Synthesis of monosubstituted thioureas by vapour digestion and mechanochemical amination of thiocarbamoyl benzotriazoles

Đud, Mateja; Magdysyuk, Oxana V.; Margetić, Davor; Štrukil, Vjekoslav (2016) Synthesis of monosubstituted thioureas by vapour digestion and mechanochemical amination of thiocarbamoyl benzotriazoles. Green Chemistry, 18 (9). pp. 2666-2674. ISSN 1463-9262

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Abstract

Thiocarbamoyl benzotriazoles, as safe and easy-to-handle isothiocyanate equivalents, were quantitatively converted to N-monosubstituted thioureas by vapour digestion synthesis under an ammonia atmosphere. This simple, but timely process provided a synthetic platform that enabled the “slow” amination reaction to be successfully transformed into a rapid one aided by mechanochemical milling. The ammonium chloride/sodium carbonate equimolar mixture allowed in situ formation of ammonia under ball-milling conditions. This novel and green approach yielded aromatic and aliphatic primary thioureas in near-quantitative isolated yields with workup entirely based on using only water. In addition, the molecular and crystal structures of selected polyaromatic primary thioureas were determined from the synchrotron powder diffraction data.

Item Type:

Article

Additional Information:

This work has been supported by the Croatian Science Foundation grant no. 9310. We gratefully acknowledge Dr Ernest Mestrovic (Pliva TAPI) for collecting the powder X-ray diffraction patterns of intermediates and thioureas. We also thank Diamond Light Source for access to beamline I12-JEEP that contributed to the results presented here.

Uncontrolled Keywords:

Thiourea ; synthesis ; mechanochemistry ; amination

Subjects:

NATURAL SCIENCES > Chemistry
NATURAL SCIENCES > Chemistry > Organic Chemistry

Divisions:

Division of Organic Chemistry and Biochemistry

Projects: