4-Methylmorpholine → HCID 22168677, 화합물

HRID 1059732

반응식

HRID 1059732 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

HCID 22168677HCID 22168677, 화합물

시약·촉매·용매 2

HCID 6228Dimethylformamide용매HCID 6344Dichloromethane용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-a02d0200287d4eba8993e7b61a876d4d
출처 데이터셋
uspto-grants-2003_02
특허 번호
US06521612B2

연결된 노트

불러오는 중…