Iodine → HCID 21949996, compound

HRID 2215777Notes

Reaction equation

HRID 2215777 reaction equation
OCCCN1C2C(=CC=CC=2)C=C1[C:14]1[C:15](=[O:29])[NH:16][C:17](=O)[C:18]=1[C:19]1[CH:20]=[CH:21][CH:22]=[C:23]2[C:27]=1[NH:26][CH:25]=[CH:24]2.II.[O:32]1[CH2:37][CH2:36]OCC1>>[OH:29][CH2:15][CH2:14][CH2:18][C:22]1[CH:21]=[C:20]2[C:25]3[C:24](=[C:14]4[C:15](=[O:29])[N:16]=[CH:17][C:18]4=[C:19]2[C:27]2[C:23]=1[CH:24]=[CH:25][N:26]=2)[C:23]1[CH2:36][C:37](=[O:32])[CH:20]=[CH:19][C:27]=1[N:26]=3

Participants

4

Reactant 3

HCID 807Iodine2×HCID 312751,4-DioxaneHCID 21950037HCID 21950037, compound

Product 1

HCID 21949996HCID 21949996, compound

Procedure

A solution of 3-[1-(3-hydroxypropyl)-1H-indol-2-yl]-4-(1H-indol-7-yl)-pyrrole-2,5-dione (243 mg, 0.631 mmol) and I2 (160 mg, 0.63 mmol) in dioxane (200 mL) was irradiated with a 450 W Hanovia medium pressure lamp through a pyrex filter for 90 min. A 10% aq solution of NaHSO3 was added, the mixture concentrated to ˜50 mL, and poured into EtOAc. The EtOAc solution was washed with 10% aq NaHSO3, saturated aq NaHCO3, and brine. The solution was dried (MgSO4 and concentrated. TLC and 1H NMR indicated a 1:1 mixture of starting material and desired product. The residue was taken up in dioxane (200 mL), I2 (74 mg, 0.29 mmol) and the photolysis continued for 2 h. The dark red mixture was worked up as described above and the dried solution was concentrated to ˜50 mL, when a precipitate started to form. The mixture was heated to reflux and filtered through a plug of glass wool. The filtrate was allowed to cool, and filtration afforded the title product as a bright red solid which was dried under vacuum at 75–80 C. overnight leaving a maroon solid (99 mg, 41%). 1H NMR (400 MHz, DMSO-d6) 12.96 (s, 1H), 11.59 (s, 1H), 9.19 (d, J=8 Hz, 1H), 8.52 (d, J=9 Hz, 1H), 8.09 (d, J=9 Hz, 1H), 7.90 (d, J=8 Hz, 1H), 7.75 (dd, J=3, 3 Hz, 1H), 7.63 (dd, J=8, 8 Hz, 1H), 7.43 (dd, J=8, 8 Hz, 1H), 6.81 (dd, J=3, 3 Hz, 1H), 5.00 (t, J=7.5 Hz, 2H), 4.90 (t, J=5 Hz, 1H), 3.63 (m, 2H), 2.18 (m, 2H). MS (electrospray, m/z) 384 (M++1), 382 (M−−1). HRMS 384.1331 (M++1, calcd for C23H18N3O3 384.1348).

Workup

  1. filtrationfilter for 90 min
  2. additionA 10% aq solution of NaHSO3 was added
  3. concentrationthe mixture concentrated to ˜50 mL
  4. additionpoured into EtOAc
  5. washThe EtOAc solution was washed with 10% aq NaHSO3, saturated aq NaHCO3, and brine
  6. dry with materialThe solution was dried (MgSO4
  7. concentrationconcentrated
  8. additiona 1:1 mixture of starting material and desired product
  9. concentrationwas concentrated to ˜50 mL, when a precipitate
  10. customto form
  11. temperatureThe mixture was heated
  12. temperatureto reflux
  13. filtrationfiltered through a plug of glass wool
  14. temperatureto cool
  15. filtrationfiltration

Sources & evidence

ORD record
ord-9ab861ba89a34deda69ef7986e8832b1
Source dataset
uspto-grants-2006_09
Patent number
US07109229B2

Reaction notes

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