Boron tribromide → HCID 178422364, compound

HRID 2260370Notes

Reaction equation

HRID 2260370 reaction equation
[CH3:1][CH:2]1[CH2:16][C:6]2[C:7](=[O:15])[CH:8]=[C:9]([O:13]C)[C:10](=[O:12])[NH:11][C:5]=2[CH2:4][CH:3]1[CH3:17].B(Br)(Br)Br.C([O-])(O)=O.[Na+]>C(Cl)Cl>[CH3:1][CH:2]1[CH2:16][C:6]2[C:7](=[O:15])[CH:8]=[C:9]([OH:13])[C:10](=[O:12])[NH:11][C:5]=2[CH2:4][CH:3]1[CH3:17]

Participants

5

Reactant 3

HCID 25134Boron tribromideHCID 516892Sodium BicarbonateHCID 10776120HCID 10776120, compound

Product 1

HCID 178422364HCID 178422364, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred suspension of 7,8-dimethyl-3-methoxy-6,7,8,9-tetrahydro1H-1-benzazepine-2,5-dione (90.0 mg, 382 μmol) in dry CH2Cl2 (2 mL, distilled from CaH2) under N2, there was added a solution of BBr3 in CH2Cl2 (1.0 mL, 1M, Aldrich) in one portion over 5 seconds at rt. A green precipitate immediately formed. The reaction was allowed to stir under N2 at rt for 45 min. The reaction was added to saturated NaHCO3 (15 mL) and the resulting orange solution was allowed to stir for 15 min. The solution was extracted with CH2Cl2 (2×4 mL). The aqueous solution was acidified with coned HCl (pH 2), the resulting precipitate collected by filtration and washed to neutrality with water (6×2 mL). Crystallization from 95% EtOH yielded pale beige needles (56 mg, 67%, pure by 1H NMR, consists of a probable mixture of cis- and trans-isomers (85:15)); mp 242°-243° C. (dec.); 1H NMR (DMSO-d6) δ0.80 (t, J=7.5 Hz, 6H), 1.79 (m, 2H), 2.03 (dd, J=7.5, 17.7 Hz, 1H), 2.21 (dd, J=6.0, 18.0 Hz, 1H), 2.35 (dd, J=5.1, 17.7 Hz, 1H), 2.58, (dd, J=5.4, 18.0 Hz, 1H), 6.29 (s, 1H), 10.15 (bs, 1H), 10.82 (s, 1H), the minor isomer displays a methyl resonance at δ0.92 (t, J=5.7 Hz); IR (KBr) 3314 (m), 1676 (m), 1664 (m), 1613 (m), 1550 (s), Anal. Calcd for C12H15NO3 : C, 65.14, H, 6.83, N, 6.33. Found: C, 65.47; H, 6.87; N, 6.32.

Workup

  1. customA green precipitate immediately formed
  2. stirringto stir for 15 min
  3. extractionThe solution was extracted with CH2Cl2 (2×4 mL)
  4. filtrationthe resulting precipitate collected by filtration
  5. washwashed
  6. customCrystallization from 95% EtOH yielded pale beige needles (56 mg, 67%
  7. additionpure by 1H NMR, consists of a probable mixture of cis- and trans-isomers (85:15))

Sources & evidence

ORD record
ord-16298a41a7e6499bb2f61f030dde3f65
Source dataset
uspto-grants-1995_12
Patent number
US05476933

Reaction notes

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