2-(Trimethylsiloxy)-1,3-butadiene → HCID 68772490, compound

HRID 1172343Notes

Reaction equation

HRID 1172343 reaction equation
[F:1][C:2]1[CH:12]=[C:11]([F:13])[C:10]([F:14])=[CH:9][C:3]=1[CH:4]=[CH:5][N+:6]([O-:8])=[O:7].C[Si](C)(C)[O:17][C:18]([CH:20]=[CH2:21])=[CH2:19]>C1(C)C=CC=CC=1>[N+:6]([C@@H:5]1[CH2:21][CH2:20][C:18](=[O:17])[CH2:19][C@H:4]1[C:3]1[CH:9]=[C:10]([F:14])[C:11]([F:13])=[CH:12][C:2]=1[F:1])([O-:8])=[O:7]

Participants

4

Reactant 2

HCID 5546572-(Trimethylsiloxy)-1,3-butadieneHCID 66605568HCID 66605568, compound

Product 1

HCID 68772490HCID 68772490, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

2,4,5-Trifluoro-β-nitrostyrene (7.8 g, 38.4 mmol) and 2-trimethylsiloxy-1,3-butadiene (8.18 g, 57.6 mmol) were mixed in toluene (10 ml). The reaction was heated to 120° C. overnight. The reaction mixture was cooled to room temperature, concentrated and treated with trifluoroacetic acid (10 mL) and CH2Cl2 (10 mL) at 0° C. It was stirred for 30 minutes, then saturated NaHCO3 was added to adjust pH (˜7). The mixture was extracted with ethyl acetate (3×) and the combined organic extracts were washed with water and brine, and then concentrated. A minimum amount of methylene chloride was added to the residue to induce crystallization. The crystals were collected by filtration and the mother liquid was subjected to column chromatography (eluting with 25% ethyl acetate/hexane). The recrystallized and chromatographed material was combined to yield the title compound (7.0, 70%). 1H NMR (300 MHz, CDCl3) δ ppm 2.29-2.82 (m, 6H), 3.73-3.89 (m, 1H), 5.06-5.29 (m, 1H), 6.86-7.12 (m, 2H). MS (ESI) m/z 274 (M+H)+.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. concentrationconcentrated
  3. additiontreated with trifluoroacetic acid (10 mL) and CH2Cl2 (10 mL) at 0° C
  4. additionsaturated NaHCO3 was added
  5. extractionThe mixture was extracted with ethyl acetate (3×)
  6. washthe combined organic extracts were washed with water and brine
  7. concentrationconcentrated
  8. additionA minimum amount of methylene chloride was added to the residue
  9. customcrystallization
  10. filtrationThe crystals were collected by filtration
  11. washthe mother liquid was subjected to column chromatography (eluting with 25% ethyl acetate/hexane)
  12. customThe recrystallized
  13. customchromatographed material

Sources & evidence

ORD record
ord-f08f1a7f576e48e59c98e3f2c7a032fd
Source dataset
uspto-grants-2010_11
Patent number
US07834012B2

Reaction notes

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