Glycoluril

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Glycoluril
Glycoluril.svg
Names
IUPAC name
Tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione
Other names
Acetylenediurea; Acetyleneurea; Acetylenediureine; Acetylene carbamide; Glyoxalbiuret; Glyoxaldiureine; Glyoxaldiurene
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.007.111 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C4H6N4O2/c9-3-5-1-2(7-3)8-4(10)6-1/h1-2H,(H2,5,7,9)(H2,6,8,10)
    Key: VPVSTMAPERLKKM-UHFFFAOYSA-N
  • InChI=1/C4H6N4O2/c9-3-5-1-2(7-3)8-4(10)6-1/h1-2H,(H2,5,7,9)(H2,6,8,10)
    Key: VPVSTMAPERLKKM-UHFFFAOYAG
  • C12C(NC(=O)N1)NC(=O)N2
Properties
C4H6N4O2
Molar mass 142.118 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Glycoluril is an organic compound with the formula (HC)2(HNC(O)NH)2. It is classified as diurea, consistinng of two cyclic urea groups sharing a two-carbon linker. It is a white powder that has been extensively examined as a precursor to macrocyclic compounds and as a precursor to amino resins used in paints and coatings. [1] Many other applications have been considered.

Contents

Production

Glycoluril can be synthesized by the reaction two equivalents of urea with glyoxal. The reaction is catalyzed by sulfuric acid: [2]

2 OC(NH2)2 + (CHO)2 → (HC)2(HNC(O)NH)2 + 2 H2O

Likewise, using other vicinal carbonyl (or carbonyl hydrate) reactants give derivatives having various functional groups in place of the hydrogen atoms on the carbon chain. [3]

Reactions

The four amide-like hydrogen atoms of glycoluril undergo a variety of reactions. Substitution with halogen atoms gives the tetrachloride and tetrabromide: [2]

(HC)2(HNC(O)NH)2 + 4 Cl2 → (HC)2(ClNC(O)NCl)2 + 4 HCl

Tetrachloromoglycoluril and tetrabromoglycoluril are halogenating agents and potential disinfectants. [4]

Condensation reactions with aldehydes results initially in hydroxyalkylation, but is often pushed to give macrocycles or polymers. One large family of rings are formed from formaldehyde:

(HC)2(HNC(O)NH)2 + 4 CH2O → (HC)2(HOCH2NC(O)NHCH2OH)2

This [tetramethylol glycoluril]] has use as a biocide in water-based paints, in liquid detergents and in care and cleaning agents (in concentrations of 0.1%). [5] It also finds utility as a crosslinker for hydroxyl-containing polymers, as an industrial fungicide and as an accelerator in cements.

6 (HC)2(HOCH2NC(O)NHCH2OH)2 → [(HC)2(CH2NC(O)NHCH2)2]6

These cucurbituril-like chains, rings, and polymers serve as hosts to bind to various neutral and cationic species. [6] [7]

Use

Glycoluril has been assessed as a controlled-release fertilizer, but the economic factors are not favorable. [8]

Tetraacetylglycoluril (TAGU) can be prepared from glycoluril by reaction with acetic anhydride. Tetraacetylglycoluril can be used, but it not very common as a bleach activator for sodium percarbonate in solid detergent formulations because of its slow biodegradability. [9] [10]

The reaction with nitrating acid (concentrated nitric acid and concentrated sulfuric acid) leads to the explosives dinitroglycoluril and tetranitroglycoluril. [11]

References

  1. ↑ Funke, Werner; Hoppe, Lutz; Hasselkus, Jürgen; Curtis, Larry G.; Hoehne, Klaus; Zech, Hans-Joachim; Heiling, Peter; Yamabe, Masaaki; Dören, Klaus; Schupp, Hans; Küchenmeister, Rolf; Schmitthenner, Martin; Kremer, Wolfgang; Wieczorrek, Wolfhart; Gempeler, Hans; Schneider, Wolfgang; White, James W.; Short, Anthony G.; Blank, Werner J.; Calbo, Leonard J.; Plath, Dieter; Wagner, Friedrich; Haller, Werner; Rödder, Karl-Martin (2010). "Paints and Coatings, 2. Types". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.o18_o01. ISBN   978-3-527-30385-4.
  2. 1 2 Meessen, Jozef H.; Petersen, Harro (2000). "Urea". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a27_333. ISBN   3-527-30673-0.
  3. ↑ Petersen, Harro (1973). "Syntheses of Cyclic Ureas by α-Ureidoalkylation". Synthesis (5): 243–292. doi:10.1055/s-1973-22190.
  4. ↑ Frank B. Slezak, Henry Bluestone, Thomas A. Magee, John H. Wotiz (1962), "Preparation of Substituted Glycolurils and Their N-Chlorinated Derivatives", The Journal of Organic Chemistry , vol. 27, no. 6, pp. 2181–2183, doi:10.1021/jo01053a069 {{citation}}: CS1 maint: multiple names: authors list (link)
  5. ↑ Verwendung von Formaldehyd oder Formaldehyd-Abspaltern in Pflege- und Reinigungsmitteln in Privathaushalten (PDF; 53 kB), Vortrag auf der BfR-Fachveranstaltung „Neubewertung von Formaldehyd – Beitrag des BfR zum Verb raucherschutz"
  6. ↑ Sijbesma, R. P.; Kentgens, A. P. M.; Lutz, E. T. G.; van der Maas, J. H.; Nolte, R. J. M. (1993). "Binding features of molecular clips derived from diphenylglycoluril" (PDF). J. Am. Chem. Soc. 115 (20): 8999–9005. Bibcode:1993JAChS.115.8999S. doi:10.1021/ja00073a015. hdl: 2066/16304 . S2CID   96246662.
  7. ↑ Branda, Neil; Grotzfeld, Robert M.; Valdes, Carlos; Rebek, Julius Jr. (1995). "Control of Self-Assembly and Reversible Encapsulation of Xenon in a Self-Assembling Dimer by Acid-Base Chemistry". J. Am. Chem. Soc. 117 (1): 85–88. Bibcode:1995JAChS.117...85B. doi:10.1021/ja00106a010.
  8. ↑ T. Shimidzu (1987), "Glycoluril as a Slow Release Nitrogen Fertilizer", Soil Science and Plant Nutrition , vol. 33, no. 2, pp. 291–298, Bibcode:1987SSPN...33..291S, doi: 10.1080/00380768.1987.10557574 , ISSN   0038-0768
  9. ↑ Mattioda, Georges; Blanc, Alain. "Glyoxal". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a12_491.pub2. ISBN   978-3-527-30673-2.
  10. ↑ Uri Zoller (2008), "Kapitel 16: Application of Surfactants in Environmental Remediation", Handbook of detergents. Part E, Applications (in German), Boca Raton, Florida: CRC Press, ISBN   978-1-4200-1816-5
  11. ↑ J. K. Agrawal, R. D. Hodgson (2007), Organic chemistry of explosives, Chichester: John Wiley & Sons, p. 278, ISBN   978-0-470-02967-1
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