Xanthate - Wikipedia, the free encyclopedia

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Xanthate
From Wikipedia, the free encyclopedia

Xanthate usually refers to a salt with the formula ROCS2M+ (R = alkyl;

+

+ [1]

M+ = Na , K ). The name xanthates is derived from Greek

[ksants], meaning yellowish, golden, and indeed most xanthate salts
are yellow. These organosulfur compounds are important in two areas, the
production of cellophane and related polymers from cellulose and
secondly in mining for the extraction of certain ores.[2] They are also versatile intermediates in
organic synthesis. Xanthates also refer to esters of xanthic acid. These esters have the structure ROC
(=S)SR'.

Contents
1 Formation and structure
2 Reactions
2.1 As ligands
3 Industrial applications
4 Related compounds
5 Environmental impacts
6 References

Formation and structure

Xanthate salts are produced by the reaction of an alcohol with sodium or potassium hydroxide and
carbon disulfide:[2][3]
ROH + CS2 + KOH ROCS2K + H2O
The reaction involves the attack of the alkoxide salt. For example, sodium ethoxide gives sodium
ethyl xanthate. Virtually any alcohol can be used in this reaction. Technical grade xanthate salts are
usually of 9095% purity. Impurities include alkali-metal sulfide, sulfate, trithiocarbonates,
thiosulfate, sulfite, or carbonate as well as residual raw material such as alcohol and alkali
hydroxide. These salts are available commercially as powder, granules, flakes, sticks, and solutions
are available. China is a major exporter of granules.
Some commercially important xanthate salts include:

sodium ethyl xanthate CH3CH2OCS2Na,

potassium ethyl xanthate, CH3CH2OCS2K,
sodium isopropyl xanthate
sodium isobutyl xanthate
potassium amyl xanthate

The OCS2 core of xanthate salts and esters is characteristically planar. The central carbon is sp2hybridized.

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Reactions
Xanthate salts characteristically decompose in acid:
ROCS2K + HCl ROH + CS2 + KCl
This reaction is the reverse of the method for the preparation of the xanthate salts. The intermediate
in the decomposition is the xanthic acid, ROC(S)SH, which can be isolated in certain cases.
Xanthate anions also undergo alkylation to give xanthate esters, which are generally stable:[4]
ROCS2K + R'X ROC(S)SR' + KX
The C-O bond in these compounds are susceptible to cleavage by the BartonMcCombie
deoxygenation, which provides a means for deoxygenation of alcohols.
They can be oxidized to the so-called dixanthogens:
2 ROCS2Na + Cl2 ROC(S)S2C(S)OR + 2 NaCl

As ligands
Analogous to their S-alkylation, xanthates bind to transition metal cations as bidentate ligands. The
charge-neutral complexes are soluble in organic solvents.[5][6]

Industrial applications
Cellulose reacts with carbon disulfide (CS2) in
presence of sodium hydroxide (NaOH) to
produces sodium cellulose xanthate, which upon
neutralization with sulfuric acid (H2SO4) gives
viscose rayon or cellophane paper (Sellotape or
Scotch Tape).
Xanthate salts are used as flotation agents in
mineral processing. They are intermediates in the
Chugaev elimination process and are used to
control radical polymerisation under the RAFT
process, also termed MADIX (macromolecular
design via interchange of xanthates).

Related compounds
Rarely encountered, thioxanthates arise by the
reaction of CS2 with thiolate salts. For example,
sodium ethylthioxanthate has the formula
C2H5SCS2Na. Dithiocarbamates are also related

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compounds, and are more useful. They arise

from the reaction of the amine with CS2. For
example, sodium diethyldithiocarbamate has the
formula (C2H5)2NCS2Na.

Environmental impacts
Xanthates may be toxic to aquatic biota at
concentrations of less than 1 mg/L.[7] Water
downstream of mining operations can be
contaminated.[8]

References
1. IUPAC does not recommend the use of the
term xanthate, although it is in current use in
the scientific literature: "IUPAC

Formation of sodium cellulose xanthate starting

from cellulose (top)

definition" (http://goldbook.iupac.org/goldbook/X06696.html).
2. Kathrin-Maria Roy "Xanthates" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH,
Weinheim. doi:10.1002/14356007.a28 423 (https://dx.doi.org/10.1002%2F14356007.a28+423)
3. This report gives a detailed procedure for the potassium ethyl xanthate: Charles C. Price and Gardner W.
Stacy (1948). "p-nitrophenyl sulfide" (http://www.orgsyn.org/demo.aspx?prep=CV3P0667). Org. Synth.
28: 82.; Coll. Vol. 3, p. 667
4. Fabien Gagosz and Samir Z. Zard (1948). "A Xanthate-Transfer Approach to Trifluoromethylamines" (http://www.orgsyn.org/demo.aspx?prep=V84P0032). Org. Synth. 84: 32.; Coll.
Vol. 11, p. 212
5. Galsbl, F.; Schffer, C. E. (1967). "Inorganic Syntheses". Inorganic Syntheses 10. p. 42.
doi:10.1002/9780470132418.ch6 (https://dx.doi.org/10.1002%2F9780470132418.ch6).
ISBN 9780470132418. |chapter= ignored (help)
6. Olav Foss Xanthates and Dithiocarbamates of Selenium(II) and Tellurium(II), 1953 vol. 4,, Pages: 91
93. doi:10.1002/9780470132357.ch32 (https://dx.doi.org/10.1002%2F9780470132357.ch32)
7. Besser, J.; Brumbaugh, W.; Allert, A.; Poulton, B.; Schmitt, C.; Ingersoll, C. (2009). "Ecological impacts
of lead mining on Ozark streams: toxicity of sediment and pore water". Ecotoxicology and environmental
safety 72 (2): 516526. doi:10.1016/j.ecoenv.2008.05.013 (https://dx.doi.org/10.1016%
2Fj.ecoenv.2008.05.013). PMID 18603298 (https://www.ncbi.nlm.nih.gov/pubmed/18603298).
8. Xu, Y.; Lay, J. P.; Korte, F. (1988). "Fate and effects of xanthates in laboratory freshwater systems".
Bulletin of Environmental Contamination and Toxicology 41 (5): 683689. doi:10.1007/BF02021019
(https://dx.doi.org/10.1007%2FBF02021019). PMID 3233367
(https://www.ncbi.nlm.nih.gov/pubmed/3233367).

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Categories: Salts Functional groups Organosulfur compounds
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