13720-52-0Relevant articles and documents
Close Amide NH···F Hydrogen Bonding Interactions in 1,8-Disubstituted Naphthalenes
Kazim, Muhammad,Siegler, Maxime A.,Lectka, Thomas
, p. 6195 - 6200 (2020)
In this note, we present a series of N-(8-fluoronaphthalen-1-yl)benzamide derivatives designed to maximize amide-NH···F hydrogen bond interactions therein. A combination of IR and NMR spectroscopy indicates a linear correlation between the high energy shi
Practical alternative synthesis of 1-(8-Fluoro-naphthalen-1-yl)piperazine
Zhu, Zhijian,Colbry, Norm L.,Lovdahl, Mark,Mennen, Kenneth E.,Acciacca, Alison,Beylin, Vladimir G.,Clark, Jerry D.,Belmont, Daniel T.
, p. 907 - 909 (2007)
Convergent synthesis of 8-fluoronaphthalen-1-ylamine (6) was achieved through the reaction of 1H-tauphtho[1,8-de][1,2,3]triazine (15) with HF-pyridine under mild conditions. This new synthesis for the preparation of 6 overcame many scale-up challenges that exist in the methods reported in the literature and provided a practical alternative synthesis of 1-(8-fluoronaphthalen-1-yl) piperazine (1).
Ethylene Polymerization with Ni(II) Diimine Complexes Generated from 8-Halo-1-naphthylamines: The Role of Equilibrating Syn/ Anti Diastereomers in Determining Polymer Properties
Wang, Bin,Daugulis, Olafs,Brookhart, Maurice
, p. 4658 - 4668 (2019)
A series of 8-halonapthalen-1-amines (6a-d, X = F, Cl, Br, I) were prepared and converted to the α-diimines of 2,3-butanedione (7a-d). The nickel dibromide and zinc dibromide complexes of these diimines (3a-d and 8a-d, respectively) were obtained in good yields from standard precursors. NMR spectroscopic analysis of the zinc diimine complexes show the existence of syn and anti diastereomers with syn/anti ratios of ca. 2:1 (F), 2:1 (Cl), 1:1.5 (Br), and ca. 1:22 (I). Variable temperature NMR spectroscopy was used to calculate barriers to interconversion of these diastereomers which fall in the range 17-18.5 kcal/mol. Activation of nickel dibromide complexes 3a-d with modified methyl alumoxane (MMAO) yields cationic diimine complexes in which the 8-halo substituents lie over the axial coordination sites. Ethylene polymerization using these activated complexes is reported. The anti diastereomer of the diiodo catalyst (10d) in which both axial sites are blocked yields high molecular weight PE (ca. 106 g/mol) as the major fraction with a high turnover frequency at 40 °C. The minor syn diastereomer of 10d in which only one axial site is blocked produces low molecular weight PE as a minor fraction. PE formed from the dichloro catalyst 10b also exhibits a bimodal polymer distribution, but the high molecular weight fraction from the anti diastereomer is minor, while the syn diastereomer produces low molecular weight PE. The dibromo complex (10c) is unique in that interchange of diastereomers is on a time scale such that the PE produced shows a very broad molecular weight distribution (MWD ca. 14), spanning the range from the low to high molecular weight regimes. Catalyst 10a, bearing the small fluoro substituents, yields very low molecular weight PE (ca. 600 g/mol).
Structural modifications of nile red carbon monoxide fluorescent probe: Sensing mechanism and applications
Klán, Petr,Madea, Dominik,Martínek, Marek,Muchová, Lucie,Váňa, Ji?í,Vítek, Libor
, p. 3473 - 3489 (2020/03/25)
Carbon monoxide (CO) is a cell-signaling molecule (gasotransmitter) produced endogenously by oxidative catabolism of heme, and the understanding of its spatial and temporal sensing at the cellular level is still an open challenge. Synthesis, optical properties, and study of the sensing mechanism of Nile red Pd-based CO chemosensors, structurally modified by core and bridge substituents, in methanol and aqueous solutions are reported in this work. The sensing fluorescence "off-on" response of palladacycle-based sensors possessing low-background fluorescence arises from their reaction with CO to release the corresponding highly fluorescent Nile red derivatives in the final step. Our mechanistic study showed that electron-withdrawing and electron-donating core substituents affect the rate-determining step of the reaction. More importantly, the substituents were found to have a substantial effect on the Nile red sensor fluorescence quantum yields, hereby defining the sensing detection limit. The highest overall fluorescence and sensing rate enhancements were found for a 2-hydroxy palladacycle derivative, which was used in subsequent biological studies on mouse hepatoma cells as it easily crosses the cell membrane and qualitatively traces the localization of CO within the intracellular compartment with the linear quantitative response to increasing CO concentrations.
NH+ - F hydrogen bonding in a fluorinated "Proton Sponge" derivative: Integration of solution, solid-state, gas-phase, and computational studies
Scerba, Michael T.,Leavitt, Christopher M.,Diener, Matthew E.,De Blase, Andrew F.,Guasco, Timothy L.,Siegler, Maxime A.,Bair, Nathaniel,Johnson, Mark A.,Lectka, Thomas
scheme or table, p. 7975 - 7984 (2011/12/01)
We report detailed studies on the characterization of an intramolecular NH - F hydrogen bond formed within a fluorinated "proton sponge" derivative. An ammonium ion, generated from 8-fluoro-N,N-dimethylnaphthalen-1- amine, serves as a charged hydrogen bond donor to a covalently bound fluorine appropriately positioned on the naphthalene skeleton. Potentiometric titrations of various N,N-dimethylnaphthalen-1-amines demonstrate a significant increase in basicity when hydrogen bonding is possible. X-ray crystallography reveals that NH - F hydrogen bonding in protonated 8-fluoro-N,N-di-methylnaphthalen-1-amine is heavily influenced by ion pairing in the solid state; bifurcated and trifurcated hydrogen bonds are formed depending on the counterion utilized. Compelling evidence of hydrogen bonding in the 8-fluoro-N,N-dimethylnaphthyl-1- ammonium cation is provided by gas-phase cryogenic vibrational photodissociation spectroscopy. Solution-phase infrared spectroscopy provides complementary results, and the frequencies of the N - H stretching mode in both phases are in excellent agreement with the computed vibrational spectra. NMR analysis of protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine demonstrates significant H - F coupling between the N - H hydrogen and fluorine that cannot be attributed to long-range, through-bond interactions; the couplings correlate favorably with calculated values. The results obtained from these experiments are congruent with the formation of an NH - F hydrogen bond upon protonation of 8-fluoro-N,N-dimethylnaphthalen-1-amine.
METHOD OF MAKING 8-FLUORO-NAPHTHALEN-1-YLAMINE AND RELATED COMPOUNDS
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Page/Page column 7-8, (2008/06/13)
A process is described for preparing 8-flouro-napthalen-l-ylamine comprising reacting lH-naphtlio[l,8-de][l,2,3]triazine with hydrogen fluoride or a complex of hydrogen fluoride and an n-donor base. A process is also set forth for using 8-fluoro- naphthalen-1-ylamine produced as described above in the preparation of l-(8-fluoro- napthalen-l-yl)-piperazine, which can be used as an intermediate in the production of 7- { 4- [4-(8-fluoro-napthalen- 1 -yl)-piperazin- 1 -yl] -butoxy } -3 ,4-dihydro- IH- [l,8]naphthyridin-2-one, a D2 partial agonist indicated for possible use in the treatment of schizophrenia.
