1-Butanol → 7-(diethylamino)-3-nitro-2H-chromen-2-one

HRID 19455

Reaction equation

HRID 19455 reaction equation
C(O)CCC.[CH2:6]([N:8]([CH2:18][CH3:19])[C:9]1[CH:10]=[C:11]([OH:17])[C:12](=[CH:15][CH:16]=1)[CH:13]=O)[CH3:7].[N+:20]([CH2:23][C:24](OCC)=[O:25])([O-:22])=[O:21].N1CCCCC1>C(O)(=O)C>[N+:20]([C:23]1[C:24](=[O:25])[O:17][C:11]2[C:12]([CH:13]=1)=[CH:15][CH:16]=[C:9]([N:8]([CH2:18][CH3:19])[CH2:6][CH3:7])[CH:10]=2)([O-:22])=[O:21]

Participants

6

Reactant 4

HCID 2631-ButanolHCID 8082PiperidineHCID 69379Ethyl nitroacetateHCID 872934-(Diethylamino)-2-hydroxybenzaldehyde

Product 1

HCID 139227357-(diethylamino)-3-nitro-2H-chromen-2-one

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A mixture containing n-butanol (20 mL), 4-diethylamino salicylaldehyde (1.4 g, 7.2 mmol), ethyl nitroacetate (0.8 mL, 7.2 mmol), molecular sieves 4 Å (100 mg), piperidine (0.1 mL) and acetic acid (0.2 mL) was refluxed for a period of 24 h. Upon cooling to room temperature, a bright yellow solid formed, which was collected and dissolved in DMF (15 mL) at 80° C. It was filtered again to remove the molecular sieves. The filtrate, upon addition to 100 ml of ice-cold water, yielded 3-nitro-7-diethylamino coumarin as a bright yellow solid: 1.40 g, 73%. A small amount of this compound was recrystallized from DMF to give an analytical sample; mp 193-195° C. 1H-NMR (CDCl3, 300 MHz) δ 1.27 (t, J=7.14 Hz, 6H), 3.48 (q, J=7.86 Hz, 4H), 6.50 (s, 1H), 6.70 (d, J=6.71 Hz, 1H), 7.42 (d, J=7.42 Hz, 2H), 8.72 (s, 1H). HRMS m/e calculated for MH+ C13H14N2O4 263.1041; found 263.1032.

Workup

  1. temperaturewas refluxed for a period of 24 h
  2. customa bright yellow solid formed
  3. customwhich was collected
  4. dissolutiondissolved in DMF (15 mL) at 80° C
  5. filtrationIt was filtered again
  6. customto remove the molecular sieves
  7. additionThe filtrate, upon addition to 100 ml of ice-cold water

Sources & evidence

ORD record
ord-2613b417d4b044bf9847bd10c60de96f
Source dataset
uspto-grants-2010_06
Patent number
US07745229B2

Linked notes

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