Benzene, 2-fluoro-4-methyl-1-nitro- → HCID 10731514, compound

HRID 2379457Notes

Reaction equation

HRID 2379457 reaction equation
C([NH:8][C@H:9]([C:15]([OH:17])=[O:16])[CH2:10][CH2:11][CH2:12][CH2:13][NH2:14])(OC(C)(C)C)=O.F[C:19]1[CH:20]=[C:21]([CH3:28])[CH:22]=[CH:23][C:24]=1[N+:25]([O-:27])=[O:26]>[OH-].[Na+].C(O)C.Cl.C(O)(=O)C>[NH2:8][C@@H:9]([CH2:10][CH2:11][CH2:12][CH2:13][NH:14][C:19]1[CH:20]=[C:21]([CH3:28])[CH:22]=[CH:23][C:24]=1[N+:25]([O-:27])=[O:26])[C:15]([OH:17])=[O:16]

Participants

7

Reactant 2

HCID 67966Benzene, 2-fluoro-4-methyl-1-nitro-HCID 2733284epsilon-tert-Butyloxycarbonyl-lysine

Product 1

HCID 10731514HCID 10731514, compoundYield 42%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent2×HCID 14798Sodium HydroxideSolvent

Procedure

A mixture of 2.37 g (10 mmol) of Nα -BOC-L-lysine and 1.65 g (11.0 mmol) of 3-fluoro-4-nitrotoluene in 10 mL of 1N NaOH and 10 mL of ethanol were heated at reflux for 48 hours, then cooled to room temperature. A precipitate was filtered off and discarded. Removal of the solvent/n vacuo gave an oil which was dissolved in 50 % ethanol/3M NH3 and taken to dryness. The residue was dissolved in 12 mL of 4N HCl in 33% acetic acid and stirred for four hours, then concentrated to dryness and purified by flash chromatography (eluting with 12:1:1 acetonitrile/water/HOAc). The resulting oil was recrystallized from water/methanol to afford 470 mg (42% yield) of the title product as bright orange prisms.: mp 234°-235° (dec.); MS M/Z (DCl/NH3): 282 [M+H]+ ; 1H NMR (300 MHz, D2O) δ: 1.1-1.45 (m, 6H), 2.78 (t, J=6.6 Hz, 2H), 2.99 (t, J=6.0 Hz, 1H), 5.88 (d, J=7.8 Hz, 1H), 6.07 (s, 1H), 7.32 (d, J=7.8 Hz, 1H). 13C NMR (75.5 MHz, D2O) δ: 185.73, 151.31,148.37, 131.02, 119.60, 116.09, 58.83, 45.20, 37.87, 31.19, 25.86; Analysis calc'd for C13H19N3O4 : C, 55.51;H, 6.81;N, 14.94; found: C, 55.25;H, 6.94; N, 14.75.

Workup

  1. temperaturewere heated
  2. temperatureat reflux for 48 hours
  3. filtrationA precipitate was filtered off
  4. customRemoval of the solvent/n vacuo
  5. customgave an oil which
  6. concentrationconcentrated to dryness
  7. custompurified by flash chromatography (eluting with 12:1:1 acetonitrile/water/HOAc)
  8. customThe resulting oil was recrystallized from water/methanol

Sources & evidence

ORD record
ord-98b9a59af64640c3bc8762ec04747c38
Source dataset
uspto-grants-1994_11
Patent number
US05362747

Reaction notes

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