Sodium Iodide → Anthrone

HRID 323695

반응식

HRID 323695 반응식
[I-].[Na+].[Li][C:4]1[C:17]2[C:16](=[O:18])[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[CH2:9][C:8]=2[CH:7]=[CH:6][CH:5]=1.[I-].S([O-])(=O)(=O)C>C1COCC1>[CH:14]1[C:15]2[C:16](=[O:18])[C:17]3[C:8](=[CH:7][CH:6]=[CH:5][CH:4]=3)[CH2:9][C:10]=2[CH:11]=[CH:12][CH:13]=1

참가 물질

5

반응물 3

HCID 5238Sodium IodideHCID 23049750HCID 23049750, 화합물HCID 178506662HCID 178506662, 화합물

생성물 1

HCID 7018Anthrone수율 75%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
100 °C

실험 절차

10,10-Bis[(2-fluoro-4-pyridinyl)methyl]-9(10H)-anthracenone (I) Two solutions are prepared. For one, 1.0 M lithium t-butoxide in THF (1.00 L, 1.00 mol) was added to a solution of anthrone (70.0 g, 0.36 mol) in THF (0.70 L) at 15-30° C. to form lithio anthrone. The second solution was prepared by mixing sodium iodide (45.0 g, 0.30 mol) VI-i (150.0 g, 0.73 mol) and THF (1.60 L) at 40° C. for 3 h to form a mixture of VI-i/VII-i. The lithio anthrone solution was added dropwise over 100 min at 40-50° C. to the iodide/mesylate solution. The reaction was aged for 1 h (the HPLC peak area of VII-i was <1%). The solution was washed with saturated aqueous brine (2×0.90 L). Volatiles were removed in vacuo and the residue was diluted with toluene (1.3 L). The solution was heated to 100° C., cooled to 90° C. and stirred with basic alumina (120 g) for 30 min. The solution was filtered through a Celite pad, concentrated by atmospheric distillation to 500 mL and cooled to 25° C. to crystallize I. Further crystallization was induced by the dropwise addition of n-heptane (0.60 L) followed by cooling to 0° C. for 2 h. The crystals were collected by filtration, washed with n-heptane (0.2 L) and dried at 60° C. in vacuo to yield 121 g of I (75% yield from anthrone, 92 HPLC wt % purity versus a reference standard).

후처리

  1. customThe second solution was prepared
  2. customto form
  3. additiona mixture of VI-i/VII-i
  4. washThe solution was washed with saturated aqueous brine (2×0.90 L)
  5. customVolatiles were removed in vacuo
  6. additionthe residue was diluted with toluene (1.3 L)
  7. temperaturecooled to 90° C.
  8. filtrationThe solution was filtered through a Celite pad
  9. concentrationconcentrated by atmospheric distillation to 500 mL
  10. temperaturecooled to 25° C.
  11. customto crystallize I
  12. customFurther crystallization
  13. additionwas induced by the dropwise addition of n-heptane (0.60 L)
  14. temperatureby cooling to 0° C. for 2 h
  15. filtrationThe crystals were collected by filtration
  16. washwashed with n-heptane (0.2 L)
  17. customdried at 60° C. in vacuo

출처 및 근거

ORD 기록
ord-63462a65f09943bf98df9ed56c02ea63
출처 데이터셋
uspto-grants-2001_04
특허 번호
US06214847B1

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