Chemistry:Glycoluril
Glycoluril is an organic compound with the formula (HC)
2(HNC(O)NH)
2. It is classified as diurea, consisting 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.
Production
Glycoluril can be synthesized by the reaction two equivalents of urea with glyoxal. The reaction is catalyzed by sulfuric acid:[2]
- 2 OC(NH
2)
2 + (CHO)
2 → (HC)
2(HNC(O)NH)
2 + 2 H
2O
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 Cl
2 → (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 CH
2O → (HC)
2(HOCH
2NC(O)NHCH
2OH)
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(HOCH
2NC(O)NHCH
2OH)
2 → [(HC)
2(CH
2NC(O)NHCH
2)
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
- ↑ Funke, Werner; Hoppe, Lutz; Hasselkus, Jürgen; Curtis, Larry G.; Hoehne, Klaus; Zech, Hans-Joachim; Heiling, Peter; Yamabe, Masaaki et al. (2010). "Paints and Coatings, 2. Types". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.o18_o01. ISBN 978-3-527-30385-4.
- ↑ 2.0 2.1 Meessen, Jozef H.; Petersen, Harro (2000). "Urea". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a27_333. ISBN 3-527-30673-0.
- ↑ Petersen, Harro (1973). "Syntheses of Cyclic Ureas by α-Ureidoalkylation". Synthesis (5): 243–292. doi:10.1055/s-1973-22190.
- ↑ 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 27 (6): 2181–2183, doi:10.1021/jo01053a069
- ↑ 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"
- ↑ 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". J. Am. Chem. Soc. 115 (20): 8999–9005. doi:10.1021/ja00073a015. Bibcode: 1993JAChS.115.8999S. https://repository.ubn.ru.nl/bitstream/2066/16304/1/10114.pdf.
- ↑ 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. doi:10.1021/ja00106a010. Bibcode: 1995JAChS.117...85B.
- ↑ T. Shimidzu (1987), "Glycoluril as a Slow Release Nitrogen Fertilizer", Soil Science and Plant Nutrition 33 (2): 291–298, doi:10.1080/00380768.1987.10557574, ISSN 0038-0768, Bibcode: 1987SSPN...33..291S
- ↑ Mattioda, Georges; Blanc, Alain. "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a12_491.pub2.
- ↑ Uri Zoller (2008), "Kapitel 16: Application of Surfactants in Environmental Remediation" (in German), Handbook of detergents. Part E, Applications, Boca Raton, Florida: CRC Press, ISBN 978-1-4200-1816-5
- ↑ 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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