Oxalyl chloride → 1-Methyl-6-oxo-4-(2,3,4-trichloro-phenylamino)-1,6-dihydro-pyridine-3-carboxylic acid amide

HRID 917781ノート

反応式

HRID 917781 の反応式
[CH3:1][N:2]1[C:7](=[O:8])[CH:6]=[C:5]([NH:9][C:10]2[CH:15]=[CH:14][C:13]([Cl:16])=[C:12]([Cl:17])[C:11]=2[Cl:18])[C:4]([C:19]([OH:21])=O)=[CH:3]1.C(Cl)(=O)C(Cl)=O.[NH3:28].O1CCOCC1>C(Cl)Cl.CN(C=O)C>[CH3:1][N:2]1[C:7](=[O:8])[CH:6]=[C:5]([NH:9][C:10]2[CH:15]=[CH:14][C:13]([Cl:16])=[C:12]([Cl:17])[C:11]=2[Cl:18])[C:4]([C:19]([NH2:28])=[O:21])=[CH:3]1

参加物

6

反応物 3

HCID 65578Oxalyl chlorideHCID 113824461-Methyl-6-oxo-4-(2,3,4-trichloro-phenylamino)-1,6-dihydro-pyridine-3-carboxylic acidHCID 66648793Ammonia dioxane

生成物 1

HCID 111988041-Methyl-6-oxo-4-(2,3,4-trichloro-phenylamino)-1,6-dihydro-pyridine-3-carboxylic acid amide

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒

実験手順

The product of Example 65, 1-methyl-6-oxo-4-(2,3,4-trichloro-phenylamino)-1,6-dihydro-pyridine-3-carboxylic acid (0.4 g, 1.15 mmol) was dissolved in DCM (20 mL). Added one drop of DMF and then oxalyl chloride (0.11 mL, 1.27 mmol) was added. Reaction was stirred at rt for 1.5 hours. Then 0.5 N NH3/dioxane (10 mL) was added and stirred for 72 hours. The solvent was removed in vacuum. Ethyl acetate was added and washed with sat. NaHCO3 soln. Filtered solid and dried in vacuum oven 1 hour. Tried to recrystalize using hexanes (5 mL) and EtOAc (30 mL) but never dissolved. Solvent removed in vacuum and took the residue up in ethyl acetate (10 mL)/MeOH (2 mL). Still did not dissolve. Cooled, filtered and dried in vacuum oven overnight at 60° C. Obtained white solid (210.0 mg, 52.7% y.). MS (APCI+) 347,349 [M+H]; HPLC 2.954 m. 94.68%; C13H10Cl3N3O2; CHN Calc. C)45.05% H)2.91% N)12.12% found C)27.56% H)1.29% N)3.96%; NMR (400 MHz, DMSO-d6) δ 13.36 (s, 1H), 8.11 (s, 1H), 7.55 (d, J=9.0 Hz, 1H), 7.51 (d, J=9.0 Hz, 1H), 5.67 (s, 1H), 3.31 (s, 3H).

後処理

  1. customReaction
  2. stirringstirred for 72 hours
  3. customThe solvent was removed in vacuum
  4. additionEthyl acetate was added
  5. washwashed with sat. NaHCO3 soln
  6. filtrationFiltered solid
  7. customdried in vacuum oven 1 hour
  8. customTried to recrystalize
  9. dissolutionnever dissolved
  10. customSolvent removed in vacuum
  11. dissolutionStill did not dissolve
  12. temperatureCooled
  13. filtrationfiltered
  14. customdried in vacuum oven overnight at 60° C
  15. customObtained white solid (210.0 mg, 52.7% y.)

出典と根拠

ORDレコード
ord-99b154168e91421c88bdf93de4f43797
出典データセット
uspto-grants-2007_09
特許番号
US07273877B2

反応ノート

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