Diphenyl Ether → 7-Bromoisoquinolin-1-ol

HRID 551272Notes

Reaction equation

HRID 551272 reaction equation
C([N:5]([CH2:10]CCC)CCCC)CCC.[Br:14][C:15]1[CH:20]=[CH:19][C:18]([CH:21]=[CH:22]C(N=[N+]=[N-])=O)=[CH:17][CH:16]=1.C1([O:34]C2C=CC=CC=2)C=CC=CC=1>>[Br:14][C:15]1[CH:16]=[C:17]2[C:18]([CH:21]=[CH:22][NH:5][C:10]2=[O:34])=[CH:19][CH:20]=1

Participants

4

Reactant 3

HCID 7583Diphenyl Ether2×HCID 7622TributylamineHCID 539034244-Bromocinnamoyl azide

Product 1

HCID 112761337-Bromoisoquinolin-1-ol

Procedure

Preheated 2 separate oil baths to 240° C. A flask containing tributylamine (6.68 g, 36.1 mmol) and diphenyl ether (80 mL) was lowered into one oil bath (A), and a flask containing 3-(4-bromophenyl)acryloyl azide (7.91 g, 31.3 mmol) and diphenyl ether (80 mL) was lowered into the other oil bath (B) [vigorous gas evolution—internal temperature must quickly reach >200° C.]. After 10 minutes, the contents of flask B are poured into flask A, and the reaction left at 230-240° C. (internal temperature) for 30 minutes. Cooled reaction mixture to ˜100° C., poured into hexanes (2 L), stirred to cool to room temperature and filtered off the precipitate. Washed precipitate with methylene chloride/hexanes (ratio 1/50), dried under high vacuum to give a colorless powder (4.20 g, 18.8 mmol). 1H NMR (DMSO) δ 11.41 (s, 1H), 8.23 (s, 1H), 7.82 (dd, 1H), 7.62 (d, 1H), 7.20 (t, 1H), 6.54 (d, 1H). ESI MS (M+1)+: 224, 226 (Br).

Workup

  1. customPreheated 2 separate oil baths to 240° C
  2. customquickly reach >200° C.
  3. additionthe contents of flask B are poured into flask A, and the reaction
  4. waitleft at 230-240° C. (internal temperature) for 30 minutes
  5. temperatureCooled
  6. customreaction mixture to ˜100° C.
  7. filtrationfiltered off the precipitate
  8. washWashed precipitate with methylene chloride/hexanes (ratio 1/50)
  9. customdried under high vacuum

Sources & evidence

ORD record
ord-69bc03cdae5d405eb924f9c73d4fb9ac
Source dataset
uspto-grants-2011_05
Patent number
US07947684B2

Reaction notes

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