Tetrahydrofuran → HCID 69204184, compound

HRID 2378208Notes

Reaction equation

HRID 2378208 reaction equation
C[Si]([N-:5][Si](C)(C)C)(C)C.[Li+].[F:11][CH:12]([F:36])[O:13][C:14]1[CH:15]=[C:16]([C:24]([C:26]2[CH:31]=[C:30]([O:32][CH3:33])[CH:29]=[C:28]([O:34][CH3:35])[CH:27]=2)=O)[CH:17]=[CH:18][C:19]=1[O:20][CH:21]([F:23])[F:22].[CH2:37]1[CH2:41]OCC1>>[F:11][CH:12]([F:36])[O:13][C:14]1[CH:15]=[C:16]([C:24]([C:26]2[CH:31]=[C:30]([O:32][CH3:33])[CH:29]=[C:28]([O:34][CH3:35])[CH:27]=2)=[CH:41][C:37]#[N:5])[CH:17]=[CH:18][C:19]=1[O:20][CH:21]([F:23])[F:22]

Participants

4

Reactant 3

HCID 8028Tetrahydrofuran2×HCID 2733832Lithium HexamethyldisilazideHCID 69206053HCID 69206053, compound

Product 1

HCID 69204184HCID 69204184, compound

Procedure

Lithium bis-(trimethylsilyl)amide (1M, 3.0 mL) was added dropwise to a stirred solution of diethyl cyanomethylphosphate (0.5 g, 3.0 mmol) in THF (10 mL) at 5-8° C. The mixture was stirred at room temperature for 40 min. A solution of (3,4-bis-difluoromethoxy-phenyl)-(3,5-dimethoxy-phenyl)-methanone (0.9 g, 2.5 mmol) in THF (20 mL) was added and the mixture was stirred at room temperature for 17 h. The resulting mixture was poured into ice water (100 mL) and extracted with CH2Cl2 (3×50 mL). The combined organic layers were washed with water (2×40 mL), brine (40 mL) and dried (MgSO4). Solvent was removed and the residue was purified by flash chromatography (Silica gel, Hexane:CH2Cl2 4:6) to afford a mixture of isomers of 3-(3,4-bis-difluoromethxoy-phenyl)-3-(3,5-dimethoxy-phenyl)-acrylonitrile (0.6 g, 59%) as a white solid: mp 60-62° C.; 1H NMR (CDCl3) δ 7.35-7.22 (m, 3H), 6.90-6.20 (m, 5H), 5.76 (5.70) (s, 1H), 3.77 (3.80) (s, 6H); 13C NMR (CDCl3) δ 160.98 (160.90), 160.65 (160.55), 143.60 (141.87), 139.92, 137.78 (137.06), 135.13, 127.99 (126.83), 123.70 (122.75), 121.84 (121.78), 117.25 (117.05), 115.68 (t, J=1047 Hz), 115.58 (t, J=1047 Hz), 106.80 (107.56), 102.51 (102.37), 96.29 (96.24); Anal Calcd for C19H15NO4F4: C, 75.44; H, 3.81; N, 3.53; F, 19.13. Found: C, 57.82; H, 3.61; N, 3.38; F, 19.39.

Workup

  1. stirringthe mixture was stirred at room temperature for 17 h
  2. extractionextracted with CH2Cl2 (3×50 mL)
  3. washThe combined organic layers were washed with water (2×40 mL), brine (40 mL)
  4. dry with materialdried (MgSO4)
  5. customSolvent was removed
  6. customthe residue was purified by flash chromatography (Silica gel, Hexane:CH2Cl2 4:6)
  7. customto afford

Sources & evidence

ORD record
ord-4eae72ee91a74f5d8571e7e915f3c3b3
Source dataset
uspto-grants-2008_12
Patent number
US07470723B2

Reaction notes

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