Dimethylformamide → HCID 22168677, compound

HRID 266850Notes

Reaction equation

HRID 266850 reaction equation
[N+:1]([C:4]1[CH:12]=[C:11]([C:13]([OH:15])=[O:14])[CH:10]=[CH:9][C:5]=1[C:6]([OH:8])=[O:7])([O-:3])=[O:2].[C:16](Cl)(=O)[C:17](Cl)=O.[CH3:22]N(C=O)C.CN1CCOCC1>C(Cl)Cl.C1COCC1>[CH2:22]([O:14][C:13]([C:11]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([N+:1]([O-:3])=[O:2])[CH:12]=1)=[O:15])[CH:16]=[CH2:17]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 79724-MethylmorpholineHCID 65578Oxalyl chlorideHCID 691221,4-Benzenedicarboxylic acid, 2-nitro-

Product 1

HCID 22168677HCID 22168677, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Nitroterephthalic acid (6.33 g) in methylene chloride (75 ml) and THF (15 ml) was converted to the mono acid chloride using oxalyl chloride (2.63 ml), DMF (2.55 ml) and N-methylmorpholine (7.95 ml) at -10° C. After 1 hour the solvents were removed and, without further purification, the product was dissolved in allyl alcohol (20 ml) and THF (10 ml) and stirred overnight at ambient temperature. The solvents were removed and the residue partitioned between EtOAc and aqueous NaHCO3. Acidification of the NaHCO3 solution and extraction with EtOAc gave the product, 4-allyloxycarbonyl-2-nitrobenzoic acid (6.8 g). Nmr (CDCl3): δ 4.89 (d, 2H); 5.31-5.49 (m, 2H); 5.95-6.15 (m. 1H); 7.94 (d, 1H); 8.36 (dd, 1H); 8.54 (d, 1H). Without purification, this acid was converted by the method above to the acid chloride which was dissolved in THF (100 ml) at 0° C. Ammonia gas was bubbled into the solution until the reaction was completed. The solution was partitioned between EtOAc and water, and the product from the organic fraction purified on silica, eluting with methylene chloride followed by EtOAc. The product (4 g), containing a small impurity, was reduced with SnCl2 by a similar method to that in example 12 giving 4-allyloxycarbonyl-2-aminobenzamide. Nmr (DMSO-d6): δ 4.79 (d, 5.22-5.46 (m, 2H); 5.91-6.13 (m, 1H); 7.02 (dd. 1H); 7.37 (d, 1H); 7.61 (d, 1H).

Workup

  1. customat -10° C
  2. customAfter 1 hour the solvents were removed and, without further purification
  3. dissolutionthe product was dissolved in allyl alcohol (20 ml)
  4. customThe solvents were removed
  5. customthe residue partitioned between EtOAc and aqueous NaHCO3
  6. extractionAcidification of the NaHCO3 solution and extraction with EtOAc

Sources & evidence

ORD record
ord-89f90793d22e4dcb9961a80166928c7b
Source dataset
uspto-grants-1997_07
Patent number
US05652233

Reaction notes

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