Micronotes by Dr. Savita Desai.

Organo sulphur compounds: [4 lectures, 5 marks]

R-SH thioalcohols, R-S-R thioethers, RCHS Thioaldehydes, RCSR thioketones etc are organo
sulphur compounds.
Chemistry of thioalcohols/thiols:
Thioalcohols: these are Sulphur derivatives of corresponding alcohols/ alkylderivatives of
Hydrogen sullphide.
Nomenclature:
compound
R-SH
CH3-SH
C2H5-SH
H3C

Common names
Alkyl thioalcohol/ alkyl mercaptan
Methyl thioalcohol/ methyl mercaptan
Ethyl thioalcohol /mercaptan
Isopropyl thioalcohol /mercaptan

SH
CH

IUPAC names
Alkane thiol
Methane thiol
Ethane thiol
Propane-2-thiol

CH3

Methods of formation:
1. From alkyl halides:
C2H5-Cl

NaSH

heat

C2H5-SH

NaCl

2. From Alcohol: vapours of alcohol and H2S are passed over heated thoria catalyst.
ThO2

C2H5-OH + SH2
alcohol

C2H5-SH

Heat

H2 O

thiol

3. From Grignard reagent:

C2H5-Mg-X

C2H5-S-Mg-X

ethyl Mg halide

C2H5-SH
thiol

intermediate

OH
Mg
X

Chemical Properties: S is less electronegative than O, also S has less tendency to form double
bond with O hence, shows different chemical properties.
A] Properties similar to alcohols:
1. Reaction with alkali metal:
2 C2H5-SH
thiol

Na

2 C2H5-SNa

H2

Na-ethyl sulphide

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Micronotes by Dr. Savita Desai.

2. Reaction with carboxylic acid and acid chlorides:

C2H5-SH

CH3COOH

CH3COSC2H5

acetone

thiol

C2H5-SH

H2 O

H Cl

ethyl thio acetate

CH3COCl

CH3COSC2H5

acetyl chloride

thiol

ethyl thio acetate

3. Reaction with aldehyde and ketones:

CH3
2 C2H5-SH

CH3CHO

acetaldehyde

thiol

SC2H5

H2 O

SC2H5
thioacetal
diethyl methyl mercaptol
CH3

2 C2H5-SH

CH3COCH3

H3C

acetone

thiol

SC2H5

H2 O

SC2H5
thioketal
diethyl dimethyl mercaptol

B] Properties different from alcohols:

1. Mild oxidation
C2H5-SH

H2O2

mild

C2H5-S-S-C2H5

+ 2 H2 O

diethyl disulphide

thiol

2. Strong oxidation.
C2H5-SH

3 [O]

strong

C2H5

SO3H

ethane sulphonic acid

thiol

Chemistry of Thioethers:
These are Sulphur derivatives of corresponding ethers/ dialkyl derivatives of Hydrogen sullphide
Nomenclature:
compound
R-S-R
CH3-S-CH3

Common names
diAlkyl thioether
dimethyl thioether

C2H5-S-C2H5

diethyl thioether

IUPAC names
Dialkyl sulphide
Dimethyl
sulphide
Diethyl sulphide

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Micronotes by Dr. Savita Desai.

Methods of formation:
1. From alkyl halides
2 C2H5-I

ethyl iodide

K2S

2 KI

C2H5-S-C2H5

C2H5-S-C2H5
thioether

K-sulphide

2. From thiosalt and alkyl halide:

C2H5-I
ethyl iodide

C2H5-S-Na
Na-ethyl mercaptide

NaI

thioether

3. From thiols and alkenes:

H2C CH2
ethene

C2H5-SH

C2H5-S-C2H5
thioether

ethane thiol

Chemical Properties:
1. Reaction with alkyl halide,
2. Mild oxidation
3. Strong oxidation
4. Addition of halogens
5. Hydrolysis
H2 O

C2H5OH

-H2S

C2H5-S-C2H5

+
S

C2H5

C2H5
H2O2

Br
S

C2H5

thioether

Br2

C2H5

I-

C2H5I

triethyl sulphonium iodide

mild oxidation
HNO3

C2H5

Br

strong oxidation

C2H5

C2H5

diethyl sulphide dibromide

C2H5

C2H5

diethyl sulphoxide

O
diethyl sulphone

*****

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