1-Fluoro-2-nitro-4-azidobenzene → N-(3-aminopropyl)-N'-(4-azido-2-nitrophenyl)-N-methyl-1,3-propanediamine

HRID 1460041Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1460041
F[C:2]1[CH:7]=[CH:6][C:5]([N:8]=[N+:9]=[N-:10])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].NCCC[CH:18]([NH:22][CH3:23])[CH2:19][CH2:20][NH2:21]>CCOCC>[NH2:8][CH2:5][CH2:4][CH2:3][N:22]([CH3:23])[CH2:18][CH2:19][CH2:20][NH:21][C:2]1[CH:7]=[CH:6][C:5]([N:8]=[N+:9]=[N-:10])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12]

Komponenten

4

Edukt 2

HCID 931211-Fluoro-2-nitro-4-azidobenzeneHCID 867534983-aminopropyl-N-methyl-1,3-propanediamine

Produkt 1

HCID 54562181N-(3-aminopropyl)-N'-(4-azido-2-nitrophenyl)-N-methyl-1,3-propanediamine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel2×

Versuchsvorschrift

The reaction was carried out in the dark. A solution of 4-fluoro-3-nitrophenyl azide (0.91 g, 5.0 mmol, Sigma) in 10 ml dry ether was added dropwise with stirring to a solution of 3.2 ml of N-(3-aminopropyl-N-methyl-1,3-propanediamine (10 mmol, Aldrich) in 20 ml dry ether and the mixture was stirred for 30 min. The reaction was monitored using TLC (alumina, elution with methanol). The solvent was removed and the red oil was dissolved in 25 ml water, 25 ml 1.0M HaOH and then extracted into ethyl acetate (2×50 ml). The organic phase was dried over MgSO4 and the solvent then removed in vacuum. TLC: (I) alumina, eluted with methanol, Rf=0.43 (II) silica gel, elution with 1:9 AcOH/H2O, Rf between Rf=0.23 and Rf=0.55. 1H NMR (CDCl3 /TMS) δ: 1.45 (2H, broad s, NH), 1.64 (2H, m, CH2), 1.87 (2H, p, J=6.52 Hz, CH2), 2.25 (3H, s, CH3), 2.43 (2H, t, CH2), 2.47 (2H, t, J=6.46 Hz, CH2), 2.73 (2H, t, J=6.89 Hz, CH2), 3.37 (2H, m, J=6.61 Hz, CH2), 6.89 (1H, d, J=9.23 Hz, ArH), 7.10 (1H, dd, J=2.73, 9.20 Hz, ArH), 7.79 (1H, d, J=2.74 Hz, ArH), 8.47 (1H, m, NH). 13C NMR (CDCl3 /TMS) δ: 143.123 (Q), 131.24 (Q), 127.91 (CH), 127.16 (Q), 115.73 (CH), 115.44 (CH), 55.70 (CH2), 55.40 (CH2), 42.03 (CH2), 41.90 (CH3), 40.50 (CH2), 30.94 (CH2), 26.20 (CH2).

Aufarbeitung

  1. washTLC (alumina, elution with methanol)
  2. customThe solvent was removed
  3. dissolutionthe red oil was dissolved in 25 ml water
  4. extraction25 ml 1.0M HaOH and then extracted into ethyl acetate (2×50 ml)
  5. dry with materialThe organic phase was dried over MgSO4
  6. customthe solvent then removed in vacuum
  7. washTLC: (I) alumina, eluted with methanol, Rf=0.43 (II) silica gel, elution with 1:9 AcOH/H2O, Rf between Rf=0.23 and Rf=0.55

Quellen und Nachweise

ORD-Eintrag
ord-fd6bce603a0f4a86908ae855e39e78f4
Quelldatensatz
uspto-grants-1998_12
Patentnummer
US05854409

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