14288-05-2

Upstream product

• 557-91-5 1,1-Dibromoethane 
• 201230-82-2 carbon monoxide 
• 109-89-7 diethylamine 
• 673-32-5 1-Phenylprop-1-yne 
• 6667-19-2 benzenenesulfenyl dimethylamine 
• 591-50-4 iodobenzene 
• 14873-98-4 bis(diethylamin)nickeldibromid 
• 594-19-4 tert.-butyl lithium 
• 88-10-8 N,N-diethylcarbamyl chloride 

Downstream Products

• 4437-51-8 3,4-hexanedione 
• 412018-06-5 diethylamino-diphenyl-acetic acid diethylamide 
• 150-77-6 N,N,N',N'-Tetraethylethylenediamine 

Relevant academic research and scientific papers

Preparation of tertiary amides from carbamoyl chlorides and organocuprates

(Chemical Equation Presented) Reaction of carbamoyl chlorides with cyano-Gilman cuprates affords tertiary amides in good to excellent yields. The reaction is general due to the possibility of using reagents made either from organolithium or from Grignard compounds. The characterization of the main side products allowed for the suggestion of a possible mechanism.

Palladium-catalyzed azathiolation of carbon monoxide

A novel palladium-catalyzed azathiolation of carbon monoxide using sulfenamide (RSNR'2) (1) is described to provide thiocarbamate 2 in good yields. The mechanistic proposal includes the following: (1) insertion of CO into Pd-S bond of Pd(SR)2(PPh3)(n) 4 to provide Pd[C(O)SR](SR)(PPh3)(n) 5 and (2) σ-bond metathesis between S-N and Pd-C(O) bonds to afford 2 with the regeneration of 4.

Cobalt-catalyzed aminocarbonylation of geminal dihaloalkanes. Formation of 2-aminoamide and malonamide derivatives

Co2(CO)8 catalyzed aminocarbonylation of geminal dihaloalkanes R2CX2 (R = H, CH3; X = Br, Cl) with NHEt2 affording R2C(NEt2)CONEt2 selectively in n-C6H14 using NEt3, while the yield of R2C(CONEt2)2 fairly increased in THF or benzene in aid of K2CO3.

Palladium-Catalysed Double Carbonylation of Aryl Halides To Give α-Keto Amides. Mechanistic Studies

Various aryl halides are catalytically converted into α-keto amides and amides on treatment with secondary amines and carbon monoxide.Palladium complexes containing tertiary phosphine ligands, particularly diphenylmethylphosphine and 1,4-bis(diphenylphosphino)butane, are most effective among other transition-metal complexes.Detailed examination of factors controlling the reaction rates and selectivity for α-keto amide formation revealed the following characteristics of the reactions. (a) Reactivity of phenyl halide decreases in the order PhI > PhBr >> PhCl. (b) Oxidative addition of phenyl bromide constitutes the rate-determining step in double carbonylation of phenyl bromide, whereas in the reaction of phenyl iodide the rate determinig step is associated with the reaction of a catalitically active palladium species with carbon monoxide. (c) Introduction of an electron-withdrawing substituent into the para position of phenyl halide enhances the reactivity but decreases the selectivity for α-keto amide. (d) Employment of amines of high basicity (pKb Et2NH > piperidine > hexamethyleneimine > Me2NH > pyrrolidine probably reflects the decrease in steric bulkiness of amines. (f) Although primary amines are in general not suitable for the double carbonylation, tert-butylamine can be used because of its inertness to the product α-keto amide.Reactivity of trans-PdPh(I)(PMePh2)2 and trans-Pd(COPh)I(PMePh2)2, supposed intermediates in the catalytic reaction of PhI, toward amines and CO was examined.The relative reactivity of six secondary amines with the benzoylpalladium complex increasing in the order Pr2NH Et2NH piperidine Me2NH hexamethyleneimine pyrrolidine was found to be inversely correlated with decreasing selectivity order for α-keto amide formation in the catalytic systems.On the basis of the experimental results, a mechanism consisting of two catalytic cycles to produce α-keto amides and amides has been proposed.

DURCH NICKEL(II)-SALZE INDUZIERTE CARBAMOYLIERUNG VON ALKINEN

Mono- and di-substituted alkynes react with CO and secondary amines such as Et2NH in the presence of NiII salts to form carbamoyl products of the types Et2NCOC(R)=C(R')CONEt2 and RCCCONEt2.Depending on the NiX2 salt (X = Cl, Br, I) employed

OXALSAEUREDERIVATE DURCH OXIDATIVE KUPPLUNG VON KOHLENMONOXID AN NICKEL

Carbon monoxide is oxidatively coupled by ligand nickel(II) compounds with secondary, primary amines and with alkali alkoxides to give oxalic acid derivatives.In the case of secondary amines the CO coupling can be run catalytically by adding oxidants like copper(II) salts.The yield of oxalic esters depends on the types of ligands and anions.