Sodium Azide → 5-Chloro-4-nitrothiophene-2-carbonyl azide

HRID 1192276Notes

Reaction equation

HRID 1192276 reaction equation
C(Cl)(=O)C(Cl)=O.[Cl:7][C:8]1[S:12][C:11]([C:13](O)=[O:14])=[CH:10][C:9]=1[N+:16]([O-:18])=[O:17].[N-:19]=[N+:20]=[N-:21].[Na+]>ClCCl.C(OCC)(=O)C>[Cl:7][C:8]1[S:12][C:11]([C:13]([N:19]=[N+:20]=[N-:21])=[O:14])=[CH:10][C:9]=1[N+:16]([O-:18])=[O:17]

Participants

6

Reactant 3

HCID 33557Sodium AzideHCID 65578Oxalyl chlorideHCID 132055635-Chloro-4-nitrothiophene-2-carboxylic acid

Product 1

HCID 602075075-Chloro-4-nitrothiophene-2-carbonyl azideYield 59.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

oxalyl chloride (460 mg, 3.62 mmol) followed by N,N-dimethylformide (0.05 mL) was added to a solution of 5-chloro-4-nitrothiophene-2-carboxylic acid (1.0 g, 14.0 mmol) in dichloromethane (20 mL) under nitrogen atmosphere and the resulting mixture was stirred at ambient temperature for 4 hours. TLC analysis showed no acid remaining so the mixture was allowed to be concentrated in vacuo. The resulting acid chloride was dissolved in dry tetrahydrofuran (10 mL). Sodium azide (190 mg, 2.89 mmol) was added to the above solution. The resulting mixture was stirred at ambient temperature for 10 hours. After this time, TLC analysis showed no acid chloride remaining so the mixture was diluted with ethyl acetate and washed with water and brine. The organic layer was separated, dried (Na2SO4), filtered and the solvent was removed to afford the title product as a brown solid (400 mg, 59% yield). 1H NMR (400 MHz, d6-DMSO) δ: 8.23 (2H, s).

Workup

  1. concentrationto be concentrated in vacuo
  2. dissolutionThe resulting acid chloride was dissolved in dry tetrahydrofuran (10 mL)
  3. stirringThe resulting mixture was stirred at ambient temperature for 10 hours
  4. washwashed with water and brine
  5. customThe organic layer was separated
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customthe solvent was removed

Sources & evidence

ORD record
ord-b67d085af0f1418fab4a0c32fc30241f
Source dataset
uspto-grants-2014_03
Patent number
US08680139B2

Reaction notes

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