Hydrochloric Acid → 7-Chloro-3,3-bis(4,6-dimethoxy-1,3,5-triazin-2-yl)phthalide

HRID 863747노트

반응식

HRID 863747 반응식
[Cl:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[C:9](=[O:10])[O:8][CH2:7]2.Cl[C:13]1[N:18]=[C:17]([O:19][CH3:20])[N:16]=[C:15]([O:21][CH3:22])[N:14]=1.Cl>C1COCC1.O>[Cl:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[C:9](=[O:10])[O:8][C:7]2([C:13]1[N:18]=[C:17]([O:19][CH3:20])[N:16]=[C:15]([O:21][CH3:22])[N:14]=1)[C:13]1[N:18]=[C:17]([O:19][CH3:20])[N:16]=[C:15]([O:21][CH3:22])[N:14]=1

참가 물질

6

반응물 3

HCID 313Hydrochloric AcidHCID 184502-Chloro-4,6-dimethoxy-1,3,5-triazineHCID 2991747-Chlorophthalide

생성물 1

HCID 190506757-Chloro-3,3-bis(4,6-dimethoxy-1,3,5-triazin-2-yl)phthalide

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매3회

반응 조건

온도
-70 °C

실험 절차

1.48 g of 7-chlorophthalide are dissolved in 80 ml of THF. The solution is cooled to -70° C. and 1.5M IDA in THF (6 ml) is syringed in at -70° C. over 3 min. Stirring is continued for 15 min at -70°, 1.54 g of 2-chloro-4,6-dimethoxy-1,3,5-triazine in 50 ml of THF added dropwise and the mixture is then allowed to warm to -20°. The mixture is again cooled to -70°, and 1 ml of conc. HCl in 10 ml of water is added. The mixture is stirred for 25 min and allowed to warm to RT and the THF is removed by evaporation. The residue is partitioned between CH2Cl2 and water (50 ml each) and the aqueous phase extracted with an additional 30 ml of CH2Cl2. The combined organic phases are washed with 30 ml of water and concentrated to give a yellow gum. This is flash chromatographed on silica gel using 60/40 hexane/ethyl acetate (1000 ml), ethyl acetate (400 ml), 80/20 acetone/methanol (500 ml) (30 fractions×50 ml, 1×200 ml). Fractions 21 and 22 yielded a yellow gum which upon recrystallization from hexane yielded title product m.p. 126°-127° as a yellow solid.

후처리

  1. temperatureto warm to -20°
  2. temperatureThe mixture is again cooled to -70°
  3. stirringThe mixture is stirred for 25 min
  4. temperatureto warm to RT
  5. customthe THF is removed by evaporation
  6. customThe residue is partitioned between CH2Cl2 and water (50 ml each)
  7. extractionthe aqueous phase extracted with an additional 30 ml of CH2Cl2
  8. washThe combined organic phases are washed with 30 ml of water
  9. concentrationconcentrated
  10. customto give a yellow gum
  11. customThis is flash chromatographed on silica gel using 60/40 hexane/ethyl acetate (1000 ml), ethyl acetate (400 ml), 80/20 acetone/methanol (500 ml) (30 fractions×50 ml, 1×200 ml)
  12. customFractions 21 and 22 yielded a yellow gum which
  13. customupon recrystallization from hexane

출처 및 근거

ORD 기록
ord-6506f8b033044c95aea80276896910ff
출처 데이터셋
uspto-grants-1996_10
특허 번호
US05561101

반응 노트

불러오는 중…