4523-45-9Relevant articles and documents
Internal conversion in 4-substituted 1-naphthylamines. Influence of the electron donor/acceptor substituent character
Suzuki, Kengo,Demeter, Attila,Kuehnle, Wolfgang,Tauer, Erich,Zachariasse, Klaas A.,Tobita, Seiji,Shizuka, Haruo
, p. 981 - 991 (2000)
The thermally activated internal conversion (IC) taking place in 4- substituted 1-(dimethylamino)naphthalenes (14DMX) and 1-aminonaphthalenes (14ANX) with X = CN, Cl, H, CH3 and OCH3 was investigated in three solvents spanning the polarity scale, hexane, diethyl ether and acetonitrile. In both series 14DMX and 14ANX, the efficiency of the IC reaction decreases substantially when X changes from CN to OCH3, the order in which the electron donor character of the 4-substituent increases. Considerably larger IC reaction rate constants are obtained for the first group of compounds. This difference is connected with the ground state structure of the amino group, which is more strongly twisted for 14DMX (ca. 60°) than for 14ANX (ca. 20°), whereas both sets of 1-naphthylamines are planarised in the S1 excited state. The IC process slows down with increasing solvent polarity for each of the 14DMX and 14ANX molecules. The substituent X and the solvent polarity mainly affect the IC activation energy E(IC). With 14DMX in hexane, E(IC) increases from 10 kJ mol-1 for X = CN to 34 kJ mol-1 for X = OCH3, whereas with, e.g., 14DMCL a solvent polarity dependent increase of E(IC) from 16 kJ mol-1 in hexane to 28 kJ mol-1 in acetonitrile is observed. The height of the barrier E(IC) is governed by the energy gap ΔE(S1,S2) between the two lowest excited singlet states. The influence of δE(S1,S2) on E(IC) is attributed to vibronic coupling caused by the proximity of the S1 and S2 states, which flattens the S1 potential energy surface and thereby lowers the IC barrier when ΔE(S1,S2) becomes smaller. It is assumed that the IC reaction of the 1-naphthylamines passes through a conical intersection, which exists as a consequence of the relative displacement of the S1 and S0 surfaces caused by the different amino twist angles in the two states.
Co(II)-Catalyzed Regioselective Cross-Dehydrogenative Coupling of Aryl C-H Bonds with Carboxylic Acids
Lan, Jianyong,Xie, Haisheng,Lu, Xiaoxia,Deng, Yuanfu,Jiang, Huanfeng,Zeng, Wei
supporting information, p. 4279 - 4282 (2017/08/23)
A cobalt(II)-catalyzed regioselective aryl C-H bond oxygenation between arenes and aryl or aliphatic carboxylic acids under bidendate-chelation assistance is developed. This method provides an efficient approach to acyoxy-substituted arenes with a broad range of functional group tolerance. Furthermore, this reaction system could be further applied to the preparation of polyfunctional naphthylenes.
Ligand free open air copper(II) mediated aryl formamidation and amination of aryl halides
Komati, Rajesh,Jursic, Branko S.
, p. 1523 - 1527 (2014/03/21)
A simple synthetic procedure for direct formamidation and amination of aryl halides mediated by copper(II) salts was developed in open air, without an external ligand in formamide with potassium carbonate as a base. This approach is particularly efficient when electron active aryl halides are used as substrates. In these cases almost quantitative formamidation was observed.