N-Alkylation of Primary and Secondary Amines by Alkyl Halides and Lithium Naphthalene

Abstract

Alkylation of trivalent nitrogen can be effected in a variety of ways, such as the action of alcohol

Pentacoordinated Carboxylate π‐Allyl Nickel Complexes as Key Intermediates for the Ni‐Catalyzed Direct Amination of Allylic Alcohols

“…N ‐Allyl‐2‐methoxyaniline ( 3 ag ):28 1 H NMR (400 MHz, CDCl 3 , 30 °C): δ =6.89–6.64 (m, 4 H, aromatic), 6.00 (tdd, J =17.1, 10.3, 5.0 Hz, 1 H, CH 2 C H CH 2 ), 5.29 (dd, J =17.3, 3.1 Hz, 1 H, C H HCHCH 2 ), 5.17 (dd, J =10.2, 3.1 Hz, 1 H, CH H CHCH 2 ), 4.65 (br s, 1 H, NH), 3.86 (s, 3 H, ArOC H 3 ), 3.81 ppm (m, 2 H, CHC H 2 N); 13 C NMR (100 MHz, CDCl 3 , 30 °C): δ =146.8, 138.0, 135.6, 121.2, 116.5, 115.8, 110.1, 109.4, 55.3, 46.2 ppm.…”

Chemoselective debenzylation of N-benzyl tertiary amines with ceric ammonium nitrate

“…Following work-up, the residue was purified by column chromatography on silica gel (hexane-Et 2 O 1 : 1 to neat Et 2 O) to give 20 as a colourless oil (257 mg, 69% at 80% conversion) with identical spectroscopic properties to those described previously. 40 24 Based upon a literature procedure, 39 trimethyl orthoformate (4.0 g, 37.9 mmol), dibenzylamine (5.0 g, 25.3 mmol) and butyraldehyde (1.8 g, 25.3 mmol) were stirred at RT in MeOH (100 ml) at pH 6 prior to the portionwise addition of NaBH 4 (0.96 g, 25.3 mmol) at 0 ЊC. After sixteen hours, the reaction was concentrated in vacuo, washed with 10% aqueous citric acid, extracted with DCM (3 × 100 ml), dried and concentrated in vacuo.…”

Reaction of Lithioamines with Alkyl Halides: A Convenient Direct Synthesis of N-Alkylaminopyridines

“…1 To prevent overalkylation, troublesome and expensive multistep methods have been derived such as partial protection of primary amines 11 and reduction of mono N-substituted amides. 12 Although there were known good methods [13][14][15] for synthesis of Nalkylation of aromatic and heteroaromatic amines, still improved selective methods continue to be sought.…”

“…According to reported paper, [13][14][15] we investigated the Nmonoalkylation of aminopyridine at −78 o C to −40 o C. However, during the experiment, we recognized that the generated lithioaminoanion from the reaction of aminopyridine with n-butyllithium is stable for 1 h at 0 o C to 25 o C.…”