4-Methylmorpholine → HCID 22168677, Verbindung

HRID 1059732

Reaktionsgleichung

Reaktionsgleichung von HRID 1059732
[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].[CH2:16]1[CH2:20]OC[CH2:17]1.C(Cl)(=O)C(Cl)=O.CN1CCOCC1>C(Cl)Cl.CN(C=O)C>[CH2:20]([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]

Komponenten

7

Edukt 4

HCID 79724-MethylmorpholineHCID 8028TetrahydrofuranHCID 65578Oxalyl chlorideHCID 691221,4-Benzenedicarboxylic acid, 2-nitro-

Produkt 1

HCID 22168677HCID 22168677, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

Nitroterephthalic acid (6.33 g) in methylene chloride 475 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, 2H); 5.22-5.46 (m, 2H); 5.91-6.13 (m, 1H); 7.02 (dd. 1H); 7.37 (d, 1H); 7.61 (d, 1H).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-a02d0200287d4eba8993e7b61a876d4d
Quelldatensatz
uspto-grants-2003_02
Patentnummer
US06521612B2

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