1,1'-Carbonyldiimidazole → HCID 69082187, compound

HRID 2362357Notes

Reaction equation

HRID 2362357 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C@@H:8]([NH:17][C:18](=[O:24])[O:19]C(C)(C)C)[C@H:9](O)[C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)[CH:5]=[CH:6][CH:7]=1.CCN(C(C)C)C(C)C.C(N1C=CN=C1)(N1C=CN=C1)=O>Cl.O1CCOCC1>[Br:1][C:2]1[CH:3]=[C:4]([C@H:8]2[C@H:9]([C:10]3[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=3)[O:24][C:18](=[O:19])[NH:17]2)[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 682631,1'-CarbonyldiimidazoleHCID 81531DiisopropylethylamineHCID 70957274HCID 70957274, compound

Product 1

HCID 69082187HCID 69082187, compoundYield 29.8%

Reagents, catalysts & solvents 1

HCID 204431481,4-Dioxane hydrochlorideSolvent

Procedure

To a mixture of (±)-tert-butyl (1R,2R)-1-(3-bromophenyl)-2-hydroxy-2-(pyridin-3-yl)ethylcarbamate (1.1 g, 2.80 mmol), was added 50 mL 4N HCl/Dioxane. The reaction mixture was allowed to stir at ambient temperature overnight and which time the white slurry was concentrated in vacuo and placed on high vac for 18 h. The resulting colorless solid was dissolved in tetrahydrofuran (25 mL) and Hunig's Base (0.586 mL, 3.36 mmol). To this solution was added carbonyldiimidazole (0.544 g, 3.36 mmol) and after 1 h, the reaction mixture was concentrated in vacuo and loaded with dichloromethane onto a 90 g silica gel cartridge prepacked with 25% ethyl acetate/hexanes. Elution was performed with 25 to 100% ethyl acetate/hexanes over 1200 mL then 100% ethyl acetate for 500 mL. Fractions containing the top spot (Rf=0.45 in 75% ethyl acetate/hexanes; UV) were pooled and concentrated to give 266 mg of trans-4-(3-bromophenyl)-5-(pyridin-3-yl)oxazolidin-2-one as a colorless solid. Anal. Calcd. for [M+H]+ C14H11BrN2O2: 319.00. found 318.85. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 8.66 (1H, dd, J=4.88, 1.53 Hz), 8.49 (1H, d, J=2.14 Hz), 7.72 (1H, dt, J=7.93, 1.98 Hz), 7.48-7.57 (2H, m), 7.40 (1H, dd, J=7.78, 4.73 Hz), 7.27-7.33 (1H, m), 7.22 (1H, d, J=7.63 Hz), 6.87 (1H, s), 5.30 (1H, d, J=7.63 Hz), 4.77 (1H, d, J=7.32 Hz). 13C NMR (126 MHz, CHLOROFORM-d) δ ppm 158.53, 150.80, 147.61, 140.18, 133.76, 132.84, 132.57, 131.09, 129.48, 125.23, 124.07, 123.64, 83.74, 64.20.

Workup

  1. concentrationwhich time the white slurry was concentrated in vacuo
  2. waitplaced on high vac for 18 h
  3. dissolutionThe resulting colorless solid was dissolved in tetrahydrofuran (25 mL)
  4. waitafter 1 h
  5. concentrationthe reaction mixture was concentrated in vacuo
  6. washElution
  7. additionFractions containing the top spot (Rf=0.45 in 75% ethyl acetate/hexanes; UV)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-b211555d652b448f99bd7b546f8734fa
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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