Sodium hydride → HCID 70978529, compound

HRID 1852169Notes

Reaction equation

HRID 1852169 reaction equation
[H-].[Na+].[F:3][C:4]([F:10])([CH3:9])[C:5]([CH3:8])([OH:7])[CH3:6].[N:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[O:17][C:18](=O)[O:19]C1C=CC=CN=1>C1COCC1.CCOC(C)=O>[C:18](=[O:19])([O:17][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][N:11]=1)[O:7][C:5]([CH3:8])([C:4]([F:10])([F:3])[CH3:9])[CH3:6]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 2757370Carbonic acid di-2-pyridyl esterHCID 866832291408291-74-6

Product 1

HCID 70978529HCID 70978529, compoundYield 13.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of sodium hydride, 60% in mineral oil (0.652 g, 16.31 mmol) in THF (25 mL) was added 3,3-difluoro-2-methylbutan-2-ol (1.84 g, 14.82 mmol) at 0° C. After stirring 30 min, the solution was transferred to a solution of di(pyridin-2-yl)carbonate (3.20 g, 14.82 mmol) in THF (25 mL) through a cannula. The formed slurry was stirred at 0° C. for 30 min. The slurry was warmed to rt and stirred for 2 h. The reaction was diluted with EtOAc, washed with brine, dried over MgSO4, filtered, concentrated to give a residue that was purified by Biotage eluting with 10-50% EtOAc in hexanes to afford the desired product 3,3-difluoro-2-methylbutan-2-yl pyridin-2-yl carbonate (500 mg, 13.76%) as an oil that later crystallized to a white solid upon standing. 1H NMR (500 MHz, CHLOROFORM-d) δ 8.43 (ddd, J=4.9, 2.0, 0.7 Hz, 1H), 7.95-7.75 (m, 1H), 7.31-7.24 (m, 1H), 7.15 (dt, J=8.2, 0.8 Hz, 1H), 1.72 (s, 6H), 1.77-1.66 (m, 3H).

Workup

  1. stirringThe formed slurry was stirred at 0° C. for 30 min
  2. stirringstirred for 2 h
  3. washwashed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give a residue that
  8. customwas purified by Biotage
  9. washeluting with 10-50% EtOAc in hexanes

Sources & evidence

ORD record
ord-d9a81cb1b26f47da9b0c3c0a6143f92c
Source dataset
uspto-grants-2015_02
Patent number
US08957203B2

Reaction notes

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