84895-10-3

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• 865-50-9 iodomethane-d3 
• 106-49-0 p-toluidine 
• 1664-98-8 paraformaldehyde-d2 
• 811-98-3 d⁽⁴⁾-methanol 

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• 1456524-38-1 C₁₂H₁₃⁽²⁾H₄NO₂ 
• 1417633-33-0 C₂₅H₁₇⁽²⁾H₆N₃ 
• 1421259-25-7 C₁₃H₁₂⁽²⁾H₃NO₂ 
• 51764-28-4 O-deuterio-1-methyl-1-phenyl-ethyl hydroperoxide 

Relevant academic research and scientific papers

N-deuterium methylamine compound and preparation method thereof

The invnetion discloses an N-deuterium methylamine compound and a preparation method thereof. The preparation method comprises the following steps: mixing an amine compound, a deuterium source and a photocatalyst, and carrying out a reaction in an inert g

Metal-Free Geminal Difunctionalization of Diazocarbonyl Compounds: A One-Pot Multicomponent Strategy for the Construction of α,β-Diamino Carbonyl Derivatives

An unprecedented three-component domino oxidative coupling of diazocompounds for the efficient synthesis of α-azido-β-amino esters with non-activated dimethylamino compounds and simple TMSN3 was achieved. The main features of this method include metal-free catalysis, satisfactory functional group tolerance, general applicability in complex molecule architectures, and excellent diastereoselectivity in the presence of chiral auxiliaries. In addition, several related control experiments have been conducted to investigate the reaction mechanism.

Mechanistic investigation of oxidative Mannich reaction with tert-butyl hydroperoxide. the role of transition metal salt

A general mechanism is proposed for transition metal-catalyzed oxidative Mannich reactions of N,N-dialkylanilines with tert-butyl hydroperoxide (TBHP) as the oxidant. The mechanism consists of a rate-determining single electron transfer (SET) that is uniform from 4-methoxy- to 4-cyano-N,N-dimethylanilines. The tert-butylperoxy radical is the major oxidant in the rate-determining SET step that is followed by competing backward SET and irreversible heterolytic cleavage of the carbon-hydrogen bond at the α-position to nitrogen. A second SET completes the conversion of N,N-dimethylaniline to an iminium ion that is subsequently trapped by the nucleophilic solvent or the oxidant prior to formation of the Mannich adduct. The general role of Rh2(cap) 4, RuCl2(PPh3)3, CuBr, FeCl 3, and Co(OAc)2 in N,N-dialkylaniline oxidations by T-HYDRO is to initiate the conversion of TBHP to tert-butylperoxy radicals. A second pathway, involving O2 as the oxidant, exists for copper, iron, and cobalt salts. Results from linear free-energy relationship (LFER) analyses, kinetic and product isotope effects (KIE and PIE), and radical trap experiments of N,N-dimethylaniline oxidation by T-HYDRO in the presence of transition metal catalysts are discussed. Kinetic studies of the oxidative Mannich reaction in methanol and toluene are also reported.

Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 CH bond and lewis acid catalysis

Ruthenium porphyrins (particularly [Ru(2,6-Cl2tpp)CO]; tpp = tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82

N-Demethylation of N,N-Dimethylanilines by the benzotriazole N-Oxyl radical: Evidence for a two-step electron transfer-proton transfer mechanism

"Chemical Equation Presented" The reaction of the benzotriazole N-oxyl radical (BTNO) with a series of 4-X-N,N-dimethylanilines (X = CN, CF 3, CO2CH2CH3, CH3, OC6H5, OCH3) has been investigated in CH 3CN. Product analysis shows that the radical, 4-X-C6H 4N(CH3)CH2·, is first formed, which can lead to the N-demethylated product or the product of coupling with BTNO. Reaction rates were found to increase significantly by increasing the electron-donating power of the aryl substituents (p+ = -3.8). With electron-donating substituents (X = CH3, OC6H5, OCH3), no intermolecular deuterium kinetic isotope effect (DKIE) and a substantial intramolecular DKIE are observed. With electron-withdrawing substituents (X = CN, CF3, CO2CH2CH 3), substantial values of both intermolecular and intramolecular DKIEs are observed. These results can be interpreted on the basis of an electron-transfer mechanism from the N,N-dimethylanilines to the BTNO radical followed by deprotonation of the anilinium radical cation (ET-PT mechanism). By applying the Marcus equation to the kinetic data for X = CH3, OC 6H5, OCH3 (rate-determining ET), a reorganization energy for the ET reaction was determined (λ BTNO/DMA= 32.1 kcal mol- 1). From the self-exchange reorganization energy for the BTNO/BTNO- couple, a self-exchange reorganization energy value of 31.9 kcal mol-1 was calculated for the DMA·+/DMA couple.

A kinetic study of the reaction of N,N-dimethylanilines with 2,2-diphenyl-1-picrylhydrazyl Radical: A Concerted Proton-Electron Transfer?

(Chemical Equation Presented) The reactivity of the 2,2-diphenyl-1- picrylhydrazyl radical (dpph?) toward the N-methyl C-H bond of a number of 4-X-substituted-N,N-dimethylanilines (X = OMe, OPh, CH3, H) has been investigated in MeCN, in the absence and in the presence of Mg(ClO4)2, by product, and kinetic analysis. The reaction was found to lead to the N-demethylation of the N,N-dimethylaniline with a rate quite sensitive to the electron donating power of the substituent (ρ+ = -2.03). With appropriately deuterated N,N-dimethylanilines, the intermolecular and intramolecular deuterium kinetic isotope effects (DKIEs) were measured with the following results. Intramolecular DKIE [(k H/kD)intra] was found to always be similar to intermolecular DKIE [(kH/kD)inter]. These results suggest a single-step hydrogen transfer mechanism from the N-C-H bond to dpph? which might take the form of a concerted proton-electron transfer (CPET). An electron transfer (ET) step from the aniline to dpph ? leading to an anilinium radical cation, followed by a proton transfer step that produces an α-amino carbon radical, appears very unlikely. Accordingly, a rate-determining ET step would require no DKIE or at least different inter and intramolecular isotope effects. On the other hand, an equilibrium-controlled ET is not compatible with the small slope value (-0.22 kcal-1 K-1) of the log kH/ΔG° plot. Furthermore, the reactivity increases by changing the solvent to the less polar toluene whereas the reverse would be expected for an ET mechanism. In the presence of Mg2+, a strong rate acceleration was observed, but the pattern of the results remained substantially unchanged: inter and intramolecular DKIEs were again very similar as well as the substituent effects. This suggests that the same mechanism (CPET) is operating in the presence and in the absence of Mg2+. The significant rate accelerating effect by Mg2+ is likely due to a favorable interaction of the Mg2+ ion with the partial negatively charged α-methyl carbon in the polar transition state for the hydrogen transfer process.

Reaction of N,N-Dimethylaniline Derivatives with Cumene Hydroperoxide. Oxazolidine Formation via Addition of α-Aminomethyl Radicals to Formaldehyde

The reactions of N,N-dimethylaniline derivatives (1) with cumene hydroperoxide in acetonitrile at 100 deg C produce significant amounts of the corresponding N-aryloxazolidine (6).Oxazolidine formation occurs by addition of α-aminomethyl radicals (7) to formaldehyde to give the alkoxy radical (8), followed by intramolecular 1,6 H-atom abstraction, oxidation, and cyclization.The results of labeling experiments and the dependence of the oxazolidine yield on the formaldehyde concentration support this mechanism.Alkoxy radical 8 was generated by an alternative route anddoes give the oxazolidine.Radical addition to the carbonyl carbon of formaldehyde is a reflection of the electron-rich, nucleophilic nature of the α-aminomethyl radical 7 and rapid trapping of the resulting alkoxy radical 8 via intramolecular H-atom abstraction through a six-membered transition state.