605-78-7Relevant articles and documents
The conformational spaces of dinaphthyl ketones, dinaphthyl thioketones, and dinaphthyl diazomethanes: 1-substituted naphthalenes versus 2-substituted naphthalenes
Assadi, Naela,Pogodin, Sergey,Cohen, Shmuel,Agranat, Israel
, p. 771 - 790,20 (2012)
1,1'-Dinaphthyl ketone (15), 1,2'-dinaphthyl ketone (18), 2,2'-dinaphthyl ketone (19), 1,1'-dinaphthyl thioketone (16), 1,2'-dinaphthyl thioketone (20), 2,2'-dinaphthyl thioketone (21), 1,1'-dinaphthyldiazomethane (17), 1,2'-dinaphthyldiazomethane (22), and 2,2'-dinaphthyldiazomethane (23) have been synthesized. Ketone 15 has been prepared from di(1-naphthyl)methanol; ketone 18 has been prepared by a Friedel-Crafts acylation of naphthalene with 2-naphthoyl chloride; ketone 19 has been prepared by a Grignard reaction of 2-naphthylmagnesium bromide with 2-naphthoyl chloride. Thioketones 16, 20, and 21 have been prepared by reactions of the corresponding ketones 15, 18, and 19 with Lawesson's reagent. The diazomethane derivatives 17, 22, and 23 have been prepared by the HgO oxidation of the respective hydrazones 25, 27, and 28 (prepared from the respective thioketones 16, 20, and 21). The crystal and molecular structures of ketones 15, 18, and 19 and of thioketone 16 have been determined. A variety of conformations in the crystal structures is noted: 1Z,1'Z (15), 1E,1'Z (16), 1E,2'E (18), 2Z,2'Z (19). The NMR experiments have demonstrated the downfield shifts of the protons peri to the carbonyl and the thiocarbonyl groups in 15, 16, and 18, but not in 20. A systematic DFT study (B3LYP/6-31G(d)) of the conformational spaces of 15-23 and their 1H and 13C NMR chemical shifts has been performed. In each series of constitutional isomers, the order of stabilities is 2,2'-(NA) 2C=X>1,2'-(NA)2C=X>1,1'-(NA)2C=X. The decrease in the stabilities of 1-naphthyl derivatives relative to 2-naphthyl derivatives is attributed to the increased overcrowding and the increased twist angles in 1-naphthyl derivatives. The increased stabilization of E-conformations with the increase of the radius of a heteroatom at C9 due to the steric reasons is noted. The DFT calculations satisfactorily describe the X-ray conformations of 15, 16, 18, and 19.
Synthesis of annulated oligothiophenes
Nenajdenko,Balenkova,Chernichenko,Vshivenko
, p. 1456 - 1462 (2012)
Reactions of 1,1-di(2-naphthyl)-2,2-dichloroethene and 1,1-di(2- benzothienyl)-2,2-dichloroethene with sulfur at 220-225 C resulted in hitherto unknown oligothiophenes. Tetrathio[6]helicene was synthesized from 1,1-di(3-benzothienyl)-2,2-dichloroethene. Preparative pathway to helicene involving intramolecular ring closure of dithiol derived from 1,1-di-(3-benzothienyl)-2,2-dichloroethene was developed as an alternative to high temperature synthesis.
Palladium nanoparticles on amino-modified silica-catalyzed C–C bond formation with carbonyl insertion
Etemadi-Davan, Elham,Khalili, Dariush,Banazadeh, Ali Reza,Sadri, Ghazal,Arshad, Pourya
, p. 1891 - 1903 (2021/02/01)
Abstract: A practical and heterogeneously catalyzed Stille, homo-coupling, and Suzuki carbonylation reaction has been reported using Pd nanoparticles supported on amino-vinyl silica-functionalized magnetic carbon nanotube (CNT@Fe3O4@SiO2-Pd) for the efficient synthesis of symmetrical and unsymmetrical diaryl ketones from aryl iodides. A wide variety of symmetrical and unsymmetrical diaryl ketones were obtained in high yields under CO gas-free conditions using Mo(CO)6 as an efficient carbonyl source. Considering the atom economy of Ph3SnCl, less than an equimolar amount can be applied in Stille transformation, which is of great importance due to the toxicity of organotin derivatives. Moreover, no phosphine ligand and external reducing agent were necessary in these coupling carbonylation reactions. This heterogeneous Pd catalyst offers high activity with very low palladium leaching. Finally, the catalyst can be reused and recycled for six steps without loss in activity, exhibiting good example of sustainable methodology. Graphic abstract: [Figure not available: see fulltext.].
Sodium Methyl Carbonate as an Effective C1 Synthon. Synthesis of Carboxylic Acids, Benzophenones, and Unsymmetrical Ketones
Hurst, Timothy E.,Deichert, Julie A.,Kapeniak, Lucas,Lee, Roland,Harris, Jesse,Jessop, Philip G.,Snieckus, Victor
supporting information, p. 3882 - 3885 (2019/06/07)
Reported is the synthesis of carboxylic acids, symmetrical ketones, and unsymmetrical ketones with selectivity achieved by exploiting the differential reactivity of sodium methyl carbonate with Grignard and organolithium reagents.
Extending the scope of the carbonyl facilitated triplet excited state towards visible light excitation
Rajagopal, Shinaj K.,Nagaraj,Deb, Somadrita,Bhat, Vinayak,Sasikumar, Devika,Sebastian, Ebin,Hariharan, Mahesh
, p. 19120 - 19128 (2018/08/07)
A series of extended π-conjugated benzophenone analogs was synthesized through a facile Lewis-acid catalyzed Friedel-Crafts reaction in order to exploit the integral triplet state properties of benzophenone. Extending the π-conjugated plane of the phenyl ring of benzophenone allowed tuning of the excitation wavelength from the far-UV end (～260 nm) to the visible spectrum (～446 nm). Compared to benzophenone, significant red-shifts in the absorption (up to 450 nm in solution) with high photostability were observed for the synthesized benzophenone analogs. As is evident from the density functional theory calculations, expansion of the ring size of the aromatic part of the benzophenone analogs induces a decrease in the HOMO-LUMO gap. The considerable extension of the electron density to the carbonyl group in the LUMO substantiates the triplet nature associated with the benzophenone analogs. By virtue of the properties of the carbonyl functionality, an apparent increase in the triplet quantum yield (ΦT = 5.4% to 87.7%) was observed for the benzophenone analogs when compared to the corresponding bare polyaromatic hydrocarbon. The spin orbit coupling was computationally estimated for the benzophenone analogs to propose pathways for the observed intersystem crossing process. The plausibility to photoexcite the aromatic-ring-fused benzophenone frameworks for triplet activation in the visible range opens the door for a new class of materials for photonic application.
