765-48-0Relevant academic research and scientific papers
AMMONIUM SALT, ELECTROLYTE FOR LITHIUM SECONDARY BATTERY, AND LITHIUM SECONDARY BATTERY USING THEM
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Paragraph 0051; 0065, (2017/12/01)
PROBLEM TO BE SOLVED: To provide: ammonium salt with low viscosity; an electrolyte for a lithium secondary battery; and the lithium secondary battery. SOLUTION: This invention relates to an ammonium salt expressed by the following chemical formula (1). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT
IONIC LIQUID
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Paragraph 0194; 0195, (2016/10/08)
PROBLEM TO BE SOLVED: To provide an ionic liquid having high electrochemical stability and a low melting point. SOLUTION: An ionic liquid represented by the following general formula (G0) is provided. In the general formula (G0), R0 to R5 are individually any of an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, and a hydrogen atom, and A- is a univalent imide-based anion, a univalent methide-based anion, a perfluoroalkyl sulfonic acid anion, tetrafluoroborate, or hexafluorophosphate. COPYRIGHT: (C)2016,JPOandINPIT
Hydroamination/cyclization of aminoalkenes using cationic zirconocene and titanocene catalysts
Gribkov, Denis V.,Hultzsch, Kai C.
, p. 5542 - 5546 (2007/10/03)
Alternative catalysts: The hydroamination of nonactivated double bonds has been the domain of rare-earth-metal catalysts. Now alkyl zirconocene and titanocene cations, which are readily prepared from commercially available precursors, are shown to be active catalysts in the hydroamination/cyclization of secondary aminoalkenes to give tertiary pyrrolidines and piperidines.
Organolanthanide-catalyzed hydroamination. A kinetic, mechanistic, and diastereoselectivity study of the cyclization of N-unprotected amino olefins
Gagné, Michel R.,Stern, Charlotte L.,Marks, Tobin J.
, p. 275 - 294 (2007/10/02)
This contribution reports the efficient, regiospecific Cp'2LnR [Cp' = η5-Me5C5; R = H, CH(TMS)2,η3-C3H5, N(TMS)2; Ln = La, Nd, Sm, Y, Lu]-catalyzed hydroamination/cyclization of the amino olefins H2NCHR1R2CH=CH2 to yield the corresponding heterocycles HNCH(R1)R2CHCH3, where R1, R2, Nt (turnover frequency, h-1), °C: H, (CH2)2, 140, 60 °C; H, CMe2CH2, 95, 25 °C; H, (CH2)3, 5, 60 °C; CH3, (CH2)2, 45, 25 °C; H, CH(Me)CH2, 38, 25 °C; and o-C6H4, CH2, 13, 80 °C. In addition, Me2Si(Me4C5)2NdCH(TMS)2 effects the cyclization of CH3HN(CH2)3CH=CH2 and H2NCH2CMe2(CH2) 3CH=CH2 with Nt = 11 h-1 (25 °C) and 0.3 h-1 (60 °C), respectively. Reactions are zero-order in substrate over 3 or more half-lives, and for the cyclization of HvN(CH2)3CH=CH2 by catalyst precursor Cp'2LaCH(TMS)2, ΔH? = 12.7 (1.4) kcal mol-1 and ΔS? = -27 (5) eu. Kinetic isotope effects (kH/kD) of 2.7 (4) (60 °C), 5.2 (8) (25 °C), and 4.1 (8) (25 °C) are observed for the Cp'2LaCH(TMS)2-induced cyclizations of D2N(CH2)3CH=CH2, D2NCH(C-H3)(CH2)2CH=CH2, and D2NCH2C(CH3)2CH 2CH=CH2, respectively. Cyclization yields the corresponding DNCH-(R1)R2CHCH2D isotopomers exclusively. Cyclization of H2NCH2C(CH3)2CH 2CH=CH2 by catalyst precursor Cp'2LaCH(TMS)2 exhibits the solvent effect, ktoluene/kTHF = 5.3 (5). The complexes Cp'2LnNHR(H2NR) (Ln = La, R = CH3, CH2CH3; Ln = Nd, R = CH2CH3) and Cp'2LaNCH(CH3)CH2CR2CH 2(HNCH(CH3)CH2CR2CH2) (R = H, CH3) were synthesized to model species in the catalytic cycle. Crystallographic data for Cp'2LaNHCH3(H2NCH3) at -120 °C were as follows: P21, Z = 4, a = 19.901 (4) A?, b = 11.695 (3) A?, c = 20.202 (3) A, β- 97.95 (2)°, and R(F) = 0.049 for 3296 independent reflections with I > 2.58σ(I). Two independent molecules crystallize per unit cell with average La-NHCH3 and La←NH2CH3 bond distances of 2.31 (1) and 2.70 (1) A?, respectively. The two molecules differ slightly in relative orientations of the NCH2 groups. The amine-amido complexes undergo rapid intramolecular proton transfer between amine and amido ligands (Δ? ≈ 12.4 ± 0.5 kcal mol-1). Intermolecular exchange with free amine is rapid on the NMR time scale at -80 °C. The ordering of precatalyst activities, (Cp'2LaCH(TMS)2 > Cp'2mCH(TMS)2 > Cp'2LuCH(TMS)2; Et2Si(C5H4)-(Me4C 5)LuCH(TMS)2 > Me2Si(Me4C5)2LuCH(TMS)2 > Cp'2LuCH(TMS)2) accords with known olefin insertion reactivities. Diastereoselection in H2NCH(CH3)(CH2)2CH=CH2 (5) cyclization depends on both lanthanide and ancillary ligation. Final 2,5-dimethylpyrrolidine transtcis ratios in LnLnR-catalyzed reactions for Ln, Ln, trans:cis, °C are as follows: Cp'2, La, 3:2, 50 °C; Cp'2, La, 5:1, 25 °C; Cp'2, La, 8:1, 0 °C; Cp'2, Nd, 1:1.25, 25 °C; Cp'2, Sm, 1:1.25, 25 °C; Cp'2, Y, 8:1, 25 °C; Me2Si(Me4C5)2, Y, 3:1, 25 °C; Et2Si(H4C5)(Me4C5), Y, 18:1, 25 °C; Et2Si(H4C5)(Me4C5), Lu, 4:1, 25 °C. For the Cp'2LaCH(TMS)2-catalyzed case, the trans:cis ratio is also dependent on the extent of conversion and initial substrate:catalyst ratio. In contrast to 5, 5d2 exhibits low diastereoselectivity which is independent of conversion. In the presence of 3 equiv of n-propylamine, the Cp'2LaCH(TMS)2-catalyzed cyclization of 5 affords a ≥50:1 trans:cis product ratio. Mechanistic evidence suggests that olefin insertion into the Ln-N bond of the amine-amido complexes is turnover-limiting and is followed by a rapid protonolysis of the resulting Ln-C bond. The proposed catalytic mechanism invokes parallel manifolds, with one manifold populated at high amine concentrations exhibiting high diastereoselectivity in the cyclization of 5, and with the second, favored at low substrate concentrations, exhibiting lower diastereoselectivity. The catalyst at high amine concentrations is postulated to be a Ln(amido)(amine)2 complex.
Highly Selective Aromatic Chlorination. Part 3. Kinetics and Mechanism of Chlorination of Electron-rich Aromatic Compounds by N-Chloroamines in Acidic Solution
Smith, John R. Lindsay,McKeer, Linda C.,Taylor, Jonathan M.
, p. 1529 - 1536 (2007/10/02)
The highly selective chlorination of electron-rich aromatic compounds with N-chloroamines in trifluoroacetic acid (TFA) is first order in both the aromatic substrate and the chlorinating agent.Kinetic and competitive kinetic studies show that electron-donating substituents on the substrate and electron-withdrawing substituents on the N-chloroamine have a marked rate-enhancing effect.Two mechanisms that fit the experimentally observed kinetics and that account for the high selectivity for 4-chlorination in terms of an electronic effect are proposed, namely an arenium-ion mechanism and an electron-transfer chain reaction.Evidence from chemical trapping experiments and from other studies suggest that for the majority of the substrates the chlorination proceeds by the arenium ion mechanism.However, for substrates, such as 1,4-dimethoxybenzene, that are very susceptible to one-electron oxidation chlorination may proceed at least in part by the electron-transfer chain reaction.
Arene-Iminium Salt Electron-Transfer Photochemistry. Mechanistically Interesting Photoaddition Processes
Borg, Robert M.,Heuckeroth, Robert O.,Lan, Alexander J. Y.,Quillen, Suzanne L.,Mariano, Patrick S.
, p. 2728 - 2737 (2007/10/02)
Studies of the electron-transfer photochemistry of arene-iminium salt systems have been explored.Fluorescence quenching investigations have demonstrated that a series of arenes including substituted toluenes and benzenes quench the fluorescence of a variety of 2-aryl-1-pyrrolinium perchlorates.Quenching rate constants in these cases correlate with the ΔGSET values as expected for quenching by reversible electron-transfer pathways.In addition, nonconjugated iminium salts quench the fluorescence of a host of arenes with kq values which parallel those predicted on the basis of electron-transfer free energy calculations.Photoaddition reactions of toluene, benzyltrimethylstannane, and 2-aryl-1-pyrrolinium salts have been explored.Likewise, electron-transfer-induced, excited-state reactions of toluene and benzyltrimethylsilane with 1,2-dimethyl-1-pyrrolinium perchlorate have been investigated.The results of these photoreactions have been interpreted in terms of steric, electrofugal group, and solvent effects upon the rates of competitive pathways available to initially formed radical cation pair intermediates.Finally, the photochemistry of benzyltrimethylstannane is described.
CYCLIZATION OF AMINYL RADICALS GENERATED BY ANODIC OXIDATION OF LITHIUM ALKENYLAMIDES. STEREO- AND REGIOSELECTIVE SYNTHESIS OF cis-1-ALKYL-2,5-DISUBSTITUTED PYRROLIDINES
Tokuda, Masao,Yamada, Yasufumi,Takagi, Toshiya,Suginome, Hiroshi,Furusaki, Akio
, p. 281 - 296 (2007/10/02)
Neutral aminyl radicals (3) generated by anodic oxidation of lithium alkenylamides (2) were found to undergo a stereo- and regioselective cyclization to give cis-1-alkyl-2,5-disubstituted pyrrolidines (5c-5h) in moderate yields.The cis stereochemistry of 5c-5h was confirmed by comparison with the corresponding trans-1-alkyl-2,5-disubstituted pyrrolidines which were prepared by aminomercuration of 1c-1h.The structure of trans-1,2-dimethyl-5-phenylpyrrolidine (17) was established by an X-ray crystallographic analysis of its ammonium bromide 21.Various aminyl radicals examined in this study were found to combine exclusively with the internal carbon of their double bond to give a five- (5a-5h) or six-membered ring (13).No product arising from the cyclization is obtained from N-methyl-1-phenylbut-3-enylamine (14).
Synthesis of Some Substituted Pyrrolidines from Cyclopropyl Carbonyl Compounds
Blake, Keith W.,Gillies, Iain,Denney, Ronald C.
, p. 700 - 702 (2007/10/02)
A series of alkyl and aryl cyclopropyl carbonyl compounds, when refluxed in N-methylformamide in the presence of magnesium chloride, gave variously substituted pyrrolidines.
