67274-51-5

Upstream product

• 10517-47-2 N-(4-acetylphenyl)hydroxylamine 
• 75-36-5 acetyl chloride 
• 100-19-6 (4-nitrophenyl)ethanone 
• 31125-05-0 1-(4-nitrosophenyl)ethan-1-one 
• 431-03-8 dimethylglyoxal 

Downstream Products

• 31125-05-0 1-(4-nitrosophenyl)ethan-1-one 
• 64-19-7 acetic acid 

Relevant academic research and scientific papers

Catalyst-free generation of acyl radicals induced by visible light in water to construct C-N bonds

We describe herein a catalyst-free and redox-neutral photochemical strategy for the direct generation of acyl radicals from α-diketones, and its selective conversion of nitrosoarenes to hydroxyamides or amides with AcOH or NaCl as an additive. The reaction was carried out under mild conditions in water with purple LEDs as the light source. A broad scope of substrates was demonstrated. Mechanistic experiments indicate that α-diketones cleave to give acyl radicals, with hydroxyamides being further reduced to amides.

TRIFLUOROMETHOXYLATION OF ARENES VIA INTRAMOLECULAR TRIFLUOROMETHOXY GROUP MIGRATION

The present invention provides a process of producing a trifluoromethoxylated aryl or trifluoromethoxylated heteroaryl having the structure: (I), wherein A is an aryl or heteroaryl, each with or without subsutitution; and R1 is -H, -(alkyl), -(alkenyl), -(alkynyl), -(aryl), -(heteroaryl), - (alkylaryl), - (alkylheteroaryl), -NH-(alkyl), -N(alkyl)2, -NH-(alkenyl), -NH-(alkynyl) -NH-(aryl), -NH-(heteroaryl), -O-(alkyl), -O-(alkenyl), -O-(alkynyl), -O-(aryl), -O-(heteroaryl), -S-(alkyl), -S- (alkenyl), -S-(alkynyl), -S-(aryl), or -S-(heteroaryl), comprising: (a) reacting a compound having the structure: (II), with a trifluoromethylating agent in the presence of a base in a first suitable solvent under conditions to produce a compound having the structure: (III); and (b) maintaining the compound produced in step (a) in a second suitable solvent under conditions sufficient to produce the trifluoromethoxylated aryl or trifluormethoxylated heteroaryl having the structure: (I).

Mechanistic studies on intramolecular C-H trifluoromethoxylation of (hetero)arenes via OCF3-migration

The one-pot two-step intramolecular aryl and heteroaryl C-H trifluoromethoxylation recently reported by our group has provided a general, scalable, and operationally simple approach to access a wide range of unprecedented and valuable OCF3-containing building blocks. Herein we describe our investigations to elucidate its reaction mechanism. Experimental data indicate that the O-trifluoromethylation of N-(hetero)aryl-N-hydroxylamine derivatives is a radical process, whereas the OCF3-migration step proceeds via a heterolytic cleavage of the N-OCF3 bond followed by rapid recombination of a short-lived ion pair. Computational studies further support the proposed ion pair reaction pathway for the OCF3-migration process. We hope that the current study would provide useful insights for the development of new transformations using versatile N-(hetero)aryl-N-hydroxylamine synthons.

Rhodium(III)-catalyzed internal oxidative coupling of N-hydroxyanilides with alkenes via C-H activation

Abstract Described herein is an efficient new method for ortho-olefination of anilides in the presence of AgSbF6 and NaOAc via rhodium(III)-catalyzed internal oxidative C-H bond activation based on hydroxyl as directing and oxidative group. A range of alkenes and functional groups on acetanilides is supported and a possible mechanism is proposed according to the experimental results.

Trifluoromethoxylation of arenes: Synthesis of ortho- Trifluoromethoxylated aniline derivatives by OCF3 migration

Aryl trifluoromethoxylation by a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxylamine derivatives and intramolecular OCF3 migration is presented. This protocol allows easy access to a wide range of synthetically useful ortho-OCF3 aniline derivatives. In addition, it utilizes bench-stable reagents, is operationally simple, shows high functional-group tolerance, and is amenable to gram-scale as well as one-pot synthesis.Areaction mechanism of a heterolytic cleavage of the N-OCF3 bond followed by recombination of the resulting nitrenium ion and trifluoromethoxide is proposed for the OCF3-migration reaction.

Laccase Variants

The present invention relates to variants of a parent laccase. The present invention also relates to polynucleotides encoding the variant laccases and to nucleic acid constructs, vectors, and host cells comprising the polynucleotides, and methods of using the variant enzymes.

ANTIMICROBIAL COMPOSITION CONTAINING AN OXIDOREDUCTASE AND AN ENHANCER OF THER N-HYDROXYANILIDE-TYPE

The present invention relates to an enzymatic composition capable of killing or inhibiting microbial cells or micro-organisms, e.g. in laundry, on hard surfaces, in water systems, on skin, on teeth or on mucous membranes. The present invention also relate

Kinetics, mechanism, and thermodynamics of aqueous iron(III) chelation and dissociation: Influence of carbon and nitrogen substituents in hydroxamic acid ligands

Thermodynamic and kinetic studies were performed to investigate the complexation of aqueous high-spin iron(III) by 12 bidentate hydroxamic acids, R1C(O)N(OH)R2, (R1 = CH3, C6H5, 4-NO2C6H4, 4-CH3C6H4, 4-CH3OC6H4; R2 = CH3, C6H5, 4-CH3C6H4, 4-ClC6H4, 4-IC6H4, 3-IC6H4, 4-NCC6H4, 3-NCC6H4, 4-CH3C(O)C6H4), in acid medium. Both complex formation and dissociation (aquation) reactions were investigated by stopped-flow relaxation methods over a range of [H+] and temperatures. A two-parallel-path mechanism without proton ambiguity is established for the reaction of Fe(H2O)63+ and Fe(H2O)5OH2+ with R1C(O)N(OH)R2 to form Fe(H2O)4(R1C(O)N(O)R2)2+. Equilibrium quotients, ΔH° and ΔS° values, rate constants, and ΔH≠ and ΔS≠ values for both reaction paths in the forward and reverse directions are reported. ΔH≠ and ΔS≠ values are found to be linearly related and compensating. On the basis of an analysis of the equilibrium quotients, rate constants, and activation parameters for the reaction in both directions, an associative interchange (Ia) mechanism is proposed for hydroxamic acid ligand substitution at Fe(H2O)63+. Similar trends for these parameters are observed for the reaction at Fe(H2O)5OH2+, suggesting an associative interchange character for this reaction path also. However, coordinated water dissociation appears to be dominant, and some associative character for this path may be the result of H-bonding interactions between the undissociated hydroxamic acid and coordinated -OH. Electron-donating and -withdrawing R1 and R2 substituents were selected in order to determine the relative influence of the C and N substituent on the hydroxamic acid and to determine the optimum hydroxamic acid structure for kinetic and thermodynamic stability of the iron(III) chelate. Kinetic and thermodynamic chelate stabilization are enhanced by increasing electron density on the carbonyl oxygen atom, which is promoted by electron donors in the R1 position and delocalization of the N atom lone pair of electrons into the C-N bond. The influence of the R2 substituent appears to be dominant with an electron-releasing alkyl group as the preferred R2 substituent for kinetic and thermodynamic stability. The optimum hydroxamic acid ligand for kinetic and thermodynamic stability of the iron(III) chelate was found to be 4-CH3OC6H4C(O)N(OH)CH3.

Temperature-Dependent Acid Dissociation Constants (Ka, ΔHa, ΔSa) for a Series of Nitrogen-Substituted Hydroxamic Acids in Aqueous Solution

The acid dissociation constants (Ka) of a series of eight substituted N-phenylacetohydroxamic acids, CH3C-(O)N(OH)C6H4X (X=H, 4-CH3, 4-Cl, 4-I, 3-I, 3-CN, 4-CN, 4-C(O)CH3), have been determined in aqueous solution (I=2.0) for a range of temperatures.The pKa data at 25 deg C exhibit a small variation with the substituent X in the direction expected according to their Hammett substituent constants (ρ ca. 0.1).These small variations in pKa values are due to compensating trends in ΔHa and ΔSa, which show significant variation with substituent.These results are discussed in terms of the substituent's influence on hydroxamate anion-solvent interactions and the relative influence on pKa of a substituted phenyl group attached to the C or N end of the hydroxamate moiety.