Isopropanol → HCID 86709880, compound

HRID 2206974Notes

Reaction equation

HRID 2206974 reaction equation
[CH3:1][CH:2]([OH:4])[CH3:3].C(N(CC)CC)C.[F:12][C:13]1[C:14]([C:22](F)=[O:23])=[N:15][C:16]([F:21])=[C:17]([F:20])[C:18]=1[F:19]>>[F:12][C:13]1[C:14]([C:22]([O:4][CH:2]([CH3:3])[CH3:1])=[O:23])=[N:15][C:16]([F:21])=[C:17]([F:20])[C:18]=1[F:19]

Participants

4

Reactant 3

HCID 3776IsopropanolHCID 8471TriethylamineHCID 86709881HCID 86709881, compound

Product 1

HCID 86709880HCID 86709880, compoundYield 79%

Procedure

Anhydrous 2-propanol (1.803 g, 30 mmol) and anhydrous tri-ethylamine (2.024 g, 20 mmol) were added drop-wise at 5-10° C. to the solution of 3,4,5,6-tetrafluoropicolinoyl fluoride provided above. The mixture was stirred at room temperature overnight. The mixture was discharged from the vessel and the salts were removed by filtration and washed with a little acetonitrile. The solvent was removed with a rotary evaporator. The crude mixture was re-dissolved in ethyl ether. The organic phase was then washed with water and dried over MgSO4. The solvent was removed with a rotary evaporator. The concentrated crude product was purified using column chromatography (silica gel) with ethyl acetate/hexanes mixture (4/50) as eluent to give 3.77 g (79% yield, 99% GC purity, 97% LC purity) of desired product as a pale yellow liquid. GC/MS results were consistent with the chemical formula of isopropyl 3,4,5,6-tetrafluoropicolinate: 70 eV EIMS (GC) m/z=196 (32%), 178 (100%), 150 (49%), 100 (33%), 43 (75%). 1H NMR (400 MHz, CDCl3) δ 5.32 (hept, J=6.3 Hz, 1H), 1.42 (d, J=6.3 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 159.82 to 159.74 (m), 149.22 to 148.85 (m), 148.02 to 147.89 (m), 146.47 to 146.17 (m), 145.63 to 145.47 (m), 138.54 (dd, J=34.3, 11.2 Hz), 135.79 (dd, J=34.3, 11.4 Hz), 129.03 to 128.74 (m), 70.98 (s), 21.61 (s). 19F NMR (376 MHz, CDCl3) δ −80.26 to −80.44 (m), −135.99 to −136.13 (m), −137.07 to −137.22 (m), −149.77 to −149.91 (m).

Workup

  1. customprovided above
  2. customthe salts were removed by filtration
  3. washwashed with a little acetonitrile
  4. customThe solvent was removed with a rotary evaporator
  5. dissolutionThe crude mixture was re-dissolved in ethyl ether
  6. washThe organic phase was then washed with water
  7. dry with materialdried over MgSO4
  8. customThe solvent was removed with a rotary evaporator
  9. concentrationThe concentrated crude product
  10. customwas purified

Sources & evidence

ORD record
ord-08ceaea8a5fc4123b294c5f5fef72bd5
Source dataset
uspto-grants-2016_06
Patent number
US09376388B2

Reaction notes

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