4-Nitrobenzoic Acid → HCID 66671357, compound

HRID 1014928Notes

Reaction equation

HRID 1014928 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:15][CH:14]([OH:16])[CH2:13][CH:12]1[CH2:17][C:18]1[C:26]2[C:21](=[N:22][CH:23]=[CH:24][CH:25]=2)[NH:20][CH:19]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+:27]([C:30]1[CH:38]=[CH:37][C:33]([C:34](O)=[O:35])=[CH:32][CH:31]=1)([O-:29])=[O:28].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[CH2:1]([O:8][C:9]([N:11]1[CH2:15][CH:14]([O:16][C:34](=[O:35])[C:33]2[CH:32]=[CH:31][C:30]([N+:27]([O-:29])=[O:28])=[CH:38][CH:37]=2)[CH2:13][CH:12]1[CH2:17][C:18]1[C:26]2[C:21](=[N:22][CH:23]=[CH:24][CH:25]=2)[NH:20][CH:19]=1)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 66670079HCID 66670079, compound

Product 1

HCID 66671357HCID 66671357, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution containing 72 (1.99 g, 5.66 mmol), p-nitrobenzoic acid (1.23 g, 7.36 mmol), and Ph3P (2.07 g, 7.92 mmol) in THF (35 mL) at 0° C. was added DIAD (1.6 mL, 8.2 mmol). After the addition was complete, the ice bath was removed and the reaction mixture was stirred at ambient temperature for 2 hat which point TLC analysis revealed complete consumption of 72 [EtOAc, Rf(72)=0.2; Rf(73)=0.6]. The solvent was removed in vacuo and the residue was dissolved in EtOAc, washed with saturated aqueous NaHCO3, brine, dried over anhydrous Na2SO4, filtered, and concentrated to afford 7 g of crude 73 which was purified by flash silica gel chromatography (20% EtOAc/hexanes) to obtained 2.68 g of 73 (95%) as a white solid 1H NMR (CDCl3, 300 MHz): δ8.3 (d, J=35 Hz, 2H), 7.6 (d, J=35 Hz, 2H), 7.2 (m, 5H), 7.0 (s, 1H), 5.2 (s, 2H), 4.4-3.2 (m, 3H), 3.0-2.9 (m, 1H), 2.2 (s, 2H), 1.9 (s, 2H) ppm.

Workup

  1. additionAfter the addition
  2. customthe ice bath was removed
  3. customconsumption of 72 [EtOAc, Rf(72)=0.2; Rf(73)=0.6]
  4. customThe solvent was removed in vacuo
  5. dissolutionthe residue was dissolved in EtOAc
  6. washwashed with saturated aqueous NaHCO3, brine
  7. dry with materialdried over anhydrous Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford 7 g of crude 73 which
  11. customwas purified by flash silica gel chromatography (20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-5a757789af804691b2622d52f3e21fa6
Source dataset
uspto-grants-2011_07
Patent number
US07985735B2

Reaction notes

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