Addition of carbon-centered radicals to imines and related compounds

The first nickel-catalyzed cross-coupling reactions between fluoroarenes and aryl organometallics using commercially available ligands are described. The nickel-catalyzed cross-coupling reactions between aryl Grignard reagents and fluoroazines and -diazines occurred in THF at room temperature using commercially available 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, or 1,1‘-bis(diphenylphosphino)ferrocene as ligand. Various fluoro substrates such as pyridines, diazines (pyrazine, pyridazine), benzodiazines (quinoxaline), and quinolines were successfully involved in the reaction with phenylmagnesium halides (phenylmagnesium chloride, 2-methoxyphenylmagnesium bromide, and 4-methoxyphenylmagnesium bromide). The conditions used also allowed the cross-coupling of 4-fluorotoluene with arylmagnesium reagents.

Cross-coupling reactions of phenylmagnesium halides with fluoroazines and fluorodiazines.

2.08 – Pyridines and their Benzo Derivatives: (v) Synthesis

Rate constants for aryl radical cyclization to aldimines : synthesis of tetrahydroisoquinolines by fast 6-endo closures to carbon

Short contact time reactions of large organic free radicals

Pyrolysis of some methyl- and benzylindoles

Maleic hydrazide (MH) has been pyrolysed at 600°C in our controlled pyrolysis apparatus. During pyrolysis volatile compounds distil out ahead of the moving heated zone and are not extensively repyrolysed, while those substances which are absorbed by pyrolysand or are relatively nonvolatile are repyrolysed. Also, reactive intermediates can react with one another or with unpyrolysed material. Pyrolysis products determined include CO2 (24 wt%), CO (2 wt%), HCN (3 wt%), NH3 (9 wt%) and N2 (3 wt%). The gases identified account for 41 % of the maleic hydrazide pyrolysed. An additional 50% of the material pyrolysed remains as a black solid having the approximate composition C15H15N5O2. Approximately 1 % of the maleic hydrazide is unchanged. Thus, the fate of 92% of the maleic hydrazide can be accounted for. A trace amount of hydrazine could be detected. The results obtained using controlled pyrolysis are compared with results obtained by us and others using different pyrolytic conditions.

Charles F. Mayer

Papers

Pyrolysis of some methyl- and benzylindoles

Controlled pyrolysis of maleic hydrazide

Controlled pyrolysis of maleic hydrazide