Thiourea

Thiourea (/ajri, ao-/[1][2] ) is an organosulfur 2 Production

compound with the formula SC(NH2 )2 . It is struc-
turally similar to urea, except that the oxygen atom The global annual production of thiourea is around
is replaced by a sulfur atom, but the properties of 10,000 tons.[3] About 40% is produced in Germany, an-
urea and thiourea dier signicantly. Thiourea is a other 40% in China, and 20% in Japan. Thiourea can be
reagent in organic synthesis. Thioureas refers to produced from ammonium thiocyanate, but more com-
a broad class of compounds with the general struc- monly it is produced by the reaction of hydrogen sulde
ture (R1 R2 N)(R3 R4 N)C=S. Thioureas are related to with calcium cyanamide in the presence of carbon diox-
thioamides, e.g. RC(S)NR2 , where R is methyl, ethyl, ide.[3]
etc.

2.1 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.[4]

General chemical structure of a thiourea

Alternatively, N,N -disubstituted thioureas can be pre-

1 Structure and bonding pared by coupling two amines with thiophosgene:[5]

Thiourea is a planar molecule. The C=S bond distance R2 NH + R2 NH + CSCl2 + 2 C5 H5 N

is 1.600.1 for thiourea (as well as many of its deriva- (R2 N)(R2 N)CS + 2 C5 H5 NH+ Cl
tives). The material has the unusual property of chang-
ing to ammonium thiocyanate upon heating above 130 Amines also condense with thiocyanates to give
C. Upon cooling, the ammonium salt converts back to thioureas:[6]
thiourea.
Thiourea occurs in two tautomeric forms. In aqueous so- R2 NH + RNCS (R2 N)(R(H)N)CS
lutions the thione form predominates. The thiol form,
which is also known as an isothiourea, can be encoun-
tered in substituted compounds such as isothiouronium 3 Applications
salts.
The main application of thiourea is in textile
processing.[3]

3.1 Organic synthesis

Thiourea reduces peroxides to the corresponding
diols.[7] The intermediate of the reaction is an unstable

1
2 3 APPLICATIONS

endoperoxide which can only be identied at 100 C. sulde forms when mercuric salts in aqueous solution are
Epidioxide is similar to epoxide except with two oxygen treated with thiourea:
atoms. This intermediate reduces to diol by thiourea.
Hg2+ + SC(NH2 )2 + H2 O HgS + OC(NH2 )2
+ 2 H+

3.2.1 Precursor to heterocycles

Thioureas are used a building blocks to pyrimidine

reduction of cyclic peroxide derivatives. Thus thioureas condense with -dicarbonyl
compounds.[10] The amino group on the thiourea initially
Thiourea is also used in the reductive workup of condenses with a carbonyl, followed by cyclization and
ozonolysis to give carbonyl compounds.[8] Dimethyl sul- tautomerization. Desulfurization delivers the pyrimidine.
de is also an eective reagent for this reaction, but it
is highly volatile (b.p. 37 C) and has an obnoxious
odor whereas thiourea is odorless and conveniently non-
volatile (reecting its polarity).

Similarly, aminothiazoles can be synthesized by the reac-

tion of -haloketones and thiourea.[11]
reduction cleavage of product from ozonolysis

3.2 Source of sulde

Thiourea is commonly employed as a source of sulde,
e.g. for converting alkyl halides to thiols. Such reac-
tions 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)+ The pharmaceuticals thiobarbituric acid and sulfathiazole
2X are prepared using thiourea.[3] 4-Amino-3-hydrazino-5-
mercapto-1,2,4-triazole is prepared by the reaction of
thiourea and hydrazine.
RSC(NH
2)+
2X 3.3 Silver polishing
+ 2 NaOH RSNa + OC(NH2 )2 + NaX
RSNa + HCl RSH + NaCl According to the label on the consumer product, the
liquid silver cleaning product TarnX contains thiourea,
In this example, ethane-1,2-dithiol is prepared from 1,2- a detergent, and sulfamic acid. A lixiviant for gold
dibromoethane:[9] and silver leaching can be created by selectively oxi-
dizing thiourea, bypassing the steps of cyanide use and
C2 H4 Br2 + 2 SC(NH2 )2 smelting.[12]
[C2 H4 (SC(NH2 )2 )2 ]Br2
[C2 H4 (SC(NH2 )2 )2 ]Br2 + 2 KOH 3.4 Organocatalysis
C2 H4 (SH)2 + 2 OC(NH2 )2 + 2 KBr
Substituted thioureas are useful catalysts for organic syn-
Like thioamides, thiourea can serve as a source of sulde thesis. The phenomenon is called thiourea organocataly-
upon reaction with soft metal ions. For example, mercury sis.[13]
 3

3.5 Other uses [9] Speziale, A. J. (1963). Ethanedithiol. Org. Synth.; Coll.
Vol., 4, p. 401
Other industrial uses of thiourea include production of
[10] Foster, H. M., and Snyder, H. R. (1963). 4-Methyl-6-
ame retardant resins, and vulcanization accelerators. hydroxypyrimidine. Org. Synth.; Coll. Vol., 4, p. 638
Thiourea is used as an auxiliary agent in diazo paper,
[11] Dodson, R. M. & King, L. C. (1945). The reaction of
light-sensitive photocopy paper and almost all other types
ketones with halogens and thiourea. J. Am. Chem. Soc.
of copy paper. 67 (12): 22422243. doi:10.1021/ja01228a059. PMID
It is also used to tone silver-gelatin photographic prints. 21005695.

Thiourea is used in the Clifton-Phillips and Beaver bright [12] Anthony Esposito. Peoles, UAM unveil pilot thiourea
and semi-bright electroplating processes.[14] It is also Au-Ag leaching plant - Mexico. Business News Ameri-
used in a solution with tin(II) chloride as an electroless cas (July 13, 2007).
tin plating solution for copper printed circuit boards.
[13] R. Schreiner, Peter (2003). Metal-free organocatalysis
through explicit hydrogen bonding interactions. Chem.
Soc. Rev. 32: 289296. doi:10.1039/b107298f. PMID
4 Safety 14518182.

[14] 81st Universal Metal Finishing Guidebook. Metal Finish-

The LD50 for thiourea is 125 mg/kg for rats (oral).[15] ing Magazine. Fall 2013. p. 285. ISSN 0026-0576.
A goitrogenic eect (enlargement of the thyroid gland) [15] http://gis.dep.wv.gov/tri/cheminfo/msds1385.txt
has been reported for chronic exposure, reecting the
ability of thiourea to interfere with iodide uptake.[3]
6 Further reading
5 References Patai, S., ed. (1977). The Chemistry of double-
bonded functional groups. New York, NY: John Wi-
[1] Thiourea. Oxford Dictionaries. Oxford University ley & Sons. pp. 13551496. ISBN 0-471-92493-8.
Press. Retrieved 2016-01-21.

[2] Thiourea. Merriam-Webster Dictionary. Retrieved

2016-01-21. 7 External links
[3] Bernd Mertschenk, Ferdinand Beck, Wolfgang Bauer INCHEM assessment of thiourea
Thiourea and Thiourea Derivatives in Ullmanns En-
cyclopedia of Industrial Chemistry 2002 by Wiley-VCH International Chemical Safety Card 0680
Verlag GmbH & Co. KGaA. All rights reserved.
doi:10.1002/14356007.a26_803

[4] Koketsu, Mamoru; Kobayashi, Chikashi; Ishi-

hara, Hideharu (2003). Synthesis of N-aryl-S-
alkylthiocarbamates. Heteroatom Chemistry. 14 (4):
374378. doi:10.1002/hc.10163.

[5] Yi-Bo Huang, Wen-Bin Yi, and Chun Cai Thiourea

Based Fluorous Organocatalyst Top Curr Chem 2012,
vol. 308, p. 191212. doi:10.1007/128_2011_248

[6] Miyabe, H.; Takemoto, Y. Discovery and application

of asymmetric reaction by multifunctional thioureas Bull
Chem Soc Jpn 2008, vol. 81, p785.

[7] C. Kaneko; A. Sugimoro & S. Tanaka (1974). A facile

one-step synthesis of cis2-cyclopentene and cis2-
cyclohexene-1,4-diols from the corresponding cyclodi-
enes. Synthesis. 1974 (12): 876877. doi:10.1055/s-
1974-23462.

[8] Gupta, D., Soman, G., and Dev, S. (1982). Thiourea,

a convenient reagent for the reductive cleavage of olen
ozonolysis products. Tetrahedron. 38 (20): 30133018.
doi:10.1016/0040-4020(82)80187-7.
4 8 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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Trilobitealive, DorganBot, MartinBotIII, Jameslwoodward, TXiKiBoT, Flyer22 Reborn, Dragnmn, Chem-awb, Puppy8800, Janstr, Wik-
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Anonymous: 46

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