Reactivity of Aldehydes

Reaction Type I: Cyantion

O NaCN HO CN
Cyanation in basic
conditions: H H2 O H

O
H H
O HO CN
CN O CN
H H H

O HCN HO CN
Cyanation in acidic
conditions: H H 2O H

*HCN is a potent neurotoxin,

-
HCN + H 2O :CN + H3O+ never do this reaction in real life

H O H H
O O HO CN
H CN
H H
H

Reaction Type I: Hydration

O OH-/ H2O HO OH
Hydration in basic
conditions: H H

O
H H
O HO OH
OH O OH
H H H

Hydration in acidic O H+/ H2O HO OH

conditions:
H H

H O H H H
O HO OH
O H O HO O H H O H
H H
H
H H H
 Reaction Type III: Organometallic Addition

R-Li Addition

O R-Li O H+/ H2O OH

H H R
R
Li
H O H
O O OH
R Li H
H H R
R

R-MgBr (Grignard) Addition

O R-MgBr O H+/ H2O OH

H H R
R

MgBr
H O H
O O OH
R MgBr H
H H R
R

Reaction Type III: Hydride Addition

Using LiAlH 4

O LiAlH 4 O H+/ H2O OH

H H
H

Li Li reacts with 3
H AlH 3 more aldehydes Al Li
H Al H O O O
H H
H H
H H 4
 Al Li AlOH Li
O OH O
+
H H O H H
H 4 H H 3

Using NaBH4

O NaBH4 OH

H CH3OH
H OMe
Na Na reacts with 3
H BH3 B Na
more aldehydes
O O
H B H O
H H H
H H H 4

BOMe Na
OH O
+
H
H 3

Reaction Type IV: Alcohol Addition

Alcohol addition in basic O ROH RO OH

conditions: -
OH
H H

O
O H R
O H O OR
R O O R
H H
H

*In basic conditions the reaction can only go to the hemi-acetal, not the acetal
 Alcohol addition in acidic O ROH RO OR
conditions: H+
H H
H O R
H
H O R H R
O
O H O HO O H H O R H O OR
H R
H H H H

H R R
H O O R O RO O H H O R RO OR
O
H R
H H H H

Reaction Type V: Oxidation CrO3 / py

CrO3 / H2O
O [O] O [O] can be... KMnO4
HNO3
H OH Na2CrO4 / H2O
Swern conditions