Methanol → HCID 69435771, compound

HRID 404900Notes

Reaction equation

HRID 404900 reaction equation
[Cl:1][C:2]1[CH:31]=[C:30]([O:32]C)[CH:29]=[CH:28][C:3]=1[O:4][C:5]1[S:6][C:7]([C:10]2[CH:14]=[C:13]([CH:15]([N:17]3[C:25](=[O:26])[C:24]4[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=4)[C:18]3=[O:27])[CH3:16])[O:12][N:11]=2)=[CH:8][N:9]=1.B(Br)(Br)Br.CO>ClCCl>[Cl:1][C:2]1[CH:31]=[C:30]([OH:32])[CH:29]=[CH:28][C:3]=1[O:4][C:5]1[S:6][C:7]([C:10]2[CH:14]=[C:13]([CH:15]([N:17]3[C:25](=[O:26])[C:24]4[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=4)[C:18]3=[O:27])[CH3:16])[O:12][N:11]=2)=[CH:8][N:9]=1

Participants

5

Reactant 3

HCID 887MethanolHCID 25134Boron tribromideHCID 69437273HCID 69437273, compound

Product 1

HCID 69435771HCID 69435771, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
25 °C

Procedure

To a solution of Example 30E (1.2 g, 2.5 mmol) in dichloromethane (20 mL) was added boron tribromide (0.95 mL, 10 mmol) at −78° C. Upon addition, the mixture was allowed to stir at 25° C. for 16 hours. The reaction was then cooled to 0° C., treated with methanol (5 mL) and diluted with dichloromethane (80 mL). The resulting mixture was washed with water (120 mL) and brine (150 mL). The organic layer was dried (MgSO4), filtered and concentrated. The concentrate was purified by flash chromatography on silica gel eluting with a solvent gradient from 20% to 60% ethyl acetate in hexanes to yield 900 mg of the title compound (77%) as a off-white solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 1.81 (d, J=6.99 Hz, 3H) 5.55-5.70 (m, 1H) 6.84 (dd, J=8.82, 2.94 Hz, 1H) 6.99 (d, J=2.57 Hz, 1H) 7.17 (s, 1H) 7.42 (d, J=8.82 Hz, 1H) 7.80-7.98 (m, 5H); MS (ESI) m/z 468.0 (M+H)+, 500.0 (M+Na)+.

Workup

  1. additionUpon addition
  2. temperatureThe reaction was then cooled to 0° C.
  3. washThe resulting mixture was washed with water (120 mL) and brine (150 mL)
  4. dry with materialThe organic layer was dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe concentrate was purified by flash chromatography on silica gel eluting with a solvent gradient from 20% to 60% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-bd518e4e385b4d9b952df9572d0653ec
Source dataset
uspto-grants-2014_06
Patent number
US08748627B2

Reaction notes

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