Application of Deep Eutectic Solvents in the Synthesis of Substituted 2-Mercaptoquinazolin-4(3H)-Ones: A Comparison of Selected Green Chemistry Methods

In this study, deep eutectic solvents (DESs) were used as green and eco-friendly media for the synthesis of substituted 2-mercaptoquinazolin-4(3H)-ones from different anthranilic acids and aliphatic or aromatic isothiocyanates. A model reaction on anthranilic acid and phenyl isothiocyanate was performed in 20 choline chloride-based DESs at 80 °C to find the best solvent. Based on the product yield, choline chloride:urea (1:2) DES was found to be the most effective, while DESs acted both as solvents and catalysts. Desired compounds were prepared with moderate to good yields using stirring, microwave-assisted, and ultrasound-assisted synthesis. Significantly, higher yields were obtained with mixing and ultrasonication (16–76%), while microwave-induced synthesis showed lower effectiveness (13–49%). The specific contribution of this research is the use of DESs in combination with the above-mentioned green techniques for the synthesis of a wide range of derivatives. The structures of the synthesized compounds were confirmed by 1H and 13C NMR spectroscopy.

A Simple and Efficient Diversity-Oriented Synthesis of New Substituted 3-(Arylamino)-6,7-dihydro-1H-indazol-4(5H)-ones by a KOH-Assisted One-Pot Reaction

A novel, simple, and straightforward combinatorial method for the synthesis of new substituted 3-(arylamino)-6,7-dihydro-1H-indazol-4(5H)-one derivatives has been developed. The synthesis was achieved via a one-pot three-component reaction of aromatic isothiocyanates, substituted 1,3-cyclohexanediones, and hydrazine hydrate in dimethyl sulfoxide as a polar aprotic solvent. This methodology has the advantages of mild reaction conditions, good to excellent yields, easily available starting materials, operational simplicity, and easy workup. This chemistry provides an efficient synthetic strategy to diversity-oriented construction of the 3-arylaminoindazole skeleton.

Site-directed spin labeling of 2′-amino groups in RNA with isoindoline nitroxides that are resistant to reduction

2'-Amino groups in RNA were selectively spin labeled with reductively stable isoindoline nitroxides through a high-yielding reaction with aromatic isothiocyanates.

Herbicidal activity of eight isothiocyanates on Texas panicum (Panicum texanum), large crabgrass (Digitaria sanguinalis), and sicklepod (Senna obtusifolia)

A greenhouse experiment was conducted to evaluate the herbicidal activity of five aliphatic (ethyl, propyl, butyl, allyl, and 3-methylthiopropyl) and three aromatic (phenyl, benzyl, 2-phenylethyl) isothiocyanates on Texas panicum, large crabgrass, and sicklepod. All isothiocyanates were applied to soil at 0, 10, 100, 1,000, and 10,000 nmol g−1of soil and incorporated. Weed emergence was generally stimulated at the lower isothiocyanate concentrations, but all isothiocyanates provided 37% or more suppression of each species at the highest concentration. Propyl and allyl isothiocyanate were most effective in suppressing Texas panicum, with 50% effective dose (ED50) values of 345 and 409 nmol g−1of soil. All aliphatic isothiocyanates reduced Texas panicum density by at least 98%. Allyl and 3-methylthiopropyl isothiocyanate were the most effective aliphatics on large crabgrass, with density reductions of 98 and 100%, respectively. All aromatic isothiocyanates reduced large crabgrass density by 86 to 96%. Sicklepod was generally the most tolerant of the three species evaluated, with ED50values for ethyl, propyl, and butyl isothiocyanate being greater than the evaluated concentrations. Maximum reduction in sicklepod density was 72, 68, 65, and 62%, which was achieved with allyl, benzyl, 3-methylthiopropyl, and phenyl isothiocyanate, respectively. This research shows that soil-applied and incorporated isothiocyanates are effective in suppressing some important weeds of the southeastern United States, but effectiveness of each isothiocyanate varies among species. Application techniques that minimize loss of volatile isothiocyanates may further improve their potential as an effective means of controlling these and other troublesome weeds.