Isothiouronium Explained

In organic chemistry, isothiouronium is a functional group with the formula [RSC(NH<sub>2</sub>)<sub>2</sub>]+ (R = alkyl, aryl) and is the acid salt of isothiourea. The H centres can also be replaced by alkyl and aryl. Structurally, these cations resemble guanidinium cations. The CN2S core is planar and the C–N bonds are short.[1]

Synthesis

Salts comprising these cations are typically prepared by alkylation of thiourea:

SC(NH2)2 + RX → [RSC(NH<sub>2</sub>)<sub>2</sub>]+X

Reactions

Hydrolysis of isothiouronium salts gives thiols.

[RSC(NH<sub>2</sub>)<sub>2</sub>]+X + NaOH → RSH + OC(NH2)2 + NaX

Isothiouronium salts in which the sulfur has been alkylated, such as S-methylisothiourea hemisulfate (CAS number: 867-44-7), will convert amines into guanidinium groups. This approach is sometimes called the Rathke synthesis[2] after Bernhard Rathke[3] who first reported it in 1881.[4]

RNH2 + [CH<sub>3</sub>SC(NH<sub>2</sub>)<sub>2</sub>]+X → [CH<sub>3</sub>N(H)C(NH<sub>2</sub>)<sub>2</sub>]+X + CH3SH

Chelating resins with isothiouronium groups are used to recover mercury and other noble metals including platinum from solutions.[5]

References

  1. 10.1107/S0108270198008166 . S-Benzylisothiouronium Chloride . 1998 . Barker . J. . Powell . H. R. . Acta Crystallographica Section C . 54 . 12 . 2019.
  2. Palmer. David C.. S-Methylisothiourea. E-EROS Encyclopedia of Reagents for Organic Synthesis. 2001. 10.1002/047084289X.rm199s. 0471936235.
  3. Heinrich Bernhard Rathke. (1840-1923). Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 8 October 1924. 57. 9. A83–A92. 10.1002/cber.19240570929. free.
  4. Rathke. B.. Ueber Derivate und Constitution des Schwefelharnstoffs. Berichte der Deutschen Chemischen Gesellschaft. July 1881. 14. 2. 1774–1780. 10.1002/cber.18810140247.
  5. Web site: Purolite S920 Isothiouronium Chelating Resin . Purolite . 2012-09-07 . 2016-03-04 . https://web.archive.org/web/20160304025747/http://www.purolite.com/default.aspx?RelID=606267&ProductID=19 . dead .