- Planar-locked Ru-PNN catalysts in 1-phenylethanol dehydrogenation
-
Ru-PNN pincer catalysts of the general form [{PNN}Ru(H)(Cl)(CO)] can dehydrogenate alcohols through inner- and outer-sphere mechanisms, but determining the favored path is challenging. To address this challenge, the following planar-locked quinoline-based PNN ligands, which cannot form key inner-sphere transition states and intermediates, were synthesized: 2-((ditertbutylphosphaneyl)methyl)-N,N-diethylquinolin-8-amine (QNPtBu), 2-((diisopropylphosphaneyl)methyl)-N,N-diethyl-quinolin-8-amine (QNPiPr), and 2-((diphenylphosphaneyl)-methyl)-N,N-diethylquinolin-8-amine (QNPPh). In addition to the quinoline-derived ligands, we also prepared the isoquinoline PNN ligand N-((1-((ditert-butylphosphaneyl)methyl)isoquinolin-3-yl)methyl)-N-ethylethanamine (IsoQNP) and two known picoline- and lutidine-derived ligands 2-((ditert-butylphosphaneyl)-methyl)pyridine (PicP) and 2-((ditert-butylphosphaneyl)methyl)-6-methylpyridine (LutP). These six ligands were coordinated to Ru(II) ions to prepare six new complexes of the general formulation [{L}Ru(H)(Cl)(CO)] analogous to Milstein’s PNN catalyst precursor (1PyCl). The X-ray structural, NMR, UV-vis, and FTIR spectroscopic properties of the new complexes are similar to parent complex 1PyCl and were used in catalytic 1-phenylethanol acceptor-less and transfer dehydrogenation. The comparative results demonstrate that 1Py outperforms the other catalysts. DFT reaction profiles were computed for 1Py and the planar-locked catalysts. The results suggest that 1Py has access to a lower-energy inner-sphere path, whereas the planar-locked catalysts can only proceed through a high-energy outer-sphere mechanism and may even get trapped in unreactive alkoxide sinks.
- Fanara, Paul M.,MacMillan, Samantha N.,Lacy, David C.
-
p. 3628 - 3644
(2020/11/03)
-
- Preparation method of nitro-substituted quinadine
-
The invention belongs to the field of organic synthesis and particularly relates to a preparation method of nitro-substituted quinadine. The preparation method is realized by the following step: underthe condition of hydrochloric acid and zinc chloride catalysis, nitroaniline reacts with a crotaldehyde compound to obtain the nitro-substituted quinadine as a target object. The preparation method provided by the invention has the benefits that under the synergistic action of hydrochloric acid and zinc chloride, through controlling the amount of all reaction raw materials and the reaction time,reaction conditions are mild, the product yield is high, and the industrialization is easy; the preparation method provided by the invention is applicable to a variety of reaction substrates, therefore, a quinadine derivative combination library with a rich structure is synthesized through screening or optimizing a reactant, which is well applied to the preparation of natural products and functional materials or bioactive compounds.
- -
-
Paragraph 0015
(2018/11/22)
-
- Approach to the synthesis of 8-nitroquinoline-2-carboxylic acid in high yield
-
A synthesis of 8-nitroquinoline-2-carboxylic acid was optimized, using the following basic scheme of transformations: 1) nitration of 2-methylquinoline with subsequent separation of a mixture of isomeric 8-nitroand 5-nitro-2-methylquinolines; 2) oxidation of the methyl group in 2-methyl-8-nitroquinoline (including consecutive steps of bromination and hydrolysis in aqueous sulfuric acid). A new method for the separation of isomeric 8-nitroand 5-nitro-2methylquinolines was suggested. The optimal conditions for the final step of hydrolysis were selected, which gave almost quantitative yield of 8-nitroquinoline-2-carboxylic acid.
- Gadomsky, S. Ya.,Yakuschenko
-
p. 816 - 818
(2016/12/27)
-
- Reaction of nitroanilines with aldehydes. Refinement of the Doebner–Miller reaction mechanism
-
Due to intramolecular hydrogen bonding between the amino and nitro groups, o-nitroaniline is incapable of forming Schiff bases in the reactions with acetaldehyde and crotonaldehyde but is converted to quinoline derivative under Doebner–Miller reaction conditions via addition to the C=C double bond of the α,β-unsaturated aldehyde. Under analogous conditions, p-nitroaniline possessing a free amino group gives rise to the product of Doebner–Miller quinoline synthesis through intermediate formation of Schiff base dimer. The reaction of p-nitroaniline with benzaldehyde also yields the corresponding Schiff base, whereas o-nitroaniline is converted to N-benzyl derivative.
- Denisov, V. Ya.,Grishchenkova,Tkachenko,Luzgarev
-
p. 1797 - 1803
(2017/02/19)
-
- Substitution effect on the one- and two-photon sensitivity of DMAQ "caging" groups
-
The systematic SAR study of a "caging" group showed a strong influence of the position of the donor dimethylamino group on the efficiency of photolysis of the DMAQ (2-hydroxymethylene-(N,N-dimethylamino)quinoline) caged acetate under one-photon near-UV or two-photon near-IR excitation. Photorelease of l-glutamate by the most efficient 8-DMAQ derivative strongly and efficiently activated glutamate receptors, generating large, fast rising responses similar to those elicited by glutamate photoreleased from the widely used MNI-caged glutamate.
- Petit, Morgane,Tran, Christine,Roger, Thomas,Gallavardin, Thibault,Dhimane, Hamid,Palma-Cerda, Francisco,Blanchard-Desce, Mireille,Acher, Francine C.,Ogden, David,Dalko, Peter I.
-
supporting information
p. 6366 - 6369
(2013/02/23)
-
- Discovery of a new antileishmanial hit in 8-nitroquinoline series
-
A series of nitrated 2-substituted-quinolines was synthesized and evaluated in vitro toward Leishmania donovani promastigotes. In parallel, the in vitro cytotoxicity of these molecules was assessed on the murine J774 and human HepG2 cell lines. Thus, a very promising antileishmanial hit molecule was identified (compound 21), displaying an IC50 value of 6.6 μM and CC 50 values ≥ 100 μM, conferring quite good selectivity index to this molecule, in comparison with 3 drug-compounds of reference (amphotericin B, miltefosine and pentamidine). Compound 21 also appears as an efficient in vitro antileishmanial molecule against both Leishmania infantum promastigotes and the intracellular L. donovani amastigotes (respective IC50 = 7.6 and 6.5 μM). Moreover, hit quinoline 21 does not show neither significant antiplasmodial nor antitoxoplasmic in vitro activity and though, presents a selective antileishmanial activity. Finally, a structure-activity relationships study enabled to define precisely the antileishmanial pharmacophore based on this nitroquinoline scaffold: 2-hydroxy-8-nitroquinoline.
- Paloque, Lucie,Verhaeghe, Pierre,Casanova, Magali,Castera-Ducros, Caroline,Dumetre, Aurelien,Mbatchi, Litaty,Hutter, Sebastien,Kraiem-M'Rabet, Manel,Laget, Michele,Remusat, Vincent,Rault, Sylvain,Rathelot, Pascal,Azas, Nadine,Vanelle, Patrice
-
experimental part
p. 75 - 86
(2012/09/08)
-
- Tri-substituted triazoles as potent non-nucleoside inhibitors of the HIV-1 reverse transcriptase
-
A new series of 1,2,4-triazoles was synthesized and tested against several NNRTI-resistant HIV-1 isolates. Several of these compounds exhibited potent antiviral activities against efavirenz- and nevirapine-resistant viruses, containing K103N and/or Y181C mutations or Y188L mutation. Triazoles were first synthesized from commercially available substituted phenylthiosemicarbazides, then from isothiocyanates, and later by condensing the desired substituted anilines with thiosemicarbazones.
- De La Rosa, Martha,Kim, Hong Woo,Gunic, Esmir,Jenket, Cheryl,Boyle, Uyen,Koh, Yung-hyo,Korboukh, Ilia,Allan, Matthew,Zhang, Weijian,Chen, Huanming,Xu, Wen,Nilar, Shahul,Yao, Nanhua,Hamatake, Robert,Lang, Stanley A.,Hong, Zhi,Zhang, Zhijun,Girardet, Jean-Luc
-
p. 4444 - 4449
(2007/10/03)
-
- 5-SUBSTITUTED QUINOLINE AND ISOQUINOLINE DERIVATIVES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS ANTIPHLOGISTICS
-
The invention relates to compounds of general formulas (IIa) or (IIb) and to their use as medicaments.
- -
-
Page/Page column 28
(2008/06/13)
-
- Synthesis of quinaldines and lepidines by a Doebner-Miller reaction under thermal and microwave irradiation conditions using phosphotungstic acid
-
A simple and efficient method has been developed for the synthesis of quinaldines and lepidines by a one-pot reaction of anilines with crotonaldehyde or methyl vinyl ketone using phosphotungstic acid, a Keggins-type heteropoly acid, under both thermal and microwave irradiation conditions.
- Sivaprasad, Ganesabaskaran,Rajesh, Rengasamy,Perumal, Paramasivan T.
-
p. 1783 - 1785
(2007/10/03)
-
- Syntheses of Novel Quinolone-Chemotherapeutics, I: Pyridoquinolines and Pyridophenanthrolines as Derivatives of "lin-benzo-Nalidixic Acid"
-
Expansion of nalidixic acid (NA) has been accomplished by linear insertion of a benzo-ring between the two pyrido moieties.The resulting compounds exhibit antibacterial activity comparable to NA and are highly fluorescent.The regioselective hydrogenation of 1,7-phenanthrolines was studied. - Keywords: lin-Benzo-analogs; Quinolones; Pyridoquinoline; Pyridophenanthroline; Pyridophenanthroline; Regioselective hydrogenation of phenanthrolines; Fluorescence
- Jordis, U.,Sauter, F.,Rudolf, M.,Cai, Gan
-
p. 761 - 780
(2007/10/02)
-
- Long-Chain Alkyl-Substituted 1,10-Phenanthrolines as Surfactant Ligands for Transition-Metal Ions. 1. Synthesis of 4- and 4,7-n-Undecyl-Substituted 1,10-Phenanthrolines
-
A convenient synthesis for 4- and 7-n-undecyl-1,10-phenanthrolines, based on a modified Doebner-von Miller reaction, is described for the following 1,10-phenanthrolines: 4-n-undecyl, 4,7-di-n-undecyl, 2-methyl-4-n-undecyl, 2,9-dimethyl-4-n-undecyl, and 2-methyl-7-n-undecyl.
- Lund, Gary K.,Holt, Smith L.
-
p. 227 - 229
(2007/10/02)
-
