Hydrochloric Acid → HCID 178422065, compound

HRID 1429108Notes

Reaction equation

HRID 1429108 reaction equation
B(Br)(Br)Br.[CH:5]([C:8]1[C:17]([O:18]C)=[C:16]([O:20]C)[CH:15]=[C:14]2[C:9]=1[C:10](=[O:44])[C:11]([CH3:43])=[C:12]([C:23]1[C:24](=[O:42])[C:25]3[C:30]([C:31](=[O:34])[C:32]=1[CH3:33])=[C:29]([CH:35]([CH3:37])[CH3:36])[C:28]([O:38]C)=[C:27]([O:40]C)[CH:26]=3)[C:13]2=[O:22])([CH3:7])[CH3:6].Cl>C(Cl)Cl>[OH:18][C:17]1[C:8]([CH:5]([CH3:7])[CH3:6])=[C:9]2[C:14](=[CH:15][C:16]=1[OH:20])[C:13](=[O:22])[C:12]([C:23]1[C:24](=[O:42])[C:25]3[C:30]([C:31](=[O:34])[C:32]=1[CH3:33])=[C:29]([CH:35]([CH3:36])[CH3:37])[C:28]([OH:38])=[C:27]([OH:40])[CH:26]=3)=[C:11]([CH3:43])[C:10]2=[O:44]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 25134Boron tribromideHCID 49840110HCID 49840110, compound

Product 1

HCID 178422065HCID 178422065, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

0.54 mL of BBr3 (1.43 g, 5.71 mmol) was added dropwise into a solution of compound 10 (260 mg, 0.48 mmol) in 10 mL of anhydrous CH2Cl2 at −78° C. Stirring was continued at −78° C. for 1 h, 0° C. for 1 h, and ambient temperature for 1 h. 50 grams of ice containing 5 mL of 6M HCl was added to the mixture and stirred for 1 h at room temperature. The aqueous layer was extracted with dichloromethane (3×50 mL). The combined organic layer was washed with water, brine and dried over MgSO4. The solvent was concentrated in vacuo and the residue was purified using C-18 column chromatography (H2O/Acetonitrile) followed by recrystallization from ethyl acetate/hexane to give 163 mg of compound 6a (70%) as brown-yellow solid. 1H NMR (600 MHz, CD3OD) δ 7.31 (s, 2H), 4.32 (m, 2H), 1.88 (s, 6H), 1.42 (s, 6H), 1.40 (s, 6H). 13C NMR (600 MHz, (CD3)2SO)) δ 187.10, 182.51, 150.92, 149.54, 147.60, 137.78, 137.10, 126.24, 125.00, 111.03, 27.07, 20.50, 20.35, 15.00. HPLC purity 99.5%, tR=11.60 min (Method A). HRMS calcd for C28H26O8 491.1700 (M+H). found 491.1696.

Workup

  1. waitambient temperature for 1 h
  2. stirringstirred for 1 h at room temperature
  3. extractionThe aqueous layer was extracted with dichloromethane (3×50 mL)
  4. washThe combined organic layer was washed with water, brine
  5. dry with materialdried over MgSO4
  6. concentrationThe solvent was concentrated in vacuo
  7. customthe residue was purified
  8. customfollowed by recrystallization from ethyl acetate/hexane

Sources & evidence

ORD record
ord-d3e6bae4ec6548a2bd8d16f47285ba7f
Source dataset
uspto-grants-2015_01
Patent number
US08937193B2

Reaction notes

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