The reduction of nitroarenes is the main methodology to produce anilines, important precursors of building blocks, dyes, and drugs. Continuing our goal of describing sustainable methodologies for the reduction of nitroarenes to their respective anilines, herein we compile selected reaction protocols, using organic medium, reported from 2017 to 2023, in order to provide a comprehensive and complementary view of the new processes and catalysts developed during this period. anilines blocks dyes drugs protocols medium 201 2023 period 20 202 2

This work describes the multigram-scale synthesis of the building-block N1 (7 chloroquinolin-4-yl)ethane-1,2-diamine via sonochemistry and its use in the synthesis of seven new quinoline-thiazole hybrids endowed with interesting anticancer activity. Target compounds were planned based on the drugs chloroquine and primaquine and the desired thiazoles were obtained through the Hantzsch thiazole synthesis, without the use of catalysts, by reacting key intermediate 1-(2-((7-chloroquinolin-4-yl)amino)ethyl)thiourea, obtained in two-steps from N1 (7-chloroquinolin-4-yl)ethane-1,2-diamine, with different 2-bromoacetophenones. The novel molecules were assessed against four different leukemia cell lines (HL60, K562, KASUMI-1, and KG-1) plus normal fibroblasts (L929), using the 3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay, and showed, overall, a high cytotoxic profile, but with interesting selectivity index, especially against K562 cells (1.89 to 5.50), when compared to standard doxorubicin (3.51). Docking studies suggest that all tested derivatives are able to interact with BCR-ABL1 tyrosine kinase enzyme, and, therefore, these molecules may be promising leads against chronic myeloid leukemia. multigramscale multigram scale buildingblock building block N 7 ( chloroquinolin4ylethane1,2diamine chloroquinolin4ylethane12diamine chloroquinolinylethanediamine chloroquinolin 4 yl ethane 1,2 diamine 1 2 quinolinethiazole quinoline activity catalysts 127chloroquinolin4ylaminoethylthiourea, 127chloroquinolin4ylaminoethylthiourea chloroquinolinylaminoethylthiourea amino ethyl thiourea, thiourea 1-(2-((7-chloroquinolin-4-yl)amino)ethyl)thiourea twosteps two steps 7chloroquinolin4ylethane1,2diamine, 7chloroquinolin4ylethane12diamine diamine, (7-chloroquinolin-4-yl)ethane-1,2-diamine 2bromoacetophenones. 2bromoacetophenones bromoacetophenones bromoacetophenones. 2-bromoacetophenones HL60, HL60 HL (HL60 K KASUMI1, KASUMI1 KASUMI 1, KASUMI-1 KG1 KG KG-1 L929, L929 L , (L929) 34,5dimethyl2thiazol2,5diphenyl2Htetrazolium 345dimethyl2thiazol25diphenyl2Htetrazolium dimethylthiazoldiphenylHtetrazolium 3 4,5 dimethyl thiazol 2,5 diphenyl 2H tetrazolium 5 H MTT (MTT assay showed overall profile index K56 1.89 189 89 (1.8 5.50, 550 5.50 50 5.50) 3.51. 351 3.51 . 51 (3.51) BCRABL1 BCRABL BCR ABL1 ABL BCR-ABL enzyme therefore chloroquinolin4ylethane1 2diamine ylethane 12 ylaminoethylthiourea 7chloroquinolin4ylethane1 7chloroquinolin4ylethane1,2diamine HL6 (HL6 KASUMI- KG- L92 (L929 34 5dimethyl2thiazol2 5diphenyl2Htetrazolium Htetrazolium 45 4, 25 2, K5 1.8 18 8 (1. 55 5.5 35 3.5 (3.51 chloroquinolinylethane chloroquinolin4ylethane 7chloroquinolin4ylethane (HL L9 (L92 dimethylthiazol 5dimethyl2thiazol diphenylHtetrazolium 1. (1 5. 3. (3.5 (L9 (3. (L (3

This work describes the synthesis of new 1,3-benzoxathiol-2-one sulfonamides and evaluation of their ability to inhibit some in vitro (coagulant, proteolytic and hemolytic) and in vivo (hemorrhagic, edematogenic and lethality) toxic activities of Bothrops jararaca and Bothrops jararacussu venoms. Compounds have been synthesized from the coupling of intermediate 5-amino-6 methoxybenzo[d][1,3]oxathiol-2-one 4 with benzenesulfonyl chlorides. Characterization of the products was achieved by nuclear magnetic resonance (NMR) and electrospray ionization mass spectra (ESI-MS) techniques. Biological assay results have shown that most of compounds inhibited the main toxic activities of the venom of the two snake species. Compound 5b (N-(6 methoxy-2 oxobenzo[d][1,3]oxathiol-5-yl)-4-nitrobenzenesulfonamide) was the most efficient in inhibiting hemolysis of B. jararaca, and coagulation and proteolysis induced by both venoms. For in vivo activities, all compounds inhibited the edema, from 35 to 72%, and most of them exhibited antihemorrhagic and antilethality activities. Thus, the results pointed to the biological potential of these compounds, being promising molecules to treat envenomation by these snakes as well as to aid the current antivenom serum therapy.