37934-89-7Relevant academic research and scientific papers
Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand
Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
supporting information, p. 10132 - 10135 (2016/08/31)
Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.
Novel flavors, flavor modifiers, tastants, taste enhancers, umami or sweet tastants, and/or enhancers and use thereof
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Page/Page column 97, (2008/06/13)
The present invention relates to the discovery that certain non-naturally occurring, non-peptide amide compounds and amide derivatives, such as oxalamides, ureas, and acrylamides, are useful flavor or taste modifiers, such as a flavoring or flavoring agents and flavor or taste enhancer, more particularly, savory (the “umami” taste of monosodium glutamate) or sweet taste modifiers,—savory or sweet flavoring agents and savory or sweet flavor enhancers, for food, beverages, and other comestible or orally administered medicinal products or compositions.
Steric and Electronic Control of the Dissociative Hydrolysis of 4-Hydoxybenzoate Esters
Thea, Sergio,Guanti, Giuseppe,Kashefi-Naini, Nasrin,Williams, Andrew
, p. 529 - 530 (2007/10/02)
The introduction of two ortho methyl substituents changes the propensity of 4-hydroxybenzoates to react via the oxo-ketene pathway by nearly one million-fold; the increased reactivity of the hindered conjugate base over that of the parent is assigned to enhanced internal nucleophilicity of the 4-oxyanion.
Syntheses of 4-Hydroxy-2,6-dimethylbenzoic Acid and Its Higher Homologues
Bhattacharya, Kalyan K.,Pal, Panchanan,Ghosh, Kalpana,Sen, P. K.
, p. 191 - 194 (2007/10/02)
Syntheses of 4-hydroxy-2,6-dimethylbenzoic acid (2a) and its higher homologues, viz 4-hydroxy-2,6-dimethylphenylacetic acid (2b), 3-(4-hydroxy-2,6-dimethylphenyl)propanoic acid (2c) and 4-(4-hydroxy-2,6-dimethylphenyl)butanoic acid (2d) are described.
Vinyl Cation Intermediates in Solvolytic and Electrophilic Reactions. 1. Solvolysis of α-Arylvinyl Derivatives
Yates, Keith,Mandrapilias, George
, p. 3892 - 3902 (2007/10/02)
The solvolysis of 16 α-arylvinyl tosylates, bromides, and chlorides has been investigated in various alcohol-water mixtures and in acetic acid at several temperatures.All substrates were substituted with either 2-methyl or 2,6-dimethyl groups to accelerate the rates of reaction.The major or exclusive product isolated in most cases was the acetophenone arising from hydrolysis of the expected enol ethers or acetates during workup.The kinetics were simple first order in the vast majority of cases, with excess base added to prevent side reactions.Leaving group effects, Winstein-Grunwald m values, Schleyer Q values, and effects of solvent nucleophilicity all point to a limiting SN1 ionization generating a vinyl cation intermediate, in which there is little rear-side nucleophilic assistance by solvent.Substituent effects led to ρ values in the range -3.9 to -5.3 vs. ?+.Activation parameters are typical for an SN1 process, and ΔS% is insensitive to the presence of zero, one, or two o-methyl groups, as are the effects of solvent polarity on the rates.The results should therefore be directly comparable with other solvolytic or electrophilic reactions generating formally similar vinyl cation intermediates.
