Ender Erdik

Effect of Copper (I) Iodide and Magnesium Chloride on Amination of Aryl Grignards with Ketoximes

Abstract Acetone oxime O-mesitylenesulphonate is shown to be a convenient reagent for amination of aryl Grignard reagents in ether-toluene in the presence of a catalytic amount of copper (I) iodide or magnesium chloride.

Electrophilic Amination of Diarylzincs and Triarylzincates with Acetone -(2,4,6-Trimethylphenylsulfonyl) Oxime and with O-Methylhydroxylamine

Abstract Diarylzines and triarylzincates react efficiently with acetone O-(2,4,6-trimethylphenylsulfonyl) oxime and O-methylhydroxylamine in the presence of CuCN to give amines in good yields.

Can we aminate Grignard reagents under Barbier conditions

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.

Voltammetric investigation of diethylstilbestrol

In this work electrooxidation of diethylstilbestrol (DES) was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) using a glassy carbon (GC) electrode. It was statistically shown that both methods could be used for the determination of DES in the concentration range of 2 x 10(-5)-6 x 10(-4) M by CV and 1 x 10(-5)-1 x 10(-3) M in methanol (MeOH) and 4 x 10(-5)-6 x 10(-4) M in acetonitrile (ACN) by DPV and both of the methods could be applied to human serum. A mechanism was proposed about the electrooxidation of this substance.

Electrophilic amination of organozinc reagents with acetone O -(2,4,6-trimethylphenylsulfonyl)oxime and O -methylhydroxylamine

Reaction of diorganozincs and triorganozincates with acetone O-(2,4,6-trimethylphenylsulfonyl)oxime or O-methylhydroxylamine in the presence of CuCN provides a new one-flask method for electrophilic amination of organozinc reagents. Considering the lithium- or magnesium-to-zinc transmetallation, this method also extends the scope of electrophilic amination of organolithiums and Grignard reagents.

Kinetics and mechanism of the C-S coupling reactions of aryl Grignard reagents with aryl arenesulfonates

The kinetics of the C-S coupling of arylmagnesium bromides with phenyl tosylate has been studied in THF: toluene at 90°C. The reaction is first order in Grignard reagent and first order in phenyl tosylate. Kinetic data, Hammett relationship and activation parameters are consistent with a nucleophilic addition mechanism involving rate determining attack of carbanion to sulfonyl group followed by a fast phenoxide group leaving.

Copper Catalyzed Reactions of Aryl Grignard Reagents with Aryl Arenesulfonates

Abstract Aryl Grignard reagents react with phenyl tosylate in uncatalyzed and Cu(I) catalyzed reactions to give sulfones, which react further with Grignard reagents to give biaryls as sole or coproducts. The outcome of the reaction depends mainly on variations in the structure of the Grignard reagent. Phenyl and p-tolyl Grignard reagents give sulfones, but p-anisyl Grignard reagent gives biaryl as main product in moderate yields.

The Effectiveness of Copper(I) Compounds as Catalysts in the Coupling of Phenyllithium with Primary Alkyl Halides and Tosylates

Abstract Various uncomplexed and complexed Cu(I) salts, Li2CuCl4, Li2CuCl3, Ph2CuLi and PhCu, have been tested as catalysts in the coupling reactions of phenyllithium with 2-chloroethanol, ethyl bromide, 2-chloroethyl tosylate and ethyl tosylate. CuBr.Me2S,-CuCN, CuI.PBu3-n and Cul have been found to be the most effective and selective catalysts in diethyl ether, respectively, for these couplings. The catalytic activity in Cu(I) catalyzed coupling reactions of phenyllithium depends on the reaction conditions, on the nucleofugal group, and on the 2-heteroatom functionality of the substrate.

Synthesis of N,N-dimethylamines via barbier -grignard -type electrophilic amination

Abstract Aryl Grignard reagents react with N,N‐dimethyl O‐(mesitylenesulfonyl)hydroxylamine in THF under Barbier conditions at room temperature and give N,N‐dimethylanilines with high yields in a 2‐h reaction. The amination yield of in situ Grignard reagents were not lower than those of preformed aryl Grignard reagents. In situ cycloalkyl‐, allyl‐, and benzylmagnesium bromides did not react with N,N‐dimethyl O‐(mesitylenesulfonyl)hydroxylamine, except that amination of in situ n‐hexylmagnesium bromide resulted in a medium yield. Grignard–Barbier‐type amination of aryl bromides with N,N‐dimethyl O‐(mesitylenesulfonyl)hydroxylamine provides a new alternative route for the synthesis of N,N‐dimethylanilines.

Catalyst Activity in the Copper(I) Catalyzed Grignard Coupling with Alkyl Halides Containing ß- and γ-Oxygen Functionality

Abstract Catalyst activity of several Cu(I) catalysts in the coupling of n-butylmagnesium chloride with alkyl halides containing β-and γ-oxygen functionality, free or blocked as acetate and tosylate, has been studied. A marked dependence of the catalyst activity on the heteroatom functionality of the organic halide was found.