4714-65-2

Upstream product

• 109-65-9 1-bromo-butane 
• 873-74-5 4-Aminobenzonitrile 
• 623-00-7 4-bromobenzenecarbonitrile 
• 109-73-9 N-butylamine 
• 66107-32-2 4-cyanophenyl trifluoromethanesulfonate 
• 109-72-8 n-butyllithium 
• 29577-88-6 (Z)-tert-Butyl (4-cyanophenyl)azo sulfide 
• 10304-39-9 4-methyl-N-quinolin-8-yl-benzenesulfonamide 
• 36268-67-4 4-((methylsulfonyl)amino)benzonitrile 
• 56768-53-7 N-(4-cyanophenyl)-4-methylbenzenesulfonamide 
• 71-36-3 butan-1-ol 

Downstream Products

• 115036-89-0 N-butyl-4-(1,4,5,6-tetrahydro-pyrimidin-2-yl)-aniline 

Relevant academic research and scientific papers

Iridium complexes with ligands of 1,8-Naphthyridine-2-carboxylic acid derivatives-preparation and catalysis

Complexation of 1,8-naphthyridine(Np)-2-carboxylic derivatives L1-L3 [L1 = Np-2-COOH, L2 = Np-2-CONH2, L3 = Np-2-CONHCH2Py] with [Ir(COD)(μ-OMe)]2 yielded the corresponding complexes [Ir(COD)(Ln)] (1~3, n = 1~3, respectively). The potential tridentate L3 behaves as a bidentate donor in the complex 3. Treatment of L1 with [Ir(COD)Cl]2 under nitrogen atmosphere gave a Ir(III) hydride complex [Ir(COD)(L1)HCl] (4). However, carrying out the reaction in the presence of oxygen rendered a Ir(III) dichloride species [Ir(COD)(L1)Cl2] (5). All these complexes were characterized by spectroscopic analyses and X-ray single crystal determination. Catalytic activity of iridium complexes in amination of amines with alcohols was screened. It appears that iridium amido complexes 2 and 3 show excellent catalytic activity on amination of anilines with alcohols in the presence of Cs2CO3 at 120 °C.

Chemoselective Deprotection of Sulfonamides under Acidic Conditions: Scope, Sulfonyl Group Migration, and Synthetic Applications

Chemoselective acidic hydrolysis of sulfonamides with trifluoromethanesulfonic acid has been evaluated as a deprotection method and further extended to more complex synthetic applications. In contrast to conventional troublesome sulfonamide hydrolysis, a near-stoichiometric amount of acid was found to be sufficient to bring about efficient deprotection of various neutral or electron-deficient N-arylsulfonamides, whereas electron-rich substrates provided sulfonyl group migration products. The deprotection method developed is fully selective for N-arylsulfonamides, and the possibility to discriminate among various different sulfonamides is demonstrated.

A general procedure to selectively prepare N-alkylanilines by an unexpected reaction of (Z)-(tert-butylsulfanyl)(aryl)diazenes with alkyllithium reagents

A general procedure has been set up to prepare, selectively, the N-monoalkylanilines 7, reacting (Z)-(tert-butylsulfanyl)(aryl)diazenes 3 with alkyllithium 6 (MeLi, BuLi, s-BuLi, n-C6H13Li). The reactions were carried out in anhydrous diethyl ether at 0°C or - 78°C, depending on the reagent 6, and then at room temperature. In optimal conditions the yields of the pure products 7 (uncontaminated by dialkylation products) were from good to excellent: for 38 considered examples, 34 were positive with yields varying between 61percent and 91percent (average yield 78percent). Collateral proofs were carried out to support a hypothesized reaction mechanism.

Palladium-Catalyzed Amination of Aryl Triflates and Importance of Triflate Addition Rate

We report that a combination of DPPF (1,1-bis(diphenylphosphino)ferrocene) and Pd(dba)2 leads to the animation of aryl triflates, a reaction that allows for the conversion of phenols to arylamines. A combination of BINAP and Pd(dba)2 also catalyzes the amination of aryl triflates, but P(o-tolyl)3 complexes were not effective catalysts. In some cases, slow addition of the aryl triflate was necessary to prevent cleavage of the triflate and generation of phenol. We found that added halide, necessary in some cross-coupling chemistry of aryl sulfonates, was an unnecessary additive and even inhibited the amination chemistry.

Palladium-Catalyzed Amination of Aryl Halides: Mechanism and Rational Catalyst Design

Palladium complexes of tri-o-tolyl phosphine and bis(diphenylphospino)ferrocene catalyze the reaction between aryl halides and either tin amides or amines in the presence of base to form aryl amines by halide substitution. This account describes our mechanistic and synthetic studies related to the amination reactions. These studies include kinetic behavior of the catalytic systems as well as direct observation of the primary stoichiometric reactions comprising the catalysis - including the rare C-N bond-forming reductive eliminations - and the mechanisms of these individual reactions. This paper also describes the development of tin-free amide sources and second generation amination catalysts that have resulted from our mechanistic understanding of the amination chemistry.