52185-81-6Relevant articles and documents
Practical and regioselective amination of arenes using alkyl amines
Ruffoni, Alessandro,Juliá, Fabio,Svejstrup, Thomas D.,McMillan, Alastair J.,Douglas, James J.,Leonori, Daniele
, p. 426 - 433 (2019/05/01)
The formation of carbon–nitrogen bonds for the preparation of aromatic amines is among the top five reactions carried out globally for the production of high-value materials, ranging from from bulk chemicals to pharmaceuticals and polymers. As a result of this ubiquity and diversity, methods for their preparation impact the full spectrum of chemical syntheses in academia and industry. In general, these molecules are assembled through the stepwise introduction of a reactivity handle in place of an aromatic C–H bond (that is, a nitro group, halogen or boronic acid) and a subsequent functionalization or cross-coupling. Here we show that aromatic amines can be constructed by direct reaction of arenes and alkyl amines using photocatalysis, without the need for pre-functionalization. The process enables the easy preparation of advanced building blocks, tolerates a broad range of functionalities, and multigram scale can be achieved via a batch-to-flow protocol. The merit of this strategy as a late-stage functionalization platform has been demonstrated by the modification of several drugs, agrochemicals, peptides, chiral catalysts, polymers and organometallic complexes.
AIBN-initiated metal free amidation of aldehydes using N-chloroamines
Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
supporting information, p. 351 - 356 (2014/01/06)
An efficient and environmentally benign amidation of aldehydes with N-chloroamines has been developed using AIBN as an initiator. This methodology offers a metal free and base free approach and is endowed with mild reaction conditions, high yields, and good functional group tolerance.
[Cp*RhCl2]2-catalyzed ortho-C-H bond amination of acetophenone o-methyloximes with primary N-chloroalkylamines: Convenient synthesis of N-alkyl-2-acylanilines
Ng, Ka-Ho,Zhou, Zhongyuan,Yu, Wing-Yiu
supporting information, p. 7031 - 7033 (2013/09/02)
Rh(iii)-catalyzed aromatic C-H amination of acetophenone o-methyloximes with primary N-chloroalkylamines was developed, and the arylamine products were obtained in up to 92% yield. The reaction probably involves rate-limiting electrophilic C-H bond cleavage (kH/kD = 2).
Titanium-mediated amination of Grignard reagents using primary and secondary amines
Barker, Timothy J.,Jarvo, Elizabeth R.
supporting information; experimental part, p. 8325 - 8328 (2011/10/31)
Make it, then break it: N-chlorosuccinimide (NCS) was employed as the oxidant in the synthesis of aniline derivatives using the title transformation (see scheme). Functionalization was well tolerated on both the amine and Grignard reagent. An androgen receptor agonist and several analogues were synthesized to demonstrate the utility of this method.
Organic chloramine analysis and free chlorine quantification by electrospray and atmospheric pressure chemical ionization tandem mass spectrometry
Takats,Koch,Cooks
, p. 4522 - 4529 (2007/10/03)
Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI), together with tandem mass spectrometry (MSn), are used to study the mechanism of chlorination of amines and to develop a method for qualitative and quantitative determination of organic chloramines. Cyclohexylamine and 1,4-butanediamine (putrescine) are used as model compounds to investigate the mechanisms of the reactions between primary aliphatic amines and hypochlorous acid (aqueous Cl2). The chlorination products are identified and characterized by collision-induced dissociation (CID) and H/D exchange. Chlorination occurs by eledtrophilic addition of Cl+ and may be followed by HCl elimination, hydrolysis, or, in the case of diamines, amine elimination by intramolecular nucleophilic substitution. The relative rates of chlorination at amine and chloramine nitrogens are a function of pH and depend on the basicity of the amine. A novel method for active chlorine quantification using ESI or APCI mass spectrometry is suggested on the basis of the extent of chlorination of a sacrifical amine standard. This measurement has a limit of detection for N-chlorocyclohexylamine in the range of 0.1-10 μM, a linear dynamic range of 102-103, and an accuracy of ±10%, as determined for wastewater samples.
Catalytic asymmetric hydroboration/amination and alkylamination with rhodium complexes of 1,1′-(2-diarylphosphino-1-naphthyl)isoquinoline
Fernandez, Elena,Maeda, Kenji,Hooper, Mark W.,Brown, John M.
, p. 1840 - 1846 (2007/10/03)
Catecholboronate esters formed by asymmetric hydroboration of arylalkenes are not directly converted to amines by reaction with hydroxylamine-O-sulfonic acid. Prior conversion to a trialkylborane by reaction with ZnEt2 or MeMgCl permits a subsequent amination reaction to occur with essentially complete retention of configuration, leading to a range of primary α-arylalkylamines in up to 97% enantiomeric excess (ee). Secondary, but not tertiary amines may be formed by a related pathway when in situ generated alkylchloramines are employed as the aminating agent. The catalytic asymmetric hydroboration, β-alkylation and amination steps may be combined in a single stage. Overall, this provides a practical procedure for the synthesis of enantiomerically enriched arylamines, exemplified inter alia by the synthesis of (S)-1,2,3,4-tetrahydro-1-naphthylamine in 95-97% ee and of (R)-N-(cyclohexyl)-1′-(4-methoxyphenyl)ethylamine in 93 % ee.
