4-Methylmorpholine → Methyl N-[(4-nitrophenoxy)carbonyl]-L-valinate

HRID 1861159Notes

Reaction equation

HRID 1861159 reaction equation
Cl[C:2]([O:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][CH:6]=1)=[O:3].Cl.[CH3:15][O:16][C:17](=[O:23])[C@H:18]([CH:20]([CH3:22])[CH3:21])[NH2:19].CN1CCOCC1>C(Cl)Cl>[CH3:15][O:16][C:17](=[O:23])[C@H:18]([CH:20]([CH3:22])[CH3:21])[NH:19][C:2]([O:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][CH:6]=1)=[O:3]

Participants

5

Reactant 3

HCID 79724-MethylmorpholineHCID 821294-Nitrophenyl chloroformateHCID 111190Methyl valinate hydrochloride

Product 1

HCID 15344176Methyl N-[(4-nitrophenoxy)carbonyl]-L-valinate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 66.1 g (0.328 mol) of 4-nitrophenyl chloroformate in 1.2 liters of CH2Cl2 was cooled to 0° C. and treated with L-valine methyl ester hydrochloride. The resulting mixture was treated slowly, with stirring, with 68.9 ml (0.626 mol) of 4-methylmorpholine. The resulting solution was allowed to slowly warm to ambient temperature and was stirred overnight. After washing with 3 portions of 10% aqueous NaHCO3, the solution was dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel chromatography by eluting with chloroform to provide the desired compound. 1H NMR (DMSO-d6) δ 0.94 (d, J=7 Hz, 3 H), 0.95 (d, J=7 Hz, 3 H), 2.12 (octet, J=7 Hz, 1 H), 3.69 (s, 3 H), 4.01 (dd, J=8, 6 Hz, 1 H), 7.41 (dt, J=9, 3 Hz, 2 H), 8.27 (dt, J=9, 3 Hz, 2 H), 8.53 (d, J=8 Hz, 1 H). Mass spectrum: (M+NH4)+314.

Workup

  1. additionThe resulting mixture was treated slowly
  2. washAfter washing with 3 portions of 10% aqueous NaHCO3
  3. dry with materialthe solution was dried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel chromatography
  6. washby eluting with chloroform

Sources & evidence

ORD record
ord-2d0ff972a6fe4bd69fcef2e9fcb53b9c
Source dataset
uspto-grants-2003_03
Patent number
US06531610B1

Reaction notes

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