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Thiourea

See also: Thioureas

Thiourea (/ˌθaɪ.oʊjʊəˈriː.ə, -ˈjʊəri-/)[2][3][4] is an organosulfur compound with the formula SC(NH2)2 and the structure H2N−C(=S)−NH2. It is structurally similar to urea (H2N−C(=O)−NH2), except that the oxygen atom is replaced by a sulfur atom (as implied by the thio- prefix); however, the properties of urea and thiourea differ significantly. Thiourea is a reagent in organic synthesis. Thioureas are a broad class of compounds with the general structure R2N−C(=S)−NR2.

Thiourea

  Carbon, C
  Hydrogen, H
  Nitrogen, N
  Sulfur, S
Names
Preferred IUPAC name
Thiourea[1]
Other names
Thiocarbamide
Identifiers
3D model (JSmol)
605327
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.494 Edit this at Wikidata
1604
KEGG
RTECS number
  • YU2800000
UNII
UN number 2811
  • InChI=1S/CH4N2S/c2-1(3)4/h(H4,2,3,4) checkY
    Key: UMGDCJDMYOKAJW-UHFFFAOYSA-N checkY
  • InChI=1/CH4N2S/c2-1(3)4/h(H4,2,3,4)
    Key: UMGDCJDMYOKAJW-UHFFFAOYAJ
  • C(=S)(N)N
Properties
SC(NH2)2
Molar mass 76.12 g·mol−1
Appearance white solid
Density 1.405 g/mL
Melting point 182 °C (360 °F; 455 K)
142 g/L (25 °C)
−4.24×10−5 cm3/mol
Hazards
GHS labelling:
GHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Warning
H302, H351, H361, H411
P201, P202, P264, P270, P273, P281, P301+P312, P308+P313, P330, P391, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
1
0
Related compounds
Related compounds
 Urea
Selenourea
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Structure and bonding

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Thiourea is a planar molecule. The C=S bond distance is 1.71 Å. The C-N distances average 1.33 Å.[5] The weakening of the C-S bond by C-N pi-bonding is indicated by the short C=S bond in thiobenzophenone, which is 1.63 Å.

Thiourea occurs in two tautomeric forms, of which the thione form predominates in aqueous solutions. The equilibrium constant has been calculated as Keq is 1.04×10−3.[6] The thiol form, which is also known as an isothiourea, can be encountered in substituted compounds such as isothiouronium salts.

 

Production

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The global annual production of thiourea is around 10,000 tonnes. About 40% is produced in Germany, another 40% in China, and 20% in Japan. Thiourea can be produced from ammonium thiocyanate, but more commonly it is manufactured by the reaction of hydrogen sulfide with calcium cyanamide in the presence of carbon dioxide.[7]

CaCN2 + 3 H2S → Ca(SH)2 + (NH2)2CS
2 CaCN2 + Ca(SH)2 + 6 H2O → 2 (NH2)2CS + 3 Ca(OH)2
Ca(OH)2 + CO2 → CaCO3 + H2O

Applications

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Thiox precursor

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Thiourea per se has few applications. It is mainly consumed as a precursor to thiourea dioxide, which is a common reducing agent in textile processing.[7]

Fertilizers

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Recently thiourea has been investigated for its multiple desirable properties as a fertilizer especially under conditions of environmental stress.[8] It may be applied in various capacities, such as a seed pretreatment (for priming), foliar spray or medium supplementation.

Other uses

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Other industrial uses of thiourea include production of flame retardant resins, and vulcanization accelerators. Thiourea is building blocks to pyrimidine derivatives. Thus, thioureas condense with β-dicarbonyl compounds.[9] The amino group on the thiourea initially condenses with a carbonyl, followed by cyclization and tautomerization. Desulfurization delivers the pyrimidine. The pharmaceuticals thiobarbituric acid and sulfathiazole are prepared using thiourea.[7] 4-Amino-3-hydrazino-5-mercapto-1,2,4-triazole is prepared by the reaction of thiourea and hydrazine.

Thiourea is used as an auxiliary agent in diazo paper, light-sensitive photocopy paper and almost all other types of copy paper.

It is also used to tone silver-gelatin photographic prints (see Sepia Toning).

Thiourea is used in the Clifton-Phillips and Beaver bright and semi-bright electroplating processes.[10] It is also used in a solution with tin(II) chloride as an electroless tin plating solution for copper printed circuit boards.

Thioureas are used (usually as hydrogen-bond donor catalysts) in a research theme called thiourea organocatalysis.[11] Thioureas are often found to be stronger hydrogen-bond donors (i.e., more acidic) than ureas.[12][13]

Reactions

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The material has the unusual property of changing to ammonium thiocyanate upon heating above 130 °C. Upon cooling, the ammonium salt converts back to thiourea.[citation needed]

Reductant

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Thiourea reduces peroxides to the corresponding diols.[14] The intermediate of the reaction is an unstable endoperoxide.

reduction of cyclic peroxide 
reduction of cyclic peroxide

Thiourea is also used in the reductive workup of ozonolysis to give carbonyl compounds.[15] Dimethyl sulfide is also an effective reagent for this reaction, but it is highly volatile (boiling point 37 °C) and has an obnoxious odor whereas thiourea is odorless and conveniently non-volatile (reflecting its polarity).

reduction cleavage of product from ozonolysis 
reduction cleavage of product from ozonolysis

Source of sulfide

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Thiourea is employed as a source of sulfide, such as for converting alkyl halides to thiols. The reaction capitalizes on the high nucleophilicity of the sulfur center and easy hydrolysis of the intermediate isothiouronium salt:

CS(NH2)2 + RX → RSC(NH2)+2X−
RSC(NH2)+2X− + 2 NaOH → RSNa + OC(NH2)2 + NaX + H2O
RSNa + HCl → RSH + NaCl

In this example, ethane-1,2-dithiol is prepared from 1,2-dibromoethane:[16]

C2H4Br2 + 2 SC(NH2)2 → [C2H4(SC(NH2)2)2]Br2
[C2H4(SC(NH2)2)2]Br2 + 2 KOH → C2H4(SH)2 + 2 OC(NH2)2 + 2 KBr

Like other thioamides, thiourea can serve as a source of sulfide upon reaction with metal ions. For example, mercury sulfide forms when mercuric salts in aqueous solution are treated with thiourea:

Hg2+ + SC(NH2)2 + H2O → HgS + OC(NH2)2 + 2 H+

These sulfiding reactions, which have been applied to the synthesis of many metal sulfides, require water and typically some heating.[17][18]

Precursor to heterocycles

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Thioureas are building blocks to pyrimidine derivatives. Thus thioureas condense with β-dicarbonyl compounds.[19] The amino group on the thiourea initially condenses with a carbonyl, followed by cyclization and tautomerization. Desulfurization delivers the pyrimidine.

 

Similarly, aminothiazoles can be synthesized by the reaction of α-haloketones and thiourea.[20]

 

The pharmaceuticals thiobarbituric acid and sulfathiazole are prepared using thiourea.[7] 4-Amino-3-hydrazino-5-mercapto-1,2,4-triazole is prepared by the reaction of thiourea and hydrazine.

Silver polishing

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According to the label on consumer products TarnX[21] and Silver Dip,[22] the liquid silver cleaning products contain thiourea along with a warning that thiourea is a chemical on California's list of carcinogens.[23] A lixiviant for gold and silver leaching can be created by selectively oxidizing thiourea, bypassing the steps of cyanide use and smelting.[24]

Kurnakov reaction

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Thiourea is an essential reagent in the Kurnakov test used to differentiate cis- and trans- isomers of certain square planar platinum complexes. The reaction was discovered in 1893 by Russian chemist Nikolai Kurnakov and is still performed as an assay for compounds of this type.[25]

Safety

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The LD50 for thiourea is 125 mg/kg for rats (oral).[26]

A goitrogenic effect (enlargement of the thyroid gland) has been reported for chronic exposure, reflecting the ability of thiourea to interfere with iodide uptake.[7]

A cyclic derivative of thiourea called Thiamazole is used to treat overactive thyroid

See also

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References

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  1. ^ Favre, Henri A.; Powell, Warren H. (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: Royal Society of Chemistry. pp. 98, 864. doi:10.1039/9781849733069. ISBN 9780854041824. OCLC 1077224056.
  2. ^ "thiourea". Lexico UK English Dictionary. Oxford University Press. Archived from the original on 2020-03-22.
  3. ^ "thiourea". Merriam-Webster.com Dictionary. Merriam-Webster. Retrieved 2016-01-21.
  4. ^ "thiourea". Dictionary.com Unabridged (Online). n.d.
  5. ^ D. Mullen; E. Hellner (1978). "A Simple Refinement of Density Distributions of Bonding Electrons. IX. Bond Electron Density Distribution in Thiourea, CS(NH2)2, at 123K". Acta Crystallogr. B34 (9): 2789–2794. Bibcode:1978AcCrB..34.2789M. doi:10.1107/S0567740878009243.
  6. ^ Allegretti, P.E; Castro, E.A; Furlong, J.J.P (March 2000). "Tautomeric equilibrium of amides and related compounds: theoretical and spectral evidences". Journal of Molecular Structure: THEOCHEM. 499 (1–3): 121–126. doi:10.1016/S0166-1280(99)00294-8.
  7. ^ a b c d e Mertschenk, Bernd; Beck, Ferdinand; Bauer, Wolfgang (2002). "Thiourea and Thiourea Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. doi:10.1002/14356007.a26_803. ISBN 3527306730.
  8. ^ Wahid, Abdul (2017-08-01). "Thiourea: A Molecule with Immense Biological Significance for Plants" (PDF). International Journal of Agriculture and Biology. 19 (4): 911–920. doi:10.17957/ijab/15.0464. ISSN 1560-8530. Archived (PDF) from the original on 2020-02-15. Retrieved 2020-12-09.
  9. ^ Foster, H. M.; Snyder, H. R. (1955). "4-Methyl-6-hydroxypyrimidine". Organic Syntheses. 35: 80. doi:10.15227/orgsyn.035.0080.
  10. ^ "81st Universal Metal Finishing Guidebook". Metal Finishing, Guidebook and Directory Issue. Metal Finishing Magazine: 285. Fall 2013. ISSN 0026-0576. Archived from the original on 2017-11-17. Retrieved 2016-10-11.
  11. ^ R. Schreiner, Peter (2003). "Metal-free organocatalysis through explicit hydrogen bonding interactions". Chem. Soc. Rev. 32 (5): 289–296. doi:10.1039/b107298f. PMID 14518182.
  12. ^ Jakab, Gergely; Tancon, Carlo; Zhang, Zhiguo; Lippert, Katharina M.; Schreiner, Peter R. (2012). "(Thio)urea Organocatalyst Equilibrium Acidities in DMSO". Organic Letters. 14 (7): 1724–1727. doi:10.1021/ol300307c. PMID 22435999.
  13. ^ Nieuwland, Celine; Fonseca Guerra, Célia (2022). "How the Chalcogen Atom Size Dictates the Hydrogen-Bond Donor Capability of Carboxamides, Thioamides, and Selenoamides". Chemistry – A European Journal. 28 (31): e202200755. doi:10.1002/chem.202200755. PMC 9324920. PMID 35322485.
  14. ^ Kaneko, C.; Sugimoro, A.; Tanaka, S. (1974). "A facile one-step synthesis of cis-2-cyclopentene and cis-2-cyclohexene-1,4-diols from the corresponding cyclodienes". Synthesis. 1974 (12): 876–877. doi:10.1055/s-1974-23462. S2CID 93207044. Archived from the original on 2021-06-12. Retrieved 2022-06-18.
  15. ^ Gupta, D., Soman, G., and Dev, S. (1982). "Thiourea, a convenient reagent for the reductive cleavage of olefin ozonolysis products". Tetrahedron. 38 (20): 3013–3018. doi:10.1016/0040-4020(82)80187-7.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  16. ^ Speziale, A. J. (1963). "Ethanedithiol". Organic Syntheses; Collected Volumes, vol. 4, p. 401.
  17. ^ Liang, Y.; et, al. (2016). "An efficient precursor to synthesize various FeS2 nanostructures via a simple hydrothermal synthesis method". CrystEngComm. 18 (33): 6262–6271. doi:10.1039/c6ce01203e.
  18. ^ Bao, N.; et al. (2007). "Facile Cd−Thiourea Complex Thermolysis Synthesis of Phase-Controlled CdS Nanocrystals for Photocatalytic Hydrogen Production under Visible Light". The Journal of Physical Chemistry C. 111 (47): 17527–17534. doi:10.1021/jp076566s.
  19. ^ Foster, H. M., and Snyder, H. R. (1963). "4-Methyl-6-hydroxypyrimidine". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 4, p. 638.
  20. ^ Dodson, R. M. & King, L. C. (1945). "The reaction of ketones with halogens and thiourea". J. Am. Chem. Soc. 67 (12): 2242–2243. doi:10.1021/ja01228a059. PMID 21005695.
  21. ^ "Tarn-X PRO Tarnish Remover" (PDF). The Betty Mills Company, Inc. Archived (PDF) from the original on 2021-06-06. Retrieved 2021-06-06.
  22. ^ "Hagerty Silver Dip". J.L. Smith & Co. Archived from the original on 2021-06-06. Retrieved 2021-06-06.
  23. ^ Expedited Cancer Potency Values and Proposed Regulatory Levels for Certain Proposition 65 Carcinogens (PDF) (Report). April 1992. Archived (PDF) from the original on 2022-01-21. Retrieved 2022-06-18.
  24. ^ Esposito, Anthony (July 13, 2007). "Peñoles, UAM unveil pilot thiourea Au-Ag leaching plant in Mexico". Business News Americas. Archived from the original on 17 February 2009.
  25. ^ Kauffman, George B. (January 1983). "Nikolaĭ Semenovich Kurnakov, the reaction (1893) and the man (1860–1941) a ninety-year retrospective view". Polyhedron. 2 (9): 855–863. doi:10.1016/S0277-5387(00)81400-X. ISSN 0277-5387. Archived from the original on 2021-03-28. Retrieved 2020-12-09.
  26. ^ "Thiourea and its properties". September 11, 1986. Archived from the original on May 27, 2010. Retrieved January 6, 2012.

Further reading

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