Primary amides are known to be oxidatively rearranged to the corresponding isocyanates when they are treated with lead tetraacetate (LTA) and with phenyliodosoacetate (PIA). The isocyanates can be isolated when the reaction is carried out in nonaqueous solvents [I]. The isocyanates are converted int
Reaction Pathway and Rate-Determining Step of the Schmidt Rearrangement/Fragmentation: A Kinetic Study
β Scribed by Akimoto, Ryo; Tokugawa, Takehiro; Yamamoto, Yutaro; Yamataka, Hiroshi
- Book ID
- 118745863
- Publisher
- American Chemical Society
- Year
- 2012
- Tongue
- English
- Weight
- 357 KB
- Volume
- 77
- Category
- Article
- ISSN
- 0022-3263
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π SIMILAR VOLUMES
## Abstract A consecutive singleβroute reaction is considered. When two (groups of) steps compete in controlling the overall reaction rate, there exists a general rule that the earlier step in the flow of the overall reaction tends to be rateβdetermining with the increase of the reaction affinity.
Overwhelming evidence has been previously reported for the existence of the so-called "dimer nucleophile mechanism" in aromatic nucleophilic substitutions by amines in aprotic solvents, for which the most prominent feature is the fourth-order kinetics (third order in amine) that has been observed wi