BenzenaMine, 2-(3,3-diMethyl-1-butyn-1-yl)-4-nitro- synthesis

Yield:682357-48-8 65%

Reaction Conditions:

with copper(l) iodide;triethylamine;trans-dichlorobis(triphenylphosphine)palladium(II) at 20;

Steps:

Synthesis of [2- (3', 3'-DIMETHYLBUT-1-YNYL)-4-NITROANILINE] (2)

In a sealed round-bottom flask, a solution of [2-IODO-4-NITROANILINE] [Sy, W. -W. Syn. Commun. 1992,22 (22), [3215]] (1,5 g, 19 [MMOL),] trans-dichlorobis(triphenyl-phosphine)palladium (ll) (665 mg, 0.95 mmol), copper [(I)] iodide (180 mg, 0.95 mmol)), triethylamine (60 mL) and 3, 3-dimethyl-1-butyne (9.3 mL, 6.2 g, 76 [MMOL)] was allowed to stir at room temperature overnight. The reaction mixture was then concentrated in vacuo and the resulting black residue was chromatographed on silica gel (10% ethyl acetate/hexanes). The desired product was isolated and triturated with hexanes to give 2.7 g (65%) as a yellow crystalline [SOLID. 1H] NMR (CDC13) [?] 8.18 (d, J=2.5 Hz, 1H), 8.00 (dd, J=9. [1,] 2.5 Hz, [1H),] 6. [67] (d, [J=9. 1] Hz, [1H),] 1. [37] (s, [9H). MS (M/Z)] : 219 (MH+).

References:

WO2004/35571,2004,A1 Location in patent:Page 24-25