41115-22-4

Upstream product

• 6781-98-2 2,6-dimethyl-1-chlorobenzene 
• 109-73-9 N-butylamine 
• 15676-66-1 tri-n-butylindium 
• 109-65-9 1-bromo-butane 
• 87-62-7 2,6-dimethylaniline 

Downstream Products

• 109472-99-3 chloro-acetic acid-(N-butyl-2,6-dimethyl-anilide) 
• 85126-08-5 C₁₄H₂₂N₄O 
• 68657-07-8 3-[1-Amino-1-methylamino-meth-(Z)-ylidene]-1-butyl-1-(2,6-dimethyl-phenyl)-urea 
• 109367-73-9 (2-hydroxy-ethoxy)-acetic acid-(N-butyl-2,6-dimethyl-anilide) 
• 68657-18-1 N-Butyl-N-(2,6-dimethylphenyl)carbamoylchlorid 

Relevant academic research and scientific papers

Halogen-Bridged Methylnaphthyl Palladium Dimers as Versatile Catalyst Precursors in Coupling Reactions

Halogen-bridged methylnaphthyl (MeNAP) palladium dimers are presented as multipurpose Pd-precursors, ideally suited for catalytic method development and preparative organic synthesis. By simply mixing with phosphine or carbene ligands, they are in situ converted into well-defined monoligated complexes. Their catalytic performance was benchmarked against state-of-the-art systems in challenging Buchwald–Hartwig, Heck, Suzuki and Negishi couplings, and ketone arylations. Their use enabled record-setting activities, beyond those achievable by optimization of the ligand alone. The MeNAP catalysts permit syntheses of tetra-ortho-substituted arenes and bulky anilines in near-quantitative yields at room temperature, allow mono-arylations of small ketones, and enable so far elusive cross-couplings of secondary alkyl boronic acids with aryl chlorides.

Benzyloxycalix[8]arene supported Pd-NHC cinnamyl complexes for Buchwald-Hartwig C-N cross-couplings

The scalable synthesis of Pd-NHC cinnamyl complexes supported on benzyloxycalix[8]arene is reported. These catalysts are very active for Buchwald-Hartwig cross-coupling reactions, allowing the coupling of aryl chlorides and bromides with a wide variety of alkyl and aryl amines using low catalytic loadings. The supported complexes also successfully afforded attractive unsymmetrical triarylamines, and in one case, promoted the synthesis of an unprecedented Pd-catalyzed C-H activation product. Thanks to the calixarenic support, the target products could be isolated with low levels of residual palladium, and in some cases, even below the restrictive toxic metal standards applied by the pharmaceutical industry. Through an easy to implement procedure, these perfectly characterised catalysts thus combine the best of homogeneous and heterogeneous catalysis: high efficiency (similar to or even better than the corresponding homogeneous complexes) and low Pd leaching levels expected from heterogeneous catalysts.

Reactions of arenediazonium o-benzenedisulfonimides with aliphatic triorganoindium compounds

The reaction of various arenediazonium o-benzenedisulfonimides with aliphatic triorganoindium compounds is described. Surprisingly, with triethyl- or tributylindium we obtained N-ethyl- or N-butylanilines, respectively. This is the first case in which, at least formally, the reactive site of a diazonium salt is the nitrogen atom directly bonded to the aromatic ring. In contrast, with trimethylindium we obtained only formaldehyde (aryl)hydrazones. In order to explain the difference between trimethyl- and triethylindium we have proposed some reaction mechanisms, supported by detailed density functional (DFT) calculations. The possible role of diazene/hydrazone tautomerism initially assumed was discarded and therefore three mechanisms for the key step (nucleophilic addition of the trialkylindium to the N=N double bond of diazene) were studied. For the favoured mechanism there is a difference in the energy barriers of 2 kcalmol-1 between the reactions with trimethyl- and triethylindium. This difference is explained on the basis of the different C-In bond energies in the two organometallics and it is assumed to be enough to explain their different behaviour under the experimental conditions. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

A diaminochlorophosphine for palladium-catalyzed arylations of amines and ketones

(Chemical Equation Presented) Sterically hindered substituents on a secondary chlorophosphine 1 prevent formation of a diaminooxophosphine, and thereby allow for highly efficient arylation reactions of amines and α-C-H acidic ketones with (hetero)aryl chlorides.

New ligands for a general palladium-catalyzed amination of aryl and heteroaryl chlorides

The synthesis and application of monodentate N-substituted heteroarylphosphines is described. In general, the ligands are conveniently prepared by selective metallation at the 2-position of the respective N-substituted heterocycle (pyrrole, indole) by using n-butyllithium/ tetramethylethylenediamine (TMEDA) followed by quenching with dialkyl- or diarylchlorophosphines. Of the different ligands prepared, the new dialkyl-2-(N-arylindolyl)phosphines (cataCXium P) perform excellently in the palladium-catalyzed amination of aryl and heteroaryl chlorides. Coupling of both activated and deactivated chloroarenes proceeds under mild conditions (room temperature to 60°C). By using optimized conditions remarkable catalyst productivity (total turnover number, TON, up to 8000) and activity (turnover frequency, TOF = 14000 h-1 at 75% conversion) are observed.

NITROGEN-CONTAINING MONODENTATE PHOSPHINES AND THEIR USE IN CATALYSIS

The present invention relates to novel nitrogen-containing monodentate phosphane ligands of formula (I) and to their use in catalytic reactions, especially in the improvement of haloaromatic compounds.

Studies on nucleophilic substitution reactions with cyclopentadienyliron complexes of some chloroarenes and nitorarenes and syntheses of substituted arenes by demetallation of the substitution products

Nucleophilic substitution reactions with the cyclopentadienyliron (CpFe) complex of m- or p-dichlorobenzene with carbanion nucleophiles derived from ethyl acetoacetate (EAA), dibenzoylmethane (DBM) or diacetylmethane (DAM) were found to give only monosubstitution as previously observed for the CpFe complex of o-dichlorobenzene.Reaction of the CpFe complex of 2,6-dimethylchlorobenzene (XIVa) or 2,6-dimethylnitorbenzene (XIVb) with nucleophiles derived from ammonia, dimethylamine, n-butylamine, pyrrolidine, ethanol, phenol, o-thiocresol and EAA all gave SNAr products, without significant steric hindrance.However, no reaction was observed in the treatment of XIVa or XIVb with DBM, suggesting that only with a bulky nucleophile such as that derived from DBM were steric hindrance effects sufficiently large to prevent an SNAr reaction with XIVa or XIVb.Pyrolytic sublimation of the various SNAr products was found to cause decomposition in some cases, but in most instances, demetallation took place giving rise to substituted arenes.New substituted arenes prepared in this way in the present work included RC6H4CH(COC6H5)2, with R = p-CH3, o-Cl, m-Cl or p-Cl, and 2,6-(CH3)2C6H3Y, with Y = CH3(CH2)3NH, C2H5O or o-CH3C6H4S.