Citric Acid → Isohexane ethyl acetate

HRID 902440Notes

Reaction equation

HRID 902440 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].[C:7](O)(=O)[CH2:8]C([CH2:14][C:15]([OH:17])=[O:16])(C(O)=O)O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(C)C=CC=CC=1>[CH3:1][CH2:2][O:17][C:15]([CH3:14])=[O:16].[CH3:7][CH2:8][CH2:1][CH:2]([CH3:5])[CH3:3]

Participants

5

Reactant 2

HCID 311Citric AcidHCID 23665647Potassium tert-butoxide

Product 1

HCID 21882781Isohexane ethyl acetateYield 20%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 1140TolueneSolvent

Procedure

A mixture of (syn)-5-chloro-N-(2-oxobicyclo[2.2.1]hept-7-yl)thiophene-2-sulfonamide (0.100 g, 0.313 mmol), methyl(triphenylphosphonium) bromide (0.125 g, 0.35 mmol) and potassium tert-butoxide (1M in THF, 1.0 mL) in dry toluene (2 mL) was reluxed under N2 for 4 h. The mixture was cooled, diluted with 1M citric acid (15 mL) and extracted with EtOAc (2×15 mL). The extracts were dried (Na2SO4), filtered and concentrated. Flash column chromatography, eluting with 10% then 20% EtOAc-isohexane, gave the title compound as a pale yellow solid (0.027 g, 28%). 1H NMR (CDCl3, 360 MHz) δ 1.30-1.34 (2 H, m), 1.69-1.73 (2 H, m), 1.96 (1 H, d, J 15), 2.26-2.35 (2 H, m), 2.41 (1 H, d, J 3), 3.42 (1 H, d, J 6), 4.55 (1 H, d, J 6), 4.83 (1 H, s), 4.95 (1 H, s), 6.92 (1 H, d, J 4), 7.39 (1 H, d, J 4); m/z 306 and 304 (M+H+).

Workup

  1. temperatureThe mixture was cooled
  2. extractionextracted with EtOAc (2×15 mL)
  3. dry with materialThe extracts were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. washFlash column chromatography, eluting with 10%

Sources & evidence

ORD record
ord-6271138765e24018ba47ccbd373efabb
Source dataset
uspto-grants-2008_04
Patent number
US07365196B2

Reaction notes

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