25556-16-5

Upstream product

• 132647-27-9 1,4-dipiperidino-cyclohexa-1,3-diene 
• 71-43-2 benzene 
• 111-24-0 1,5-dibromo-pentane 
• 106-50-3 1,4-phenylenediamine 
• 110-89-4 piperidine 
• 108-94-1 cyclohexanone 
• 106-37-6 1.4-dibromobenzene 
• 106-46-7 para-dichlorobenzene 
• 2359-60-6 4-(1-piperidino)aniline 
• 111-29-5 1 ,5-pentanediol 
• 150-76-5 4-methoxy-phenol 
• 15368-96-4 2,3,5,6-tetrafluoro-1,4-bis(piperidin-1-yl)benzene 

Downstream Products

• 1166111-35-8 (E,E)-2,5-bis[2-(ethoxycarbonyl)ethenyl]-1,4-dipiperidinobenzene 

Relevant academic research and scientific papers

Preparation of functionalized p-phenylenediamine derivatives using arene-iron chemistry

Selective displacement of chloride from cyclopentadienyl(1,4-dichlorobenzene)iron(1+) by a series of cyclic secondary amine nucleophiles is described. This selectivity, in combination with further manipulation of the complexes, allows access to a series of unsymmetrical and/or functionalized etraalkyl-p-phenylenediamine complexes. A series of demetalated phenylenediamines were shown by CV to have redox potentials distributed over a range of 320 mV, as a consequence of remote functionality. Preliminary fluorescence studies on a series of electron acceptor-substituted phenylenediamines indicated quenching of the phenylenediamine fluorescence, attributable to rapid electron transfer.

Manipulation of the reduction potentials of Wurster's blue derivatives via steric and conformational effects

Using [η6-cyclopentadienyliron]+-mediated S(N)Ar chemistry, a series of symmetrical and 2-alkyl tetra-alkyl-p-phenylenediamines have been prepared. The amine/amine.+ first redox couple has been determined for each member of the series and is influenced by remote steric, electronic, and conformational effects.

Catalytic Amination of Phenols with Amines

Given the wide prevalence and ready availability of both phenols and amines, aniline synthesis through direct coupling between these starting materials would be extremely attractive. Herein, we describe a rhodium-catalyzed amination of phenols, which provides concise access to diverse anilines, with water as the sole byproduct. The arenophilic rhodium catalyst facilitates the inherently difficult keto–enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. We demonstrate the generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines. Several examples of late-stage functionalization of structurally complex bioactive molecules, including pharmaceuticals, further illustrate the potential broad utility of the method.

Benzimidazolin-2-ylidene N-heterocyclic carbene complexes of ruthenium as a simple catalyst for the N-alkylation of amines using alcohols and diols

Simple air and moisture stable ruthenium complexes 1-3 and 3a were synthesized from readily available benzannulated N-heterocyclic carbene ligands (bimy = benzimidazolin-2-ylidene). These complexes were found to be efficient catalysts for the alkylation of amines using alcohols as alkylating agents. Catalysts 1, 2 and 3a gave excellent yields of up to 99% for the alkylation of various amines using benzylic and aliphatic alcohols at 130 °C for 18 h under solventless conditions. Catalyst 3a bearing both phosphine and carbene ligands gave excellent yields of up to 98% for the synthesis of heterocyclic amines by double alkylation of primary amines using linear diols. The practical utility of these catalysts was demonstrated for the synthesis of pharmaceutically important amines in a more environmentally benign way under solventless conditions.

Synthesis and structural characterization of palladium(II) thiosemicarbazone complex: Application to the Buchwald-Hartwig amination reaction

A simple route to synthesize mononuclear palladium(II) thiosemicarbazone complex has been described. Elemental analysis, spectral methods and single crystal X-ray diffraction analysis were used to confirm the composition of the complex. The new complex acts as an active homogeneous catalyst for the Buchwald-Hartwig amination reaction of a wide range of aryl and heteroaryl halides (bromides and chlorides), including activating, neutral and deactivating substrates, with various secondary amines under optimized conditions.

Ni(II)-(σ-aryl) complex: A facile, efficient catalyst for nickel-catalyzed carbon-nitrogen coupling reactions

(Chemical Equation Presented) trans-Haloarylbis(triphenylphosphine) nickel(II), a type of air-and moisture-stable Ni(II)-(σ-aryl) complex, was examined as catalyst precursor in the C-N coupling reaction. This type of Ni(II) pre-catalyst, associated with N-heterocyclic carbene ligands, is found to easily produce the catalytically active Ni(0) species in situ without the aid of external reductants and allows for the efficient amination of aryl chlorides with secondary cyclic amines and anilines under mild conditions.

A new route to polykis(dialkylamino)benzenes and -naphthalenes based on protodefluorination of electron-rich fluoroaromatics: Anion radicals of arenes as a simple and effective alternative to 'classical' LAH-based systems

A simple and effective procedure for protodefluorination of electron-rich fluoroaromatic compounds has been developed. It operates with aromatic anion radicals as reducing agents and shows superior results over 'classical' lithium aluminum hydride based s

Nickel-mediated amination chemistry. Part 1: Efficient aminations of (het)aryl 1,3-di and 1,3,5-trichlorides

The first Ni-catalysed synthesis of di- and triamino substituted benzenes and diamino substituted pyridines from the corresponding aryl chlorides and amines is described. (C) 2000 Elsevier Science Ltd.

Palladium-catalyzed amination of aryl dibromides with secondary amines: Synthetic and mechanistic aspects

Diaminobenzenes are obtained starting from m- and p-dibromobenzenes and secondary amines in the presence of Pd(dba)2/P(o-tolyl)3 and sodium tert- butoxide in moderate to good yields. Reductive dehalogenation of aryl dibromides is a major side reaction under these conditions. The study of this reaction has shown that the formation of reductive dehalogenation products occurs according to two independent ways. The first one proceeds via the well-known β-hydride elimination from amido-coordinated palladium complexes. The second one involves the formation of hydrido palladium complexes from amino-coordinated derivatives. Although our results do not allow us to propose a detailed mechanistic scheme, they clearly show that the deprotonation step of the catalytic amination cycle has a major effect on the amine/arene ratio.