Dimethyl Sulfoxide → 6-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-formyl-1-pyridinyl)-2H-benzo[b]pyran

HRID 487640ノート

反応式

HRID 487640 の反応式
CS(C)=O.[C:5]([C:7]1[CH:27]=[CH:26][C:10]2[O:11][C:12]([CH3:25])([CH3:24])[CH:13]=[C:14]([N:15]3[CH:20]=[CH:19][C:18]([CH2:21][OH:22])=[CH:17][C:16]3=[O:23])[C:9]=2[CH:8]=1)#[N:6].C(N(CC)CC)C.O>C(Cl)Cl.C(Cl)(=O)C(Cl)=O>[C:5]([C:7]1[CH:27]=[CH:26][C:10]2[O:11][C:12]([CH3:24])([CH3:25])[CH:13]=[C:14]([N:15]3[CH:20]=[CH:19][C:18]([CH:21]=[O:22])=[CH:17][C:16]3=[O:23])[C:9]=2[CH:8]=1)#[N:6]

参加物

7

反応物 4

HCID 679Dimethyl SulfoxideHCID 962WaterHCID 8471TriethylamineHCID 190925956-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-hydroxymethyl-1-pyridinyl)-2H-benzo[b]pyran

生成物 1

HCID 190925656-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-formyl-1-pyridinyl)-2H-benzo[b]pyran収率 99.8%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 65578Oxalyl chloride溶媒

実験手順

In 200 ml of anhydrous methylene chloride, is dissolved 3.84 ml of oxalyl chloride. After cooling the resulting solution to -50° C. to -60° C., 6.24 ml of dimethyl sulfoxide is dropped thereinto and stirred at that temperature for 5 minutes. Then, 200 ml of a solution containing 12.3 g of 6-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-hydroxymethyl-1-pyridinyl)-2H-benzo[b]pyran obtained in Example 9 (or Example 22) in anhydrous methylene chloride is added at that temperature over a period of 25 minutes and reacted at that temperature for 20 minutes. After adding 27.9 ml of triethylamine to the reaction mixture and stirred at that temperature for 10 minutes, the temperature is slowly elevated to room temperature. After stirring the mixture at room temperature for an additional one hour, the reaction is stopped by adding water, and the reaction mixture is extracted with methylene chloride. The organic layer is washed with saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. The inorganic matter is filtered off and the filtrate is concentrated under reduced pressure. The residue is purified by silica gel column chromatography using 1/30 mixture of methanol/methylene chloride as a developing solvent. Thus, 12.2 g of 6-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-formyl-1-pyridinyl)-2H-benzo[b]pyran is obtained.

後処理

  1. temperatureAfter cooling the resulting solution to -50° C. to -60° C.
  2. additionis added at that temperature over a period of 25 minutes
  3. customreacted at that temperature for 20 minutes
  4. stirringstirred at that temperature for 10 minutes
  5. customis slowly elevated to room temperature
  6. stirringAfter stirring the mixture at room temperature for an additional one hour
  7. extractionthe reaction mixture is extracted with methylene chloride
  8. washThe organic layer is washed with saturated aqueous solution of sodium chloride
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationThe inorganic matter is filtered off
  11. concentrationthe filtrate is concentrated under reduced pressure
  12. customThe residue is purified by silica gel column chromatography
  13. addition1/30 mixture of methanol/methylene chloride as a developing solvent

出典と根拠

ORDレコード
ord-6bbc1aa504a94ae8b0e7b8564617208b
出典データセット
uspto-grants-1994_03
特許番号
US05296492

反応ノート

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