35031-52-8Relevant academic research and scientific papers
Solvent free, light induced 1,2-bromine shift reaction of α-bromo ketones
An, Sejin,Moon, Da Yoon,Park, Bong Ser
, p. 6922 - 6928 (2018/10/24)
Photolysis of α-bromopropiophenones in acetonitrile results in formation of β-bromopropiophenones with good product selectivity, which can be coined as 1,2-Br shift reaction. The product selectivity increases when the reaction is done in neat or solid state, where only the 1,2-Br shift product is formed in some cases. The reaction is suggested to proceed by C–Br bond homolysis to give a radical pair, followed by disproportionation and conjugate addition of HBr to the α,β-unsaturated ketone intermediate. When the unsaturated intermediate is stabilized by an extra conjugation, the reaction stops at the stage, in which the unsaturated ketone becomes a major product. The synthetic method described in this research fits in a category of eco-friendly organic synthesis nicely since the reaction does not use volatile organic solvents and any other additives such as acid, base or metal catalysts, etc. Besides, the method fits into perfect atom economy, which does not give any side products. The synthetic method should find much advantage over other alternative methods to obtain β-bromo carbonyl compounds.
Photoenolization-induced oxirane ring opening in 2,5-dimethylbenzoyl oxiranes to form pharmaceutically promising indanone derivatives
Solomek, Tomas,Stacko, Peter,Tazhe Veetil, Aneesh,Pospisil, Tomas,Klan, Petr
experimental part, p. 7300 - 7309 (2011/01/12)
Irradiation of 2,5-dimethylbenzoyl oxiranes results in a relatively efficient and high-yielding formation of β-hydroxy functionalized indanones that structurally resemble biologically active pterosines. Nanosecond laser flash photolysis and quantum-chemical calculations based on density functional theory provided evidence that this photochemical transformation proceeds primarily via a photoenolization mechanism. Our study revealed considerable complexity of the mechanism and that structural modifications can significantly alter the reaction pathway and yield different products. The scope of this photochemical transformation for the synthesis of some pharmaceutically important compounds was investigated.
Friedel-Crafts acylation reaction using carboxylic acids as acylating agents
Kawamura, Masato,Cui, Dong-Mei,Shimada, Shigeru
, p. 9201 - 9209 (2007/10/03)
Dehydrative Friedel-Crafts acylation reaction of aromatic compounds with carboxylic acids as acylating agents was investigated in the presence of Lewis acid- or Br?nsted acid-catalyst. Various metal triflates and bis(trifluoromethanesulfonyl)amides showed catalytic activity at high temperature, among which Eu(NTf2)3 proved to be the most effective and efficiently catalyzed the acylation reaction of alkyl- and alkoxybenzenes with aliphatic and aromatic carboxylic acids at 250 °C. Bi(NTf2)3 was more effective than Eu(NTf2)3 at lower temperature, but proved to be hydrolyzed in the presence of a small amount of water to give HNTf2 and [Bi6O4(OH)4(H2O)6](NTf2)6. The structure of the latter compound was confirmed by a single crystal X-ray analysis. Among five Br?nsted acids, HOTf, HNTf2, HCTf3, TsOH, and Nafion SAC-13, HNTf2 has proved to be the most efficient catalyst and more effective than Eu(NTf2)3 for the acylation of p-xylene with heptanoic acid at 220 °C or lower temperature. HNTf2 catalyzed the acylation of anisole with carboxylic acids in high yields in refluxing toluene with azeotropic removal of water.
Lewis acid-catalyzed Friedel-Crafts acylation reaction using carboxylic acids as acylating agents
Kawamura, Masato,Cui, Dong-Mei,Hayashi, Teruyuki,Shimada, Shigeru
, p. 7715 - 7717 (2007/10/03)
Rare-earth metal Lewis acids, in particular Eu(NTf2) 3, were found to be efficient catalysts for Friedel-Crafts acylation reaction using aliphatic as well as aromatic carboxylic acids as acylating agents at high temperature.
Synthesis of substituted indeno[1,2-b]quinoline-6-carboxamides, [1]benzothieno[3,2-b]quinoline-4-carboxamides and 10H-quindoline-4-carboxamides: Evaluation of structure-activity relationships for cytotoxicity
Chen, Junjie,Deady, Leslie W.,Desneves, Jose,Kaye, Anthony J.,Finlay, Graeme J.,Baguley, Bruce C.,Denny, William A.
, p. 2461 - 2466 (2007/10/03)
New substituted indeno[1,2-b]quinoline-6-carboxamides, [1]benzothieno[3,2-b]quinoline-4-carboxamides and 10H-quindoline-4-carboxamides were prepared from methyl 2-amino-3-formylbenzoate by a new Friedlander synthesis. Evaluation of these carboxamides for cytotoxicity in a panel of cell lines showed that small lipophilic substituents in the non-carboxamide ring, in a pseudo-peri position to the side chain, significantly increased cytotoxic potency while retaining a pattern of cytotoxicity consistent with a non-topo II mode of action. The methyl-substituted indeno[1,2-b]quinoline-6-carboxamide demonstrated substantial effectiveness (20-day growth delays) in a sub-cutaneous colon 38 in vivo tumor model. This is comparable to that reported for the dual topo I/II inhibitor DACA that is in clinical trial. Copyright (C) 2000 Elsevier Science Ltd.
Photoenolization with α-Chloro Substituents
Bergmark, William R.,Barnes, Curtis,Clark, Jeffrey,Paparian, Seth,Marynowski, Susan
, p. 5612 - 5615 (2007/10/02)
Irradiation of a methanol solution of 2,5-dimethyl-α-chloropropiophenone (1a) produces 2,6-dimethyl-1-indanone (2a), 2-(methoxymethyl)-5-methylpropiophenone (3a), 2,5-dimethylpropiophenone (4a), and methyl 2-(2,5-dimethylphenyl)propionate (5a).It is proposed that the first two products arise from hydrogen abstraction followed by chlorine loss, the latter two from initial loss of chlorine.Making the chlorine-bearing carbon primary suppresses the formation of the latter two products, while maintaining the carbonyl nearly planar with the ring suppresses all product formation.Other examples are presented.
