N Chloroaniline

In a series of papers beginning in 1968, Gassman and co-workers examined the solvolysis of N-terf-butyl-N-chloroanilines (14, Scheme 8) in MeOH and In EtOH buffered with AcOH/NaOAc, the solvolysis rate constants for 14a-f correlated well with The for the reaction was —6.4,... 

By the late 1980s it was clear that a significant number of thermal and photochemical reactions of arylhydroxylamines and their derivatives, N-chloroanilines, aryl azides, anthranilium salts, and other compounds could be explained in terms of nitrenium ions or transition states that resembled nitrenium ions. Since no monoarylnitrenium ion had been directly observed, and data on the lifetimes and quantitative reactivity/selectivity of these species were not available, it was not possible to assess whether the reactions that had been observed were due to free ions, or ion pairs, or preassociation processes. In many cases Sn2 reactions could not be ruled out because appropriate kinetics experiments had not been performed. Most authors had attributed the presence of reduction products in thermal and photochemical reactions to triplet ions, but calculations suggested that the triplet species may not be accessible in thermal processes. It was clear that singlet ions could be reduced under certain conditions, so the presence of the... 

Chloroaniline, CgHgClN. Its three isomers of the formula Cl.C.H, NH0 are described in Ref 1. There is also an isomer, CgHg. NHC1, called N-Chloroaniline or Phenylchloramine... 

Figure 5.5.10. Solvent effect on the decomposition of Figure 5.5.11. Solvent effect on the decomposition of N-chloroaniline in acetonitrile-water mixtures. The N-chloroleucine in 2-propanol-water mixtures. The smooth curve is drawn with eq. 5.5.49. (Reproduced smooth curve is drawn with eq. 5.5.49. (Reproduced...

A -Chloroanilines have sometimes been used to prepare nitrenes (or nitrenoids) recently a nitrenoid (11), which is produced by treating N-chloroaniline with butyllithium at — 100°C, has been trapped with trichlorosilane. " ... 

A useful method for ort/io-alkylation of aromatic amines is based on [2,3]-sigmatropic rearrangement of 5-anilinosulfonium ylides. These ylides are generated from anilinosulfonium ions, which can be prepared from N-chloroanilines and sulfides. 

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