2358-90-9

Upstream product

• 57380-82-2 N,N-dimethyl-2-(4-methylphenyl)thioacetamide 
• 122-00-9 para-methylacetophenone 
• 699-02-5 4-Methylphenethyl alcohol 
• 124-40-3 dimethyl amine 
• 104-81-4 4-Methylbenzyl bromide 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 102101-48-4 Dimethyl-(4-methyl-benzyl)-trimethylsilanylmethyl-ammonium; bromide 

Relevant academic research and scientific papers

Dimethylamination of Primary Alcohols Using a Homogeneous Iridium Catalyst: A Synthetic Method for N, N-Dimethylamine Derivatives

A new catalytic system for N,N-dimethylamination of primary alcohols using aqueous dimethylamine in the absence of additional organic solvents has been developed. The reaction proceeds via borrowing hydrogen processes, which are atom-efficient and environmentally benign. An iridium catalyst bearing an N-heterocyclic carbene (NHC) ligand exhibited high performance, without showing any deactivation under aqueous conditions. In addition, valuable N,N-dimethylamine derivatives, including biologically active and pharmaceutical molecules, were synthesized. The practical application of this methodology was demonstrated by a gram-scale reaction.

Rhodium-catalyzed anti-Markovnikov hydroamination of vinylarenes

The transition metal-catalyzed anti-Markovnikov hydroamination of unactivated vinylarenes with a rhodium complex of DPEphos is reported. The reaction of electron-neutral or electron-rich vinylarenes with a variety of secondary amines in the presence of catalyst forms the products from anti-Markovnikov hydroamination in high yields. Reactions of morpholine, N-phenylpiperazine, N-Boc-piperazine, piperidine, 2,5-dimethylmorpholine, and perhydroisoquinoline reacted with styrene to form the amine product in 51-71% yield. Reactions of a variety of vinylarenes with morpholine generated amine as the major product. Reactions of morpholine with electron-poor vinylarenes gave lower amine:enamine ratios than reactions of electron-rich vinylarenes at the same concentration of vinylarene, but conditions were developed with lower concentrations of electron-poor vinylarene to maintain formation of the amine as the major product. Reactions of dimethylamine with vinylarenes were fast and formed amine as the major product. Mechanistic studies on the hydroamination process showed that the amine:enamine ratio was lower for reactions conducted with higher concentrations of vinylarene and that one vinylarene influences the selectivity for reaction of another. A mechanism proceeding through a metallacyclic intermediate that opens in the presence of a second vinylarene accounts for these and other mechanistic observations. Copyright

Intermediate in Sommelet-Hauser Rearrangement of N,N-Dimethylbenzylammonium N-Methylides

Formation of benzylammonium N-methylides by fluoride anion induced desilylation of dimethyl(4-substituted benzyl)ammonium halides (1) and 3-substituted benzyl analogues (6) was examined to isolate 5--6-methylene-1,3-cyclohexadienes (isotoluene intermediates, 3,8,10) in the Sommelet-Hauser rearrangement.Some isotoluenes were isolated and their structures were confirmed by 1H NMR analysis.The stability of the isotoluenes was dependent on the electron-donating effects of the substituents on the conjugated bonds, and 3-methoxy-substituted isotoluene 3a was the most stable compound studied.

A Convenient Synthesis of o-Methylbenzylamine Derivatives from Benzyl Halides: The Improved Sommelet-Hauser Rearrangement

Desilylation by fluoride anion of benzyldimethyl(trimethylsislylmethyl)ammonium halides having a Cl(1-), CN(1-), or AcO(1-) substituent on the benzene ring gave high yields of the Sommelet-Hauser rearrangement products at room temperature.