Preparation of Polyfunctional Amines by the Addition of Functionalized Organomagnesium Reagents to Nitrosoarenes

Abstract

The addition of functionalized arylmagnesium reagents to nitrosoarenes at -20 °C in THF furnishes after a reductive workup polyfunctional diarylamines in 43-74% yield.

Key words

diarylamines - nitrosoarenes - organomagnesium reagents - arylation of amines - amination reaction

References

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9

Analytical data of 3d:
Mp: 103-104 °C; ¹H NMR (300 MHz, CDCl₃): δ [ppm] = 5.59 (br s, 1 H, NH), 6.73-6.76 (d, ³ J = 8.48 Hz, 2 H, CH_arom.), 6.87-6.99 (m, 3 H, CH_arom.), 7.18-7.23 (m, 2 H, CH_arom.), 7.42-7.45 (d, ³ J = 8.48 Hz, 2 H, CH_arom.); ¹³C NMR (75 MHz, CDCl₃): δ [ppm] = 82.07, 118.53, 119.25, 121.80, 129.42, 138.06, 142.16, 143.13; IR (KBr): [cm^-1] = 3399 (s), 3054 (w), 3028 (w), 1932 (w), 1603 (s), 1581(vs), 1503(vs), 1482(vs), 1441 (m), 1387 (m), 1338 (w), 1315(vs), 1282 (m), 1238 (m), 1175 (m), 1154 (w), 1106 (w), 1078 (w), 1058 (w), 1027 (w), 1000 (w), 932 (w), 873 (w), 836 (m), 826 (m), 806 (m), 749 (s), 702 (m), 691 (s), 670 (w), 650 (w), 626 (w), 588 (w), 502 (m), 488 (w); MS (EI): m/z (I): 295 (100, M⁺), 167 (31), 139 (2), 84 (8), 77 (2); HRMS: calcd: 294.9858; found: 294.9856; C₁₂H₁₀IN: calcd: C: 48.84; H: 3.42; N: 4.75; I: 43.00; found: C: 48.93; H: 3.40; N: 4.74; I: 42.99.