Thiourea dioxide or thiox is an
organosulfur compound
Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature abounds with organosulfur compounds—sulf ...
that is used in the
textile
Textile is an umbrella term that includes various fiber-based materials, including fibers, yarns, filaments, threads, different fabric types, etc. At first, the word "textiles" only referred to woven fabrics. However, weaving is not t ...
industry. It functions as a
reducing agent
In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ).
Examples of substances that are commonly reducing agents include the Earth m ...
. It is a white solid, and exhibits tautomerism.
Structure
The structure of thiourea dioxide depends on its environment. Crystalline and gaseous thiourea dioxide adopts a structure with C
2v symmetry. Selected
bond length
In molecular geometry, bond length or bond distance is defined as the average distance between nuclei of two bonded atoms in a molecule. It is a transferable property of a bond between atoms of fixed types, relatively independent of the rest ...
s: S-C = 186, C-N = 130, and S-O = 149 pm. The sulfur center is pyramidal. The C-S bond length is more similar to that of a single bond. For comparison, the C=S bond in thiourea is 171 pm.
The long C-S bond indicates the absence of C=S character. Instead the bonding is described with a significant contribution from a dipolar resonance structure with multiple bonding between C and N. One consequence of this bonding is the planarity of the nitrogen centers.
[ In the presence of water or ]DMSO
Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula ( CH3)2. This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds a ...
, thiourea dioxide converts to the tautomer
Tautomers () are structural isomers (constitutional isomers) of chemical compounds that readily interconvert.
The chemical reaction interconverting the two is called tautomerization. This conversion commonly results from the relocation of a hyd ...
, a sulfinic acid
Sulfinic acids are oxoacids of sulfur with the structure RSO(OH). In these organosulfur compounds, sulfur is pyramidal.
Structure and properties
Sulfinic acids RSO2H are about 1000x more acidic than the corresponding carboxylic acid RCO2H. Sul ...
, (H2N)HN=CS(O)(OH), named formamidine sulfinic acid.
Synthesis
Thiourea dioxide was first prepared in 1910 by the English chemist Edward de Barry Barnett.
Thiourea dioxide is prepared by the oxidation
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...
of thiourea
Thiourea () is an organosulfur compound with the formula and the structure . It is structurally similar to urea (), except that the oxygen atom is replaced by a sulfur atom (as implied by the '' thio-'' prefix); however, the properties of ur ...
with hydrogen peroxide
Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3% ...
.[D. Schubart "Sulfinic Acids and Derivatives" in ''Ullmann's Encyclopedia of Industrial Chemistry'', 2012, Wiley-VCH, Weinheim. ]
:(NH2)2CS + 2H2O2 → (NH)(NH2)CSO2H + 2H2O
The mechanism of the oxidation has been examined. An aqueous solution of thiourea dioxide has a pH about 6.5 at which thiourea dioxide is hydrolyzed to urea
Urea, also known as carbamide, is an organic compound with chemical formula . This amide has two amino groups (–) joined by a carbonyl functional group (–C(=O)–). It is thus the simplest amide of carbamic acid.
Urea serves an important ...
and sulfoxylic acid
Sulfoxylic acid (H2SO2) (also known as hyposulfurous acid or sulfur dihydroxide) is an unstable oxoacid of sulfur in an intermediate oxidation state between hydrogen sulfide and dithionous acid. It consists of two hydroxy groups attached to a sulfu ...
. It has been found that at pH values of less than 2, thiourea and hydrogen peroxide react to form a disulfide
In biochemistry, a disulfide (or disulphide in British English) refers to a functional group with the structure . The linkage is also called an SS-bond or sometimes a disulfide bridge and is usually derived by the coupling of two thiol groups. In ...
species. It is therefore convenient to keep the pH between 3 and 5 and the temperature below 10 °C
The degree Celsius is the unit of temperature on the Celsius scale (originally known as the centigrade scale outside Sweden), one of two temperature scales used in the International System of Units (SI), the other being the Kelvin scale. The d ...
. It can also be prepared by oxidation of thiourea with chlorine dioxide
Chlorine dioxide is a chemical compound with the formula ClO2 that exists as yellowish-green gas above 11 °C, a reddish-brown liquid between 11 °C and −59 °C, and as bright orange crystals below −59 °C. It is usually ...
.[Rábai, G.; Wang, R. T.; Kustin, Kenneth (1993). "Kinetics and mechanism of the oxidation of thiourea by chlorine dioxide" International Journal of Chemical Kinetics. Volume 25: 53–62. ] The quality of the product can be assessed by titration with indigo
Indigo is a deep color close to the color wheel blue (a primary color in the RGB color space), as well as to some variants of ultramarine, based on the ancient dye of the same name. The word "indigo" comes from the Latin word ''indicum'', ...
.[
]
Uses
Thiourea dioxide is used in reductive bleaching
Bleach is the generic name for any chemical product that is used industrially or domestically to remove color (whitening) from a fabric or fiber or to clean or to remove stains in a process called bleaching. It often refers specifically, to ...
in textile
Textile is an umbrella term that includes various fiber-based materials, including fibers, yarns, filaments, threads, different fabric types, etc. At first, the word "textiles" only referred to woven fabrics. However, weaving is not t ...
s. Thiourea dioxide has also been used for the reduction of aromatic
In chemistry, aromaticity is a chemical property of cyclic (ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to sat ...
nitroaldehydes and nitroketones
In organic chemistry, a ketone is a functional group with the structure R–C(=O)–R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group –C(=O)– (which contains a carbon-oxygen double bon ...
to nitroalcohols.
References
{{Reflist
Sulfinic acids
Thioureas
Amidines
Reducing agents
Substances discovered in the 1910s