Thionyl Chloride → HCID 68295546、化合物

HRID 572524ノート

反応式

HRID 572524 の反応式
[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[C:9]1[C:18]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:12](=[O:19])[N:11]([CH3:20])[C:10]=1[C:21](O)=O.S(Cl)([Cl:26])=O.[BH4-].[Na+]>CO>[Cl:26][CH2:21][C:10]1[N:11]([CH3:20])[C:12](=[O:19])[C:13]2[C:18]([C:9]=1[C:3]1[CH:4]=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=1[CH3:1])=[CH:17][CH:16]=[CH:15][CH:14]=2

参加物

5

反応物 3

HCID 24386Thionyl ChlorideHCID 4311764Sodium borohydrideHCID 68294980HCID 68294980、化合物

生成物 1

HCID 68295546HCID 68295546、化合物収率 76%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
70 °C

実験手順

A suspension of 4-(2,4-dimethylphenyl)-2-methyl-1-oxo-1,2-dihydroisoquinoline-3-carboxylic acid (21.6 g) in thionyl chloride (218 mL, 2987 mmol) was heated at 70° C. for 2 hours. The mixture was concentrated, dissolved in tetrahydrofuran (THF) (15 mL), and treated with sodium borohydride (0.929 g, 24.56 mmol). The resulting mixture was heated to 70° C. for 2 hours until LCMS indicated complete reaction. The mixture was cooled to 0° C. and methanol was added until gas evolution ceased. The mixture was concentrated, diluted with water and then extracted three times with dichloromethane. The combined extracts were washed with brine, dried over Na2SO4, filtered and concentrated. The residue was treated with thionyl chloride (20 mL) and heated at 70° C. for 2 hours. The mixture was concentrated and then purified on silica gel (0-70% EA/Hexane) to afford the title compound (1.17 g, 76%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.46-8.59 (m, 1 H) 7.47-7.57 (m, 2 H) 7.05-7.24 (m, 3 H) 6.87-6.99 (m, 1 H) 4.43-4.55 (m, 1 H) 4.31-4.41 (m, 1 H) 3.86 (s, 3 H) 2.43 (s, 3 H) 2.01 (s, 3 H). LC/MS (m/z) ES+=312 (M+1).

後処理

  1. concentrationThe mixture was concentrated
  2. dissolutiondissolved in tetrahydrofuran (THF) (15 mL)
  3. temperatureThe resulting mixture was heated to 70° C. for 2 hours until LCMS
  4. customreaction
  5. temperatureThe mixture was cooled to 0° C.
  6. concentrationThe mixture was concentrated
  7. additiondiluted with water
  8. extractionextracted three times with dichloromethane
  9. washThe combined extracts were washed with brine
  10. dry with materialdried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. additionThe residue was treated with thionyl chloride (20 mL)
  14. temperatureheated at 70° C. for 2 hours
  15. concentrationThe mixture was concentrated
  16. custompurified on silica gel (0-70% EA/Hexane)

出典と根拠

ORDレコード
ord-8ca060ef96584e62915dedac44983ceb
出典データセット
uspto-grants-2015_05
特許番号
US09029391B2

反応ノート

読み込み中…