HCID 66676719, compound → HCID 21113031, compound

HRID 554715Notes

Reaction equation

HRID 554715 reaction equation
C([O:5][C:6](=[O:28])[CH2:7][N:8]([C:11]([O:13][CH2:14][CH:15]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:21]2[C:16]1=[CH:17][CH:18]=[CH:19][CH:20]=2)=[O:12])[NH:9][CH3:10])(C)(C)C>Cl>[C:11]([N:8]([CH2:7][C:6]([OH:28])=[O:5])[NH:9][CH3:10])([O:13][CH2:14][CH:15]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:21]2[C:16]1=[CH:17][CH:18]=[CH:19][CH:20]=2)=[O:12]

Participants

3

Reactant 1

HCID 66676719HCID 66676719, compound

Product 1

HCID 21113031HCID 21113031, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

1 L, two-neck, round-bottomed-flask was fitted with a glass stopper and reflux condenser connected to a calcium tube. (N-Fmoc-N′-methyl-hydrazino)-acetic acid t-butyl ester (20 g, 52 mmol) was added. A solution of HCl (150 mL, 4 M solution in dioxane) was added slowly with vigorous stirring in an ice water bath. The reaction mixture was stirred at RT over 1 day. The solution was concentrated completely under reduced pressure at 40° C. A saturated aq. NaHCO3 solution (100 mL) was added and the aqueous layer was washed with diethyl ether (100 mL). Conc. HCl was added dropwise slowly at 0° C. (pH 2-3). The mixture was extracted and the organic layer was retained (500 mL, MC). The solution was dried with sodium sulfate and evaporated in vacuo. The residue was purified by recrystallization with n-hexane and ethyl acetate to give (N-Fmoc-N′-methyl-hydrazino)-acetic acid (12 g, 72%). 1H-NMR (DMSO-d8) δ 12.38 (5, 1H), 8.56 (b, 1H), 7.89˜7.86 (d, J=9 Hz, 2H), 7.70˜7.67 (d, J=9 Hz, 2H), 7.43˜7.29 (m, 4H), 4.29˜4.27 (d, J=6 Hz, 2H), 4.25˜4.20 (t, J=6 Hz, 1H), 3.47 (s, 2H), 2.56 (s, 3H).

Workup

  1. custom1 L, two-neck, round-bottomed-flask was fitted with a glass stopper
  2. temperaturereflux condenser
  3. customconnected to a calcium tube
  4. stirringThe reaction mixture was stirred at RT over 1 day
  5. concentrationThe solution was concentrated completely under reduced pressure at 40° C
  6. additionA saturated aq. NaHCO3 solution (100 mL) was added
  7. washthe aqueous layer was washed with diethyl ether (100 mL)
  8. additionConc. HCl was added dropwise slowly at 0° C. (pH 2-3)
  9. extractionThe mixture was extracted
  10. dry with materialThe solution was dried with sodium sulfate
  11. customevaporated in vacuo
  12. customThe residue was purified by recrystallization with n-hexane and ethyl acetate

Sources & evidence

ORD record
ord-fca7a730abda4e0f9f1a2763999f84cf
Source dataset
uspto-grants-2011_11
Patent number
US08049008B2

Reaction notes

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