Hydrazine → HCID 67437264, compound

HRID 340126Notes

Reaction equation

HRID 340126 reaction equation
[C:1]([O:5][C:6]([NH:8][CH:9]([C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=1)[C:10](O)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].[NH2:20][NH2:21]>C(Cl)Cl>[Cl:19][C:16]1[CH:17]=[CH:18][C:13]([CH:9]([NH:8][C:6](=[O:7])[O:5][C:1]([CH3:4])([CH3:3])[CH3:2])[C:10]([NH:20][NH2:21])=[O:11])=[CH:14][CH:15]=1

Participants

4

Reactant 2

HCID 9321HydrazineHCID 27567812-(((Tert-butoxy)carbonyl)amino)-2-(4-chlorophenyl)acetic acid

Product 1

HCID 67437264HCID 67437264, compoundYield 72.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

1,1-Carbonyldiimidazole (1.60 g, 9.89 mmol) was added to a solution of 2-(tert-butoxycarbonylamino)-2-(4-chlorophenyl)acetic acid (2.57 g, 9.00 mmol) in CH2Cl2 (22.5 mL, 9.00 mmol), and the mixture was stirred for 30 minutes until gas evolution ceased. Hydrazine (0.367 mL, 11.7 mmol) was then added to this solution, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was diluted with CH2Cl2 and washed with NaHCO3 (10%). The organic layer was dried (Na2SO4) and concentrated. The residue was purified by reversed-phase chromatography (Biotage SP4, 40+M, C18, 25% to 100% MeCN/H2O). Fractions containing product were poured into a separatory funnel and extracted with ethyl acetate (3×). The combined organic layers were dried and concentrated to give tert-butyl 1-(4-chlorophenyl)-2-hydrazinyl-2-oxoethylcarbamate as a solid (1.95 g, 72%). LCMS (APCI+) M+H+: 299 (5%); M+H+-Boc: 199 (100%); rt=2.78 minutes. 1H NMR (400 MHz, CDCl3) δ 7.73 (s, 1H), 7.30 (s, 4H), 5.85 (d, J=6.6 Hz, 1H), 5.21 (s, 1H), 3.87 (s, 2H), 1.42 (s, 9H).

Workup

  1. stirringthe mixture was stirred at room temperature for 12 hours
  2. washwashed with NaHCO3 (10%)
  3. dry with materialThe organic layer was dried (Na2SO4)
  4. concentrationconcentrated
  5. customThe residue was purified by reversed-phase chromatography (Biotage SP4, 40+M, C18, 25% to 100% MeCN/H2O)
  6. additionFractions containing product
  7. additionwere poured into a separatory funnel
  8. extractionextracted with ethyl acetate (3×)
  9. customThe combined organic layers were dried
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-31ed5f2508714656b5b690abdc1fdf95
Source dataset
uspto-grants-2014_11
Patent number
US08895566B2

Reaction notes

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