The first
chemical contrast of thiols and sulfides with alcohols and ethers is acidity
which is important in organic reactions. Thiols are stronger acids than relevant
alcohols and phenols. Thiolate conjugate bases are easily formed, and are
excellent nucleophiles in SN2 reactions of alkyl halides and tosylates. The
nucleophilicity of sulfur is much greater than that of oxygen, resulting in a
number of useful electrophilic substitution reaction that are rare by oxygen.
For example, sulfides form (with alkyl halides) ternary sulfonium salts, in the
same alkylattion of tert-amines quaternary ammonium salts, whereas ternary
oxonium salts are prepared only under extream conditions. Without exception,
sulfoxides, sulfinate salts and sulfite anion also alkylate on sulfur, despite
of the partial negative formal charge on oxygen and partial positive charge on
sulfur. The second character is the oxidation states of sulfur. Oxygen has only
two oxidation states, whereas sulfur covers from –2 to +6 as follows:
- -2: Hydrogen
Sulfide (H2S), sulfides,
sulfonium ions
- -1:
disulfides
- 0: S
elemental, sulfoxides, sulfenic acids
- +2:
sulfones, sulfinic acids
- +4: sulfonic
acids, sulfite esters
- +6: sulfate
esters
One more
sulfur compound's contrast with oxygen analog is in oxidation chemistry.
Oxidation of sulfur compounds changes the oxidation state of sulfur rather than
carbon, whereas, oxidation of alcohols to aldehydes and ketones changes the
oxidation state of carbon not oxygen. Thiols is oxidized to S-S single bond
(disufide) which is stronger than O–O bond in peroxide. Disufide forms sulfenyl
chlorides (with chlorine in mild condition) or sulfonic acids under harder
condition. Oxidation of sulfides with hydrogen peroxide (or peracids) yields
sulfoxides and then to sulfones. A certain sulfoxide compound such as dimethyl
sulfoxide can be used as an effective oxygen source in the oxidation reaction of
primary and secondary alcohols to aldehydes and ketones. DMSO easily is reduced
to dimethyl sulfide and water is taken up by the electrophile. oxidation
procedure is very mild and tolerates a variety of other functional groups,
including those having oxidizable nitrogen and sulfur atoms. Sulfinic acid is an organic compound containing -SO2H group which is bonded to a
carbon atom. Toluenesulfonate esters are useful for the application as alkylating agents in
organic synthesis. p-Toluenesulfonic acid is used as a non-oxidizing catalyst
in the manufacture of plasticizers It is used as a curing agent for
epoxy-phenolic resins. Toluene sulfonic acids are used in preparing hydrazine
based blowing agents such as p-Toluenesulfonylhydrazide, p,p'-Oxybis(benzenesulfonylhydrazide), p-Toluenesulfonyl acetone hydrazone. Toluene
sulfonic acids and their derivatives are used as intermediates for the synthesis of isocyanate
compounds used as water scavengers and catalysts for the production of
thermosetting resins. They are synthetic intermediates for a number of
biologically active compounds, pharmaceuticals, herbicides, dyes and pigments candidates.
p-Toluene
sulfonic acid is often used as a catalyst in the formation of acetal which water must be removed from the reaction mixture to
escape reversible reaction. Water is removed azeotropically
by distilation. (Toluene is the solvent). Sodium p-toluenesulfinate is used as a discharge medium of dyes and
pigments. Other applications include as a chemical intermediate for the
production of synthetic drugs, dyestuffs, fluorescent pigments and fabric
adhesive. It is used as an electroplating brightening agent and a curing agent.
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