Methylation of Metalated Indene and Methylindene

Abstract

The reaction of metallic lithium and potassium with indene and floorene in reflusing 1,2-di~nethosyethane (DivIE) yields reduction products of indene and fluorene, 1-metalated indene, and 9-metalated fluorene, and as well is accompanied by the production of some hydrogen gas due to the acidic rnethylene group. The amount of hydrogen is small for fluorene b u t quite substantial for indene.Metalation of indene, 1-methylindene, and 3-methylindene in reflusing DME, followed by methylation of these metalated indenes a t OD, gave a misture consisting of starting material, the corresponding indan, nio~lo~iiethylindene, din~ethylindene, and in some cases trimethylindene. Two competing reaction mechanisms resulting in the formati011 of the metalated indenes are suggested and possible routes for the foriliation of the di-and tri-methylindenes are examined.

Flash Vacuum Pyrolysis of Pyrazoles as an Alternative Way to Study Vinylcarbenes

“…IR (NaBr) 2259 cm -1 (C⋮C). Compound 8 : 1 H NMR (DMSO- d 6 ), δ (ppm) 1.33 (3H, d, J = 7 Hz), 3.15 (1H, q, J = 7 Hz), 6.15 (2H, dd, J = 2 and 6 Hz), 7.10 (4H, m) . MS m / z (relative intensity) 130 (M + , 100).…”

“…MS m / z (relative intensity) 130 (M + , 100). Compound 9 : 1 H NMR (DMSO- d 6 ) δ (ppm) 2.25 (3H, s), 3.35 (2H, m), 6.38 (1H, m), 7.20−7.50 (4H, m); MS m / z (relative intensity) 130 (M + , 100). Compound 10 : 1 H NMR (DMSO- d 6 ) δ (ppm) 2.18 (3H, s), 3.30 (2H, s), 6.50 (1H, s), 7.10−7.40 (4H, m); MS (relative intensity) 130 (M + , 100).…”

Products and transients in the photolysis of methylated 2-indanones. Observation and kinetics of o-xylylenes

“…Irradiation of 1,1,3,3-tetramethyl-2indanone (la) gives l-isopropenyl-2-isopropylbenzene (9) as was originally reported by Starr and Eastman.3 Similarly, 1,1 -dimethyl-2-indanone (lb) gives 1 -isopropenyl-2-methylbenzene (10) on irradiation. The latter (10) showed ]H NMR resonances at 7.11 (m, 4 H, aromatics), 5.16 and 4.82 (multiplets, each 1 H, vinylic), 2.29 (s, 3 H, methyl), and 2.02 (d, J = 2.0 Hz, 3 H, methyl).…”