Sodium Carbonate → 4-({[(9H-fluoren-9-yl)methoxy]carbonyl}amino)-2-nitrobenzoic acid

HRID 629670Notes

Reaction equation

HRID 629670 reaction equation
[NH2:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([N+:11]([O-:13])=[O:12])[CH:3]=1.C(=O)([O-])[O-].[Na+].[Na+].[CH:20]1[C:32]2[CH:31]([CH2:33][O:34][C:35](Cl)=[O:36])[C:30]3[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=3)[C:24]=2[CH:23]=[CH:22][CH:21]=1.O1CCOCC1>O>[CH:20]1[C:32]2[CH:31]([CH2:33][O:34][C:35]([NH:1][C:2]3[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([N+:11]([O-:13])=[O:12])[CH:3]=3)=[O:36])[C:30]3[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=3)[C:24]=2[CH:23]=[CH:22][CH:21]=1

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 343679-Fluorenylmethyl chloroformateHCID 2357134-Amino-2-nitrobenzoic Acid

Product 1

HCID 687014474-({[(9H-fluoren-9-yl)methoxy]carbonyl}amino)-2-nitrobenzoic acidYield 67.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a solution of 11.4 g 4-amino-2-nitro-benzoic acid in 228 ml of water containing 6.63 g of sodium carbonate were added 17.0 g of 9-fluorenylmethyl-chloroformate and dropwise 20 ml of dioxane. After stirring for 20 hours under nitrogen, the mixture was filtered and the filtrate was washed five times with methyl-tert.-butylether. Residual methyl-tert.-butylether was removed from the aqueous phase by evaporation under vacuum. To the aqueous phase were added 456 g of 0° C. cold water. The mixture was adjusted to pH=3 by addition of 31 ml of 2M aqueous hydrochloric acid. The precipitate was sucked off, washed with 513 ml of water, dried at 40° C. in vacuum to give 17.0 g of 4-(((9H-fluorene-9-yl)methoxy)carbonylamino)-2-nitrobenzoic acid as off-white crystals.

Workup

  1. filtrationthe mixture was filtered
  2. washthe filtrate was washed five times with methyl-tert.-butylether
  3. customResidual methyl-tert.-butylether was removed from the aqueous phase by evaporation under vacuum
  4. additionTo the aqueous phase were added 456 g of 0° C. cold water
  5. additionThe mixture was adjusted to pH=3 by addition of 31 ml of 2M aqueous hydrochloric acid
  6. washwashed with 513 ml of water
  7. customdried at 40° C. in vacuum

Sources & evidence

ORD record
ord-d6cb7201f2884a5bb789fd868afb2045
Source dataset
uspto-grants-2016_04
Patent number
US09315506B2

Reaction notes

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