85328-29-6Relevant academic research and scientific papers
Exploration of mechanochemical activation in solid-state fluoro‐grignard reactions
Hanusa, Timothy P.,Speight, Isaiah R.
supporting information, (2020/02/06)
Owing to the strength of the C–F bond, the ‘direct’ preparation of Grignard reagents, i.e., the interaction of elemental magnesium with an organic halide, typically in an ethereal solvent, fails for bulk magnesium and organofluorine compounds. Previously described mechanochemical methods for preparing Grignard reagents have involved ball milling powdered magnesium with organochlorines or bromines. Activation of the C–F bond through a similar route is also possible, however. For example, milling 1- and 2-fluoronaphthalene with an excess of magnesium metal for 2 h, followed by treatment with FeCl3 and additional milling, produces the corresponding binaphthalenes, albeit in low yields (ca. 20%). The yields are independent of the particular isomer involved and are also comparable to the yields from corresponding the bromonaphthalenes. These results may reflect similar charges that reside on the α-carbon in the naphthalenes, as indicated by density functional theory calculations.
Control of tandem isomerizations: Flow-assisted reactions of: O -lithiated aryl benzyl ethers
Lee, Hyune-Jea,Kim, Heejin,Yoshida, Jun-Ichi,Kim, Dong-Pyo
, p. 547 - 550 (2018/01/19)
Tandem chemical changes are often difficult to control at will, because they proceed rapidly through multiple unstable reactive intermediates. It is desirable to develop a novel method for controlling such tandem changes to obtain desired products with high selectivity. Herein, we report a flow microreactor platform for controlling tandem isomerizations of o-lithiated aryl benzyl ethers based on precise residence time control.
On the Reactivity of o-Lithioaryl Ethers: Tandem Anion Translocation and Wittig Rearrangement
Barluenga, Jose,Fananas, Francisco J.,Sanz, Roberto,Marcos, Cesar,Trabada, Marta
, p. 1587 - 1590 (2007/10/03)
(matrix presented) Allyl and benzyl 2-lithioaryl ethers, generated by bromine-lithium exchange in THF, undergo a new tandem anion translocation-[1,2]-Wittig rearrangement allowing the isolation of the corresponding benzylic alcohols.
Cycloallenes. Part 15:1 3δ2-1H-naphthalene (2,3-didehydro-1,2- dihydronaphthalene) from 3-bromo-1,2-dihydronaphthalene
Groetsch, Stefan,Spuziak, Joanna,Christl, Manfred
, p. 4163 - 4171 (2007/10/03)
As a test as to whether the title intermediate 13 can be liberated from 3-bromo-1,2-dihydronaphthalene (19), the latter was treated with potassium tert-butoxide (KOtBu). Being the major products, naphthalene (20) and 3-tert- butoxy-1,2-dihydronaphthalene (21) provide unambiguous evidence for the intermediacy of 13. When the reaction was carried out in the presence of furan, 2,5-dimethylfuran and spiro[2,4]hepta-4,6-diene, expected (31, 32, 33, 34) and unexpected compounds (30, 35-37) were formed, which either directly resulted from the cycloaddition of 13 or were consecutive products of cycloadducts. Performed in the presence of benzophenone, the generation of 13 gave, inter alia, naphth-2-yldiphenylmethanol (27). This product testifies the intermediacy of the naphth-2-yl anion (24), which emerged from the deprotonation of 13 and was trapped by benzophenone. (C) 2000 Elsevier Science Ltd.
Influence of some novel N-substituted azoles and pyridines on rat hepatic CYP3A activity
Slama, James T.,Hancock, Julie L.,Rho, Taikyun,Sambucetti, Lidia,Bachmann, Kenneth A.
, p. 1881 - 1892 (2008/04/18)
A series of N-substituted heteroaromatic compounds structurally related to clotrimazole was synthesized, and the effects of these compounds on ethosuximide clearance in rats were determined as a measure of their abilities to induce cytochrome P4503A (CYP3A) activity. Ethosuximide clearance and in vitro erythromycin N-demethylase activity were shown to correlate. In this series, imidazole or other related heteroaromatic 'head groups' were linked to triphenylmethane or other phenylmethane derivatives. Within the series, it was found that 1-triphenylmethane-substituted imidazoles elicited the greatest increase in CYP3A activity, and that among the triphenylmethyl-substituted imidazoles, the highest activities were achieved by the substitution of F- or Cl- in either the meta or para position of one of the phenyl rings. Diphenylmethylsubstituted pyridine was effectively devoid of activity. Compounds eliciting the largest increase in CYP3A activity (viz. 1-[(3-fluorophenyl)diphenylmethyl]imidazole, 1-[(4- fluorophenyl)diphenylmethyl]imidazole, and 1-[tri-(4- fluorophenyl)methyl]imidazole) produced little or no increase in ethoxyresorufin O-dealkylase (EROD) activity (i.e. CYP1A), whereas benzylimidazole, which elicited only a small increase in CYP3A activity, produced an almost 9-fold increase in CYP1A activity. For a series of eleven compounds exhibiting a wide range of influence on CYP3A activity, a positive correlation was found between ethosuximide clearance and hepatic CYP3A mRNA levels.
Allene/haloolefin electrocyclic reactions: A new route to stable triarylmethyl radicals
Porter, Ned A.,Hogenkamp, Derk J.,Khouri, Farid F.
, p. 2402 - 2407 (2007/10/02)
Electrocyclization of allene 1,1-diphenyl-3-[2-(2-bromoethenyl)phenyl]propadiene (5), followed by one-electron reduction with elemental mercury, gives β-naphthyldiphenylmethyl radical 6 in good yield. In the absence of mercury, the only product isolated i
ONE-STEP SYNTHESIS OF KETONES FROM CARBOXYLIC ACIDS AND GRIGNARD REAGENTS IN THE PRESENCE OF A NICKEL(II)-PHOSPHINE CATALYST.
Fiandanese, V.,Marchese, G.,Ronzini, L.
, p. 3677 - 3680 (2007/10/02)
A one-step synthesis of diaryl and alkyl-aryl ketones by the reaction of carboxylic acid with Grignard reagents in the presence of NiCl2(Ph2PCH2CH2PPh2) as catalyst is described.In the nickel-catalyzed Grignard reaction the formation of alcohols is nearly completely suppressed.
