Hydrazine hydrate (1:1) → HCID 12275569, compound

HRID 1944196Notes

Reaction equation

HRID 1944196 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([CH2:15][CH:16]([N+:18]([O-])=O)[CH3:17])[CH:12]=[CH:11][C:10]=1[O:21][CH3:22])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.NN>[Ni].CO>[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([CH2:15][CH:16]([NH2:18])[CH3:17])[CH:12]=[CH:11][C:10]=1[O:21][CH3:22])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 68497223HCID 68497223, compound

Product 1

HCID 12275569HCID 12275569, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent2×

Conditions

Temperature
40 °C

Procedure

Raney nickel (50%, slurry in water, 2.0 g) was washed with MeOH (3×). To this was added MeOH (70 ml) and 209 (3.05 g, 10.1 mmol). The mixture was cooled (ice-bath) and hydrazine hydrate (2.53 g, 50.5 mmol) was added dropwise. The mixture was heated to 40° C. for 1 h, then further Raney nickel (50% slurry in water, 1.0 g) was added as a suspension in MeOH (10 ml). The reaction mixture was heated at 40° C. for a further 18 h. The resulting solution was cooled to rt and filtered through celite, washing through with MeOH (200 ml). The filtrate was concentrated in vacuo and purification (flashmaster: 50 g, EtOAc/MeOH) afforded the title compound (2.074 g, 76%) as a pale yellow oil. 1H NMR (270 MHz; CDCl3) 1.04 (3H, d, J=6.4 Hz, CH3), 2.36 (1H, dd, J=13.3, 8.2 Hz, CHH), 2.58 (1H, dd, J=13.3, 5.2 Hz, CHH), 2.98-3.1 (1H, m, CH), 3.86 (3H, s, OCH3), 5.13 (2H, s, CH2), 6.67-6.83 (3H, m, 3×CH), 7.25-7.43 (5H, m, 5×CH, phenyl). LC/MS (ES+) tr=1.82 min, m/z 272.19 (M++H).

Workup

  1. washRaney nickel (50%, slurry in water, 2.0 g) was washed with MeOH (3×)
  2. additionwas added dropwise
  3. temperatureThe reaction mixture was heated at 40° C. for a further 18 h
  4. temperatureThe resulting solution was cooled to rt
  5. filtrationfiltered through celite
  6. washwashing through with MeOH (200 ml)
  7. concentrationThe filtrate was concentrated in vacuo and purification (flashmaster: 50 g, EtOAc/MeOH)

Sources & evidence

ORD record
ord-9a219029df064f09a28a85185c380505
Source dataset
uspto-grants-2013_03
Patent number
US08394825B2

Reaction notes

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