93416-35-4

Upstream product

• 36637-30-6 O-(4-chlorophenyl)hydroxylamine 
• 407-25-0 trifluoroacetic anhydride 
• 3412-99-5 2-(3-chlorophenylamino)methylenemalonic acid diethyl ester 
• 76-05-1 trifluoroacetic acid 
• 2106-05-0 5-chloro-2-fluoroaniline 
• 95-85-2 2-hydroxy-5-chloro-aniline 

Downstream Products

• 227796-00-1 7,16-bis(5-chloro-2-hydroxy-3-trifluoroacetamidobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane 
• 93416-20-7 5-chloro-2-(trifluoromethyl)benzo[d]oxazole 

Relevant academic research and scientific papers

Direct C-N bond cleavage of N-vinyl or N-allyl arylamines: A metal-free strategy for N-devinylation and N-deallylation

A simple and convenient N-devinylation and N-deallylation strategy for N-vinyl and N-allyl arylamines in the presence of TFA/oxone is presented with the formation of selective ortho-hydroxylated and N-trifluoroacylated arylamine product in good yields. Th

Metal-free chemoselective ortho -C(sp2)-F bond hydroxylation and N-trifluoroacylation of fluoroarylamines for domino synthesis of 2-(N-trifluoroacyl)aminophenols

Abstract A novel chemoselective reaction for the formation of C-O bonds by C(sp2)-F bond cleavage and concomitant N-trifluoroacylation of fluoroanilines using trifluoroacetic acid and Oxone is presented. This domino reaction gives o-hydroxy-N-trifluoroacetanilides in good yields under metal-free conditions in a single step. Selective ortho-directed monohydroxylation and N-trifluoroacylation of 2- and 6-fluoro- or 2,6-difluoro-substituted anilines takes place in this transformation.

Diaza-18-Crown-6 Ligands Containing Two Aminophenol Side Arms: New Heterobinuclear Metal Ion Receptors

Three diaza-18-crown-6 ligands substituted with two aminophenol side arms were synthesized as possible heterobinuclear metal ion receptors. Bis(p-aminophenol)-substituted diaza-18-crown-6 ligand (13) was prepared by treating the diazacrown with α-bromo-4-nitro-o-cresol in the presence of N,N-diisopropylethylamine followed by reduction of the nitro groups. Bis(o-aminophenol)-substituted diaza-18-crown-6 ligands (11 and 12) were prepared in two steps by the aminomethylation of either an o-nitrophenol or o-(trifluoroacetamido)phenol followed by reduction of the nitro groups or hydrolysis of the trifluoroacetamide groups. All new bisphenol-armed diazacrown ligands were purified by ultrasonication in MeOH followed by filtration and drying. Interaction of the ligands with Na+, K+, Ag+, and Cu2+ was evaluated by a calorimetric titration technique at 25°C in MeOH. The complexes of Ag+ and Cu2+ are much more stable than those of Na+ and K+. Heterobinuclear complexes were observed for 11-Cu2+ - Na+ and 12-Cu2+-Na+ but not for 13-Cu2+-Na+ or for 12-Cu2+-Ag+.

3-(2-aminomethyl)-4-[3-trifluoromethyl)benzoyl]-3-4 dihydro-2h-1,4-benzoxazine derivatives and their therapeutic application

Compounds of the general formula (I) STR1 wherein R1 represents a hydrogen, fluorine or chlorine atom or a methyl, C1 -C3 alkoxy or nitro group; R3 represents a hydrogen atom or a C1 -C3 alkyl group; R4 represents a 2,3-dihydro-1H-inden-2-yl, 2,3-dihydro-1H-inden-1-yl or 1,2,3,4-tetrahydronaphthalen-1-yl group; or alternatively R3 and R4 complete, with the nitrogen atom to which they are attached, a 1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indol-2-yl, 1,2,3,4-tetrahydro-9H-pyrido[4,3-b]indol-3-yl, 4,5,6,7-tetrahydrothieno[2,3-c]pyrid-6-yl, 4,5,6,7-tetrahydrothieno[3,2-c]pyrid-6-yl or 2,3-dihydro-1H-isoindol-2-yl group; are useful for the treatment and prevention of cerebral disorders.

Acid-catalyzed amino-migration of O-phenylhydroxylamines

The mechanism of amino-migration of O-phenylhydroxylamine (1a) was studied. It was found that 1 rearranges to give 2-aminophenol (50%) and 4-aminophenol (7%) in trifluoroacetic acid (TFA). The predominance of the ortho rearrangement of 1 clearly distinguishes this process from the Bamberger rearrangement. From cross-coupling experiments employing stable isotopes, it was clarified that the ortho rearrangement proceeds intramolecularly and the para rearrangement involves both intra- and intermolecular processes. Good first-order kinetics were obtained for the rearrangement. The Hammett plot (σ+) with a large negative slope (ρ = -7.8) indicates that initial heterolytic N-O bond cleavage of 1 occurs and generates a positive charge on the oxygen atom with considerable delocalization into the aromatic ring. An ion-molecule pair involving a phenoxenium ion and an ammonia molecule as an intermediate rationalizes all of the results. In this pair, intramolecular combination to the ortho position proceeds preferentially over that to the para position. Formation of catechol and hydroquinone can be explained in terms of nucleophilic attack of TFA on the phenoxenium ion in a solvent-separated pair.