Week 11

Chemical Properties
1. Addition Reactions
A. With NH3
1. With Aldehyde form addition products except formaldehyde
CH3CHO + NH3 🡪 CH3CH(OH)(NH2)

2. With Ketones form addition products of the aldol type

CH3COCH3 + NH3 🡪 CH3C(CH3) (OH)(NH2)

B. With NaHSO3
1. With Aldehyde
CH3CH2CHO + NaHSO3 🡪 CH3 CH2CH(ONa)(HSO3)

2. With Ketones
CH3CH2COCH3 + NaHSO3 🡪 CH3 CH2C(CH3) (ONa)(HSO3)

C. With Grignard Reagent

1. With aldehyde
CH3CHO + CH3MgBr 🡪 CH3CH(OMgBr)(CH3) + H2O 🡪
CH3CH(OH)(CH3) + MgOHBr

2. With Ketones
CH3COCH3 + CH3MgCl 🡪 CH3C(CH3)(OMgBr)(CH3) + H2O
CH3C(CH3)2 (OH) + MgOHCl

2.Addition Reactions followed by the loss of water

A. With alcohols
1.With Aldehyde
CH3CH2CHO + CH3CH2OH 🡪 CH3CH2CH(HO)(CH3CH2O) + CH3CH2OH 🡪
CH3CH2CH(CH3CH2O)2 + H2O

2.With Ketones
CH3COCH3 + CH3CH2OH 🡪 CH3C(HO)(CH3) (CH3CH2O) + CH3CH2OH 🡪
(CH3)2 C(CH3CH2O)2 + H2O

B. With Phenylhydrazine
1. With Aldehyde
CH3CHO + 2 C6H5N=NH2 🡪 CH3CH(C6H5N=N)2 + H2O
 2. With Ketones
CH3COCH3 + 2 C6H5N=NH2 🡪 (CH3)2C(C6H5N=N)2 + H2O

3.Reduction
A. Catalytic Hydrogenation
1.With Aldehydes
CH3CHO + H2 🡪 CH3CH2OH

3. With ketones
CH3COCH3 + H2 🡪 CH3CH(OH)CH3

B. Canizarro’s Reaction
1. Formaldehyde
3HCOH + NaOH 🡪 H2C(OH)- H2C(OH)- H2C(OH)

3. trimethyl-acetaldehyde and
3 C(CH3)3CHO + NaOH 🡪
C(CH3)3CH(OH) C(CH3)3CH(OH) C(CH3)3CH(OH)

3. all aromatic aldehyde which have no

alpha hydrogen will show intermolecular oxidation and reduction when warm
with sodium hydroxide

4.Substitution
A. with halogen
1.With Aldehyde
CH3CH2CHO + 2HCl 🡪 CH3CH2CHCl2 + H2O

3. With Ketone
CH3COCH3 + 2HCl 🡪 CH3CCl2CH3 + H2O

B. Haloform reaction
1.With Aldehyde
CH3CHO + 3Cl2 🡪 CCl3CHO + 3HCl

2.With Ketone
CH3COCH3 + 3Cl2 🡪 CCl3COCH3 + 3HCL

C. with PCl5
1.With Aldehyde
CH3CH2CHO + PCl5 🡪 CH3CH2CHCl2 + POCl3
 2. With Ketone
CH3COCH3 + PCl5 🡪 CH3CCl2CH3 + POCl3

5.Polymerization
1.With formaldehyde if heated on a steam bath produces a linear polymer known
as paraformaldehyde

2. With acetaldehyde if a trace of sulfuric acid is added, a cyclic trimer known as

as paraldehyde is formed
6. Replacement of carbonyl oxygen with sulfur produces thioaldehydes (thials) and
thioketones (thiones).These are unstable and readily decompose.
7. Replacement of the carbonyl carbon atom with sulfur produces sulfoxides.
a. Sulfoxides are much more stable than thiocarbonyls
b. Most important example: DMSO (dimethyl sulfoxide)
c. DMSO is an odorless liquid with excellent solvent properties
d. DMSO is quickly absorbed into the body and is known to relieve pain and
inflammation
e. Not approved by the FDA for medical uses because of possible side effects

8 Reducing Properties
1. Tollen’s test (silver mirror test): Tollens reagent [aqueous silver nitrate (AgNO3)
and ammonia (NH3)] when added to an aldehyde, Ag + ion is reduced to silver metal, which
deposits on the inside of the test tube, forming a silver mirror. The Ag ion will not oxidize
ketones.
2. Benedict’s Test- the metal ion oxidizing agent is Cu2+. Cu 2+ ion is reduced to Cu
ion, which precipitates from solution as Cu2O (brick-red colored solid)
3. Schiff’s Test – if Schiff’s reagent is added to aldehyde a magenta red color is
Obtained.

Uses
Formaldehyde
1. Mainly used for the manufacturing of polymers
2. Formalin is used for preserving biological specimens
3. For silvering mirrors.
4. For embalming
5. Use in the manufacture of Bakelite plastics.
Acetone

1. Colorless liquid with mild sweet odor.

2. Excellent solvent: it is miscible in both water and organic solvents.
3. Acetone is the main ingredient in gasoline treatments designed to solubilize water in the
gas tank and allow it to pass through the engine in miscible form.
4. Major component of nail polish remover.
5. Patients with diabetes produce large amounts of acetone.
◦ Diabetic breath has mild sweet odor because of acetone.
◦ Presence of acetone in urine indicates diabetes.
6. The unmistakable odor of melted butter is largely due to the four-carbon diketone -
butanedione.