36458-78-3Relevant academic research and scientific papers
Metal-Free Decarboxylative Trichlorination of Alkynyl Carboxylic Acids: Synthesis of Trichloromethyl Ketones
Jayaraman, Aravindan,Cho, Eunjeong,Irudayanathan, Francis Mariaraj,Kim, Jimin,Lee, Sunwoo
, p. 130 - 141 (2017/12/26)
2,2,2-Trichloroacetophenone derivatives were synthesized via decarboxylative trichlorination from arylpropiolic acids and trichloroisocyanuric acid (TCCA). The reaction was performed in the presence of water at room temperature, and the desired products were obtained in good yields. The reaction showed good functional group tolerance towards halide, cyano, nitro, ketone, ester and aldehyde groups. In addition, the 2,2,2-trichloroacetophenone derivatives were readily transformed into esters, amides, and hydrazides. Based on experiments with H218O (water-18O), we proposed a cationic reaction pathway as the mechanism and suggested two different pathways for producing aryl- and alkyl-substituted propiolic acids. (Figure presented.).
A novel β-(oxy)alkyl radical during copper(I)-mediated stereoselective synthesis of (Z)-ene-1,4-diones in a reaction of 2,2,2-trichloro-1-phenylethanone
Ram, Ram N.,Tittal, Ram K.
, p. 2437 - 2440 (2016/05/19)
A novel β-(oxy)alkyl radical derived from trichloro methyl compound containing neither a suitably located C-C multiple bond nor a leaving group or a H-atom at the β-position of the radical in a reaction of 2,2,2-trichloro-1-phenyl-ethanone with 2 mol equiv each of CuCl and bpy in refluxing DCE under a N2 atm underwent intramolecular heterolysis (just like formation of intact radical cation-anion pair) during stereoselective radical dimerization to Z-ene-1,4-dione along with small amount of reductive dechlorination product. The stereochemistry was established by X-ray diffraction spectroscopy of various solid crystalline products.
The Reaction of Trihalgenomethyl Anions with Carbonyl Compounds: Competitive Reactivity Comparisons and Applications to the Synthesis of α-Trihalogenomethyl Alcohols
Atkins, Paul J.,Gold, Victor,Wassef, Wasfy N.
, p. 1247 - 1252 (2007/10/02)
Trihalogenomethyl anions, generated by decarboxilation of trichloro- and tribromo-acetic acid in dimethyl sulphoxide solution, react with added aldehydes.In the presence of 1,3,5-trinitrobenzene, the reaction with aldehydes competes with the formation of the coloured Meisenheimer adduct.The reduction in absorbance from the value in the absence of aldehyde has been used tomeasure the reactivity of trihlogenomethyl anions towards a series of aldehydes relative to their reactivity towards trinitrobenzene.For 4-substituted benzaldehydes, the reactivities obey a linear p?- relationship.The most reactive aldehyde used is only two times less reactive towards CCl3(1-) or CBr3(1-) than hydrogen ions, and it is concluded that, in dimethyl sulphoxide solutions, the reaction between trichloromethyl anions and hydrogen ions is not encounter-controlled.The reactions with aldehydes have been used to prepare several new compounds of the formula RCH(OY)CX3 where R = aryl or pyridyl, X = Br or Cl, and Y = H or COCH3.
