Nitric Acid → HCID 86627630, compound

HRID 604649Notes

Reaction equation

HRID 604649 reaction equation
[N+:1]([O-:4])(O)=[O:2].[F:5][C:6]([F:37])([F:36])[C:7]1[CH:8]=[C:9]([C@H:17]2[O:21][C:20](=[O:22])[N:19]([CH2:23][C:24]3[C:33]([I:34])=[CH:32][C:31]4[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=4)[CH:25]=3)[C@H:18]2[CH3:35])[CH:10]=[C:11]([C:13]([F:16])([F:15])[F:14])[CH:12]=1>C(O)(=O)C.C([O-])(O)=O.[Na+]>[F:37][C:6]([F:5])([F:36])[C:7]1[CH:8]=[C:9]([C@H:17]2[O:21][C:20](=[O:22])[N:19]([CH2:23][C:24]3[C:33]([I:34])=[CH:32][C:31]4[C:26](=[CH:27][CH:28]=[CH:29][C:30]=4[N+:1]([O-:4])=[O:2])[CH:25]=3)[C@H:18]2[CH3:35])[CH:10]=[C:11]([C:13]([F:15])([F:16])[F:14])[CH:12]=1

Participants

5

Reactant 2

HCID 944Nitric AcidHCID 86627631HCID 86627631, compound

Product 1

HCID 86627630HCID 86627630, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 516892Sodium BicarbonateSolvent

Procedure

Fuming nitric acid was added dropwise to a stirred solution of (4S,5R)-5-[3,5-bis(trifluoromethyl)phenyl]-3-[(3-iodo-2-naphthyl)methyl]-4-methyl-1,3-oxazolidin-2-one (synthesized from INTERMEDIATE 16 using a method analogous to that described in EXAMPLE 1, Step E) in acetic acid at room temperature. The reaction was stirred at room temperature for 3 h. The reaction was diluted with saturated NaHCO3 (10 mL) and extracted with EtOAc (3×20 mL). The combined extracts were dried (Na2SO4) and concentrated in vacuo to give the crude product as a mixture of product isomers. The main isomer was purified by flash chromatography (Si, 12×160 mm, 0-20% EtOAc in hexanes gradient) to afford (4S,5R)-5-[3,5-bis(trifluoromethyl)phenyl]-3-[(3-iodo-5-nitro-2-naphthyl)methyl]-4-methyl-1,3-oxazolidin-2-one. Rf=0.11 (20% EtOAc/hexanes). LCMS calc.=625.0; found=624.6 (M+1)+. 1H NMR (600 MHz, CDCl3): δ 9.20 (s, 1H); 8.28 (dd, J=1.0, 7.7 Hz, 1H); 8.10 (d, J=8.2 Hz, 1H); 7.93 (s, 1H); 7.89 (s, 1H); 7.81 (s, 2H); 7.61 (t, J=7.9 Hz, 1H); 5.82 (d, J=7.9 Hz, 1H); 4.98 (d, J=15.9 Hz, 1H); 4.48 (d, J=15.9 Hz, 1H); 4.21-4.15 (m, 1H); 0.84 (d, J=6.5 Hz, 3H).

Workup

  1. customat room temperature
  2. extractionextracted with EtOAc (3×20 mL)
  3. dry with materialThe combined extracts were dried (Na2SO4)
  4. concentrationconcentrated in vacuo
  5. customto give the crude product
  6. additionas a mixture of product isomers
  7. customThe main isomer was purified by flash chromatography (Si, 12×160 mm, 0-20% EtOAc in hexanes gradient)

Sources & evidence

ORD record
ord-40586cc93335455491714a3971149c7f
Source dataset
uspto-grants-2011_03
Patent number
US07910592B2

Reaction notes

Loading…