Anioni si carbanioni

  _
O H O + H+

X   X _
Y C H Y C + H+
Z Z

_ _
B H R1 R1
Nu H + B + Nu _ _
R2 C H + B R2 C
Substrat (Ka substr.) Produit (Ka prod.) -B H
R3 R3
Ka substr.
Ke =
Ka prod.
 O CN pKa = 10,0 O CN
_
H _
B
CH3 N COOEt CH3 N COOEt
H H
pKa = 28,0
pKa = 17,0

pKa = 10,0
OH _ OH
HO
_
COOH COO
pKa = 3,0
_
SH S
pKa = 7,0
CO32

pKa = 10,0
OH OH
Alegerea bazei H2CO3 NaHCO3 H 2O

pKa 6,5 10,2 15,7

1. Specii anorganice

HCO3 NaCO3 HO

10,0 OH + NaOH ONa+ + H 2O


17,0 CH3 CH2 OH + NaOH CH3 CH2 O Na+ + H 2O
 2. Alcoxizii
_ _
CH3 CO CH2 COOEt + CH3 CH2 O CH3 CO CH COOEt + CH3 CH2 OH

pKa1 = 13,0 pKa2 = 17,0

3. Combinatiile organometalice
CH3 _
_ _ _
CH3 Li + CH3CH2CH2CH2 Li + CH3 C Li+ C6H5 Li+
CH3
RMgBr sau RZnI (Cl, Br)
 O O

4. Aminele NEt3
N N N N
H H
CH3

N N
N
N N

DIEA DBU DNU

_ (CH3)3Si _
+
N Li N
_ N K+
K+ (CH3)3Si
(Li+)
LDA KTMP KHMDS
(LTMP)
Stabilitate carbanioni
 Reactiile carbanionilor

_ R X _
Nu H - H+ Nu R + X
Nu
SN2
Base Lewis
R
C O R R
+ _ _ +H +
Nu H -H R' Nu C O Nu C OH
Nu
Base Lewis AN
R' R'

O _
Nu O Nu O
_ +H +
Nu H - H+ R R'
Nu R R'
Michael R R'
Base Lewis
R
C O R R
+ _ _ _
Nu H -H X C O + X
Nu Nu C O
AN Nu
Base Lewis X
SN2
a a a
Y- + C X Y C X Y C + X-
b b
c c b c

AN
-  
Y C O Y C O

‐ Efecte inductive
‐ Efecte de rezonanta (conjugare)
‐ Efecte sterice
 O CHO
O
CH2CHO
H
O

O O
H3C
H3C
O
CH3

O
(CH3)2N
O
Michael

O _
Nu O Nu O
+ _ +H +
-H R R'
Nu H Nu
Michael R R' R R'
Base Lewis

CH3 CH3
_
NC NO2 NC NO2
H3C H3C
_ O
(EtOCO)2CH
(EtOCO)2CH O
CH3
C6H5 CH3

_ O
NO2CH2 NO2 CH2 O

H3C CH3 CH3 CH3

O O
_ _
B trop réactive
- H+

HN N O O O

H3C CH3 CH3 CH3

Aditii‐eliminari

R
C O R R
+ _ _ _
Nu H -H X C O + X
Nu Nu C O
AN Nu
Base Lewis X

Condensari

H
+ _ rapidement N C
NH2 + C O N C O N C OH
- H2O
H H
 H H
X _ _ rapidement
CH + C O X C C O +
X C C OH
Y H
Y Y
produit d'addition nucléophile
(produit de condensation aldolique)
H X
X C C OH C C produit d'addition-élimination
- H2O Y (produit de condensation crotonique)
Y
Eliminari

Elimination E1
+
R CH2 CH2 X _ R CH CH2 R CH CH2
-X +
-H
H

Elimination E2
- HOH
R CH CH2 X _ R CH CH2
-X
H
_
HO

- HOH
R CH CH2 X R CH CH2 X _ R CH CH2
-X
H H
_
HO HO
 C6H5
C6H5 H
H3C   Cl - HOH
_
C C C C
- Cl
H H H3C CH3
_ CH3
HO

OTs
_
HO
(CH3)3C
(CH3)3C
H
_
HO
_
OTs HO OH
(CH3)3C (CH3)3C

H H
Cl _
HO
Zaitsev

NMe3 _
HO NMe3 HO

Hofmann
 Cl OH
O2N NO2 O2N NO2
Substitutia nucleofila aromatica NaOH

HO Cl
NO2 NO2
Chlorure de picryl Acide picrique

+
_ N _
O O

Cl HO Cl OH
_ HO Cl HO Cl
HO _ _ O2N NO2
_
_
- Cl

NO2 NO2 N+ _ NO2 NO2

O O

HO Cl

NO2