Oxygen → HCID 11675958, compound

HRID 426373Notes

Reaction equation

HRID 426373 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].[I:13][C:14]1[CH:21]=[CH:20][C:17]([CH:18]=O)=[CH:16][CH:15]=1.O=O.I[CH2:25][CH2:26][CH3:27].C1CCN2C(=NCCC2)CC1>CC#N.C1CCN2C(=NCCC2)CC1.C(OCC)(=O)C.CN1C(=O)CCC1>[C:10]([C:5]1[C:6]([C:8]#[N:9])=[CH:7][C:2]2[N:1]([CH2:25][CH2:26][CH3:27])[C:18]([C:17]3[CH:20]=[CH:21][C:14]([I:13])=[CH:15][CH:16]=3)=[N:12][C:3]=2[CH:4]=1)#[N:11]

Participants

10

Reactant 5

HCID 977OxygenHCID 336431-Iodopropane2×HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 966574-IodobenzaldehydeHCID 6763684,5-Diaminophthalonitrile

Product 1

HCID 11675958HCID 11675958, compoundYield 65.5%

Reagents, catalysts & solvents 4

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneCatalystHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
120 °C

Procedure

A 25 mL round-bottom flask was charged with 3 (340 mg, 2.15 mmol), NMP (10 mL), 4-iodobenzaldehyde, (499 mg, 2.15 mmol), and a magnetic stirring bar. The flask was fitted with a Hickman still, placed in an oil bath heated to 120° C., and stirred for 1 h. Then FeCl3.6H2O (29 mg, 0.11 mmol) was added to the reaction vessel and oxygen was bubbled through the mixture as it was heated and stirred for an additional 24 h. The reaction mixture was then removed from heat and added to ethyl acetate. The ethyl acetate solution was washed three times with water, then washed with brine, dried over Na2SO4, filtered, and concentrated to dryness. The residue (603 mg, 1.63 mmol) was suspended in CH3CN and heated to 80° C. Then DBU (243 μL, 1.63 μmol) was added and the mixture was stirred for 2 min, and iodopropane (159 μL, 1.63 mmol) was added. After 20 min, the mixture was treated with a second round of DBU and iodopropane, and after an additional 20 min, a third round of reagents was added. After a final 20 min of heating, the mixture was transferred to ethyl acetate and washed three times with water, followed by brine. After drying the organic layer over Na2SO4, the mixture was filtered, concentrated to dryness, and chromatographed (silica, CHCl3, 5% ethyl acetate), giving a white solid (440 mg, 50%): mp 208-209° C.; 1H NMR (CDCl3) δ 0.91 (t, J=7.6 Hz, 3H), 1.80-1.91 (m, 2H) 4.26 (t, J=7.6 Hz, 2H), 7.46 (d, J=8.0 Hz, 2H), 7.87 (s, 1H), 7.95 (d, J=8.0 Hz, 2H), 8.22 (s, 1H); 13C NMR (CDCl3) δ 11.4, 23.6, 47.4, 98.4, 109.0, 109.3, 116.55, 116.62, 116.9, 126.7, 128.2, 130.9, 137.8, 138.7, 145.3, 158.4; Anal. Calcd for C18H13IN4: C, 52.45; H, 3.18; N, 13.59. Found: C, 52.40; H, 3.06; N, 13.40.

Workup

  1. customThe flask was fitted with a Hickman still
  2. customplaced in an oil bath
  3. customwas bubbled through the mixture as it
  4. temperaturewas heated
  5. stirringstirred for an additional 24 h
  6. customThe reaction mixture was then removed
  7. temperaturefrom heat
  8. additionadded to ethyl acetate
  9. washThe ethyl acetate solution was washed three times with water
  10. washwashed with brine
  11. dry with materialdried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated to dryness
  14. temperatureheated to 80° C
  15. stirringthe mixture was stirred for 2 min
  16. waitAfter 20 min
  17. waitafter an additional 20 min
  18. additiona third round of reagents was added
  19. temperatureAfter a final 20 min of heating
  20. washwashed three times with water
  21. dry with materialAfter drying the organic layer over Na2SO4
  22. filtrationthe mixture was filtered
  23. concentrationconcentrated to dryness
  24. customchromatographed (silica, CHCl3, 5% ethyl acetate)

Sources & evidence

ORD record
ord-673237710d67495cb9a112a19cc43c59
Source dataset
uspto-grants-2012_01
Patent number
US08106393B2

Reaction notes

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