N,N-bis(3-aminopropyl)methylamine → N1-(3-Aminopropyl)-N3-(4-azido-2-nitrophenyl)-N1-methyl-1,3-propanediamine

HRID 1940871Notes

Reaction equation

HRID 1940871 reaction equation
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].[NH2:14][CH2:15][CH2:16][CH2:17][N:18]([CH3:23])[CH2:19][CH2:20][CH2:21][NH2:22]>CCOCC>[NH2:14][CH2:15][CH2:16][CH2:17][N:18]([CH3:23])[CH2:19][CH2:20][CH2:21][NH:22][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]

Participants

4

Reactant 2

HCID 7777N,N-bis(3-aminopropyl)methylamineHCID 931211-Fluoro-2-nitro-4-azidobenzene

Product 1

HCID 54562181N1-(3-Aminopropyl)-N3-(4-azido-2-nitrophenyl)-N1-methyl-1,3-propanediamine

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

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 NaOH 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: 143.23 (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).

Workup

  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 NaOH 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

Sources & evidence

ORD record
ord-cd2a3c065b9d4ff1bfb2dd370c15ad3f
Source dataset
uspto-grants-1997_12
Patent number
US05700921

Reaction notes

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