Thiourea dioxide or thiox is an

organosulfur compound Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur der ...

that is used in the

textile Textile is an Hyponymy and hypernymy, umbrella term that includes various Fiber, fiber-based materials, including fibers, yarns, Staple (textiles)#Filament fiber, filaments, Thread (yarn), threads, and different types of #Fabric, fabric. ...

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 common reducing agents include hydrogen, carbon ...

. It is a white solid, and exhibits tautomerism in solution.

Structure

Crystalline and gaseous thiourea dioxide adopts a C_2v-

symmetric Symmetry () in everyday life refers to a sense of harmonious and beautiful proportion and balance. In mathematics, the term has a more precise definition and is usually used to refer to an object that is invariant under some transformations ...

structure. Selected

bond length In molecular geometry, bond length or bond distance is defined as the average distance between Atomic nucleus, nuclei of two chemical bond, bonded atoms in a molecule. It is a Transferability (chemistry), transferable property of a bond between at ...

s: S-C = 186, C-N = 130, and S-O = 149 pm. The sulfur center is pyramidal. The C-S bond length is close to that of a single bond. For comparison, the C=S bond in thiourea is 171 pm. 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 . This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds and is ...

, thiourea dioxide converts to the

tautomer In chemistry, 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 reloca ...

, 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 typically more acidic than the corresponding carboxylic acid RCO2H. Su ...

, (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 or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...

thiourea Thiourea () is an organosulfur compound with the formula and the structure . It is structurally similar to urea (), with the oxygen atom replaced by sulfur atom (as implied by the '' thio-'' prefix). The properties of urea and thiourea differ s ...

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 viscosity, viscous than Properties of water, water. It is used as an oxidizer, bleaching agent, and antiseptic, usua ...

.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 called carbamide (because it is a diamide of carbonic acid), is an organic compound with chemical formula . This amide has two Amine, amino groups (–) joined by a carbonyl functional group (–C(=O)–). It is thus the simplest am ...

and sulfoxylic acid. It has been found that at pH values of less than 2, thiourea and hydrogen peroxide react to form a

disulfide In chemistry, a disulfide (or disulphide in British English) is a compound containing a functional group or the anion. The linkage is also called an SS-bond or sometimes a disulfide bridge and usually derived from two thiol groups. In inorg ...

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 temperature scale "Celsius temperature scale, also called centigrade temperature scale, scale based on 0 ° for the melting point of water and 100 ° for the boiling point ...

. 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

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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 from (i.e. to whiten) fabric or fiber (in a process called bleaching) or to disinfect after cleaning. It often refers specifically t ...

s. Thiourea dioxide has also been used for the reduction of

aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...

nitroaldehydes and nitro

ketones In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...

to nitroalcohols.

References

{{Reflist Sulfinic acids Thioureas Amidines Reducing agents Substances discovered in the 1910s