Iodine → HCID 69216232, compound

HRID 1296508Notes

Reaction equation

HRID 1296508 reaction equation
[Mg].II.Br[CH2:5][CH2:6][CH2:7][CH2:8]Br.[CH3:10][O:11][C:12](=O)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[NH2:19].C1N=CN(C(N2C=NC=C2)=[O:27])C=1>CCOCC.C1COCC1>[C:12]12([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[NH:19][C:10](=[O:27])[O:11]1)[CH2:8][CH2:7][CH2:6][CH2:5]2

Participants

8

Reactant 5

HCID 807IodineHCID 80561,4-DibromobutaneHCID 8635Methyl AnthranilateHCID 682631,1'-CarbonyldiimidazoleHCID 5462224Magnesium

Product 1

HCID 69216232HCID 69216232, compoundYield 27%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of magnesium turnings (19.44 g, 800 mmol) and a catalytic amount of iodine in ether (500 mL) was slowly added 1,4-dibromobutane (24.0 mL, 200 mmol). The reaction was stirred until reflux ceased. The magnesium was decanted and the solution was slowly added to 2-aminobenzoic acid methyl ester (8.0 mL, 61.70 mmol) in THF (600 mL) at 0° C. The solution was stirred overnight at room temperature, quenched with ammonium chloride solution (sat.) and extracted several times with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate and concentrated. The crude material was taken up in THF (150 mL) and CDI (9.17 g, 56.53 mmol) was added. The reaction mixture was stirred overnight at room temperature and partitioned between ammonium chloride solution (sat) and ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated. Flash silica gel column separation with 20% ethyl acetate/hexane gave spiro[4H-3,1-benzoxazine-4,1′-cyclopentan]-2(1H)-one as a white solid (2.60 g, 27%). 1H NMR (DMSO-d6): δ 10.15 (s, 1H), 7.28 (m, 2H), 7.03 (t, J=7.6 Hz, 1H), 6.89 (dd, J=7.9, 0.8 Hz, 1H), 2.15 (m, 2H), 2.07 (m, 2H), 1.90 (m, 4H); MS (ESI) m/z 204 ([M+H]+); Anal. calcd for C12H13NO2: C, 70.92; H, 6.45 N, 6.89. Found: C, 70.84; H, 6.42; N, 6.77.

Workup

  1. temperatureuntil reflux
  2. customThe magnesium was decanted
  3. stirringThe solution was stirred overnight at room temperature
  4. customquenched with ammonium chloride solution (sat.)
  5. extractionextracted several times with ethyl acetate
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated
  9. stirringThe reaction mixture was stirred overnight at room temperature
  10. custompartitioned between ammonium chloride solution (sat) and ethyl acetate
  11. dry with materialThe organic layer was dried over magnesium sulfate
  12. concentrationconcentrated
  13. customFlash silica gel column separation with 20% ethyl acetate/hexane

Sources & evidence

ORD record
ord-b5b29fdfcc2a4fcda5690e89ef346c58
Source dataset
uspto-grants-2007_07
Patent number
US07247625B2

Reaction notes

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