Benzene → HCID 56652976, compound

HRID 2410204Notes

Reaction equation

HRID 2410204 reaction equation
[C:1]([C:5]1[CH:6]=[C:7](/[CH:19]=[CH:20]/[C:21](=[O:29])[C:22]2[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][CH:23]=2)[CH:8]=[C:9]2[C:14]=1[O:13][C:12](=[O:15])C(C(O)=O)=[CH:10]2)([CH3:4])([CH3:3])[CH3:2].S(Cl)(Cl)=[O:31].[CH2:34]([NH:36][CH2:37][CH3:38])[CH3:35].[CH:39]1[CH:44]=CC=CC=1>>[C:1]([C:5]1[CH:6]=[C:7](/[CH:19]=[CH:20]/[C:21](=[O:29])[C:22]2[CH:23]=[CH:24][C:25]([CH3:28])=[CH:26][CH:27]=2)[CH:8]=[C:9]2[C:14]=1[O:13][C:12](=[O:15])[C:35]([C:34]([N:36]([CH2:44][CH3:39])[CH2:37][CH3:38])=[O:31])=[CH:10]2)([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 4

HCID 241BenzeneHCID 8021DiethylamineHCID 24386Thionyl ChlorideHCID 86692172HCID 86692172, compound

Product 1

HCID 56652976HCID 56652976, compound

Procedure

To a suspension of (E)-8-tert-butyl-2-oxo-6-(3-oxo-3-p-tolylprop-1-enyl)-2H-chromene-3-carboxylic acid of the formula (V) (0.5 g, 1.28 mmol) in benzene (10 mL), added thionyl chloride (1.0 mL), was refluxed for 2 h. The resulting solution was evaporated to dryness under reduced pressure, and the residue was dispersed in benzene (10 mL). The solvent was eliminated under reduced pressure. Dispersion in solvent and solvent elimination was repeated twice. The residue was dissolved in organic solvent benzene (10 mL) and added with stirring to a solution of the diethyl amine (0.09 g, 1.28 mmol). After 30 min at room temperature, the solvent was removed by evaporation under reduced pressure and extracted 3-fold with CHCl3 (30 mL). The combined organic layers were dried on Na2SO4, filtered, and concentrated to dryness under reduced pressure. The residue was chromatographed over silica gel (SiO2, 230-400 flash), eluting with a gradient of 20% ethyl acetate in hexane to 40% ethyl acetate in hexane, which upon concentration provides (E)-8-tert-butyl-N,N-diethyl-2-oxo-6-(3-oxo-3-p-tolylprop-1-enyl)-2H-chromene-3-carboxamide (General Formula VI). (0.37 g, 65% yield). White solid, m. p. 170-171° C.; 1H NMR (CDCl3 300 MHz): δ 7.94 (d, J=8.1 Hz, 2H), 7.81-7.76 (m, 3H), 7.64 (d, J=1.7 Hz, 1H), 7.52 (d, J=15.7 Hz, 1H), 7.32 (d, J=8.0 Hz, 2H), 3.57 (q, J=7.1 Hz, 2H), 3.34 (q, J=7.0 Hz, 2H), 2.45 (s, 3H), 1.55 (brs, 9H), 1.28 (t, J=7.1 Hz, 3H), 1.21 (t, J=7.1 Hz, 3H); 13C NMR (CDCl3, 75 MHz): δ 189.7, 164.3, 157.3, 153.8, 144.0, 142.8, 141.7, 138.9, 135.4, 131.3, 129.8, 129.5, 128.8, 126.6, 126.2, 122.8, 119.2, 43.4, 39.6, 35.2, 29.8, 21.8, 14.3, 12.8; ESI-MS (m/z): 446 (M+H)+.

Workup

  1. temperaturewas refluxed for 2 h
  2. customThe resulting solution was evaporated to dryness under reduced pressure
  3. additionthe residue was dispersed in benzene (10 mL)
  4. dissolutionThe residue was dissolved in organic solvent benzene (10 mL)
  5. additionadded
  6. customthe solvent was removed by evaporation under reduced pressure
  7. extractionextracted 3-fold with CHCl3 (30 mL)
  8. customThe combined organic layers were dried on Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated to dryness under reduced pressure
  11. customThe residue was chromatographed over silica gel (SiO2, 230-400 flash)
  12. washeluting with a gradient of 20% ethyl acetate in hexane to 40% ethyl acetate in hexane, which upon concentration

Sources & evidence

ORD record
ord-ba4da27972ce4dbca3885617a171448c
Source dataset
uspto-grants-2014_08
Patent number
US08815940B2

Reaction notes

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