1-Chloro-2,4-Dinitrobenzene → 2,4-Dinitro-N-3,6,9,12,15,18,21,24-octaoxaheptacos-26-yn-1-ylbenzenamine

HRID 929609Notes

Reaction equation

HRID 929609 reaction equation
[CH2:1](N)[CH2:2][O:3][CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][C:14]#[CH:15].C([N:19]([CH2:22][CH3:23])[CH2:20][CH3:21])C.ClC1C=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][C:26]=1[N+:34]([O-:36])=[O:35]>CCO>[N+:34]([C:26]1[CH:27]=[C:28]([N+:31]([O-:33])=[O:32])[CH:29]=[CH:23][C:22]=1[NH:19][CH2:20][CH2:21][O:3][CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:1][CH2:2][O:3][CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][C:14]#[CH:15])([O-:36])=[O:35]

Participants

5

Reactant 3

HCID 61-Chloro-2,4-DinitrobenzeneHCID 8471TriethylamineHCID 86580391H2N-PEG4-Propyne

Product 1

HCID 580788652,4-Dinitro-N-3,6,9,12,15,18,21,24-octaoxaheptacos-26-yn-1-ylbenzenamineYield 276.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

3,6,9,12-tetraoxapentadec-14-yn-1-amine (815 mg, 2.27 mmol, 1 equiv.) was dissolved in EtOH (10 mL), and triethylamine (666 μL, 0.726 mmol, 1.5 equiv.) and 1-chloro-2,4-dinitrobenzene (505 mg, 2.5 mmol, 1.5 equiv.) were added. The reaction flask was fitted with a reflux condenser and the reaction was heated to reflux for 48 h, cooled, and concentrated to a yellow oil. The crude mixture was purified by flash chromatography (3 cm×20 cm Silica, 3% MeOH:CH2Cl2) to yield N-(2,4-dinitrophenyl)-3,6,9,12,15,18,21,24-octaoxaheptacos-26-yn-1-amine (10) as a yellow solid (1.15 g, >95% yield). IR (thin film/NaCl) 3363 (w), 2871 (s), 1621 (s), 1337 (m), 1103 (s) cm−1; 1H-NMR (500 MHz, CDCl3) δ 9.08 (d, 1H, J=2.6 Hz), 8.77 (bs, 1H), 8.21 (dd, 1H, J=2.6, J=9.5 Hz), 6.94 (d, 1H, J=9.5 Hz), 4.16 (6, 2H, J=2.4 Hz), 3.78 (t, 2H, J=5.0 Hz), 3.64 (m, 32H), 3.58 (q, 2H), 2.41 (t, 1H, 2.38 Hz); 13C-NMR (125 MHz, CDCl3) δ 148.5, 136.1, 130.5, 130.29, 124.3, 114.3, 79.8, 74.6, 70.7, 70.6, 70.5, 69.2, 68.7, 58.5, 43.3; HRMS (EI) calc'd for C25H39N3O12 (M+H) m/z 574.260650. Found 574.26106.

Workup

  1. customThe reaction flask was fitted with a reflux condenser
  2. temperaturethe reaction was heated
  3. temperatureto reflux for 48 h
  4. temperaturecooled
  5. concentrationconcentrated to a yellow oil
  6. customThe crude mixture was purified by flash chromatography (3 cm×20 cm Silica, 3% MeOH:CH2Cl2)

Sources & evidence

ORD record
ord-3b53c08a48384af09b0b7711af048ea5
Source dataset
uspto-grants-2016_03
Patent number
US09296708B2

Reaction notes

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