Methyl chloroformate → 6-bromo-7,8,9,9a-tetrahydro-3H-naptho[1,8-de][1,3]oxazine-2-one

HRID 2114545Notes

Reaction equation

HRID 2114545 reaction equation
Cl[C:2]([O:4][CH3:5])=[O:3].[NH2:6][C:7]1[CH:8]=[CH:9][C:10]([Br:18])=[C:11]2[C:16]=1C(O)[CH2:14][CH2:13][CH2:12]2.C(=O)([O-])[O-].[K+].[K+]>CN(C1C=CN=CC=1)C.N1C=CC=CC=1>[Br:18][C:10]1[CH:9]=[CH:8][C:7]2[NH:6][C:2](=[O:3])[O:4][CH:5]3[CH2:14][CH2:13][CH2:12][C:11]=1[C:16]=23

Participants

6

Reactant 3

HCID 6586Methyl chloroformateHCID 11430Potassium CarbonateHCID 692133418-Amino-5-bromo-1,2,3,4-tetrahydronaphthalen-1-ol

Product 1

HCID 692149946-bromo-7,8,9,9a-tetrahydro-3H-naptho[1,8-de][1,3]oxazine-2-one

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Conditions

Temperature
100 °C

Procedure

To prepare this compound, DMAP (6 mg, 0.043 mmol) and methyl chloroformate (27 mg, 0.29 mmol) were added to a solution of 8-amino-5-bromo-1,2,3,4-tetrahydronaphthalen-1-ol (70 mg, 0.29 mol) in 1.5 mL pyridine at −10° C. The reaction was stirred for 0.5 hour, then extracted with ethyl acetate and water. The organic layer was washed sequentially with 2% aqueous HCl solution, water, and brine an then was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was dissolved in 1.5 ml dry DMF and then potassium carbonate (80 mg, 0.58 mmol) was added. That suspension was heated at 100° C. for 2 hours, and was extracted with EtOAc and water. The organic layer from that extraction was washed sequentially with 2% aqueous HCl, water, and brine and was then dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford 6-bromo-7,8,9,9a-tetrahydro-3H-naptho[1,8-de][1,3]oxazine-2-one. 1H NMR (500 MHz, CDCl3) δ 8.55 (broad s, 1H), 7.41 (d, J=8.2, 1H), 6.60 (d, J=8.4, 1H), 5.3-5.4 (m, 1H), 2.90 (dd, J=17.8, 5.0, 1H), 2.55-2.65 (m, 1H), 2.40-2.50 (m, 1H), 2.15-2.25 (m, 1H), 1.70-1.90 (m, 2H).

Workup

  1. extractionextracted with ethyl acetate and water
  2. washThe organic layer was washed sequentially with 2% aqueous HCl solution, water, and brine
  3. dry with materialan then was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in 1.5 ml dry DMF
  7. extractionwas extracted with EtOAc and water
  8. extractionThe organic layer from that extraction
  9. washwas washed sequentially with 2% aqueous HCl, water, and brine
  10. dry with materialwas then dried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-bd986f9336e54e56bef3f4daec3210dd
Source dataset
uspto-grants-2008_10
Patent number
US07435733B2

Reaction notes

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