95064-52-1

Upstream product

• 67-56-1 methanol 
• 874-90-8 4-methoxybenzonitrile 

Downstream Products

• 62230-46-0 C₈H₁₁N₃O 
• 75129-04-3 6-(4-methoxyphenyl)-2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 
• 95064-55-4 methyl 2-methoxy-N-methoxycarbonylbenzenecarboximidate 
• 2564-57-0 4-carbomethoxy-2-(4-methoxyphenyl)-δ²-thiazoline 
• 23275-45-8 N-cyano-4-methoxy-benzamidine 
• 2519-93-9 2-(4-methoxyphenyl)-4,5-dihydro-1,3-thiazole 

Relevant academic research and scientific papers

Mechanism of generation of: Closo -decaborato amidrazones. Intramolecular non-covalent B-H?π(Ph) interaction determines stabilization of the configuration around the amidrazone CN bond

Three types of N(H)-nucleophiles, viz. hydrazine, acetyl hydrazide, and a set of hydrazones, were used to study the nucleophilic addition to the CN group of the 2-propanenitrilium closo-decaborate cluster (Ph3PCH2Ph)[B10H9NCEt], giving N-closo-decaborato amidrazones. A systematic mechanistic study of the nucleophilic addition is provided and included detailed synthetic, crystallographic, computational and kinetic work. As a result, two possible mechanisms have been proposed, which consist of firstly a consecutive incorporation of two Nu(H) nucleophiles, with the second responsible for a subsequent rapid proton exchange. The second possible mechanism assumes a pre-formation of a dinuclear [Nu(H)]2 species which subsequently proceeds with the nucleophilic attack on the boron cluster. The activation parameters for hydrazones indicate a small dependence on bond formation [ΔH? = 6.8-15 kJ mol-1], but significantly negative entropies of activation [ΔS? ranges from -139 to -164 J K-1 mol-1] with the latter contributing some 70-80% of the total Gibbs free energy of activation, ΔG?. In the X-ray structure of (Z)-(Ph3PCH2Ph)[B10H9N(H)C(Et)NHNCPh2], very rare intramolecular non-covalent B-H?π(Ph) interactions were detected and studied by DFT calculations (M06-2x/6-311++G?? level of theory) and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method). The estimated strength of these non-covalent interactions is 0.8-1.4 kcal mol-1.

Flow rhodaelectro-catalyzed alkyne annulations by versatile C-H Activation: Mechanistic support for rhodium(III/IV)

A flow-metallaelectro-catalyzed C-H activation was realized in terms of robust rhodaelectro-catalyzed alkyne annulations. To this end, a modular electro-flow cell with a porous graphite felt anode was designed to ensure efficient turnover. Thereby, a variety of C-H/N-H functionalizations proved amenable for alkyne annulations with high levels of regioselectivity and functional group tolerance, viable in both an inter- or intramolecular manner. The electro-flow C-H activation allowed easy scale up, while in-operando kinetic analysis was accomplished by online flow-NMR spectroscopy. Mechanistic studies suggest an oxidatively induced reductive elimination pathway on rhodium(III) in an electrocatalytic regime.

Synthesis of amidines and benzoxazoles from activated nitriles with Ni(0) catalysts

Amidines and 2-substituted benzoxazoles were synthesized from N-heterocyclic nitriles under mild conditions (50 °C, 48 h, two steps) in an atom-economical process that involves addition of methanol, the solvent, to a nitrile moiety to yield a methyl imidate and the subsequent extrusion of solvent in the presence of amines to afford the title compounds. Methyl imidate formation was achieved by developing a new catalytic pathway using [(dippe)Ni(H)]2 (dippe = 1,2-bis(diisopropylphosphino)ethane), [Ni(cod)2]/dppe, or [Ni(cod)2]/P(OPh)3 (cod = 1,5-cyclooctadiene, dppe = 1,2-bis(diphenylphosphino)ethane, P(OPh)3 = triphenyl phosphite) as the catalyst precursor. Regarding the ligands, for a given substrate, namely 4-cyanopyridine, the best performance for the Ni(0)-catalyzed system was found for the σ-donor bidentate dippe, whereas the monodentate π acceptor P(OPh)3 was less efficient. In relation to the substrates, for a given Ni-dippe system, steric hindrance and, more importantly, substrate electron-withdrawing character control imidate formation and thus the yield of amidines and benzoxazoles.

Synthesis and analgesic-antiinflammatory activity of some 4- and 5-substituted heteroarylsalicylic acids

We have made a series of 4- and 5-aryl- and 4- and 5-heteroarylsalicylic acid derivatives with the objective of reducing gastric irritation and increasing potency. Here we describe a series of 4- and 5-heterocyclic salicylic acids and their antiinflammatory-analgesic potencies measured in comparison to aspirin. An improvement of the therapeutic index over aspirin of 100 was achieved; however, the heterocyclic salicylic acids lacked antipyretic activity. Some physicochemical parameters which may bear on the antiinflammatory activity of these compounds are discussed.