The Influence of a Terminal Chlorine Substituent on the Kinetics and the Mechanism of the Solvolyses of n-Alkyl Chloroformates in Hydroxylic Solvents

A previous study of the effect of a 2-chloro substituent on the rates and the mechanisms of the solvolysis of ethyl chloroformate is extended to the effect of a 3-chloro substituent on the previously studied solvolysis of propyl chloroformate and to the effect of a 4-chloro substituent on the here reported rates of solvolysis of butyl chloroformate. In each comparison, the influence of the chloro substituent is shown to be nicely consistent with the proposal, largely based on the application of the extended Grunwald–Winstein equation, of an addition-elimination mechanism for solvolysis in the solvents of only modest solvent ionizing power, which changes over to an ionization mechanism for solvents of relatively high ionizing power and low nucleophilicity, such as aqueous fluoroalcohols with an appreciable fluoroalcohol content.

Palladium-catalyzed C8–H alkoxycarbonylation of 1-naphthylamines with alkyl chloroformates

A simple and efficient protocol for palladium-catalyzed C8–H alkoxycarbonylation of 1-naphthylamine derivatives with alkyl chloroformates has been developed.

Synthesis of phthalic acid derivatives via Pd-catalyzed alkoxycarbonylation of aromatic C–H bonds with alkyl chloroformates

A Pd(ii)-catalyzed alkoxycarbonylation of benzamide β-C–H bonds and 2-phenylacetamide γ-C–H bonds with alkyl chloroformates has been reported.

Novel Conversion of 4-Aminoquinolines to New Tricyclic (R,S)-3-Methylazeto[3,2-c] Quinolin-2(2aH)-Ones and Versatile One Step Synthesis of N-(Quinolin-4-yl) Carbamates from 4-Aminoquinolines

Reaction of 4-aminoquinolines with 4-nitrophenyl chloroformate have resulted in finding a novel transformation of 4-aminoquinolines to tricyclic (R,S)-3-methylazeto[3,2-c]quinolin-2(2aH)-ones. The structure of azeto-quinolinone was determined via spectroscopic and chemical methods. Various alcohols were used as nucleophiles to open the 1-azetinone ring to give the corresponding N-(quinolin-4-yl)carbamates in good yields. We also found a new and versatile one step synthesis of N-(quinolin-4-yl)carbamates by reacting 4-aminoquinolines with alkyl chloroformates in the presence of anhyd K2CO3 in acetonitrile.