|Preferred IUPAC name
3D model (JSmol)
|Molar mass||76.12 g/mol|
|Melting point||182 °C (360 °F; 455 K)|
|142 g/l (25 °C)|
|Carc. Cat. 3|
Repr. Cat. 3
Dangerous for the environment (N)
|R-phrases (outdated)||R22, R40, R51/53, R63|
|S-phrases (outdated)||(S2), S36/37, S61|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
|what is ?)(|
Thiourea (//) is an organosulfur compound with the formula SC(NH2)2 . It is structurally similar to urea, except that the oxygen atom is replaced by a sulfur atom, but the properties of urea and thiourea differ significantly. Thiourea is a reagent in organic synthesis. "Thioureas" refers to a broad class of compounds with the general structure (R1R2N)(R3R4N)C=S. Thioureas are related to thioamides, e.g. RC(S)NR2, where R is methyl, ethyl, etc.
Structure and bonding
Thiourea is a planar molecule. The C=S bond distance is ±0.1 Å for thiourea (as well as many of its derivatives). The material has the unusual property of changing to 1.60ammonium thiocyanate upon heating above °C. Upon cooling, the ammonium salt converts back to thiourea. 130
Thiourea occurs in two tautomeric forms, of which the thione form predominates in aqueous solutions. The equilibrium constant has been calculated as being Keq = 1.04·10−3. The thiol form, which is also known as an isothiourea, can be encountered in substituted compounds such as isothiouronium salts.
The global annual production of thiourea is around 10,000 tons. 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 produced by the reaction of hydrogen sulfide with calcium cyanamide in the presence of carbon dioxide.
Synthesis of substituted thioureas
Many derivatives of thiourea are useful in organocatalysis. N,N′-unsubstituted thioureas can be generally prepared by treating the corresponding cyanamide with "LiAlHSH" in the presence of 1 N HCl in anhydrous diethyl ether. The "LiAlHSH" is prepared by treating lithium aluminium hydride with elemental sulfur.
- R2NH + R′2NH + CSCl2 + 2 C5H5N → (R2N)(R′2N)CS + 2 C5H5NH+Cl−
Amines also condense with thiocyanates to give thioureas:
- R2NH + R′NCS → (R2N)(R′(H)N)CS
The main application of thiourea is in textile processing.
Thiourea reduces peroxides to the corresponding diols. The intermediate of the reaction is an unstable endoperoxide which can only be identified at . Epidioxide is similar to −100 °Cepoxide except with two oxygen atoms. This intermediate reduces to diol by thiourea.
Thiourea is also used in the reductive workup of ozonolysis to give carbonyl compounds. Dimethyl sulfide is also an effective reagent for this reaction, but it is highly volatile (b.p. ) and has an obnoxious odor whereas thiourea is odorless and conveniently non-volatile (reflecting its polarity). 37 °C
Source of sulfide
Thiourea is commonly employed as a source of sulfide, e.g. for converting alkyl halides to thiols. Such reactions proceed via the intermediacy of isothiuronium salts. The reaction capitalizes on the high nucleophilicity of the sulfur center and easy hydrolysis of the intermediate isothiouronium salt:
- CS(NH2)2 + RX → RSC(NH
+ 2 NaOH → RSNa + OC(NH2)2 + NaX
- RSNa + HCl → RSH + NaCl
- 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
- Hg2+ + SC(NH2)2 + H2O → HgS + OC(NH2)2 + 2 H+
Precursor to heterocycles
Thioureas are used as building blocks to pyrimidine derivatives. Thus thioureas condense with β-dicarbonyl compounds. The amino group on the thiourea initially condenses with a carbonyl, followed by cyclization and tautomerization. Desulfurization delivers the pyrimidine.
According to the label on the consumer product, the liquid silver cleaning product TarnX contains thiourea, a detergent, and sulfamic acid. A lixiviant for gold and silver leaching can be created by selectively oxidizing thiourea, bypassing the steps of cyanide use and smelting.
Other industrial uses of thiourea include production of flame retardant resins, and vulcanization accelerators.
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.
Thiourea is used in the Clifton-Phillips and Beaver bright and semi-bright electroplating processes. It is also used in a solution with tin(II) chloride as an electroless tin plating solution for copper printed circuit boards.
- Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 98, 864. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
- "Thiourea". Oxford Dictionaries. Oxford University Press. Retrieved 2016-01-21.
- "Thiourea". Merriam-Webster Dictionary. Retrieved 2016-01-21.
- 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.
- Bernd Mertschenk, Ferdinand Beck, Wolfgang Bauer "Thiourea and Thiourea Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry 2002 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved. doi:10.1002/14356007.a26_803
- Koketsu, Mamoru; Kobayashi, Chikashi; Ishihara, Hideharu (2003). "Synthesis of N-aryl-S-alkylthiocarbamates". Heteroatom Chemistry. 14 (4): 374–378. doi:10.1002/hc.10163.
- Yi-Bo Huang, Wen-Bin Yi, and Chun Cai "Thiourea Based Fluorous Organocatalyst" Top Curr Chem 2012, vol. 308, p. 191–212. doi:10.1007/128_2011_248
- Miyabe, H.; Takemoto, Y. "Discovery and application of asymmetric reaction by multifunctional thioureas" Bull Chem Soc Jpn 2008, vol. 81, p785ff.
- C. Kaneko; A. Sugimoro & S. Tanaka (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.
- 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.
- Speziale, A. J. (1963). "Ethanedithiol". Organic Syntheses.; Collective Volume, 4, p. 401
- Foster, H. M., and Snyder, H. R. (1963). "4-Methyl-6-hydroxypyrimidine". Organic Syntheses.; Collective Volume, 4, p. 638
- 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.
- Anthony Esposito. "Peñoles, UAM unveil pilot thiourea Au-Ag leaching plant - Mexico". Business News Americas (July 13, 2007).
- R. Schreiner, Peter (2003). "Metal-free organocatalysis through explicit hydrogen bonding interactions". Chem. Soc. Rev. 32: 289–296. doi:10.1039/b107298f. PMID 14518182.
- 81st Universal Metal Finishing Guidebook. Metal Finishing Magazine. Fall 2013. p. 285. ISSN 0026-0576.
- Patai, S., ed. (1977). The Chemistry of double-bonded functional groups. New York, NY: John Wiley & Sons. pp. 1355–1496. ISBN 0-471-92493-8.