1‐Methyl‐3‐phenyl‐3‐thiocyanato‐1H,3H‐quinoline‐2,4‐dione: A novel thiocyanating agent

Abstract

Under mild reaction conditions, the thiocyanato group is selectively transferred from 1‐methyl‐3‐phenyl‐3‐thiocyanato‐1H,3H‐quinoline‐2,4‐dione (3) to some nucleophiles. Aliphatic primary and secondary amines are converted to S‐cyanothiohydroxylamines, anilines afford p‐thiocyanatoanilines, Wittig reagent is thiocyanated in α‐position, and thiols are oxidized to disulfides.

Novel Tandem Hydration/Cyclodehydration of α-Thiocyanatoketones to 2-Oxo-3-thiazolines. Application to Thiazolo[5,4-c]quinoline-2,4(3aH,5H)-dione Synthesis

“…We recently reported the high reactivity of 2,3-dioxo-1,2,3,4-tetrahydroquinolin-3-yl thiocyanates 10 2 toward water leading to 1 (Scheme ), and as noted in this paper, the same applies to the thiocarbamates 3 . This high water sensitivity renders the hydration of 2 to 3 nontrivial, and we anticipated it could only be accomplished using a “water-containing water-reactive” agent.…”

Reaction of Some 2‐Quinolone Derivatives with Phosphoryl Chloride: Synthesis of Novel Phosphoric Acid Esters of 4‐Hydroxy‐2‐quinolone

“…In addition to 1m, 2,2 0 -dithiobis(benzothiazole) was isolated. These results are similar to the transfer of thiocyanato groups from 3-thiocyanatoquinoline-2,4-diones to 2-sulfanylbenzo-thiazoles [22]. However, the reaction of 2f with 2,5-dimethylaniline leads only to N-alkylation along with formation of compound 6f.…”

“…Therefore, we considered a cleavage of the C (3)─Cl bond as the first reaction step in the transformation of compounds 2k−m. The transfer of a chlorine atom (or a bromine atom or a thiocyanato group) from position 3 of the corresponding quinoline-2,4-diones to a nucleophile has been observed previously [20][21][22]. Hydroxide ions [20], sulfide ions [21], amines [22], thioalcohols [22], or activated aromatic compounds [22] can act as nucleophile.…”

“…Compound was prepared from 1b (Method A1, Table 2), 2b, and 2e (Method B, Table 1). Colorless crystals, mp 71−72°C (hexane); For 4b, mp 72−73°C (ethanol) was referred [1]; For NMR see Table 3; EI-MS (m/z, %): 289 (14), 288 (5), 287 (22), 254 (6), 253 (6), 252 (19), 251 (9), 250 (7), 217 (25), 216 (100), 215 (9), 214 (13), 189 (8), 126 (13), 125 (6), 113 (6), 108 (27), 95 (15), 94 (6), 89 (6), 63 (11), 51 (11). Anal.…”