Hexane → HCID 69085480, compound

HRID 2362382Notes

Reaction equation

HRID 2362382 reaction equation
[F:1][C:2]1[CH:16]=[CH:15][C:14]([F:17])=[CH:13][C:3]=1[CH2:4]P(=O)(OCC)OCC.[Br:18][C:19]1[CH:20]=[N:21][CH:22]=[C:23]([CH:26]=1)[CH:24]=O.CC(C)([O-])C.[K+].CCCCCC>O1CCCC1.CCOCC>[Br:18][C:19]1[CH:20]=[N:21][CH:22]=[C:23](/[CH:24]=[CH:4]/[C:3]2[CH:13]=[C:14]([F:17])[CH:15]=[CH:16][C:2]=2[F:1])[CH:26]=1

Participants

7

Reactant 4

HCID 8058HexaneHCID 27847345-Bromo-3-pyridinecarboxaldehydeHCID 23665647Potassium tert-butoxideHCID 86673423HCID 86673423, compound

Product 1

HCID 69085480HCID 69085480, compoundYield 72.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of diethyl 2,5-difluorobenzylphosphonate (63.5 g, 240 mmol) and 5-bromonicotinaldehyde (50.7 g, 264 mmol) in tetrahydrofuran (1923 ml) was added potassium tert-butoxide in tetrahydrofuran (312 ml, 312 mmol) at −10° C. After three hours, the reaction mixture was allowed to warm to ambient temperature and stirring was continued for another 16 hours at which time the reaction mixture was diluted with ether (800 mL) and washed with H2O. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to provide a yellow wax to which was added 300 mL of hexane and after sonication filtered to provide (E)-3-bromo-5-(2,5-difluorostyryl)pyridine (54 g, 173 mmol, 72.1%) as a white solid. 1H NMR (500 MHz, DMSO-d6) δ 8.78 (d, J=1.8 Hz, 1H), 8.63 (d, J=2.1 Hz, 1H), 8.44 (t, J=2.0 Hz, 1H), 7.67 (ddd, J=9.4, 6.0, 3.2 Hz, 1H), 7.56-7.48 (m, 1H), 7.46-7.40 (m, 1H), 7.34 (td, J=9.6, 4.6 Hz, 1H), 7.24 (tt, J=8.3, 3.6 Hz, 1H). MS Anal. Calcd. for [M+H]+ C13H9BrF2N: 296.0. found 298.1.

Workup

  1. waitwas continued for another 16 hours at which time
  2. washwashed with H2O
  3. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto provide a yellow wax to which
  7. customafter sonication
  8. filtrationfiltered

Sources & evidence

ORD record
ord-2d05708da1fc44b4a77ff800144776eb
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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