36622-84-1

Upstream product

• 88889-00-3 N-methyl-N-(methyl-d₃)aniline 
• 91632-85-8 N-(trideuteriomethyl)-4-toluenesulfonanilide 
• 86099-83-4 2-(N-trideuteriomethylanilino)indan-1-one 
• 865-50-9 iodomethane-d3 
• 62-53-3 aniline 
• 541-41-3 chloroformic acid ethyl ester 
• 3422-01-3 tert-butyl phenylcarbamate 
• 68-34-8 phenyl toluenesulfonamide 
• 4019-61-8 N,N-bis(trideuteromethyl)aniline 
• 2291-80-7 iso-butyl N-phenylcarbamate 
• 811-98-3 d⁽⁴⁾-methanol 
• 1849-29-2 1,1,1-trideuteromethanol 

Downstream Products

• 86099-83-4 2-(N-trideuteriomethylanilino)indan-1-one 
• 4019-61-8 N,N-bis(trideuteromethyl)aniline 

Relevant academic research and scientific papers

A re-examination of the S0 -> S1 excitation spectrum of dimethylaniline

A new assignment for the S0->S1, transition of N,N-dimethylaniline (DMA) and related derivatives is presented.The 1ow frequency bands and long Franck-Condon envelope observed in DMA-h6 and DMA-d6 are assigned to the coupled methyl torsion mode of the amino group, not to torsion of the amino substituent about the C-N bond.This new assignment is consistent with the change in frequency of the excitation bands upon deuteration of the methyl groups and the strong origin transitions observed in the excitation spectra of other alkyl anilines.The assignment was confirmed by simulations of the excitation spectra of DMA-h6 and DMA-d6, with parameters of the calculated potential energy surface determined to be V3=148.0+/-0.5 cm-1, V+=-31.6+/-0.5 cm-1, V-=8.5+/-0.5 cm-1, and V6=-15+/-0.5 cm-1.By Franck-Condon analysis, it was determined that the weak origin transition is due to the shifting of the S1 torsion minimum by 40 deg along the gearing coordinate relative to the corresponding minimum in the ground state.

On isotope effects for the cytochrome P-450 oxidation of substituted N,N-dimethylanilines

Isotope effects were determined for the oxidative demethylation of the substituted N-methyl-N-(trideuteriomethyl)anilines 1a-d, and the corresponding N,N-bis(dideuteriomethyl)anilines 2a-d, by microsomal cytochrome P-450. The pairs of p-cyano- and p-nitro

Environmentally Benign Synthesis of Quinoline-Spiroquinazolinones by Iron-Catalyzed Dehydrogenative [4 + 2] Cycloaddition of Secondary/Tertiary Anilines and 4-Methylene-quinazolinones

We report an efficient iron-catalyzed cross-dehydrogenative coupling [4 + 2] annulation of secondary/tertiary anilines with quinazolinones to generate quinoline-spiroquinzolinones. The reaction proceeds smoothly with a relatively broad variety of function

Efficient methylation of anilines with methanol catalysed by cyclometalated ruthenium complexes

Cyclometalated ruthenium complexes4-10allow the effective methylation of anilines with methanol to selectively giveN-methylanilines. This hydrogen autotransfer procedure proceeds under mild conditions (60 °C) in a practical manner (NaOH as base). Mechanistic investigations suggest an active homogenous ruthenium complex and β-hydride elimination of methanol as the rate determining step.

Ru-Catalyzed Selective Catalytic Methylation and Methylenation Reaction Employing Methanol as the C1 Source

Methanol can be employed as a green and sustainable methylating agent to form C-C and C-N bonds via borrowing hydrogen (BH) methodology. Herein we explored the activity of the acridine-derived SNS-Ru pincer for the activation of methanol to apply it as a C1 building block in different reactions. Our catalytic system shows great success toward the β-C(sp3)-methylation reaction of 2-phenylethanols to provide good to excellent yields of the methylated products. We investigated the mechanistic details, kinetic progress, and temperature-dependent product distribution, which revealed the slow and steady generation of in situ formed aldehyde, is the key factor to get the higher yield of the β-methylated product. To establish the environmental benefit of this reaction, green chemistry metrics are calculated. Furthermore, dimerization of 2-naphthol via methylene linkage and formation of N-methylation of amine are also described in this study, which offers a wide range of substrate scope with a good to excellent yield.

Photon-initiated heterogeneous redox couples for methylation of anilines under mild conditions

Methylation of anilines has drawn a lot of attention due to their valuable applications and directly using methanol as a methylation reagent is of great advantage. Photon-initiated heterogeneous catalysis of this methylation process meets the requirements of green chemistry. Herein we show that balanced redox zones within carbon nitride supported Pd nanoparticles boost the selectivity of methylation of anilines under mild conditions.

Catalytic Selective Oxidative Coupling of Secondary N-Alkylanilines: An Approach to Azoxyarene

Azoxyarenes are among important scaffolds in organic molecules. Direct oxidative coupling of primary anilines provides a concise fashion to construct them. However, whether these scaffolds can be prepared from secondary N-alkylanilines is not well explored. Here, we present a catalytic selective oxidative coupling of secondary N-alkylaniline to afford azoxyarene with tungsten catalyst under mild conditions. In addition, azoxy can be viewed as a bioisostere of alkene and amide. Several "azoxyarene analogues" of the corresponding bioactive alkenes and amides showed comparable promising anticancer activities.

N-Monomethylation of Aromatic Amines with Methanol via PNHP-Pincer Ru Catalysts

The use of methanol for the selective methylation of aromatic amines with RuHCl(CO)(PNHP) (PNHP = bis(2-diphenylphosphinoethyl)amine) is reported. Various aromatic amines were transformed into their corresponding monomethylated secondary amines in high yields at 150 °C with a very low catalyst loading (0.02-0.1 mol %) in the presence of KOtBu (20-60 mol %). The catalyst precursor, RuHCl(CO)(PNHP), was converted to [RuH(CO)2(PNHP)]+ under the catalytic conditions and also serves as a highly effective catalyst. The robustness of this catalyst contributes to its outstanding catalytic activity, even under reaction conditions, in which CO is liberated from methanol.

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.

Anilinic N-oxides support cytochrome P450-mediated N-dealkylation through hydrogen-atom transfer

The mechanism of N-dealkylation mediated by cytochrome P450 (P450) has long been studied and argued as either a single electron transfer (SET) or a hydrogen atom transfer (HAT) from the amine to the oxidant of the P450, the reputed iron-oxene. In our study, tertiary anilinic N-oxides were used as oxygen surrogates to directly generate a P450-mediated oxidant that is capable of N-dealkylating the dimethylaniline derived from oxygen donation. These surrogates were employed to probe the generated reactive oxygen species and the subsequent mechanism of N-dealkylation to distinguish between the HAT and SET mechanisms. In addition to the expected N-demethylation of the product aniline, 2,3,4,5,6-pentafluoro-N,N-dimethylaniline N-oxide (PFDMAO) was found to be capable of N-dealkylating both N,N-dimethylaniline (DMA) and N-cyclopropyl-N-methylaniline (CPMA). Rate comparisons of the N-demethylation of DMA supported by PFDMAO show a 27-fold faster rate than when supported by N,N-dimethylaniline N-oxide (DMAO). Whereas intermolecular kinetic isotope effects were masked, intramolecular measurements showed values reflective of those seen previously in DMAO- and the native NADPH/O2-supported systems (2.33 and 2.8 for the N-demethylation of PFDMA and DMA from the PFDMAO system, respectively). PFDMAO-supported N-dealkylation of CPMA led to the ring-intact product N-cyclopropylaniline (CPA), similar to that seen with the native system. The formation of CPA argues against a SET mechanism in favor of a P450-like HAT mechanism. We suggest that the similarity of KIEs, in addition to the formation of the ring-intact CPA, argues for a similar mechanism of Compound I (Cpd I) formation followed by HAT for N-dealkylation by the native and N-oxide-supported systems and demonstrate the ability of the N-oxide-generated oxidant to act as an accurate mimic of the native P450 oxidant.