Boron tribromide → HCID 178424050, compound

HRID 2260374Notes

Reaction equation

HRID 2260374 reaction equation
C[O:2][C:3]1[C:4](=[O:16])[NH:5][C:6]2[CH:14]=[CH:13][CH:12]=[C:11]([CH3:15])[C:7]=2[C:8](=[O:10])[CH:9]=1.B(Br)(Br)Br.C([O-])(O)=O.[Na+].[K+].[Br-]>C(Cl)Cl>[OH:2][C:3]1[C:4](=[O:16])[NH:5][C:6]2[CH:14]=[CH:13][CH:12]=[C:11]([CH3:15])[C:7]=2[C:8](=[O:10])[CH:9]=1

Participants

6

Reactant 4

HCID 25134Boron tribromideHCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 10488953HCID 10488953, compound

Product 1

HCID 178424050HCID 178424050, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of 3-methoxy-6-methyl-1H-1-benzazepine-2,5-dione (350 mg, 1.61 mmol) in dry CH2Cl2 (25 mL, distilled from CaH2) under N2, there was added a solution of BBr3 in CH2Cl2 (5 mL, 1M, Aldrich) in one portion over 30 seconds at rt. The reaction solution immediately became orange, then an orange precipitate formed during the addition. The reaction was allowed to stir under N2 at rt for 65 min. The reaction was added to saturated NaHCO3 (50 mL) and the resulting mixture was vigorously stirred for 15 min to give biphasic system containing some solid material. The phases were separated and the aqueous portion vacuum filtered. The clear, pale yellow, aqueous portion was extracted with CH2Cl2 (1×10 mL). The aqueous portion was acidified with concd HCl (pH 2). The resulting precipitate was collected by filtration, washed to neutrality with water (6×2 mL) and dried in vacuo to yield a highly electrostatic, colorless powder (mass could not be determined). Crystallization from EtOAc (dissolved in 15 mL, hot filtered, concd to 7 mL, allowed to cool to rt) initially yielded near colorless needles, which upon standing overnight at rt, transformed into beige cubes (146 mg, 45%, pure by 1H NMR); mp 187.5°-188.5° C. (dec.); 1H NMR (DMSO-d6) δ2.34 (s, 3H), 6.30 (s, 1H), 7.09 (d, J=7.2 Hz, 1H), 7.21 (d, J=8.1 Hz, 1H), 7.37 (t, J=7.8 Hz, 1H), 10.39 (s, 1H), 11.20 (s, 1H); IR (KBr) 3207 (m), 3047 (m), 1642 (s), 1607 (s), 1598 (s), 1348 (m), 789 (m); Anal. Calcd for C11H9NO3 : C, 65.02, H, 4.46, N, 6.89. Found: C, 65.26; H, 4.54; N, 6.89. Concentration of the mother liquor yielded an additional portion of orange cubes (30 mg, 9%, pure by 1H NMR); mp 184.5°-188° C. In one crystallization, the above mentioned needles were collected; mp 177°-179° C. (dec); IR (KBr) 3389 (m), 3193 (m), 1661 (s), 1646 (s), 1601 (m), 1580 (m), 1350 (m), 1204 (m).

Workup

  1. customThe reaction solution immediately became orange, then an orange precipitate formed during the addition
  2. stirringthe resulting mixture was vigorously stirred for 15 min
  3. customto give biphasic system
  4. additioncontaining some solid material
  5. customThe phases were separated
  6. filtrationthe aqueous portion vacuum filtered
  7. extractionThe clear, pale yellow, aqueous portion was extracted with CH2Cl2 (1×10 mL)
  8. filtrationThe resulting precipitate was collected by filtration
  9. washwashed
  10. customdried in vacuo
  11. customto yield a highly electrostatic, colorless powder (mass could not
  12. customCrystallization from EtOAc (dissolved in 15 mL, hot filtered, concd to 7 mL, allowed to cool to rt)
  13. custominitially yielded near colorless needles, which
  14. waitupon standing overnight at rt
  15. customConcentration of the mother liquor yielded an additional portion of orange cubes (30 mg, 9%, pure by 1H NMR)
  16. customIn one crystallization
  17. customwere collected

Sources & evidence

ORD record
ord-f15e6fa4629b48ed8ecc159925f074b8
Source dataset
uspto-grants-1995_12
Patent number
US05476933

Reaction notes

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