Tetrahydrofuran → HCID 68770032, compound

HRID 1172351Notes

Reaction equation

HRID 1172351 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([CH:8]([CH2:13][CH:14]=[CH2:15])[CH2:9][N+:10]([O-:12])=[O:11])[C:5]([F:16])=[CH:4][C:3]=1[F:17].Br/[C:19](=C\C)/C([O-])=O.[OH-:25].[Na+].[CH2:27]1[CH2:31][O:30][CH2:29][CH2:28]1>C(OC)(C)(C)C>[CH2:19]=[C:28]([CH2:27][CH:9]([N+:10]([O-:12])=[O:11])[CH:8]([C:6]1[CH:7]=[C:2]([F:1])[C:3]([F:17])=[CH:4][C:5]=1[F:16])[CH2:13][CH:14]=[CH2:15])[C:29]([O:30][CH3:31])=[O:25]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 14798Sodium HydroxideHCID 68768173HCID 68768173, compoundHCID 131728428HCID 131728428, compound

Product 1

HCID 68770032HCID 68770032, compound

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
5 °C

Procedure

To a cooled (5° C.) and mechanically-stirred solution of 1,2,4-trifluoro-5-(1-nitropent-4-en-2-yl)benzene (266.3 g, 1.09 mol) and bromocrotonate (151 mL, 1.13 mol) in THF (270 mL), NaOH (322 mL, 1.61 mol, 5 M) was added. The resulting biphasic mixture was stirred vigorously for thirty minutes. The mixture was allowed to warm to room temperature, and was then diluted with methyl t-butyl ether (950 mL). The layers were separated, and the organic was washed with H2O (2×500 mL) and brine (1×500 mL). The organic layer was dried with anhydrous Na2SO4 and concentrated under reduced pressure to give the title compound as a 1:1 mixture of erythro and threo isomers (365 g, 98%). Threo isomer: 1H NMR (300 MHz, CDCl3) δ ppm 7.00-6.86 (m, 2H), 6.25 (s, 1H), 5.66 (br s, 1H), 5.57 (dddd, J=6.8, 6.8, 10.5, and 17.3 Hz, 1H), 5.12-4.97 (m, 2H), 3.80 (s, 3H), 3.50 (ddd, J=5.4, 9.5 and 9.5 Hz, 1H), 3.12 (ddd, J=1.0, 2.7, and 14.0 Hz, 1H), 2.72 (dd, J=11.2 and 14.0 Hz, 1H), 2.63-2.59 (m, 1H), and 2.52-2.38 (m, 1H). Erythro isomer: 1H NMR (300 MHz, CDCl3) δ ppm 7.09-6.91 (m, 2H), 6.20 (br s, 1H), 5.60 (br s, 1H), 5.56-5.42 (m, 1H), 5.09-4.91 (m, 2H), 3.75 (s, 3H), 3.55 (ddd, J=6.1, 10.5, and 10.5 Hz, 1H), 2.62-2.59 (m, 2H), and 2.44-2.38 (m, 2H).

Workup

  1. additionwas added
  2. temperatureto warm to room temperature
  3. customThe layers were separated
  4. washthe organic was washed with H2O (2×500 mL) and brine (1×500 mL)
  5. dry with materialThe organic layer was dried with anhydrous Na2SO4
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-84cd7750e2f447979f3d07f5a6bbff01
Source dataset
uspto-grants-2010_11
Patent number
US07834012B2

Reaction notes

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