15016-99-6

Upstream product

• 121-69-7 N,N-dimethyl-aniline 
• 701-56-4 4-methoxy-N,N-dimethylanilne 
• 100-61-8 N-methylaniline 
• 104-94-9 4-methoxy-aniline 
• 108-86-1 bromobenzene 
• 5369-34-6 N,N,N'-trimethyl-p-phenylenediamine 
• 586-77-6 4-bromo-N,N-dimethylaniline 

Relevant academic research and scientific papers

Polycationic states of oligoanilines based on Wurster's blue

Polycations of two oligoanilines based on Wurster's blue, N,N',N-tris[4-(dimethylamino)phenyl]-N,N',N-trimethyl1,3,5-benzenetriamine (2) and N,N'-bis(3-{N-[4-(dimethylamino)phenyl]-N-methylamino}phenyl)-N,N'-dimethyl- pphenylenediamine (3), have been generated efficiently by a stepwise oxidation procedure, Their redox behavior was characterized in terms of the embedded p-phenylenediamine (PD) units and their intramolecular connectivity, EPR analysis of the oxidized 2 and 3 species revealed the existence of high-spin species in solution. It was found that spin multiplicities of the dominant polycationic species of 2 and 3 formed by 3 equiv, of oxidant can be assigned to quartet: and doublet states, respectively on the basis of pulsed EPR spectroscopy, These results demonstrate that the intramolecular connectivity between the spin-containing units decisively influences the spin preference of the multispin systems based on oligoanilines.

(t-Bu)2PN=P(i-BuNCH2CH2)3N: New efficient ligand for palladium-catalyzed C-N couplings of aryl and heteroaryl bromides and chlorides and for vinyl bromides at room temperature

(Chemical Equation Presented) By employing Pd(OAc)2, Cs 2CO3, or NaOH, and the new ligand (t-Bu) 2PN=P(i-BuNCH2CH2)3N (3a), an electronically diverse array of aryl bromides and chlorides possessing base-sensitive substituents (nitro, ester, and keto) provide coupling products with bulky aryl amines in good to excellent yields. Aryl halides possessing other functional groups including cyano, amino, trifluoromethyl, and phenol, coupled with equal ease, producing highly functionalized amines in good to excellent yields. Moreover, an aryl chloro group can be preserved in the presence of a bromo substituent under our reaction conditions. BOC-protected amines also participated efficiently. Heterocyclic bromides and chlorides underwent clean couplings with amines in excellent yields. An important strength of our protocol is the use of lower palladium loadings than those reported earlier, without compromising yields. The air-stable palladium complex (η3-cinnamyl)PdCl·(3a) (5) was also employed successfully in C-N coupling reactions while the crotyl analogue was less efficacious. The 3a/Pd(OAc)2 catalyst system promotes, for the first time, efficient coupling of vinyl bromides with a variety of amines to produce imines and enamines at room temperature.

Bulky alkylphosphines with neopentyl substituents as ligands in the amination of aryl bromides and chlorides

Di(tert-butyl)neopentylphosphine (DTBNpP) in combination with palladium sources provided catalysts with comparable or better activity for the Hartwig-Buchwald amination of aryl bromides than tri(tert-butyl)phosphine (TTBP) under mild conditions. DTBNpP also provided effective catalysts for amination reactions of aryl chlorides at elevated temperatures. Further replacement of tert-butyl groups with neopentyl substituents resulted in less effective ligands for amination reactions. Computationally derived cone angles showed that replacement of a tert-butyl group with a neopentyl group significantly increased the cone angle of the phosphine. The larger cone angle of DTBNpP than TTBP appears to correlate with the higher activity of catalysts derived from DTBNpP in the amination of aryl bromides. TTBP is a stronger electron donor than DTBNpP, which may explain the higher activity for TTBP-derived catalysts toward aryl chlorides.

Oxidative activation in aromatic substitutions. Reactions of N,N- dimethylanilines with secondary anilines promoted by thallium triacetate

The reactions of N,N-dimethyl-p-anisidine (1a), N,N-dimethylaniline (1b), and N,N-dimethyl-p-fluoroaniline (1c) toward secondary anilines 2(a- d)-H in the presence of thallium triacetate sesquihydrate have been studied as representative of a novel oxidatively activated aromatic substitution affording 1,4-benzenediamine derivatives 3a-d. All of the substrates considered gave substitution with diphenylamine (2d-H). However, with anilines 2b,c-H, only 1a underwent substitution, and substrates 1b,c were practically unreactive. The observed differences in reactivity are well accounted for within a mechanistic framework wherein oxidative activation of both the substrate and the secondary aniline is regarded as alternatively (or simultaneously) possible, depending on the redox characteristics of the reactants. For instance, it can be stated, beyond any reasonable doubt, that reactions of 1a with 2b,c-H proceed via nucleophilic attack of the latter on 1a+., and that the reaction of 1a-c with 2d-H must involve the diphenylamino radical 2d·.

ON THE ESR IDENTIFICATION OF PARAMAGNETIC SPECIES OBSERVED DURING SET OXIDATION OF N,N-DIMETHYL-p-ANISIDINE

During SET oxidation of the title compound, N,N,N'-trimethyl-N'-(4-methoxyphenyl)-1,4-phenylendiamine radical cation was detected by e.s.r.; this derives from an oxidatively activated nucleophilic substitution on N,N-dimethyl-p-anisidine.Revised e.s.r. parameters for N,N-dimethyl-p-anisidinium radical are also reported.