159201-01-1Relevant articles and documents
Acylanthranils. 12. Reaction of Acetylanthranil with Alcohols To Give Products of Self-Condensation
Errede, L.A.,Hill, J.R.,McBrady, J.J.
, p. 3829 - 3835 (1982)
Material-balance studies on the reaction of acetylanthranil (I) in acidified alcohol showed that the end produt is neither the expected N-(2-carboxyphenyl)acetimidate, 3, nor the o-acetamidobenzoate ester, 4, but rather mixtures of N-(2-carboxyphenyl)-2-methylquinazol-4-one (5), o-(o-acetamidobenzamido)benzoic acid (6), CH3CO2R, and R2O, where R is the alkyl group of the alcohol.The stoichiometry in anhydrous media is consistent with the following equation: 2I + (1+2x)ROH -> (1-x)5 + x6 + CH3CO2R + xROR.Time studies of this self-condensation, monitored by proton NMR, showed that the acetimidate 3 is indeed formed as expected, but it establishes equilibrium with 1 within minutes.The acetimidate, however, reacts slowly with solvent and residual 1 to give products 5 and 6, respectively, with concomitant formation of CH3CO2R and ROR as side products.The instantaneous selectivity ratio (1-x)/x increases monotonically with percent conversion to acids 5 and 6.The disappearance of 1 in alcohol solution is pseudo first order.Initially, the rate-controlling step is the slow conversion of 3 to secondary intermediates Y and Z, but ultimately it is the subsequent very slow conversion of Y an Z to end products.
Hydroxamic acid rearrangement method for O-amino aromatic acid
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Paragraph 0018-0026, (2021/09/29)
The invention relates to the field of organic functional new material chemicals, and discloses a novel process technology for preparation of a hydroxamic acid precursor body weight discharge method of a plurality of o-amino aromatic acids in the first time. These substances are well known dyes and pigment and pharmaceutical pesticide-related fields and have a wide range of critical fine chemicals.
Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
, p. 3943 - 3957 (2021/04/12)
The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.
