HCID 86700500, compound → HCID 86700499, compound

HRID 589535Notes

Reaction equation

HRID 589535 reaction equation
[CH2:1]([O:3][C:4]1[C:9]([CH:10]([CH3:12])[CH3:11])=[CH:8][C:7]([N+:13]([O-])=O)=[CH:6][C:5]=1[CH:16]([C:32]1[CH:37]=[C:36]([N+:38]([O-])=O)[CH:35]=[C:34]([CH:41]([CH3:43])[CH3:42])[C:33]=1[O:44][CH2:45][CH3:46])[C:17]1[CH:22]=[C:21]([N+:23]([O-])=O)[CH:20]=[C:19]([CH:26]([CH3:28])[CH3:27])[C:18]=1[O:29][CH2:30][CH3:31])[CH3:2]>CCO.C1COCC1.[Ni]>[CH:16]([C:17]1[C:18]([O:29][CH2:30][CH3:31])=[C:19]([CH:26]([CH3:28])[CH3:27])[CH:20]=[C:21]([CH:22]=1)[NH2:23])([C:32]1[C:33]([O:44][CH2:45][CH3:46])=[C:34]([CH:41]([CH3:43])[CH3:42])[CH:35]=[C:36]([CH:37]=1)[NH2:38])[C:5]1[C:4]([O:3][CH2:1][CH3:2])=[C:9]([CH:10]([CH3:11])[CH3:12])[CH:8]=[C:7]([CH:6]=1)[NH2:13]

Participants

4

Reactant 1

HCID 86700500HCID 86700500, compound

Product 1

HCID 86700499HCID 86700499, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 21873804Tetrahydrofuran ethanolSolvent

Procedure

In a three-neck round-bottom flask, a sample of 4 (3.63 g, 5.69 mmol) was dissolved in a solution of EtOH/THF (25/180 mL). Rainey nickel (˜100 mg) was added to the mixture, which was then degassed by the freeze-pump-thaw method and the flask was backfilled with anhydrous H2 gas. The reaction was stirred at room temperature under a constant H2 stream for two days and then filtered to remove the Rainey nickel The solvent was removed under reduced pressure. The residue was dissolved in diethyl ether and extracted with a 10% HCl solution (3×, 50 mL). The aqueous phase was washed with hexanes (3×50 mL) followed by addition of 2 M NaOH to a final pH of 10. The precipitated solid was extracted into dichloromethane (3×50 mL). The combined organics were dried with sodium sulfate and the volatiles removed under reduced pressure. The residue was then recrystallized from methanol yielding 2.53 g (81%) of 5 as a colorless crystalline solid. 1H NMR (CDCl3-d) δ ppm 1.14 (18 H, d, J=6.9 Hz), 1.19 (9 H, t, J=7.0 Hz), 3.09 (6 H, br. s.), 3.21 (3 H, spt, J=6.9 Hz), 3.38 (6 H, q, J=6.9 Hz), 6.26 (3 H, d, J=2.9 Hz), 6.37 (3 H, d, J=2.7 Hz), 6.51 (1 H, s). 13C-{1H} NMR, δ 15.5, 24.0, 26.3, 38.4, 69.4, 111.1, 115.2, 138.9, 141.6, 142.9, 147.3. Anal. calcd. for C34H49N3O3: C, 74.55; H, 9.02; N, 7.67. Found: C, 74.26; H, 9.24; N, 7.59.

Workup

  1. customwas then degassed by the freeze-pump-thaw method
  2. filtrationfiltered
  3. customto remove the Rainey nickel The solvent
  4. customwas removed under reduced pressure
  5. dissolutionThe residue was dissolved in diethyl ether
  6. extractionextracted with a 10% HCl solution (3×, 50 mL)
  7. washThe aqueous phase was washed with hexanes (3×50 mL)
  8. additionfollowed by addition of 2 M NaOH to a final pH of 10
  9. extractionThe precipitated solid was extracted into dichloromethane (3×50 mL)
  10. dry with materialThe combined organics were dried with sodium sulfate
  11. customthe volatiles removed under reduced pressure
  12. customThe residue was then recrystallized from methanol yielding 2.53 g (81%) of 5 as a colorless crystalline solid

Sources & evidence

ORD record
ord-3f82daadb9eb475ba416b40978a26e8b
Source dataset
uspto-grants-2016_01
Patent number
US09233364B2

Reaction notes

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