40938-34-9Relevant academic research and scientific papers
Room-temperature copper-catalyzed electrophilic amination of arylcadmium iodides with ketoximes
Korkmaz, Adem
, p. 3119 - 3125 (2021/05/10)
We started our study by preparation two ketoximes. Later, there were studies to reveal these ketoximes' effects in the electrophilic amination reaction with organocadmium reagents. Primarily, it was observed that arylcadmium iodides could not be reacted with ketoximes at room temperature in the absence of a catalyst. CuCN was a suitable catalyst for this electrophilic amination reaction of arylcadmium iodides and allowed the preparation of functionalized aniline derivatives in good yields under mild reaction conditions. We obtained the results indicated that the yield of primary arylamines was strongly dependent on the steric and electronic effects of organocadmium reagent and amination agent. In the case of both amination reagents, meta-substituted arylamines were obtained in higher yields than para-substituted arylamines. We observed that acetone O-(4-chlorophenylsulfonyl)oxime, 1, as an aminating agent, was more successful than acetone O-(2-Naphthylsulfonyl)oxime, 2, in the synthesis of functionalized arylamines by electrophilic amination of corresponding aryl cadmium iodides. In this method, there is no cadmium release to the environment.
Aryl C-N bond formation by electrophilic amination of diarylcadmium reagents with O-substituted ketoximes
Da?kapan, Tahir,Korkmaz, Adem
supporting information, p. 813 - 817 (2016/07/06)
Diorganocadmium reagents cannot react with ketoxime at room temperature. CuCN catalysis allows diarylcadmium reagents to react with ketoxime and to give corresponding arylamines in good to high yields at room temperature. According to the electronic effects of the substituent attached to the aromatic ring, functionalized diarylcadmium reagents show meta-para selectivity in their amination reactions. Also compared to diarylzinc reagents, diarylcadmium reagents react with O-substituted ketoxime under milder reaction conditions and they form corresponding arylamines in higher yields. CuCN cannot help dialkyl-, dicycloalky-, and dibenzylcadmium reagents to react with ketoxime. Our Aryl C-N bond formation method does not include cadmium excretion into the environment.
Can we aminate Grignard reagents under Barbier conditions?
Erdik, Ender,Da?kapan, Tahir
, p. 6237 - 6239 (2007/10/03)
The reaction of aryl bromides with acetone O-(2,4,6-trimethylphenylsulfonyl)oxime and magnesium in THF at reflux temperature for 3 h provides a one-pot procedure for amination of aryl Grignard reagents under Barbier conditions.
Thermolysis of 5,5-dimethyl-4-aryl-Δ1-1,2,4-triazolin-3-ones in solution. Products, kinetics, substituent effects, and solvent effects
Cabelkova-Taguchi, Lubomira M.,Warkentin, John
, p. 100 - 105 (2007/10/02)
A series of 5,5-dimethyl-4-Δ1-1,2,4-triazolin-3-ones (Ar=C6H5, p-C6H4CH3, p-C6H40CH3,p-C6H4Cl, and p-C6H4Br) were prepared from the corresponding 4-arylsemicarbazones of acetone by oxidative cyclization on alumina.The triazolines decompose in solution to N2,CO, and isopropylidene aryl amine, with first order kinetics, in the temperature range 148-200 deg C.Average activation parameters are ΔH*=35 kcal*mol-1 and ΔS*=8 cal*K-1*mol-1.Substituent effects are correlated through Σ-constants but the thermolyses are relatively insensitive to substituents, with p=-0.17 at 172.5 deg C.Solvent effects indicate a transition state that is less polar than the ground state.It is tentatively concluded that the triazolinone fragmentation, like the analogous thermolysis of a Δ3-1,3,4-oxadiazolin-2-one, may be a fully-concerted but nonsynchronous process with a transition state involving little, if any, charge separation.Other mechanisms, except for those involving highly polar (e.g. zwitterionic) transition states, have not been ruled out.
