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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
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
Li
2. Carbon Acids
3. Enolization
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
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.
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.
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
+ 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
H2O
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
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
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.
Na
O C OEt Na CH C OEt O
RX
O C OEt R CH C OEt O
H+,H2O heat
diethyl malonate
Na
H+,H2O heat
O C OH R C R' C OH O
-CO2 heat
R CHCOOH R'
5. Organomettalic compounds
1. With Formaldehyde: product is 1o alcohol
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
e.g.
H3C
2R
R2
Li
CuI
R'
R2
CuLi
+
+ LiX
LiI
R'
+ R
Cu
e.g.
H3C
H2C
b) Mechanism:
Example:
8. Dickmann condensation
9. Reformatsky reaction
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