Die Spaltung der 1,1′‐Dianthryl‐2,2′‐dicarbonsäure in optische Antipoden

Copper(II)-Mediated Oxidative Coupling of 2-Aminonaphthalene Homologues. Competition between the Straight Dimerization and the Formation of Carbazoles

“…The reaction of 2-aminoanthracene ( 8 ) with CuCl 2 −PhCH 2 NH 2 (MeOH, rt, 24 h; Scheme ) afforded a mixture of diamine 15 (43%) and carbazole 16 (39%, entry 4), a result similar to that obtained for 7c (entry 3) . The couplings of 9-aminophenanthrene ( 10 ), 3-phenyl-1-aminonaphthalene ( 11 ), and 2-aminochrysene ( 12 ) turned out to give mainly the carbazoles 19 , 20 , and 21 (Scheme ), respectively (entries 6−8); the corresponding diamines were either formed in minute quantities (2% of 18 ; entry 6), or not at all (entries 7 and 8).…”

“…2,2 ‘ -Diamino-1,1 ‘ -bianthryl (15): mp 160−3 °C (toluene), 165−8 °C (benzene−ethanol; lit 14b. gives 233 °C for the compound crystallized from benzene−ethanol); 1 H NMR (400 MHz, CDCl 3 ) δ 3.76 (br s, 4 H, NH 2 ), 7.19−7.31 (m, 6 H), 7.53 (dd, J = 8.4 and 0.8 Hz, 2 H), 7.34 (s, 2 H), 7.92 (dd, J = 8.2 and 0.8 Hz, 2 H), 8.06 (dd, J = 9.6 and 0.8 Hz, 2 H), 8.40 (s, 2 H); 13 C NMR δ 110.12 (s), 120.14 (d), 121.21 (d), 123.99 (d), 125.20 (d), 126.84 (d), 127.93 (d), 127.94 (d), 128.26 (s), 129.61 (s), 130.01 (d), 131.93 (s), 132.64 (s), 141.98 (s); IR (CHCl 3 ) ν 3390 and 3486 (NH) cm -1 ; MS (EI) m / z (%) 384 ([M] +• , 100), 383 (14), 368 (24), 367 (C 28 H 17 N, 37), 192 (M 2+ , 8), 190 (8), 183.5 (13), 183 (11), 182.5 (17), 176 (10), 169.5 (14); HRMS for C 28 H 20 N 2 calcd 384.1626 found 384.1629.…”

“…The crystals (240 mg) thus formed contained the enantiomerically pure ( R )-(−)- 15 , as revealed by chiral chromatography: mp 240−242 °C. Dissolving these crystals in dichloromethane followed by chromatography on silica gel with CH 2 Cl 2 afforded pure ( R )-(−)- 15 (132 mg, 34%): mp 253−5 °C (benzene−ethanol; lit 14b. gives 182−4 °C from the same solvent or 174−5 °C from an unidentified solvent 14a ); [α] D −302 ( c 4, CHCl 3 ) [lit.…”

Kenichi Fukui, Frontier Molecular Orbital Theory, and the Woodward‐Hoffmann Rules. Part III. Fukui's Science and Technology, 1918–1965†**

“…Now to Laurer's background. In the 1930s, Lauer published with at least nine chemists from Kyoto University including Shingu, the others being Toshisada Aoyama, [116] Keiichi Atarashi, [131] Yoshio Hirata, [132] Masao Horio, [133][134][135] Kiichi Irie, [136] Masao Miyawaki, [137] at least 15 papers with Ryohei Oda, [137][138][139][140][141][142][143][144][145][146][147][148][149][150][151] and Keiji Tamura. [151] Lauer also taught Junji Furukawa, a rubber chemist, though they apparently did not publish together.…”

Conformation and Optical Rotation of Restricted Biphenyls. Configurational Correlation of Biaryls by Optical Displacement. The Absolute Configuration of Restricted 1,1'-Binaphthyls1

“…The conformation of the bridge system has features closely resembling those of cyclohexane, the racemization of the cis compound corresponding to an interconversion of aa-and ee-isomers, and the mutarotation to an interconversion of aa-and ee-isomers. Rate constants of racemization and mutarotation in neutral and basic solvents have been determined; the cis isomer racemizes with 23. kcal./mole.…”