Copper(ii)-catalyzed oxidative N-nitrosation of secondary and tertiary amines with nitromethane under an oxygen atmosphere

2015 ◽  
Vol 51 (58) ◽  
pp. 11638-11641 ◽  
Author(s):  
Norio Sakai ◽  
Minoru Sasaki ◽  
Yohei Ogiwara
Keyword(s):  
Aromatic Amines ◽  
Oxygen Atmosphere ◽  
Aliphatic Amines ◽  
Tertiary Amines

The combination of Cu(OTf)2 and DBU under an O2 atmosphere effectively promoted the N-nitrosation of both secondary aromatic/aliphatic amines and tertiary aromatic amines with nitromethane (CH3NO2).

Efficient Copper-Catalysed Synthesis of Carbazoles by Double N-Arylation of Primary Amines with 2,2′-Dibromobiphenyl in the Presence of Air

Synlett ◽  
2021 ◽  
Author(s):  
Tran Quang Hung ◽  
Tuan Thanh Dang ◽  
Peter Langer ◽  
Ha Nam Do ◽  
Nguyen Minh Quan ◽  
...  
Keyword(s):  
Aromatic Amines ◽  
Aliphatic Amines ◽  
Primary Amines ◽  
Coupling Reactions ◽  
Carbazole Derivatives ◽  
High Yields

AbstractAn efficient Cu-catalyzed synthesis of carbazole derivatives is reported, which proceeds by double C–N coupling reactions of 2,2′-dibromobiphenyl and amines in the presence of air. The reaction is robust, proceeds in high yields, and tolerates a series of amines including neutral, electron-rich, electron-deficient aromatic amines and aliphatic amines.

Addition of Aliphatic and Aromatic Amines to Catechol in Aqueous Solution Under Oxidizing Conditions

1989 ◽  
Vol 42 (3) ◽  
pp. 365 ◽  
Author(s):  
MK Manthey ◽  
SG Pyne ◽  
RJW Truscott
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Aromatic Amines ◽  
Aliphatic Amines ◽  
Substitution Pattern ◽  
Vinylogous Amides ◽  
The Stability

The oxidation of catechol in the presence of two aliphatic and aromatic amines has been investigated. In aqueous solutions of pH 7.0 and 11.7, the substitution pattern of the adduct was dependent on the type of amine used. Aromatic amines produced 4,5-disubstituted o-quinones, whereas aliphatic amines gave either 2,4,5-trisubstituted or 2,4-disubstituted o-quinone adducts. A rationale based upon the stability of vinylogous amides is presented to account for the observed substitution pattern.

scholarly journals Preparation and in situ use of unstable N-alkyl a-diazo-g-butyrolactams in RhII-catalyzed X-H insertion reactions

2020 ◽  
Author(s):  
Maria Eremeyeva ◽  
Daniil Zhukovsky ◽  
Dmitry Dar'in ◽  
Mikhail Krasavin
Keyword(s):  
Aromatic Amines ◽  
Aliphatic Amines ◽  
Insertion Reactions ◽  
Sterically Hindered

N-Alkyl a-diazo-g-butyrolactams previously found to be unstable and undergo unproductive dimerization to bis-hydrazones, were successfully converted immediately to various X-H insertion products with alcohols, aromatic amines and thiols via an in situ RhII-catalyzed reaction. With aliphatic amines or unreactive, sterically hindered anilines, the reaction tends to yield enamine adducts.

Ni-Catalyzed Oxidative Transamidation of Tertiary Aromatic Amines with N-Acyl Saccharin

Synlett ◽  
2021 ◽  
Author(s):  
Shengzhang Liu ◽  
Lingyun Yang ◽  
Jiasi Tao ◽  
Weijie Yu ◽  
Tao Wang ◽  
...  
Keyword(s):  
Aromatic Amines ◽  
Secondary Amines ◽  
Tertiary Amines ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

Employment of tertiary amines as the surrogates for secondary amines has prominent superiority in stabilization and easy handle. Herein, a Ni-catalyzed transamidation of N-acyl saccharin amides with tertiary aromatic amines has been reported. By using tert-butyl hydroperoxide (TBHP) as the terminal oxidant, this reaction is featured with a selective cleavage of the C(sp3)–N bonds of the unsymmetrical tertiary aromatic amines depending on the sizes of the alkyl substituents.

ChemInform Abstract: A Method for the Selective Protection of Aromatic Amines in the Presence of Aliphatic Amines.

ChemInform ◽  
2009 ◽  
Vol 40 (22) ◽  
Author(s):  
Valerie Perron ◽  
Shaun Abbott ◽  
Nancie Moreau ◽  
Devin Lee ◽  
Christopher Penney ◽  
...  
Keyword(s):  
Aromatic Amines ◽  
Aliphatic Amines ◽  
Selective Protection

Activity of ceria and ceria-supported gold nanoparticles for the carbamoylation of aliphatic amines by dimethyl carbonate

2011 ◽  
Vol 84 (3) ◽  
pp. 685-694 ◽  
Author(s):  
Raquel Juárez ◽  
Avelino Corma ◽  
Hermenegildo García
Keyword(s):  
Gold Nanoparticles ◽  
Catalytic Activity ◽  
Aromatic Amines ◽  
Au Nanoparticles ◽  
Dimethyl Carbonate ◽  
Aliphatic Amines ◽  
Supported Gold Nanoparticles ◽  
Supported Gold

Aliphatic amines react sluggishly with dimethyl carbonate (DMC) to give a mixture of N-methylation and carbamoylation. Nanoparticulated ceria as catalyst increases, in general, conversion and selectivity toward carbamoylation. This increase in catalytic activity and selectivity toward carbamoylation is even increased by deposition of Au nanoparticles on ceria. However, in contrast to aromatic amines for which a complete selectivity toward carbamoylation using ceria-supported Au nanoparticles can be achieved, the catalytic carbamoylation of aliphatic amines by ceria-supported Au nanoparticles occurs only with moderate selectivity.

A study of negative catalysis in the gas phase I. The action of aliphatic amines on the slow oxidation of diethyl ether in the gas phase

1962 ◽  
Vol 265 (1323) ◽  
pp. 436-446 ◽  
Keyword(s):  
Free Radicals ◽  
Phase I ◽  
Gas Phase ◽  
Diethyl Ether ◽  
Reaction Vessel ◽  
Aliphatic Amines ◽  
Tertiary Amines ◽  
Amine Molecule ◽  
Primary Compounds

A study of the inhibition of the slow oxidation of diethyl ether by aliphatic amines is reported. Secondary and tertiary amines are more powerful inhibitors than the primary compounds. It is shown that the surface of the reaction vessel does not play a large part in the reaction. It is therefore suggested that amines must inhibit by stabilizing free radicals formed during the oxidation of ether; this may be done by forming addition compounds with the radicals in the gas phase or by an oxygenated radical abstracting hydrogen from an amine molecule.

Structure-Making with 3,5-Dimitrosalicylic Acid. I. The Proton Transfer Compounds of 3,5-Dinitrosalicylic Acid with a Series of Aliphatic Amines

2002 ◽  
Vol 55 (5) ◽  
pp. 349 ◽  
Author(s):  
G. Smith ◽  
U. D. Wermuth ◽  
P. C. Healy ◽  
R. C. Bott ◽  
J. M. White
Keyword(s):  
Hydrogen Bonding ◽  
Proton Transfer ◽  
Lewis Base ◽  
Aliphatic Amines ◽  
Tertiary Amines ◽  
Carboxylate Oxygen ◽  
Phenolic Oxygen ◽  
Phenolic Group ◽  
Intramolecular Hydrogen ◽  
Proton Transfer Compounds

The crystal structures of the proton-transfer compounds of 3,5-dinitrosalicylic acid (dnsa) with ammonia (two polymorphs) and a series of common aliphatic amines (methylamine, triethylamine, hexamethylenetetramine and ethylenediamine) have been determined and the hydrogen-bonding associations in each analysed. The compounds are [(NH4)+(dnsa)-] (1A, 1B), [(CH3NH3)+(dnsa)-] (2), [{(C2H5)3NH}+(dnsa)-] (3), [(C6H12 N4H)+(dnsa)-] (4) and [{(CH2 NH3) 2}2+(dnsa)2-�H2O] (5). It is of interest that with hydrate (5) the phenolic proton of dnsa is also lost on reaction, giving a rare dianionic species. In all compounds, protonation of the amino group of the Lewis base occurs, with subsequent hydrogen bonding via this and other hydrogens variously to the carboxylic, nitro and phenolic oxygens of dnsa, and in the case of (5), the lattice water. The result is the formation of simple linear associations with the tertiary amines, or network polymers with the less-substituted examples. Short intramolecular hydrogen bonds between the phenolic group and the carboxylate group are found in all compounds except (5), with the proton localized on the carboxylate oxygen rather than on the phenolic oxygen, but in the case of (3), delocalized within the hydrogen bond.

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