Ethanol → HCID 69032049, compound

HRID 2253292Notes

Reaction equation

HRID 2253292 reaction equation
CCO.CO.[BH4-].[Na+].[CH3:8][O:9][C:10]([C:12]1[C:13]2[C:14](/[CH:35]=[CH:36]/[N+:37]([O-:39])=[O:38])=[C:15]([C:22]3[CH:27]=[CH:26][C:25]([CH2:28][N:29]([C:31]([O:33][CH3:34])=[O:32])[CH3:30])=[CH:24][CH:23]=3)[NH:16][C:17]=2[CH:18]=[C:19]([F:21])[CH:20]=1)=[O:11]>O.C(O)(=O)C>[CH3:8][O:9][C:10]([C:12]1[C:13]2[C:14]([CH2:35][CH2:36][N+:37]([O-:39])=[O:38])=[C:15]([C:22]3[CH:27]=[CH:26][C:25]([CH2:28][N:29]([C:31]([O:33][CH3:34])=[O:32])[CH3:30])=[CH:24][CH:23]=3)[NH:16][C:17]=2[CH:18]=[C:19]([F:21])[CH:20]=1)=[O:11]

Participants

7

Reactant 4

HCID 702Ethanol2×HCID 887MethanolHCID 4311764Sodium borohydrideHCID 69030041HCID 69030041, compound

Product 1

HCID 69032049HCID 69032049, compoundYield 45%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
15 °C

Procedure

EtOH (900 ml) and MeOH (90 ml) were added to a 2 L flask. Powdered sodium borohydride (20.5 g, 0.55 mol) was then added. The suspension was cooled to 15° C. Nitroalkene 12 (49.0 g, 0.11 mol) was added in portions over 45 minutes while the temperature was maintained at ˜15° C. After addition was complete, additional EtOH (800 ml) was added. The reaction mixture was stirred for 15 minutes. TLC analysis indicated the completion of the reaction. A mixture of acetic acid (40 ml) and water (40 ml) was added slowly to quench the excess of sodium borohydride. A reddish suspension was obtained. Solvent was removed in a rotovap. The residue was partitioned between EtOAc (600 ml) and water (300 ml). Aqueous phase was separated. The solid in organic layer was collected by filtration and dried to afford 21.94 g of product 13 (45% yield). The organic filtrate was concentrated to dryness. The residue was then reslurried with EtOAC (70 ml)/heptane (200 ml). The solid was collected by filtration and dried to afford second crop of product (21.74 g, 44% yield). The combined yield for this step is 89%. 1H NMR (300 MHz, DMSO-d6) δ 2.87 (s, 3H), 3.584 (t, 2H, J=7.8 Hz), 3.661 (s, 3H), 3.903 (s, 3H), 4.519 (s, 2H), 4.607 (t, 2H, J=7.8 Hz), 7.41 (m, 4H), 7.58 (d, 2H, J=8.10 Hz), 12.0 (s, br, 1H). Exact mass calculated for C22H23FN3O6: 444.1571. Found: 444.1559.

Workup

  1. temperaturewas maintained at ˜15° C
  2. additionAfter addition
  3. customthe completion of the reaction
  4. additionwas added slowly
  5. customto quench the excess of sodium borohydride
  6. customA reddish suspension was obtained
  7. customSolvent was removed in a rotovap
  8. customThe residue was partitioned between EtOAc (600 ml) and water (300 ml)
  9. customAqueous phase was separated
  10. filtrationThe solid in organic layer was collected by filtration
  11. customdried

Sources & evidence

ORD record
ord-42a1582329ed4a55a0bd09433db36683
Source dataset
uspto-grants-2008_01
Patent number
US07323562B2

Reaction notes

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