Oxidative carbonylation of primary amines to ureas using tungsten carbonyl catalysts

Organometallics

Volumn 17, Issue 18, 1998, Pages 4037-4041

  McCusker, Jennifer E ^a   Logan, Jennifer ^a   McElwee White, Lisa ^a  

^a University of Florida ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000974352     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980389n     Document Type: Article

References (39)

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2. For monographs on the topic, see: (a) Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V. Carbonylation: Direct Synthesis of Carbonyl Compounds; Plenum: New York, 1991. (b) Sheldon, R. A. Chemicals from Synthesis Gas; Dordrecht: Boston, 1983. (c) Wender, I.; Pino, P. Organic Syntheses via Metal Carbonyls; Wiley-Interscience: New York, 1968.
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29. + would then yield the urea. We cannot rule out this alternative. However, we still favor the mechanism shown in Scheme 1 due to the literature precedent in ref 6 and our observation of small amounts of isocyanates in some of the reaction mixtures by GC. The GC evidence should be viewed with some skepticism since the observed isocyanates could arise from cracking of labile species in the injection port. However, their presence does provide some support for Scheme 1.
30. Note that since dimer 1 is cleaved to mononuclear complexes in the presence of amines, each tungsten is turning over six times. However, since the tungsten was added to the reaction mixtures in the form of 1, the yields are reported on this basis.
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37. 6 involve photolysis. However, the more complex carbonylation reaction mixtures may provide alternative pathways for oxidation.
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39. Proper safety precautions against explosion hazards were employed during this work.