Hydroxylamine → tert-butyl N-{4-[amino(hydroxyimino)methyl]-2-fluorobenzyl}-N-methylglycinate

HRID 2404309Notes

Reaction equation

HRID 2404309 reaction equation
[NH2:1][OH:2].[C:3]([C:5]1[CH:21]=[CH:20][C:8]([CH2:9][N:10]([CH3:19])[CH2:11][C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])=[C:7]([F:22])[CH:6]=1)#[N:4]>CCO>[NH2:4][C:3](=[N:1][OH:2])[C:5]1[CH:21]=[CH:20][C:8]([CH2:9][N:10]([CH3:19])[CH2:11][C:12]([O:14][C:15]([CH3:17])([CH3:16])[CH3:18])=[O:13])=[C:7]([F:22])[CH:6]=1

Participants

4

Reactant 2

HCID 787HydroxylamineHCID 66677678tert-butyl N-(4-cyano-2-fluorobenzyl)-N-methylglycinate

Product 1

HCID 76685325tert-butyl N-{4-[amino(hydroxyimino)methyl]-2-fluorobenzyl}-N-methylglycinateYield 89%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A 50% aqueous solution of hydroxylamine (345 mL, 5.85 mol) was added dropwise over 10 minutes into a solution of tert-butyl N-(4-cyano-2-fluorobenzyl)-N-methylglycinate (325 g, 1.17 mol) in EtOH (2.1 L). The reaction mixture was stirred at RT for 20 hours. Solvents were concentrated under vacuum and water (2 L) was added. The resulting suspension was filtered off, washed with water (1 L) and dried under vacuum to give title compound as white powder (323 g, 89%). 1H NMR (DMSO-d6, 300 MHz) δ 9.74 (s, 1H), 7.51 (dd, J=8.0, 1.6 Hz, 1H), 7.45-7.36 (m, 2H), 5.87 (s, 2H), 3.70 (s, 2H), 3.17 (s, 2H), 2.26 (s, 3H), 1.42 (s, 9H). LC/MS (Method B): 312.3 (M+H)+.

Workup

  1. concentrationSolvents were concentrated under vacuum and water (2 L)
  2. additionwas added
  3. filtrationThe resulting suspension was filtered off
  4. washwashed with water (1 L)
  5. customdried under vacuum

Sources & evidence

ORD record
ord-fd755fbd082e463e920f1c90ca5220b4
Source dataset
uspto-grants-2014_08
Patent number
US08802704B2

Reaction notes

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