Dimethylformamide → HCID 22168677、化合物

HRID 341882

反応式

HRID 341882 の反応式
[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]

参加物

7

反応物 4

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

生成物 1

HCID 22168677HCID 22168677、化合物

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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, 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).

後処理

  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

出典と根拠

ORDレコード
ord-bc7d2bf587b143b99ed22fd905063932
出典データセット
uspto-grants-1999_01
特許番号
US05856321

関連ノート

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