Synthese von octahydro-dibenzophenanthrolin-dionen und eines dodecahydrodichin[2,3-a;2′,3′-c]acridin-trions

Alkylation of heteroaryl halides by 2:1 Grignard reagent/copper(I) mixtures. Synthesis of alkylated octahydrodibenzo[b,j][1,10]phenanthrolines

“…Column chromatography of the residue (EtOAc/ CHgOH, 4:1) gave 75% of spectroscopically pure product as a white solid: mp 220 °C dec; M+ m/z caled for C22H24N2 316.1956, found, 316.1930 (100%); NMR (300 MHz) 1.95 (m, CH2, H2, H3, H10, Hll, 8 ), 2.60 (s,CH3,6 H), 2.92 (m, CH2, H4, H9, 4 H), 3.34 (m, CH2, HI, H12, 4 ), 7.90 (s, CH, 2 H); 13C NMR (75.5 MHz) 13.9, 22.8, 23.3, 27.1, 35.0, 120.9, 125.7, 129.9,141.1, 143.5,158.3; IR (KBr) 2940 (s), 2870 (m), 1490 (s), 1440 (m), 1387 (m), cm™1. 5,2,3,4,9,10,ll, ][ 1,1 OJphenanthroline (3b). This reaction was conducted exactly as in the case of 3a, except that CuCN (2.14 g, 24 mmol) and 2 M ethereal ferf-butylmagnesium chloride were used, and the product was chromatographed by using CH2Cl2/hexanes as eluent (65% yield).…”

Benzothiet-2-ones: synthesis, reactions, and comparison with benzoxet-2-ones and benzazetin-2-ones

“…We find that benzothietone (5) does not just dimerize: it dimerizes, trimerizes, and polymerizes, and the polymer is by far the major product. The trimer and the polymer both have strong IR bands near 900 cm"1, but the dimer does not; instead the dimer has a double band at 920 and 930 cm"1.…”

“…Figure Results and Discussion Benzothiet-2-one. Benzothietone (5) is obtained in nearly quantitative yield (94%) as a pale-yellow solid by flash vacuum pyrolysis (FVP) of benzothiophene-2,3-dione ( 9) at 650 °C. The product is isolated on a cold finger cooled with liquid nitrogen.…”

“…A degassed solution of 16 (20 mg) in 20 mL of spectroscopic grade acetone was irradiated for 21 h by using a 450-w Hanovia lamp with a Pyrex filter. Removal of the solvent in vacuo gave essentially pure 17, contaminated with <2% of 16. for 17: mp 367 °C dec; NMR 6.89 (s, 2 ), 1.48 (s, 6 ), 1.28 (s, 6 ), 1.19 (s, 6 ), 1.14 (s, 6 ), 0.96 (s, 6 ), 0.34 (s, 6 H); 13C NMR 199.03,136.87,136.12,117.59,54.70,45.32,42.07,39.96,35.97,23.00,17.65,13.13,9.96,7.83,5.60; mass spectrum, m/e (relative intensity) 430 (100), 415 (84), 387 (16), 361 (12), 333 (11), 303 (10), 275 (8), 245 (9), 205 (3), 97 (57); IR (KBr) 2975, 2921, 1715,1460,1387,1323,1270,1048, 985 cm™1; high resolution mass spectrum caled for C30H38O2 430.28716, found 430.28701.…”

“…In the sulfur series (3) no stable thietone has been prepared prior to this work. Chapman and McIntosh obtained benzothietone (5) by photolysis of 2-phenyl-3,lbenzoxathian-4-one (4) at 77 K.12 5 was observed by IR spectroscopy ( = 1803 cm-1) and dimerized at -40 °C to 6. Trapping with methanol gave the methyl ester 7.12 In subsequent work, the carbonyl absorption at 1803 cm-1 was also observed by IR spectroscopy at -180 °C following irradiation of the thiadiazine 8.13 The photoelectron spectrum of 5 was obtained by gas-phase pyrolysis of both benzothiophene-2,3-dione (9) and 2-mercaptobenzoic acid (10).14…”