39058-29-2Relevant 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.
Transfer of amido groups from isolated rhodium(I) amides to alkenes and vinylarenes
Zhao, Pinjing,Krug, Christopher,Hartwig, John F.
, p. 12066 - 12073 (2007/10/03)
The reaction of monomeric and dimeric rhodium(l) amido complexes with unactivated olefins to generate imines is reported. Transamination of {(PEt 3)2RhN(SiMePh2)2} (1a) or its -N(SiMe3)2 analogue 1b with p-toluidine gave the dimeric [(PEt3)2Rh(M-NHAr)]2 (Ar = p-tolyl) (2a) in 80% isolated yield. Reaction of 2a with PEt3 generated the monomeric (PEt3)3Rh(NHAr) (Ar = p-tolyl) (3a). PEt 3-ligated arylamides 2a and 3a reacted with styrene to transfer the amido group to the olefin and to form the ketimine Ph(Me)-C=N(p-tol) (4a) in 48-95% yields. The dinuclear amido hydride (PEt3)4Rh 2(μ-NHAr)(μ-H) (Ar = p-tolyl) (5a) was formed from reaction of 2a in 95% yield, and a mixture of this dimeric species and the (PEt 3)nRhH complexes with n = 3 and 4 was formed from reaction of 3a in a combined 75% yield. Propene reacted with 2a to give Me 2C=N(p-tol) (4b) and 5a in 90 and 57% yields. Propene also reacted with 3a to give 4b and 5a in 65 and 94% yields. Analogues of 2a and 3a with varied electronic properties also reacted with styrene to form the corresponding imines, and moderately faster rates were observed for reactions of electron-rich arylamides. Kinetic studies of the reaction of 3a with styrene were most consistent with formation of the imine by migratory insertion of olefin into the rhodium-amide bond to generate an aminoalkyl intermediate that undergoes β-hydrogen elimination to generate a rhodium hydride and an enamine that tautomerizes to the imine.
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.
