Dimethylformamide → Methyl 3-carbamoyl-5-nitrobenzoate

HRID 964485Notes

Reaction equation

HRID 964485 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:14]([O-:16])=O)[CH:7]=[C:8]([CH:13]=1)[C:9]([O:11][CH3:12])=[O:10])([O-:3])=[O:2].S(Cl)(Cl)=O.C[N:22](C=O)C>C1COCC1.C(Cl)Cl>[CH3:12][O:11][C:9]([C:8]1[CH:7]=[C:6]([CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:13]=1)[C:14]([NH2:22])=[O:16])=[O:10]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 6931682Monomethyl-5-nitroisophthalate

Product 1

HCID 3741295Methyl 3-carbamoyl-5-nitrobenzoateYield 81%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of mono-methyl 5-nitroisophthalate (45.0 g, 200 mmol), thionyl chloride (71.4 g, 600 mmol) and DMF through SiO2 (125 μL) in dry THF (100 mL) and dry CH2Cl2 (300 mL) was refluxed overnight. See, FIG. 1C, step 1. The reaction mixture was evaporated in vacuo and then added dry CH2 Cl2 (200 mL) and hexanes (500 mL). Ammonia gas was introduced into the solution and the precipitation was collected on a glass-filter. Id., step 2. The cake was suspended in 1N HCl (500 mL), filtered again and then washed with saturated NaHCO3 aq. (500 mL) and water (500 mL). The product was dried in vacuo to give ivory powder (36.3 g, 81%): 1H NMR (300 MHz, DMSO-d6) δ 8.918 (t, J=1.8 Hz, 1H), 8.816 (t, J=1.2 Hz, 1H), 8.773 (t, J=1.6 Hz, 1H), 8.716 (s, 1H, NH), 7.859 (s, 1H, NH), 3.944 (s, 3H); 13C NMR (300 MHz, DMSO-d6) δ 164.9, 164.2, 148.1, 136.4, 134.9, 133.8, 133.3, 131.5, 126.4, 126.0, 53.1.

Workup

  1. customThe reaction mixture was evaporated in vacuo
  2. additionadded
  3. dry with materialdry CH2 Cl2 (200 mL) and hexanes (500 mL)
  4. additionAmmonia gas was introduced into the solution
  5. customthe precipitation
  6. customwas collected on a glass-filter
  7. filtrationfiltered again
  8. washwashed with saturated NaHCO3 aq. (500 mL) and water (500 mL)
  9. customThe product was dried in vacuo

Sources & evidence

ORD record
ord-5e5b3dca38a54e6a8184605d0e8cfd47
Source dataset
uspto-grants-1998_06
Patent number
US05770380

Reaction notes

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