An intensified chlorination process of 4-nitroaniline in liquid-liquid microflow system

A strategy of dissolving chlorine gas in 1,2-dichloroethane as the chlorine source for the liquid-liquid two-phase chlorination reaction was proposed in this study to resolve the problems of low efficiency,...

Synthesis of the BEAC4ND4 Ionophore from p-t-Butylcalix[4]arene Carboxylic Acid

The BEAC4ND4 ionophore has been successfully synthesized from p-t-butylcalix[4]arene carboxylic acid. The BEAC4ND4 ionophore was obtained in two steps of the synthesis reaction. The first step is the chlorination reaction of p-t-butylcalix[4]arene carboxylic acid with thionyl chloride in dry benzene solvent. The chlorination reaction product is p-t-butylcalix[4]arene acyl chloride in the form of the light brown viscous liquid with a yield of 78.25% and TLC (SiO2, CH3OH: CH2Cl2 = 1: 1 v/v, Rf = 0.65). The second step is the amidation reaction of ethyl 2-aminoacetate with p-t-butylcalix[4]arene acyl chloride in dry tetrahydrofuran solvent. The product of the amidation reaction is p-t-butylcalix[4]arene ethylesteramide or the BEAC4ND4 ionophore in the form of a white solid with the yield of 75.22%, a melting point of 314-316°C, and TLC (SiO2, CH3OH: CH2Cl2 = 1: 1 v/v, Rf = 0.75).

Catalytic Allylic Chlorination of Natural Terpenic Olefins Using Supported and Nonsupported Lewis Acid Catalysts

A mild and convenient method for the allylic chlorination of naturally occurring terpenic olefins was investigated in the presence of different supported and non-supported Lewis acid catalysts. The reaction has been tested on carvone as a model substrate in the presence of sodium hypochlorite as chlorine donor. The scope and limitations of transition metal-based Lewis acid catalysts, stoichiometry, and substrate structure were evaluated. Among the iron precursors used, FeCl3 and FeCl2 provide the promise of a general approach to allylic or vinylic chlorination reaction. Various terpenic olefins were examined in the presence of FeCl3/NaOCl combination system. The catalytic chlorination proceeds under mild conditions with short reaction time and shows a high selectivity affording the corresponding chlorides in good to excellent yields.