited to the synthesis of symmetric alkanes. If two dissimilar alkyl halides are taken as reactants, then the product is a mixture of alkanes, that is, often, difficult to separate

Corey-House Synthesis
R X

2 Li

diethylether (Et2O)

Li

LiX

alkyl lithium May be a primary, secondary or tertiary alkyl halide

CH 3 H2 C H2 C C H2 Cl H3C H2 C CH Cl CH 3 H3C Cl C CH 3

e.g.

H3C

2R
R2

Li

CuI
R'

R2

CuLi

+
+ LiX

LiI

Lithium dialkyl cuprate

CuLi

R'

+ R

Cu

May be a methyl halide, primary halide or a secondary cyclic halide

H2 C H3C C H2 H2 C Cl H2 C CH H2C C H2 Br

e.g.

H3C

H2C

7. Beta elimination of vicinal dihalides

Dehalogenation of vicinal dihalides to form alkenes: Beta Elimination. a) Overall reaction:

b) Mechanism:

Example:

8. Dickmann condensation

9. Reformatsky reaction

10. Favorskii reaction

11. Reimer Tiemenn Reaction

Thank You