Aldehyde Reactions Saudi arabia

R NH2 H2O OH
imine H3C CH N R H3 C C OH geminal diol
1ry Amine H +
H

H2N NH2 OH OCH3

hydrazone H3C CH N NH2
Hydrazine CH3-OH H3 C C OCH3 CH3-OH H3 C C OCH3
+
phenyl Ph-NH-NH2
H H
hemiacetal H+ H
H C CH N NH Ph
acetal
hydrazone 3 phenyl hydrazine O OH
O O
H3 C C OH
Oxime H 3C CH N OH NH2-OH H +
H3C C
H H
Hydroxyl Amine acetaldehyde
OH OH
KCN H2/Ni
NH H 3C C C N H 3C CH CH2 NH2
enamine H2C CH N or NaCN H
2ry Amine
O Zn/Hg/HCl
+ H3 C CH3
H 3C C K2Cr2O7/H
OH
Clemensen Red
or CrO3/H3O+
or
Ag2O/NH4OH/H2O

Dr/Ahmed El ayde 1
 Saudi

R NH2 H 2O OH
imine H CH N R H C OH geminal diol
1ry Amine H +
H

H2N NH2 OH OCH3

hydrazone H CH N NH2
Hydrazine CH3-OH H C OCH3 CH3-OH H C OCH3
+ H +
phenyl
H hemiacetal H H
Ph-NH-NH2 acetal
H CH N NH Ph
hydrazone phenyl hydrazine O OH
O O
C OH
H H H C
Oxime H CH N OH NH2-OH + H
Hydroxyl Amine Formaldehyde H
OH OH
KCN H2/Ni
NH H C C N H CH CH2 NH2
No Rx or NaCN H
2ry Amine
O Zn/Hg/HCl
K2Cr2O7/H + CH4
H C Clemensen Red
OH
or CrO3/H3O+
or
Ag2O/NH4OH/H2O

2 ‫أحمد العايدى‬/‫د‬ 01010288200

 Saudi arabia
HO OH

R NH2 H2O
N R
H+
HO OCH3 H 3 CO
OCH3

Ph-NH-NH2 CH3-OH CH3-OH

N NH Ph
phenyl hydrazine H+ hemiketal H+
ketal
O
OH O O
N OH NH2-OH OH
Hydroxyl Amine
H+
HO C N
+
K2Cr2O7/H KCN
No Rx
or Ag2O / H2O or NaCN

O RCOOOH Zn/Hg/HCl
O
Baeyer-villiger Clemensen Red
Oxid

Dr/Ahmed El ayde 3
 Saudi

2ry Amine
 Aldehydes are more reactive than ketones …. Explain .

Baeyer-villiger Oxidation

1)

2)  Aldehyde C=O is more polarized than ketone C=O

 As in carbocations, more alkyl groups stabilize + character
 Ketone has more alkyl groups, stabilizing the C=O carbon
inductively

 Ease of nucleophilic attack on carbonyl carbon atom

3)

4)

4 ‫أحمد العايدى‬/‫د‬ 01010288200

 Saudi arabia
Alcohol preparation

a) Reduction : using [ LiAlH4 or NaBH4 ] b) Grignard reagent RMgX [increase number of carbon]

Acid Ester Acid Halide Aldehyde Ketone Preparation : Mg

R X R Mg X
LiAlH4 1ry alcohol 1ry alcohol 1ry alcohol 1ry alcohol 2ry alcohol Dry Ether
- Mg+
O O X OH
NaBH4 - - - 1ry alcohol 2ry alcohol
R Mg X H2O
C H C R H C R
H H
Mechanism H H
-
O O O OH Formaldehyde 1ry alcohol
H- H- H+ - +
C C C C O O Mg X OH
R LG R H R H R H
H H R MgX 1 H2O 1
1 C R C R R C R
R H
LG=OH,OR,Cl Aldehyde Alkoxide ion 1ry Alcohol H H

- other aldehyde 2ry alcohol

O O OH - +
H- H+ O O Mg X OH
C C C R MgX 1 H2O
R R R R R R 1
1 C 2 R C R R C R
H H R R 2 2
Ketone Alkoxide ion R R
2ry Alcohol
Ketone 3ry alcohol
 Non-selective Reduction O O O
-
OH
R MgX R MgX H2O
H2/Ni , H2/Pt , H2/Pd , Na/ETOH , Na/NH3 , Zn/AcOH , Zn/HCl C R
C
R C C
R OR R R R R
R R
OH O OH Ester ketone Alkoxide ion 3ry Alcohol
LiAlH4 H2/Ni
No reaction in acidic media “OH,NH,SH”
or NaBH4 O O
R Mg X + R H
C C - +
R OH
Dr/Ahmed El ayde R 5 O Mg X