Sulfoxide (R2SO) is any of various organic sulfur compounds having the group -SO
(sulfinyl group) whereas sulfone (RSOOR) with the group -SO2 (sulfonyl group).
They are derived from oxidation of sulfides ((R-S-R). Thioethers (organic sulfides) can be oxidized either to oxidation state -1
"disulfides (R-S-S-R)" or to oxidation state 0 "sulfoxides (R-S(=O)-R)"
which can be
further oxidized to the corresponding oxidation state +2 "sulfones (R-S(=O)2-R)"
depending on the structure of the thioether. They are widely used as solvent of
both extraction and reaction as well as intermediates for the synthesis of
textile chemicals and pharmaceuticals and agrochemicals.
Dimethyl sulfoxide
(DMSO) is a clear hygroscopic liquid; melting point
18 C; boiling point 189 C. It is has little odor. It
smells garlic like odor due to the impurity of dimethyl sulfide.
It is miscible with water; readily
soluble in almost all organic solvents such as alcohols, esters, ketones,
chlorinated solvents and aromatic hydrocarbons. Dimethyl sulfoxide is produced
as a by-product of wood pulping. DMSO is a highly dipolar organic liquid, that is used as a powerful
solvent
in organic synthesis and industrial applications including paint stripper
and coating remover as the alternative to chlorinated
solvents and nitroalkanes.
DMSO's high polarity solvates polymeric materials
by itself or in combination with other solvents. Its application
is extended as a chemical reactant undergoing a
chemical change. DMSO proved to be an excellent
reaction solvent for SN2
alkylation. DMSO is used in oxidation reactions which a primary or
secondary alcohol is oxidized to the corresponding aldehyde or ketone (Swern oxidation).
Sulfoxonium ion reacts with sodium hydride
to form sulfur ylide which converts carbonyl to epoxide (Johnson-Corey-Chaykovsky reaction). It
is widely used in the synthesis of pharmaceuticals,
biocides and pesticides insecticides as a
reactant, reaction solvent, in combinations of these
applications. Some examples are diphenyl ether compounds, imidazolinone compounds, and
pyrethroids. The
catalysts in hydrocracking, hydrodenitrification, hydrodesulfurization
and reforming processes are used in oxide forms, which
must be converted to the active sulfide form during
the start-up to prevent the reduction of the catalysts
to their base material by heat. The sulfur sources include
alkyl mercaptans (methyl mercaptan, ethyl mercaptan,
butyl mercaptan), dimethyl sulfide, dimethyl sulfoxide,
dimethyl disulfide, and tert-nolyl polysulfide. They
are used to modify the reactivity of catalysts to use
in high temperature process furnaces. Dimethyl Sulfoxide is
used as an effective extraction solvent and
solvent improver for the separation of aromatic compounds
(benzene, toluene and xylenes) from aliphatic hydrocarbons, and for fractionation of
unsaturated components (olefins and alkynes) from saturated feedstock.
Pharmaceutical grade
DMSO demonstrates a range of
pharmacological activity including analgesia and anti-inflammation. Due to its ability to penetrate biological membranes, it is used as a
vehicle for the transdermal delivery of active pharmaceuticals. It is also used to protect
tissue during cryopreservation
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Solvent is a substance, usually a liquid, that acts as a dissolving agent or
that is capable of dissolving another substance. In solutions of solids or gases
in a liquid, the liquid is the solvent. In all other homogeneous mixtures (i.e.,
liquids, solids, or gases dissolved in liquids; solids in solids; and gases in
gases), solvent is the component of the greatest amount. The minor proportion
substances are called solutes. The solvent offers several functions during a
chemical reaction. It solves not only the substance that reacts with another one
to produce a new set of substances (reactant) but also the compound that
supplies the molecule, ion, or free radical, which is considered as the
attacking species in a chemical reaction (reagent). The solvent is conductive to
collisions between the reactants and reagents to transform the reactants to new
products. The solvent also takes roll of temperature control, either to provide
the energy of the colliding particles for speedy reaction and to absorb heat in
exothermic reaction. The appropriate solvent should be selected based on the
inactivity in the reaction conditions, dissolving the reagents as well as
reactants, appropriate boiling point and easy removal at the end of the
reaction.
Polarity
The most common solvent is water. Other common
solvents which dissolve substances that are insoluble (or nearly insoluble) in
water are acetone, alcohol, formic acid, acetic acid, formamide. BTX, carbon
disulfide, diemthyl sulfoxide, carbon tetrachloride, chloroform, ether,
tetrahydrofuran, furfural, hexane and turpentine. They may be classified as
polar and non-polar. Polar solvents, like water, have molecules whose electric
charges are unequally distributed, leaving one end of each molecule more
positive than the other. Usually polar solvent has O-H bond of which water
(HOH), (CH3OH) and acetic acid (CH3COOH) are examples.
Propanol, butanol, formic acid, formamide are polar solvents. Dipolar solvents
which contain a C-O solid bond without O-H bond are acetone [(CH3)2C=O], ethyl
acetate (CH3COOCH2CH3), methyl ethyl ketone, acetonitrile, N,N-dimethylformamide
and diemthyl sulfoxide. Nonpolar solvents, like carbon tetrachloride (CCl4),
benzene (C6H6), and diethyl ether ( CH3CH2OCH2CH3), have molecules whose
electric charges are equally distributed and are not miscible with water. Hexane, tetrahydrofuran and methylene chloride are non-polar solvents. Polar
solvents are hydrophilic but non-polar solvents are lipophilic. Polar reactants
will dissolve in polar solvents. Non-polar solvents dissolve non-polar compounds
best. Oil and water don't mix but separate into two layers. There are three
measures of the polarity as "dipole moment", "dielectric constant" and
"miscibility with water". Though low dipole moments and small dielectric
constants indicates non-polar solvents, sharp boundaries between polar and
non-polar solvents are not available. The polarity reflects the balance between
a polar component (OH) and a non-polar hydrocarbon component, existing in the
same molecule. If hydrocarbon character increases relatively, the polarity
decreases. On an operational basis, solvents that are miscible with water are
polar.
Polar Protic and Dipolar Aprotic
Protic refers to a hydrogen atom
attached to an electronegative atom. Protic solvents can donate an H+ (proton)
since they contain dissociable H+, such as hydrogen attached to oxygen as in a
hydroxyl group, nitrogen as in a amine group. Examples are water, methanol,
ethanol, formic acid, hydrogen fluoride and ammonia. Aprotic solvents don't has
O-H bond but a C=O bond typically. Examples are acetone [(CH3)2C=O] and ethyl
acetate (CH3COOCH2CH3). Polar protic solvents are useful in SN1 reaction, while
polar aprotic solvents are SN2 reaction.
Solvents |
Boiling
point C |
Dipole Moment |
Dielectric Constant
|
Density
(g/ml)
|
Polar Protic |
Water |
100 |
1.85 |
80 |
0.998
|
Methanol |
68 |
1.70 |
33 |
0.791
|
Ethanol |
78 |
1.69 |
24.3 |
0.789
|
n-Propanol |
97 |
1.68 |
20.1 |
0.803
|
n-Butanol |
118 |
1.66 |
17.8 |
0.810
|
Formic acid |
100 |
1.41 |
58 |
1.21
|
Acetic acid |
118 |
1.74 |
6.15 |
1.049
|
Formamide |
210 |
3.73 |
109 |
1.134 |
Polar Aprotic |
Acetone |
56 |
2.88 |
20.7 |
0.786
|
Tetrahydrofuran |
66 |
1.63 |
7.52 |
0.886
|
Methyl ethyl ketone |
80 |
2.78 |
18.5 |
0.805
|
Ethyl acetate |
78 |
1.78 |
6.02 |
0.894
|
Acetonitrile |
81 |
3.92 |
36.6 |
0.786
|
N,N-Dimethylformamide |
153 |
3.82 |
38.3 |
0.944
|
Diemthyl sulfoxide |
189 |
3.96 |
47.2 |
1.092
|
Non-Polar |
Hexane |
69 |
- |
2.02 |
0.655
|
Benzene |
80 |
0 |
2.28 |
0.879
|
Diethyl ether |
35 |
1.15 |
4.34 |
0.713
|
Methylene chloride |
40 |
1.60 |
9.08 |
1.326
|
Carbon tetrachloride |
76 |
0 |
2.24 |
1.594 |
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