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Trithioacetone

(Redirected from 2,2,4,4,6,6-hexamethyl-1,3,5-trithiane)

Trithioacetone (2,2,4,4,6,6-hexamethyl-1,3,5-trithiane) is an organic chemical with formula C
9H
18S
3. Its covalent structure is [–C(CH
3)
2–S–]
3, that is, a six-membered ring of alternating carbon and sulfur atoms, with two methyl groups attached to each carbon.[4][2] It can be viewed as a derivative of 1,3,5-trithiane, with methyl-group substituents for all of the hydrogen atoms in that parent structure.

Trithioacetone
Names
Preferred IUPAC name
Hexamethyl-1,3,5-trithiane
Other names
Trithioacetone[1]
Identifiers
3D model (JSmol)
5-19-09-00119
ChEMBL
ChemSpider
ECHA InfoCard 100.011.438 Edit this at Wikidata
EC Number
  • 212-582-5
UNII
  • InChI=1S/C9H18S3/c1-7(2)10-8(3,4)12-9(5,6)11-7/h1-6H3
    Key: NBNWHQAWKFYFKI-UHFFFAOYSA-N
  • C1(SC(SC(S1)(C)C)(C)C)(C)C
Properties
C9H18S3
Molar mass 222.42 g·mol−1
Odor Unpleasant, sulfurous
Density 1.0660 to 1.0700 g/mL[2]
Melting point 21.8°C[3]
Boiling point 107°C/10mmHg[2]
1.5390 to 1.5430[2]
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H315, H319, H335
P261, P264, P271, P280, P302 P352, P304 P340, P305 P351 P338, P312, P321, P332 P313, P337 P313, P362, P403 P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

The compound Trithioacetone is a stable cyclic trimer of thioacetone (propane-2-thione), which by itself is an unstable compound.[5][6] In contrast, the analogous trioxane compound, 2,2,4,4,6,6-hexamethyl-1,3,5-trioxane (Triacetone), with oxygen atoms in place of the sulfur atoms, seems to be unstable, while its corresponding monomer acetone (2-propanone) is stable.

Synthesis

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Trithioacetone was first made in 1889 by Baumann and Fromm, by reaction of hydrogen sulfide with acetone.[6] In the presence of an acidified ZnCl
2 catalyst at 25 °C, one obtains a product that is 60–70% trithioacetone, 30–40% of 2,2-propanedithiol, and small amounts of two isomeric impurities, 3,3,5,5,6,6-hexamethyl-1,2,4-trithiane and 4-mercapto-2,2,4,6,6-pentamethyl-1,3-dithiane.[6] The product can also be obtained by pyrolysis of allyl isopropyl sulfide.[7][8]

Reactions

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Pyrolysis of trithioacetone at 500–650 °C and 5–20 mm of Hg gives thioacetone, that can be collected by a cold trap at −78 °C.

 
Pyrolysis/polymerization between trithioacetone (left) and thioacetone (right).

Uses

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Trithioacetone is found in some flavoring agents. Its FEMA number is 3475.[9][10][11][12]

Toxicity

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The LD50 (oral) in mice is 2.4 g/kg.[9][3]

See also

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References

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  1. ^ "Trithioacetone". Online chemical data sheet, accessed on 2020-01-01.
  2. ^ a b c d TCI America (2020): "Product H1278: 2,2,4,4,6,6-Hexamethyl-1,3,5-trithiane". Online catalog page, accessed on 2020-01-01.
  3. ^ a b NCBI PubChem (2010): "2,2,4,4,6,6-Hexamethyl-1,3,5-trithiane". Online chemical data sheet, accessed on 2020-01-01.
  4. ^ David S. Breslow, Herman Skolnik (2009): Multi-Sulfur and Sulfur and Oxygen Five- and Six-Membered Heterocycles, Part 2; page 712. Volume 68 of Chemistry of Heterocyclic Compounds. ISBN 9780470188330
  5. ^ R. D. Lipscomb and W. H. Sharkey (1970): "Characterization and polymerization of thioacetone". Journal of Polymer Science – Part A: Polymer Chemistry, volume 8, issue 8, pages 2187–2196. doi:10.1002/pol.1970.150080826
  6. ^ a b c William H. Sharkey (1979): "Polymerization through the carbon-sulfur double bond". Polymerization, series Advances in Polymer Science, volume 17, pages 73–103. doi:10.1007/3-540-07111-3_2
  7. ^ William J. Bailey and Hilda Chu (1965): "Synthesis of polythioacetone". ACS Polymer Preprints, volume 6, pages=145–155
  8. ^ Horst Bohme, Hans Pfeifer, and Erich Schneider (1942): "Dimeric thioketones". Berichte der Deutschen Chemischen Gesellschaft, volume 75B, issue 7, pages 900–909. doi:10.1002/cber.19420750722 Note: This early report mistakes the trimer for the monomer.
  9. ^ a b E. J. Moran, O. D. Easterday, and B. L. Oser (1980): "Acute oral toxicity of selected flavor chemicals". Drug and Chemical Toxicology, volume 3, issue 3, pages 249–258.PMID 7449655 doi:10.3109/01480548009002221
  10. ^ World Health Organization (1999): "Trithioacetone[dead link‍]". Online data sheet in the Evaluation of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Accessedd on 2020-01-02.
  11. ^ G. Ohloff and I. Flament (1979): "The Role of Heteroatomic Substances in the Aroma Compounds of Foodstuffs". In Fortschritte der Chemie Organischer Naturstoffe (Progress in the Chemistry of Organic Natural Products), volume 36, pages 231–283. doi:10.1007/978-3-7091-3265-4_2
  12. ^ EUR-Lex (2012): "Table entry 15.009: Trithioacetone". In EU Regulation No. 872/2012, Document 32012R0872, Official Journal of the EU – Series L, volume 267, pages 1–161.
  13. ^ Stuart D. Brewer and Charles P. Haber (1948): "Alkylsilazanes and Some Related Compounds". Journal of the American Chemical Society, volume 70, issue 11, pages 3888–3891. doi:10.1021/ja01191a106
  14. ^ B. M. Mikhova (2008), "NMR Data for Carbon-13 – C6H18Se3Sn3" in Landolt-Börnstein – Group III Condensed Matter, volume 35 Nuclear Magnetic Resonance Data, subvolume D5, Organometallic Compounds. doi:10.1007/978-3-540-74189-3_1362
  15. ^ Martin Dräger, Axel Blecher, Hans-Jürgen Jacobsen, Bernt Krebs (1978): "Molekül- und kristallstruktur von hexamethylcyclo-tristannaselenan [(CH
    3    )
    2    SnSe]
    3    ". Journal of Organometallic Chemistry, volume 161, issue 3, pages 319–325. doi:10.1016/S0022-328X(00)92243-5
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