Refernces
10.1021/jo016196i
The study presents a novel method for synthesizing 2-chloroquinolines from 2-vinylanilines using diphosgene in acetonitrile as the solvent. The researchers detail a three-step reaction mechanism involving the generation of phenylisocyanate, quinoline ring formation, and chlorination at the C2 position of the quinoline. The purpose of the chemicals used in the study was to facilitate these steps, with diphosgene reacting with 2-vinylanilines to produce phenyl isocyanate, which then reacts with the acetonitrile to form the quinoline ring. The final step involves the chlorination of the C2 position. This new method eliminates the need for the hazardous use of excess phosphorus oxychloride, which was previously required in the synthesis of 2-chloroquinolines from 2(1H)-quinolinones. The study also discusses the role of acetonitrile as a reactive solvent in the process and provides evidence that the third step, chlorination, is likely the rate-determining step in the reaction.
10.1055/s-1985-31216
The research aims to improve the yield and purity of isocyanide synthesis using phosphoryl chloride and disopropylamine. Traditionally, isocyanides are synthesized by dehydrating formamides, often using reagents like phosgene or diphosgene, which are highly toxic and costly. This study explores an alternative method using phosphoryl chloride combined with disopropylamine as a base. The researchers found that replacing the commonly used triethylamine with disopropylamine significantly enhances the yield and purity of isocyanides, often eliminating the need for chromatographic purification. The method is particularly effective for synthesizing ferrocenylalkyl isocyanides, where other methods fail or produce impurities. The study concludes that this new method is milder, more reproducible, and yields higher purity isocyanides compared to traditional methods, making it a valuable improvement in the field of isocyanide synthesis.
10.1055/s-1988-27683
Yoshibiko Ito et al. describe the preparation of o-di(formamido)arenes through formylation of o-diaminoarenes using phenyl formate, which yielded better results than other formylating agents. The key step involves the dehydration of o-di(formamido)arenes with trichloromethyl chloroformate at low temperatures (-78°C to 0°C) in the presence of triethylamine, resulting in significantly higher yields compared to previous methods. The study reports the synthesis of several new o-disocyanoarenes with yields ranging from 51% to 92%, as detailed in a table that includes product yields, melting points, molecular formulas, IR spectra, and 'H-NMR data. The authors also note that the reaction temperature is crucial for achieving high yields. The synthesized compounds are being investigated for potential applications in polymerization processes.