Thiourea dioxide

Thiourea dioxide
Names
Preferred IUPAC name
Amino(imino)methanesulfinic acid
Other names
Thiourea dioxide, DegaFAS, Reducing Agent F, Depilor, Formamidine Sulfinic Acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.015.598
UNII
  • InChI=1S/CH4N2O2S/c2-1(3)6(4)5/h(H3,2,3)(H,4,5)
    Key: FYOWZTWVYZOZSI-UHFFFAOYSA-N
  • C(=N)(N)S(=O)O
Properties
CH4N2O2S
Molar mass 108.12 g·mol−1
Appearance White powder
Melting point 126 °C (259 °F; 399 K)
3.0 g/100 mL
Hazards
GHS labelling:
GHS02: FlammableGHS05: CorrosiveGHS07: Exclamation markGHS08: Health hazard
Danger
H252, H302, H315, H318, H332, H335, H373
P235+P410, P270, P280, P305+P351+P338, P310, P407, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N (what is checkY☒N ?)
Infobox references

Thiourea dioxide or thiox is an organosulfur compound that is used in the textile industry.[1] It functions as a reducing agent.[2] It is a white solid, and exhibits tautomerism in solution.[3]

Structure

Crystalline and gaseous thiourea dioxide adopts a C2v-symmetric structure. Selected bond lengths: 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.[4][5] 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.[6] In the presence of water or DMSO, thiourea dioxide converts to the tautomer, a sulfinic acid, (H2N−)(HN=)C−S(=O)(−OH), named formamidine sulfinic acid.[6]

Structure of the sulfinic acid tautomer of thiourea dioxide, as exists in aqueous solution

Synthesis

Thiourea dioxide was first prepared in 1910 by the English chemist Edward de Barry Barnett, through a method not dissimilar from the modern synthesis.[7]

Thiourea dioxide is prepared by the oxidation of thiourea with hydrogen peroxide,[8] while maintaining a pH between 3 and 5 and temperature below 10 °C:[9]

(NH2)2CS + 2 H2O2 → (NH)(NH2)CSO2H + 2 H2O

It can also be prepared by oxidation with chlorine dioxide.[10] The quality of the product can be assessed by titration with indigo.[8]

Properties

Below pH 6.5, thiourea dioxide hydrolyzes to sulfoxylic acid and urea.[9] Further oxidation with a peracid gives the corresponding sulfonic acid.[11]

Uses

Thiourea dioxide is used in reductive bleaching in textiles.[12] Thiourea dioxide has also been used for the reduction of aromatic nitroaldehydes and nitroketones to nitroalcohols.[13]

References

  1. ^ Fischer, Klaus (2003). "Textile Auxiliaries". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a26_227. ISBN 9783527303854. OCLC 55738480. Archived from the original on 2022-06-18. Retrieved 2022-06-18.
  2. ^ Milne, George W. A. (11 July 2005). Gardner's Commercially Important Chemicals: Synonyms, Trade Names, and Properties. Hoboken, New Jersey, USA: Wiley-Interscience. doi:10.1002/0471736627.ch1. ISBN 9780471735182. OCLC 57392953. Archived from the original on 18 June 2022. Retrieved 18 June 2022.
  3. ^ Makarov, Sergei V.; Horváth, Attila K.; Silaghi-Dumitrescu, Radu; Gao, Qingyu (2014). "Recent Developments in the Chemistry of Thiourea Oxides". Chemistry – A European Journal. 20 (44): 14164–14176. doi:10.1002/chem.201403453.
  4. ^ Sullivan, R. A. L.; Hargreaves, A. (1962). "The Crystal and Molecular Structure of Thiourea Dioxide". Acta Crystallographica. 15 (7): 675–682. Bibcode:1962AcCry..15..675S. doi:10.1107/S0365110X62001851.
  5. ^ Chen, I-C.; Wang, Y. (1984). "Reinvestigation of the Structure of Thiourea S,S-Dioxide, CH4N2O2S". Acta Crystallographica. 40 (11): 1937–1938. Bibcode:1984AcCrC..40.1937C. doi:10.1107/S010827018401012X.
  6. ^ a b Makarov, S. V. (2001). "Recent Trends in the Chemistry of Sulfur-Containing Reducing Agents". Russian Chemical Reviews. 70 (10): 885–895. Bibcode:2001RuCRv..70..885M. doi:10.1070/RC2001v070n10ABEH000659. S2CID 250741549.
  7. ^ Barnett, Edward de Barry (1910) "The action of hydrogen dioxide on thiocarbamides," Archived 2020-06-06 at the Wayback Machine Journal of the Chemical Society, Transactions, 97 : 63–65.
  8. ^ a b D. Schubart "Sulfinic Acids and Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry, 2012, Wiley-VCH, Weinheim. doi:10.1002/14356007.a25_461
  9. ^ a b US patent 2783272, James H. Young, "PRODUCTION OF FORMAMIDINE SULFINIC ACID", issued 1957-2-26  For the reaction's general kinetics and pH-dependence, see Hoffmann, Michael; Edwards, John O. (1977). "Kinetics and Mechanism of the Oxidation of Thiourea and N,N'-dialkylthioureas by Hydrogen Peroxide". Inorganic Chemistry. 16 (12): 3333–3338. doi:10.1021/ic50178a069.
  10. ^ 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. doi:10.1002/kin.550250106
  11. ^ Miller, Audrey; Palmer, David C. (15 April 2001). "Aminoiminomethanesulfonic acid". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.ra091.
  12. ^ Hebeish, A.; El-Rafie, M. H.; Waly, A.; Moursi, A. Z. (1978). "Graft copolymerization of vinyl monomers onto modified cotton. IX. Hydrogen peroxide–thiourea dioxide redox system induced grafting of 2-methyl-5-vinylpyridine onto oxidized celluloses". Journal of Applied Polymer Science. 22 (7): 1853–1866. doi:10.1002/app.1978.070220709.
  13. ^ Sambher, Shikha; Baskar, Chinnappan; Dhillon, Ranjit S. (22 May 2009). "Chemoselective reduction of carbonyl groups of aromatic nitro carbonyl compounds to the corresponding nitroalcohols using thiourea dioxide". Arkivoc. 2009 (10): 141–145. doi:10.3998/ark.5550190.0010.a14. hdl:2027/spo.5550190.0010.a14.
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