Diethyl benzylphosphonate → HCID 86673442, compound

HRID 2362420Notes

Reaction equation

HRID 2362420 reaction equation
[Br:1][C:2]1[N:7]=[C:6]([CH:8]=O)[C:5]([F:10])=[CH:4][CH:3]=1.[CH2:11](P(=O)(OCC)OCC)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC(C)([O-])C.[K+]>O1CCCC1>[Br:1][C:2]1[N:7]=[C:6](/[CH:8]=[CH:11]/[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:5]([F:10])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 14122Diethyl benzylphosphonateHCID 164142386-Bromo-3-fluoropyridine-2-carbaldehydeHCID 23665647Potassium tert-butoxide

Product 1

HCID 86673442HCID 86673442, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 6-bromo-3-fluoropicolinaldehyde (2.147 g, 10.5 mmol) and diethyl benzylphosphonate (2.413 mL, 11.6 mmol) in tetrahydrofuran (80 mL) at 0° C., was added potassium tert-butoxide(1M in tetrahydrofuran, 11.6 mL, 11.6 mmol) dropwise over a couple of minutes. When addition was complete, the reaction was allowed to stir at 0° C. for 45 min and quenched by addition of saturated ammonium chloride. The reaction was diluted with ether, washed with water (4×), then brine, dried over magnesium sulfate, and concentrated. Column chromatography (8%→15% EtOAc/Hex) gave 121 mg (4.1%). 1H NMR (CDCl3) δ: 7.86 (d, J=16.2 Hz, 1H), 7.64 (d, J=7.3 Hz, 2H), 7.39-7.47 (m, 2H), 7.22-7.39 (m, 4H). 19F NMR (CDCl3) δ: −130.05 (br. s., 1F). Mass spec.: 278.0 (MH)+.

Workup

  1. additionWhen addition
  2. customquenched by addition of saturated ammonium chloride
  3. additionThe reaction was diluted with ether
  4. washwashed with water (4×)
  5. dry with materialbrine, dried over magnesium sulfate
  6. concentrationconcentrated
  7. customColumn chromatography (8%→15% EtOAc/Hex) gave 121 mg (4.1%)

Sources & evidence

ORD record
ord-683d2211f08b4b9298da3c1887e09980
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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