carbonyl chemistry -...
TRANSCRIPT
R R
O
aldehydesketones
R X
O
carboxylic acidand derivatives
Carbonyl Chemistry
R R
O
R R
OElectrophiles (eg. H+)
Nucleophiles (eg. CH3MgBr)
O
OH
H
BaseO
O
an enolate
O
Acid Catalyzed Hydration
HA OH
moreelectrophilic
H2OHO O
HH
A HO OH
Base Catalyzed Hydration
O OH O OH HO OHH2O
O HA
Mechanism for Acetal Formation
OH
OHR
O O HR
H A O O R
H
Hemiacetal-H2O
O RO R
resonance structures
HA
O O R
H
RAO O RR
OH
resonance structures
HO R O O R
H
H
O
HA
Mechanism for Imine Formation
OH H2N RO N
H HR
H A O NH
R
H
Hemiaminal
O NH
R
H
H-H2ON
H
RNH R
resonance structures
AN R
imine
HA
O
HA
Mechanism for Enamine Formation
OHHN R
O NR H
RH A O N
R
R
H
Hemiaminal
O NR
R
H
H-H2ON
R
RNR R
resonance structures
AN R
enamine
HA R
H
R
O
a
b
O
a
b
O
a
b
O1
2 34
H2O1
2 34
OH OH
O1
2 34
H2O1
2 34
OHOH O1
2 34
OHtautomerize
1,2-addition
1,4-addition (conjugate addition)
1,4-addition
OCH3NH2
O
NHCH3
1,4-addition
O O
Ph
1) Ph2CuLi2) H3O+
1,2-addition
O 1) PhMgBr2) H3O+ HO Ph
1,2-addition
O 1) PhLi2) H3O+ HO Ph
1,2-addition
O 1) NaBH42) H3O+ HO H
1,2-addition
O 1) LiAlH42) H3O+ HO H
R Y
O Nuc
R YO Nuc
R Nuc
O+ Y
Cl
O
Acid Halides(acetyl chloride)
O
Acid anhydrides(acetic anhydride)
OCH3
O
Esters(methyl acetate)
NH2
O
Amides(acetamide)
O
O
More Reactive Less Reactive
R Y
O+ Nuc-H General NAS ReactionR Nuc
O+ HY
R Y
O+ HO-H HydrolysisR OH
O+ HY
R Y
O+ R'O-H AlcoholysisR OR'
O+ HY
R Y
O+ NH3 AminolysisR NH2
O+ HY
R Y
O H-
R H
O+ Y-
R Y
O R'MgB r
R R'
O+ HY
ReductionH-
R'MgB r
R HO H
R R'O R' Grignard
R Cl
O R'2CuLi
R R'
O
R OCH3
O DIBAL
R H
O
NH2
O HA
NH2
OH
NH2
OH H2O
NH2
OH OH
H
A
NH2
OH O H
HA
NH2
OH O H
HOH
OH
OH
OH
OH
O A
Acid Catalyzed Hydrolysis of Amides
O
Acid Catalyzed Enol Equilibrium
OHHA OH OHH
A
O
Base Catalyzed Enol Equilibrium
OHOH O OH
HA
O OHH+ Br Br OBr + HBr
OBr2
CH3CO2H
OBr pyridine
O
OH
OR
PBr3Br2
then H2OOH
OR
Br
N LiO+
O+
LDAlithium
diisopropyl amide
N H
100%
O 1) LDA2) CH3I
OCH3
OpKa = 20
OpKa = 9
O
OEt
OpKa =13
EtO
O
OEt
O
EtO
O NaOEt, EtOH
R BrOEt
O
EtO
O
R
H3O+, Heat
HO
O
OEt
O
EtO
O
R
R + CO2
H3O+
O
O
HO
O
R
H Heat
HO
OH
R
-CO2
tautomerize
OEt
O NaOEtEtOH
+ Br
O CO2EtO
H3O+, Heat
+ CO2
O
