A high temperature investigation using microwave synthesis for electronically and sterically disfavoured substrates of the Newman-Kwart rearrangement

Tetrahedron

Volumn 63, Issue 19, 2007, Pages 4120-4125

  Moseley, Jonathan D ^a   Lenden, Philip ^a  

^a ASTRAZENECA   (United Kingdom)

Author keywords

Microwave; Newman Kwart; Rearrangement

Indexed keywords

ARTICLE; BIOCHEMICAL EQUIPMENT; ELECTRONICS; HIGH TEMPERATURE; MICROWAVE IRRADIATION; PRIORITY JOURNAL; REACTION ANALYSIS;

EID: 34047252164     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2007.02.101     Document Type: Article

References (47)

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21. It is worth noting the pioneering work of Strauss in the mid 1990s, who reported on the design of both prototype batch and continuous flow microwave reactors, which were capable of reaching 260 °C. This was judged to meet the needs of most organic chemistry reactions and so ∼250 °C is the limit that most commercial microwave reactors have subsequently followed. See:
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36. Caution: This procedure takes the temperature (and potentially the pressure) above the standard operating limits of the CEM Discover's reaction tubes, which are rated to 300 °C and 300 psi (20 bar). However, we have suffered no failures using this technique on a small scale (2-4 mL), probably because this reaction generates no pressure other than the mechanical pressure of the solvent. This procedure is only possible on the CEM Discover due to the placement of the IR pyrometer at the base of the reaction tube. Some larger-scale instruments also have IR pyrometers reading the temperature at the base of their respective reaction tubes, but these are not intended to be accurate, and are for approximate temperature monitoring between reaction vessels in multiple vessel instruments (e.g., Anton Paar Synthos 3000, CEM Mars).
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47. Newman and Karnes demonstrated that the rearrangement of the 4-nitrophenyl-O-thiocarbamate was first order up to ∼0.2 M, and assumed that this would be true for other substrates (Ref. 2a). We have confirmed this for several other compounds in dilute solutions (up to ∼0.4 M); Moseley, J. D.; Cox, B. G. Unpublished results.