Oxygen → HCID 66630267, compound

HRID 426371Notes

Reaction equation

HRID 426371 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([C:8]#[N:9])[C:5]([C:10]#[N:11])=[CH:4][C:3]=1[NH2:12].C(O)CCCC.[CH2:19]([CH:25]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])[CH:26]=O)[CH2:20][CH2:21][CH2:22]CC.O=O>CN1C(=O)CCC1>[C:10]([C:5]1[C:6]([C:8]#[N:9])=[CH:7][C:2]2[N:1]=[C:26]([CH:25]([CH2:19][CH2:20][CH2:21][CH3:22])[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])[NH:12][C:3]=2[CH:4]=1)#[N:11]

Participants

6

Reactant 4

HCID 977OxygenHCID 62761-PentanolHCID 6763684,5-DiaminophthalonitrileHCID 137000212-Hexyloctanal

Product 1

HCID 66630267HCID 66630267, compoundYield 87.8%

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
120 °C

Procedure

A 100 mL round-bottom flask was charged with 3 (1.32 g, 8.37 mmol), pentanol (42 mL), 2-hexyl-1-octanal (1.77 g, 8.37 mmol), and a magnetic stirring bar. The flask was fitted with a Hickman still and placed in an oil bath heated to 120° C. NMP (4.0 mL) was added to fully dissolve the solid material. The mixture was heated and stirred for 2 h. Then FeCl3.6H2O (113 mg, 0.42 mmol) was added to the reaction vessel and oxygen was bubbled through the mixture as it was heated and stirred for an additional 12 h. The reaction mixture was then removed from heat and added to 200 mL diethyl ether. The ether solution was washed three times with water, then washed with brine, dried over Na2SO4, filtered, and concentrated to dryness. The residue was chromatographed (silica, CHCl3), yielding a tan solid (2.37 g, 81%): 1H NMR δ 0.82 (t, J=7.6 Hz, 6H), 1.10-1.30 (m, 16H), 1.77-1.87 (m, 2H), 2.90-3.04 (m, 1H), 8.07 (br s, 2H), 10.36 (br s, 1H); 13C NMR δ 14.2, 22.8, 27.7, 29.4, 31.8, 34.9, 41.3, 108.4, 117.0, 165.3; FAB-MS obsd 351.2551, calcd 351.2549 (C22H30N4).

Workup

  1. customThe flask was fitted with a Hickman still
  2. customplaced in an oil bath
  3. dissolutionto fully dissolve the solid material
  4. temperatureThe mixture was heated
  5. customwas bubbled through the mixture as it
  6. temperaturewas heated
  7. stirringstirred for an additional 12 h
  8. customThe reaction mixture was then removed
  9. temperaturefrom heat
  10. additionadded to 200 mL diethyl ether
  11. washThe ether solution was washed three times with water
  12. washwashed with brine
  13. dry with materialdried over Na2SO4
  14. filtrationfiltered
  15. concentrationconcentrated to dryness
  16. customThe residue was chromatographed (silica, CHCl3)

Sources & evidence

ORD record
ord-7e17847b8c2c4a51843a8dea1b27f038
Source dataset
uspto-grants-2012_01
Patent number
US08106393B2

Reaction notes

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