Sodium Azide → 4-Amino-2-azido-3-chloro-5-nitro-benzoic acid methyl ester

HRID 2039604Notes

Reaction equation

HRID 2039604 reaction equation
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([NH2:13])=[C:6]([Cl:14])[C:5]=1F.[N-:17]=[N+:18]=[N-:19].[Na+]>CN(C=O)C.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CCOC(C)=O>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([NH2:13])=[C:6]([Cl:14])[C:5]=1[N:17]=[N+:18]=[N-:19]

Participants

6

Reactant 2

HCID 33557Sodium AzideHCID 858681944-Amino-3-chloro-2-fluoro-5-nitro-benzoic acid methyl ester

Product 1

HCID 578559864-Amino-2-azido-3-chloro-5-nitro-benzoic acid methyl esterYield 95.5%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 7 g (28.16 mmol) of 4-amino-3-chloro-2-fluoro-5-nitro-benzoic acid methyl ester (known from WO 03/077914) in 140 mL of DMF, 5.49 g (84.44 mmol) of sodium azide and 908 mg (2.82 mmol) of tetrabutyl ammonium bromide is added. Then the mixture is stirred and heated at 50° C. for 4 h. After cooling to ambient temperature, the mixture is diluted in EtOAc and washed with H2O (5 times). The organic phase is dried on Na2SO4, filtrated and evaporated. The crude compound (7.3 g, 26.88 mmol, 95%) obtained as a yellow solid is used without more purification in the next step. 1H-NMR (CDCl3, 300 MHz): ? ppm=3.95 (s, 3H), 8.82 (s, 1H).

Workup

  1. temperatureAfter cooling to ambient temperature
  2. washwashed with H2O (5 times)
  3. customThe organic phase is dried on Na2SO4
  4. filtrationfiltrated
  5. customevaporated

Sources & evidence

ORD record
ord-e4933795487a477693d0242dca139091
Source dataset
uspto-grants-2013_11
Patent number
US08580785B2

Reaction notes

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