Synthesis of Primary Aryl Amines Through a Copper-Assisted Aromatic Substitution Reaction with Sodium Azide

Abstract

A method is presented by which aryl halides and azides are converted to the corresponding primary aryl amines with copper(I) and sodium azide.

A green route for the cross-coupling of azide anions with aryl halides under both base and ligand-free conditions: exceptional performance of a Cu2O–CuO–Cu–C nanocomposite

“…16 Bewildering arrays of reports and the formation of different products led to the selective synthesis of aryl azides using the obtained nanocomposites.…”

Incorporating a Piperidinyl Group in the Fluorophore Extends the Fluorescence Lifetime of Click-Derived Cyclam-Naphthalimide Conjugates

“…Conversion of bromide 12 to the corresponding azide 13 was initially attempted with sodium azide in the presence of sodium ascorbate, copper(I) iodide and N , N ′-dimethylethylenediamine (DMEDA) at reflux in either an ordinary round-bottomed flask or a pressure tube. [33]–[35] A solvent screen including methanol/water, ethanol/water or dimethyl sulfoxide (DMSO)/water (7∶3 in all cases) failed to afford the desired azide 13 , giving instead full recovery of starting material 12 ; this outcome may be attributed to the extraordinarily low solubility of bromide 12 in these solvent combinations. Switching to tetrahydrofuran (THF)/water (7∶3), all reactants and reagents were dissolved at reflux in the pressure tube and reaction proceeded to give azide 13 in 50% yield.…”

“…The corresponding amine was also detected by LCMS analysis of the reaction mixture, consistent with previous observations that both azide and amine may be generated through a copper-assisted aromatic substitution reaction with sodium azide. [33] Reacting each of the three precursors 13 , 17 and 20 individually with the complementary propargyl-tri-Boc cyclam [23], [36] or azidoethyl-tri-Boc cyclam [24] under standard click conditions [24], [36] yielded the Boc-protected cyclam-piperidinylnaphthalimide conjugates 14 , 18 and 21 respectively in good to excellent yields. Removal of Boc groups from these conjugates was effected in a mixture of TFA/DCM/H 2 O (90∶5∶5), [23], [36], [37] followed by basification to recover the corresponding free amines 8 – 10 .…”

Structurally diverse low molecular weight activators of the mammalian pre-mRNA 3′ cleavage reaction

“…2-Naphthylamine 44 (0.37 g, 2.6 mmol) was added followed by HOAt (0.89 g, 6.54 mmol) and EDC (0.76 g, 3.96 mmol). After 1.5 h, the solution was concentrated and purified by flash chromatography, eluting with chloroform/ethyl acetate (4:1) to give 6a (800 mg, 1.58 mmol), in 61% yield.…”

“…2-Naphthylamine 44 (470 mg, 3.28 mmol) was added followed by HOAt (929 mg, 6.83 mmol) and EDC (785 mg, 4.09 mmol). Reaction progress was monitored by TLC.…”