The Synthesis of Chiral Perylene and Naphthalene Diimides (original) (raw)
Inorg. Chem. Front., 2015,.pdf
A potential tetradentate monoanionic N 2 O 2 chelator, HL, derived from the condensation of o-vanillin and N,N-dimethylethylenediammine, has been reacted with nickel perchlorate and sodium azide to yield the dinuclear Ni(II) complex [Ni(L)(μ 1,1 -N 3 )Ni(L)(OH 2 ) 2 ]·ClO 4 (1), where L = Me 2 N(CH 2 ) 2 NvCH-C 6 H 3 (O − )-(OCH 3 ). The complex has been characterized by X-ray diffraction analysis and different spectroscopic techniques. The coordination geometry around the Ni(II) centres is a distorted octahedron, with the azide ligand and the phenolato oxygen atom bridging in μ 1,1 and μ 2 mode, respectively. The EPR spectra, recorded at liquid nitrogen temperature (77 K) and room temperature ), show g factors of 2.080 and 2.085, in agreement with the structure determined by X-ray diffraction analysis. The VTM study confirms that there are ferromagnetic interactions between the bridging binuclear Ni(II) ions (S = 1). The evaluation of cytotoxic effects on different human cancer cell lines (A-549, MCF-7 and CaCo-2) suggests that both the ligand and complex 1 have potential anticancer properties. Furthermore, they also exhibit anti-mycobacterial activity against M. tuberculosis H37Rv (ATCC 27294) and M. tuberculosis H37Ra (ATCC 25177) strains. Molecular docking of HL with the enoyl acyl carrier protein reductase of M. tuberculosis H37R v (PDB ID: 4U0K) has been examined, showing that HL forms two hydrogen bonds with Lys165 (1.94 and 2.53 Å) in its best docked pose. † Electronic supplementary information (ESI) available. CCDC 894363. For ESI and crystallographic data in CIF or other electronic format see
European Polymer Journal, 2007
(Z)-4-(4-cyanophenylamino)-4-oxobut-2-enoic acid (LH) and its new triphenyltin (IV) derivative (Ph 3 SnL) were synthesized and further investigated for their binding with ds.DNA under physiological conditions {pH: 4.7 (stomach); 7.4 (blood), 37°C} using UV-Visible/fluorescence spectroscopy, cyclic voltammetry and viscosity measurement techniques. Spectral responses as well as experimental findings from all the techniques i.e., binding constant (K b), binding site size (n) and free energy change (DG) correlated with each other and indicated formation of spontaneous compound-DNA complexes via intercalation of compounds into the DNA base pairs. Values of kinetic parameter, K b , revealed comparatively greater binding of both the compounds with DNA at stomach pH (4.7). However among both compounds organotin complex (Ph 3 SnL) showed comparatively greater binding than that of its ligand (LH) as evident from its, K b , values at both the pH values. In general, K b values were evaluated greater for Ph 3 SnL at stomach pH {: K b : 8.65 • 10 4 M À1 (UV); 5.49 • 10 4 M À1 (fluorescence); 8.85 • 10 4 M À1 (CV)}. Voltammetric responses of both compounds before and after the addition of DNA indicated that diffusion controlled processes are involved. Complex Ph 3 SnL exhibited the best antitumor activity.
Linear free energy relations. III. Electrochemical characterization of salicylaldehyde anils
The Journal of Organic Chemistry, 1975
The polarographic half-wave potential in a series of 14 salicylaldehyde anils is a linear function of ux-(except for the m-and p-NO2 compounds in which the nitro group is electroactive); analyses of potential as a function of the currents indicate a one-electron process. The half-wave oxidation potential is directly proportional to ux+ (except for m-and p-NMe2 compounds in which the dimethylamino group is electroactive). Cyclic voltammetry reveals that the reduction process is irreversible. Oxidative cyclic voltammetry demonstrates that with the exception of the nitro and dimethylamino compounds the initial irreversible one-electron oxidation product undergoes chemical transformation to a tertiary product that forms a reversible one-electron couple; the average of the peak potentials, Le., the half-wave potential, of the couple is directly proportional to the normal Hammett substituent constant, u. In addition to the anils, the half-wave reduction and oxidation potentials of the isoelectronic series stilbene, benzaldehyde anil, and azobenzene were linearly correlated to the calculated energies of the lowest unoccupied and highest occupied molecular orbitals, respectively. The effects of anil substituent and intramolecular hydrogen bonding are rationalized on this basis.
6.10a. Inorg. Chem. 31,1233.pdf
The ruthenium complex [Ru2(CloHsN2)(CO),(PiPr3),] (1) (CloHIoN2 = 1,8-diaminonaphthalene) reacts with 1 equiv of HgX, (X = C1, Br, I, 02CCH,, 02CPh, 02CCH2C1, 02CCF3, SCN, ONC) to give the adducts [(1)HgX2], in which the Hg atoms are bonded to both Ru atoms of complex 1. Correlations between the 2J(3'P-199Hg) coupling constants of their 31P NMR spectra and the corresponding halogen electronegativities or acid pK,s have been observed. With the exception of [(1)Hg(O2CCF,),], which does not react with any other mercury(I1) salt, the compounds [(l)HgX,] react with HgX', (X' = C1, Br, I, 02CCH3, 02CPh, 02CCH2C1) to give the insertion products [(l)Hg(p-X'),HgX,] only when X' is more electron-withdrawing than X; otherwise, the addition products [(l)Hg(pX),HgX',] are formed. All reactions of [(l)HgX,] with Hg(02CCF3), give the same substitution product [(l)Hg(02CCF3)2]. The molecular structures of [(l)Hg(O,CCF,),] and [(l)Hg(p-Cl),HgCI,] have been confirmed by X-ray crystallography. [(l)Hg(O,CCF,),]: monoclinic, space group C2/c, a = 23.730 (9) A, b = 12.578 (4) A, c = 14.51 1 (7) A, fl = 94.76 (5)O, Z = 4. [(1)Hg(p-C1),HgC1,]~CH2Cl2: monoclinic, space group P 2 , / n , a = 15.840 (7) A, b = 12.694 (4) A, c = 23.366 (2) A, fl = 105.74 (2)O, Z = 4. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Garda-Granda, S.; Van Der Maelen, J. F. Inorg. Chim. Acta 1991, 185, 187. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Pellinghelli, M. A.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1991, 371. Andreu, P. L.; Cabeza, J. A.; Riera, V.; Robert, F.; Jeannin, Y. J. Organomet. Chem. 1989, 372, C15. Oro, L. A.; Fernindez, M. J.; Modrego, J.; Foces-Foces, C.; Cano, F. H. Angew. Chem., Inr. Ed. Engl. 1984, 23, 913. Fernindez, M. J.; Modrego, J.; Oro, L. A.; Apreda, M. C.; Cano, F. H.; Foces-Foces, C. J. Chem. SOC., Dalton Trans. 1989, 1249. See, for example: Panizo, M.; Cano, M. J. Organomet. Chem. 1984, 266,247. Pardo, M. P.; Cano, M. J. Organomet. Chem. 1983,247,293. Faraone, F.; Lo Schiavo, S.; Bruno, G.; Bombieri, G. J. Chem. Soc., Chem. Commun. 1984, 6. (a) Ermer, S.; King, K.; Rosenberg, E.; Manotti-Lanfredi, A. M.; Tiripicchio, A.; Tiripicchio-Camellini, M. Inorg. Chem. 1983, 22, 1339. (b) Rosenberg, E.; Ryckman, D.; Hsu, I.-N.; Gellert, R. W. Inorg. Chem. 1986, 25, 194. (c) Rosenberg, E.; Hardcastle, K. I.; Day, M. W.; Gobetto, R.; Hajela, S.; Muftikian, R. Organometallics 1991, 10, 203. (d) Fadel, S.; Deutcher, J.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1977, 16, 704. (e) Fajardo, M.; Holden, H. D.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R. J. Chem. SOC., Chem. Commun., 1984, 24. (f) G6mez-Sa1, M. P.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R.; Syed-Mustaffa, S. N. A. B.
Russ. Chem. Bull., Int. Ed. 2004, 53, №12, 2816-2929
Regioselectivity of the intramolecular electrophilic substitution in a series of N (m R phenyl) and N (α naphthyl) 2 allyl(methallyl) 6 carboxy 4 oxo 3 aza 10 oxatri cyclo[5.2.1.0 1,5 ]dec 8 enes in reactions with phosphoric acid was studied. The reactions of N (m R phenyl) substituted derivatives proceed nonregioselectively to form mixtures of 2 R and 4 R substituted isoindolo[2,1 a]quinolines, whereas the reactions of N (α naph thyl) substituted derivatives occur regioselectively at the β position of the naphthyl fragment.
J. Org. Chem. 2009, 74, 2780–2787.pdf
The enantioselective hydrogenation of 2-benzylquinolines and 2-functionalized and 2,3-disubstituted quinolines was developed by using the [Ir(COD)Cl] 2 /bisphosphine/I 2 system with up to 96% ee. Moreover, mechanistic studies revealed the hydrogenation mechanism of quinoline involves a 1,4-hydride addition, isomerization, and 1,2-hydride addition, and the catalytic active species may be a Ir(III) complex with chloride and iodide. tion of quinoline derivatives using [Ir(COD)Cl] 2 /MeO-BiPhep/I 2 as catalyst with high enantioselectivity, 7 and this methodology has been successfully applied to the synthesis of some tetrahydroquinoline alkaloids. 8 † (1) For some reviews and books on hydrogenation of aromatic compounds, see: (a) Rylander, P. N. Barbaro, P.; Scapacci, G.; Farnetti, E.; Graziani, M. Organometallics 1998, 17, 3308-3310. (b) Henschke, J. P.; Burk, M. J.; Malan, C. G.; Herzberg, D.; Peterson, J. A.; Wildsmith, A. J.; Cobley, C. J.; Casy, G. Kashiwabara, M.; Sato, K.; Ito, T.; Kaneda, K.; Ito, Y. Tetrahedron: Asymmetry 2006, 17, 521-535. (5) Kuwano, R.; Kashiwabara, M.; Ohsumi, M.; Kusano, H. J. Am. Chem. Soc. 2007, 129, 808-809. (6) (a) Ohta, T.; Miyake, T.; Seido, N.; Kumobayashi, H.; Takaya, H.