4-Nitrobenzoic Acid → HCID 69216045, compound

HRID 2219296Notes

Reaction equation

HRID 2219296 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[O:12][C@:11]([CH3:18])([CH:13]([O:16][CH3:17])[O:14][CH3:15])[C@@H:10]([OH:19])[C@H:9]([N:20]([C:28]3[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][CH:29]=3)[CH2:21][C:22]3[N:23]=[N:24][N:25]([CH3:27])[N:26]=3)[C:8]=2[CH:35]=1)([O-:3])=[O:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+](C1C=CC(C(O)=O)=CC=1)([O-])=O.CC(C[AlH]CC(C)C)C>[Cl-].[Na+].O.C1(C)C=CC=CC=1.O1CCCC1>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[O:12][C@:11]([CH3:18])([CH:13]([O:16][CH3:17])[O:14][CH3:15])[C@H:10]([OH:19])[C@H:9]([N:20]([C:28]3[CH:29]=[CH:30][C:31]([Cl:34])=[CH:32][CH:33]=3)[CH2:21][C:22]3[N:23]=[N:24][N:25]([CH3:27])[N:26]=3)[C:8]=2[CH:35]=1)([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 14487Diisobutylaluminum hydrideHCID 10311369HCID 10311369, compound

Product 1

HCID 69216045HCID 69216045, compoundYield 19%

Reagents, catalysts & solvents 2

HCID 22635083Tetrahydrofuran tolueneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

(2S,3S,4R)-6-nitro-4-[N-(4-chlorophenyl)-N-(2-methyl-2H-tetrazol-5-ylmethyl)amino]-3-hydroxy-2-methyl-2-dimethoxymethyl-3,4-dihydro-2H-1-benzopyran (100 mg, 0.20 mmol) was dissolved in the mixed solvent (3.8 ml, toluene/tetrahydrofuran=1/1). Triphenyl phosphine (268 mg, 0.99 mmol) and 4-nitrobenzoic acid (149 mg, 0.87 mmol) were added to the solution at 0° C. Thereafter, diethyl azocarboxylte (156 μl, 0.99 mmol) was slowly added to the reaction through syringe. The reaction mixture was stirred for 3 days at the room temperature. The solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by short silica gel column chromatoghaphy to semi-product. Further purification was not accomplished. The crude product was dissolved in dichloromethane. DIBAL-H (1 M in hexane, 1.36 mmol) was slowly added to the solution dropwise at −20° C. The reaction mixture was stirred for 20 min. To terminate the reaction, the saturated brine solution was added to the reaction mixture. The organic layer was separated. The solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent-n-hexane:ethyl acetate=1:2), to give desired compound (18 mg, yield: 19%).

Workup

  1. additionThereafter, diethyl azocarboxylte (156 μl, 0.99 mmol) was slowly added to the reaction through syringe
  2. customThe solvent was removed under reduced pressure
  3. customto obtain a crude product
  4. customThe crude product was purified by short silica gel column chromatoghaphy to semi-product
  5. customFurther purification
  6. dissolutionThe crude product was dissolved in dichloromethane
  7. stirringThe reaction mixture was stirred for 20 min
  8. customTo terminate
  9. customthe reaction
  10. customThe organic layer was separated
  11. customThe solvent was removed under reduced pressure
  12. customto obtain a crude product
  13. customThe crude product was purified by silica gel column chromatography (developing solvent-n-hexane:ethyl acetate=1:2)

Sources & evidence

ORD record
ord-5a4fbbd854c64e7bba46a90dc5f86042
Source dataset
uspto-grants-2008_08
Patent number
US07414068B2

Reaction notes

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