36375-86-7Relevant academic research and scientific papers
Zinc-mediated radical reactions of per- (or poly)fluorophenyl aromatic aldimines in aqueous media
Liu, Xinyuan,Zhu, Shizheng,Wang, Shaowu
, p. 683 - 691 (2004)
The intermolecular additions of alkyl halides to per- (or poly)fluorophenyl aromatic aldimines using zinc as a single-electron-transfer radical initiator have been studied in aqueous media. The reaction proceeds well for imines with different substituents at room temperature under air atmosphere and the corresponding fluorine-containing amines and 1,2-diamines are obtained in poor to good yields. A tentative reaction mechanism is proposed.
Preparation method of polyfluoroaniline
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Paragraph 0050; 0051; 0052; 0053, (2018/08/03)
The invention relates to a preparation method of polyfluoroaniline, according to the method, the polyfluoroaniline is prepared by a two-step common reaction from polyfluorobenzene as a raw material, the method has the characteristics of low reaction temperature, small pressure, low cost, and the like, is suitable for industrial production application, and is convenient for large-scale production;the polyfluoroaniline product obtained by the method has less impurities and high product purity.
Benzimidazolium sulfonate ligand precursors and application in ruthenium-catalyzed aromatic amine alkylation with alcohols
Kaloglu, Nazan,?zdemir, Ismail,Gürbüz, Nevin,Achard, Mathieu,Bruneau, Christian
, p. 33 - 38 (2015/11/17)
New benzimidazolium sulfonate salts have been prepared and fully characterized. They have been associated in situ with [RuCl2(p-cymene)]2 to generate efficient catalytic systems operating at 120 °C under neat conditions in the presence of potassium tert-butylate for selective N-alkylation of primary aromatic amines into secondary amines.
Selective radical amination of aldehydic C(sp2)-H bonds with fluoroaryl azides via Co(ii)-based metalloradical catalysis: Synthesis of N-fluoroaryl amides from aldehydes under neutral and nonoxidative conditions
Jin, Li-Mei,Lu, Hongjian,Cui, Yuan,Lizardi, Christopher L.,Arzua, Thiago N.,Wojtas, Lukasz,Cui, Xin,Zhang, X. Peter
, p. 2422 - 2427 (2014/05/20)
The Co(ii) complex of the D2h-symmetric amidoporphyrin 3,5-DitBu-IbuPhyrin, [Co(P1)], has proven to be an effective metalloradical catalyst for intermolecular amination of C(sp2)-H bonds of aldehydes with fluoroaryl azides. The [Co(P1)]-catalyzed process can employ aldehydes as the limiting reagents and operate under neutral and nonoxidative conditions, generating nitrogen gas as the only byproduct. The metalloradical aldehydic C-H amination is suitable for different combinations of aldehydes and fluoroaryl azides, producing the corresponding N-fluoroaryl amides in good to excellent yields. A series of mechanistic studies support a stepwise radical mechanism for the Co(ii)-catalyzed intermolecular C-H amination. This journal is the Partner Organisations 2014.
Elevated catalytic activity of ruthenium(II)-porphyrin-catalyzed carbene/nitrene transfer and insertion reactions with n-heterocyclic carbene ligands
Chan, Ka-Ho,Guan, Xiangguo,Lo, Vanessa Kar-Yan,Che, Chi-Ming
supporting information, p. 2982 - 2987 (2014/04/03)
Bis(NHC)ruthenium(II)-porphyrin complexes were designed, synthesized, and characterized. Owing to the strong donor strength of axial NHC ligands in stabilizing the trans Mi￡CRR′/Mi￡NR moiety, these complexes showed unprecedently high catalytic activity towards alkene cyclopropanation, carbene C-H, N-H, S-H, and O-H insertion, alkene aziridination, and nitrene C-H insertion with turnover frequencies up to 1950 min-1. The use of chiral [Ru(D4-Por)(BIMe)2] (1 g) as a catalyst led to highly enantioselective carbene/nitrene transfer and insertion reactions with up to 98 % ee. Carbene modification of the N terminus of peptides at 37 °C was possible. DFT calculations revealed that the trans axial NHC ligand facilitates the decomposition of diazo compounds by stabilizing the metal-carbene reaction intermediate.
Isomerization and deuterium scrambling evidence for a change in the rate-limiting step during imine hydrogenation by Shvo's hydroxycyclopentadienyl ruthenium hydride
Casey, Charles P.,Johnson, Jeffrey B.
, p. 1883 - 1894 (2007/10/03)
Hydroxycyclopentadienyl ruthenium hydride 5 efficiently reduces imines below room temperature. Better donor substituents on nitrogen give rise to faster rates and a shift of the rate-determining step from hydrogen transfer to amine coordination. Reduction of electron-deficient N- benzilidenepentafluoroaniline (8) at 11°C resulted in free amine and kinetic isotope effects of kOH/kOD = 1.61 ± 0.08, k RuH/kRuD = 2.05 ± 0.08, and kRuHOH/ kRuDOD = 3.32 ± 0.14, indicative of rate-limiting concerted hydrogen transfer, a mechanism analogous to that proposed for aldehyde and ketone reduction. Reduction of electron-rich N-alkyl-substituted imine, N-isopropyl-(4-methyl)benzilidene amine (9), was accompanied by facile imine isomerization and scrambling of deuterium labels from reduction with 5-RuDOH into the N-alkyl substituent of both the amine complex and into the recovered imine. Inverse equilibrium isotope effects were observed in the reduction of N-benzilidene-tert-butylamine (11) at -48°C (kOH/kOD = 0.89 ± 0.06, kRuH/kRuD = 0.64 ± 0.05, and kRuHOH/kRuDOD = 0.56 ± 0.05). These results are consistent with a mechanism involving reversible hydrogen transfer followed by rate-limiting amine coordination.
Chemistry and kinetics of singlet (pentafluorophenyl)nitrene
Poe, Russell,Schnapp, Karlyn,Young, Mary J.T.,Grayzar, Jennifer,Platz, Matthew S.
, p. 5054 - 5067 (2007/10/02)
The chemistry and kinetics of singlet (pentafluorophenyl)nitrene were studied by chemical trapping and laser flash photolysis techniques. Photolysis of pentafluorophenyt azide in cyclohexane, benzene, diethylamine, pyridine, tetramethylethylene, tetrahydrofuran, dimethyl sutfoxide, and dimethyl sulfide forms adducts in fair to good yields. At ambient temperature singlet (pentafluorophenyl)nitrene is intercepted, and intersystem crossing to the lower energy triplet state is unimportant. Triplet nitrene chemistry can be achieved by benzoylbiphenyl photosensitization, the presence of methanol or ethyl iodide, or by lowering the reaction temperature below 0 °C. The singlet nitrenc adduct formed in pyridine is an ylide whose structure has been determined by X-ray crystallography. The ylide has an intense absorption maximum at 390 nm which varies only slightly with solvent. The pyridine ylicle is a useful probe for monitoring the absolute kinetics of singlet (pentafluorophenyl)nitrene by laser flash photolysis techniques.
