28833-53-6

Upstream product

• 109745-70-2 methyl glyoxylate methyl hemi-acetal 
• 119-26-6 (2,4-dinitro-phenyl)-hydrazine 
• 316790-99-5 dimethyl 2-anilino-3-(isoquinolin-1-yl)succinate 
• 89-91-8 Methyl dimethoxyacetate 
• 92516-25-1 Acetoxy-(4-methoxy-2,6-dimethyl-phenyl)-acetic acid methyl ester 
• 92516-16-0 Hydroxy-(4-methoxy-2,6-dimethyl-phenyl)-acetic acid methyl ester 
• 67-56-1 methanol 
• 75-87-6 chloral 

Relevant academic research and scientific papers

Experimental and DFT study of the aza-Diels-Alder reaction between cyclopentadiene and protonated benzylimine derivated from glyoxylates

The Diels-Alder reaction of protonated N-benzyl imine of methyl glyoxylate with cyclopentadiene in different solvents gave mixtures of exo/endo adducts. The exo/endo selectivity of the reaction was elucidated by NMR experiments. Theoretical calculations by means of density functional theory (DFT) at the B3LYP/6-31G(d) level have also been performed to elucidate the molecular mechanism of this reaction. The DFT results suggest a highly asynchronous concerted mechanism, which in turn can explain the preferred exo stereoselectivity of the reaction. Inclusion of solvent effects enhances the exo selectivity, and this effect increases with the polarity of the solvent, in good agreement with the experimental findings.

The astounding chemistry of a 2-amino-1,2-dihydroisoquinoline derivative

The cycloadducts of isoquinolinium N-phenyl imide 2 with C=C bonds are derivatives of 2-amino-1,2-dihydroisoquinoline. Their Nβ-vinylphenylhydrazine system is amenable to an acid-catalyzed [3,3]-sigmatropic shift; the formation of pentacyclic aminals is exemplified by 6 → 8. The dimethyl maleate adduct 11, C21H20N2O4, is exceptional by being converted on treatment with acid to bright-yellow crystals, C24H22N2O6 (additional C3H2O2). X-Ray crystal-structure analysis and NMR spectra reveal structure 13, and mechanistic studies indicated an initial β-elimination at the N-N bond of 11 to yield 18; this step is followed by a retro-Mannich-type cleavage that gives methyl isoquinoline-1-acetate (14) and methyl 2-(phenylimino)acetate (15), according to the sequence C21H20N2O4 (11) → 18 → C12H11NO2 (14)+C9H9NO2 (15). In the second act of the drama, electrophilic attack by 15-H+ on the ene-hydrazine group of a second molecule of 11 furnishes 13 by a polystep intramolecular redox reaction. All rate constants must be fine-tuned in this reaction cascade to give 13 in yields of up to 78% with an overall stoichiometry: 2 C21H20N2O4 (11) → C24H22N2O6 (13) + C12H11NO2 (14) + aniline. Interception and model experiments confirmed the above pathway. A by-product, C33H31N3O6 (62), arises from an acid-catalyzed dimerization of 11 and subsequent elimination of 15.

Bromination of 2,6-Dimethyl-4-methoxybenzyl Alcohol Derivatives

The reaction of 2,6-dimethyl-4-methoxybenzyl alcohols, ethyl ethers, and acetates, possessing electrondonating and -withdrawing groups at the benzylic position, with bromine water was studied at different temperatures.The reaction was strongly affected by the electronegativity of a benzyl substituent to afford bromination products of aromatic nuclei and 2,4-dibromo-3,5-dimethylmethoxybenzene along with 2,4,6-tribromo derivatives formed by the cleavage of C-C bond.