each d. each 1C. o-C(N0,)). 126.02 (s. C3). 129.29. 129.58 (each d, each 1 C, n-C(NO,)), 141.34 (d. C2). 146.58 (s,)). 148.05 (s. CNO,). 148.88 (d, C5); EI-MS (70eV): i n : 275 (Mi, 29%). 260 (M' -Me, 100). 199 (30), 180(33). 137(18). 73 (Si(CH,),. 27). 4j: To a solution of 3j (7 mmol) in CH,CI, (200 mL) was added slowly a 1.0 M solution of BCI, in CH,CI, (14 mL) under a nitrogen atmosphere at room temperature. The reaction was quenched with 2 M Na2C0, solution. and the mixtureextracted with ether(3 x 20 mL). The organic layer wasdried (MgSO,). and the solvent evaporated off. The crude product was chromatographed (SO,. 250 g, hexanes/ether, 1 :1) to give 4j (0.98 g, 61 %) as a semisolid. ' HNMR(250.132Hz.CDC13.25 C ) : d = 4 . 1 1 (a.2H.CH2).7.16(s.1H.H5). 7.34(d,2H.J=8.6Hr,111-H(NO,)),7.83(~.1H.H2),8.08(d,2H.J=8.6Hz. o-H(N02)); I3C NMR (62.896 Hz. CDCI,). 6 = 30.80 (CH,). 113.85 (br. b. C3). 123.45. 123.61 (each d. each 1C. o-C(NO~)). 126.11 (s. C4). 129.11. 129 33 (each d. each 1C. in-C(N0,)). 141.98 (d. C5). 146 80 (s. p-C(N0,)). 148.17 (s, CNO,). 155.19(d,C2), El-MS(70eV):m z687(M ' . 19"/0),203(75). lX(100).
5j: A mixtureof4j(0.32 mmol). 9-bromophenanthrene(0.96 mmol). and [Pd(P-Ph,),] (0.1 mmol) in methano1,toluene (30 mL. 1 : I ) was stirred for 5 min. where upon 2 M Na,CO, solution (3 mL) was added. The reaction mixture was again stirred while heating at reflux for 5 h at 140 C. After addition of water (50 mL) and cooling to room temperature. the mixture was extracted with ether ( 3 x 20 mL). The combined organic solution was washed with water. dried (MgSO,). and concentrated. Purification by column chromatography (SiO?; 20 g. hexanesi'ether. 7 : l ) yielded Sj (317 mg. 87%) as semisolid. ' H NMR (250.132Hz. CDCI, 25 C ) , d = 3 . 5 1 ( s , 2 H , C H I ) . 6 . 8 0 ( d . 2 H . J = X . S H z , in-H(NO,)). 7.24-7.68 (m. IOH). 8.53 (t. 2H. ./ = 8.0Hz. o-H(NO,)): "C NMR (62.896 Hz, CDCI,): 6 = 30.23 (CH,). 122.52. 122.85, 123.13.