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

HRID 1460041ノート

反応式

HRID 1460041 の反応式
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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-fd6bce603a0f4a86908ae855e39e78f4
出典データセット
uspto-grants-1998_12
特許番号
US05854409

反応ノート

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