Carbon Dioxide → O,O-Diethyl 3-Trifluoromethylphenyl(3-trifluoromethylbenzyl)methylphosphonate

HRID 1720858Notes

Reaction equation

HRID 1720858 reaction equation
[F:1][C:2]([F:19])([F:18])[C:3]1[CH:4]=[C:5]([CH:15]=[CH:16][CH:17]=1)[CH2:6][P:7](=[O:14])([O:11][CH2:12][CH3:13])[O:8][CH2:9][CH3:10].C(=O)=O.C([Li])CCC.[F:28][C:29]([F:39])([F:38])[C:30]1[CH:31]=[C:32]([CH:35]=[CH:36][CH:37]=1)[CH2:33]Br>O1CCCC1>[F:19][C:2]([F:18])([F:1])[C:3]1[CH:4]=[C:5]([CH:6]([P:7](=[O:14])([O:11][CH2:12][CH3:13])[O:8][CH2:9][CH3:10])[CH2:33][C:32]2[CH:35]=[CH:36][CH:37]=[C:30]([C:29]([F:28])([F:38])[F:39])[CH:31]=2)[CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 4

HCID 280Carbon Dioxide2×HCID 1230611-(Bromomethyl)-3-(trifluoromethyl)benzeneHCID 11162251Diethyl 3-trifluoromethylbenzylphosphonateHCID 178418339Butyllithium

Product 1

HCID 22416502O,O-Diethyl 3-Trifluoromethylphenyl(3-trifluoromethylbenzyl)methylphosphonate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of O,O-diethyl 3-trifluoromethylbenzylphosphonate (20.0 g, 67.5 mmol) in tetrahydrofuran (90 mL) was cooled to -70° C. (dry ice bath), under N2, and a solution of butyllithium (1.6M, in hexanes, 46.4 mL, 74.3 mmol) in 90 mL of dry tetrahydrofuran cooled to -70° C. (dry ice) was added. After 15 minutes, a solution of 3-trifluoromethylbenzylbromide (10.3 mL, 67.5 mmol)in tetrahydrofuran (90 mL) was added. The green reaction mixture turned yellow and was brought to room temperature and allowed to stir for 4 hours. The mixture was then quenched with H2O (200 mL), and extracted with ether (2×200 mL). The combined ether extracts were dried (MgSO4), filtered, and concentrated to dryness to give a yellow oil, 32.3 g. The crude product was chromatographed on a silica gel column. Elution with ethyl acetate/hexane (1:1) afforded analytically pure product as a pale yellow oil, 24.1 g (78.4 %). 300 MHz 1H NMR (CDCl3): δ, 3.16-4.20 (m,7H, PCH, PhCH2, 2(OCH2). MS: 455 (M+1).

Workup

  1. additionwas added
  2. customwas brought to room temperature
  3. customThe mixture was then quenched with H2O (200 mL)
  4. extractionextracted with ether (2×200 mL)
  5. dry with materialThe combined ether extracts were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated to dryness
  8. customto give a yellow oil, 32.3 g
  9. customThe crude product was chromatographed on a silica gel column
  10. washElution with ethyl acetate/hexane (1:1)
  11. customafforded analytically pure product as a pale yellow oil, 24.1 g (78.4 %)

Sources & evidence

ORD record
ord-433c3b6ff15247198e9c7ca6d2c63ba0
Source dataset
uspto-grants-1996_04
Patent number
US05508273

Reaction notes

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