Pyridine → HCID 58831675, compound

HRID 2375145Notes

Reaction equation

HRID 2375145 reaction equation
[N-:1]=[N+]=[N-].N1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.Cl[C:11]([O:13][C:14]1C=CC=CC=1)=[O:12].C1(P([C:33]2[CH:38]=[CH:37]C=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:39]([O:42][CH2:43][CH3:44])(=[O:41])[CH3:40]>ClCCl.S([O-])([O-])(=O)=O.[Na+].[Na+].C(Cl)(Cl)Cl.O.C1COCC1>[CH2:43]([O:42][C:39]([C@@H:40]1[C@H:14]([CH:38]([CH3:37])[CH3:33])[O:13][C:11](=[O:12])[NH:1]1)=[O:41])[C:44]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

11

Reactant 5

HCID 1049PyridineHCID 8857Ethyl AcetateHCID 11776TriphenylphosphineHCID 15891Phenyl chloroformateHCID 33558Azide

Product 1

HCID 58831675HCID 58831675, compoundYield 93%

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolventHCID 24436Sodium SulfateSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of the azide, Compound 4 (prepared essentially by the method of Hruby et al., J. Org. Chem. 2002, 67, 3514-3517) (2.0 g, 7.6 mmol, 1 equiv) in dichloromethane at 23° C. (20 mL), was added pyridine (920 μL, 11.5 mmol, 2.5 equiv), followed by phenyl chloroformate (1.05 mL, 8.35 mmol, 1.1 equiv). After 1 h the resulting suspension was partitioned between dichloromethane (50 ml) and aqueous hydrochloric acid (2N, 50 mL). The organics were dried over sodium sulfate and concentrated in vacuo. To the resultant residue was added THF (20 mL), water (2 mL) and triphenylphosphine (2.2 g, 8.35 mmol, 1.1 equiv). The resulting solution was heated to 50° C. for 1 h, during which time gas evolution was observed. The reaction was diluted with dichloromethane (100 mL) and sodium sulfate was added to the resultant solution. The organics were filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel, gradient elution (40-50-60-70% ethyl acetate in hexanes) to give the oxazolidinone, Compound 5 (1.85 g, 7.1 mmol, 93%) as a colorless solid mp=99-101° C., Rf=0.29 (50% ethyl acetate in hexanes), [α]23D−12.5 (c 1.15, CHCl3); FTIR (neat), cm−1: 3288, 2971, 1762, 1739, 1214; 1H NMR (500 MHz, CDCl3), δ: 7.37 (m, 5H), 5.71 (bs, 1H), 5.22 (ABO, 2H, J=12 Hz), 4.37 (m, 1H), 1.76 (m, 1H), 0.97 (d, 3H, J=6.5 Hz), 0.92 (d, 3H, J=7 Hz); 13C NMR (100 MHz, CDCl3), δ: 169.4, 159.5, 134.6, 128.7, 128.6, 128.6, 67.6, 58.0, 29.0, 18.7, 18.4. LRMS Calcd for C14H17NO4 [M]+ 263.1. Found [M+NH4]+ 281.2.

Workup

  1. customAfter 1 h the resulting suspension was partitioned between dichloromethane (50 ml) and aqueous hydrochloric acid (2N, 50 mL)
  2. dry with materialThe organics were dried over sodium sulfate
  3. concentrationconcentrated in vacuo
  4. filtrationThe organics were filtered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography on silica gel, gradient elution (40-50-60-70% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-1e3e250874c94052a789c5e754ce4017
Source dataset
uspto-grants-2008_12
Patent number
US07465720B2

Reaction notes

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