Boron tribromide → HCID 60171588, compound

HRID 1754032Notes

Reaction equation

HRID 1754032 reaction equation
[Cl:1]/[C:2](=[CH:12]/[CH2:13][C:14]1[CH:19]=[C:18]([O:20]C)[C:17]([Cl:22])=[CH:16][C:15]=1[O:23]C)/[CH2:3][C:4]1[CH:5]=[C:6]([OH:11])[CH:7]=[C:8]([OH:10])[CH:9]=1.B(Br)(Br)Br>C(Cl)Cl.[Al]>[Cl:1]/[C:2](=[CH:12]/[CH2:13][C:14]1[CH:19]=[C:18]([OH:20])[C:17]([Cl:22])=[CH:16][C:15]=1[OH:23])/[CH2:3][C:4]1[CH:5]=[C:6]([OH:11])[CH:7]=[C:8]([OH:10])[CH:9]=1

Participants

5

Reactant 2

HCID 25134Boron tribromideHCID 60164930HCID 60164930, compound

Product 1

HCID 60171588HCID 60171588, compoundYield 100.3%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 5359268AluminumSolvent

Conditions

Temperature
0 °C

Procedure

A stirred solution of 13 (0.0500 g, 0.135 mmol, 1 equiv) in CH2Cl2 (7 mL) was enclosed in aluminum foil and cooled 0° C. To the stirred solution was added dropwise BBr3 (1 M in CH2Cl2; 0.677 mL, 0.677 mmol, 5 equiv). The resulting solution was allowed to slowly warm to room temperature and stir for 18 h. The reaction mixture was quenched with a saturated aqueous solution of NaHCO3 (8 mL) and allowed to stir at room temperature for an additional hour. The solution was acidified with HCl, extracted with EtOAc (×2) and the combined organic layers were dried (MgSO4), filtered, and concentrated under reduced pressure. The crude product was purified by chromatography on SiO2 (chloroform/acetone, 3:1) to give 0.0462 g (96% yield) of 14 as a slight yellow film. An analytically pure sample was obtained via SFC chromatography using the semi-prep (250×10 mm) silica column (RT=4.68 min, 8 mL/min, 25% methanol, 220 nm detection): Rf 0.15 (acetone/chloroform, 2:8); IR (neat) 3343, 1692, 1599, 1495, 1417, 1329, 1184, 1143, 1005, 822 cm−1; 1H NMR (600 MHz (CD3)2CO) δ 8.17 (bs, 4 H), 6.86 (s, 1 H), 6.84 (s, 1 H), 6.29 (d, 2 H, J=2.4 Hz), 6.32 (t, 1 H, J=7.8 Hz), 3.69 (s, 2 H), 3.47 (d, 2 H, J=7.8 Hz); 13C NMR (150 MHz, CDCl3) δ 159.5, 149.0, 146.9, 140.5, 133.7, 128.0, 127.0, 118.5, 118.5, 116.7, 108.0, 101.8, 40.2, 29.5; HRMS (ES−) [2M-H]− m/z calcd for C32H27O8Cl4 679.0460, found 679.0482.

Workup

  1. temperatureto slowly warm to room temperature
  2. customThe reaction mixture was quenched with a saturated aqueous solution of NaHCO3 (8 mL)
  3. stirringto stir at room temperature for an additional hour
  4. extractionextracted with EtOAc (×2)
  5. dry with materialthe combined organic layers were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe crude product was purified by chromatography on SiO2 (chloroform/acetone, 3:1)

Sources & evidence

ORD record
ord-84a4012bda9b481fa036e10c9c1e3d2a
Source dataset
uspto-grants-2015_10
Patent number
US09169182B2

Reaction notes

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