Triethylamine → 6-Chloro-3-(2-fluorophenyl)-7-(trimethylsilyl)-[1,2,4]triazolo[4,3-b]pyridazine

HRID 1369434

반응식

HRID 1369434 반응식
[Cl:1][C:2]1[N:3]=[N:4][C:5]([NH:12][NH:13][C:14](=O)[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[F:21])=[CH:6][C:7]=1[Si:8]([CH3:11])([CH3:10])[CH3:9].BrC(Cl)(Cl)C(Cl)(Cl)Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>C(#N)C.ClCCl>[Cl:1][C:2]1[C:7]([Si:8]([CH3:11])([CH3:10])[CH3:9])=[CH:6][C:5]2[N:4]([C:14]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=3[F:21])=[N:13][N:12]=2)[N:3]=1

참가 물질

7

반응물 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 694261,2-Dibromo-1,1,2,2-tetrachloroethaneHCID 15486174N'-(6-Chloro-5-(trimethylsilyl)pyridazin-3-yl)-2-fluorobenzohydrazide

생성물 1

HCID 154861756-Chloro-3-(2-fluorophenyl)-7-(trimethylsilyl)-[1,2,4]triazolo[4,3-b]pyridazine수율 83.3%

시약·촉매·용매 2

HCID 6342Acetonitrile용매HCID 6344Dichloromethane용매

반응 조건

온도
1 °C

실험 절차

To a stirred suspension of 3-chloro-6-[2-(2-fluorobenzoyl)hydrazino]-4-(trimethylsilyl)pyridazine (9.72 g, 28.7 mmol) and 1,2-dibromotetrachloroethane (18.68 g, 57.4 mmol) in anhydrous acetonitrile (170 ml), cooled under nitrogen to 1° C., was added portionwise, over 21 min, solid triphenylphosphine (30.10 g, 115 mmol), keeping the temperature below 5° C. The mixture was stirred at 2° C. for 10 min, then anhydrous triethylamine (32.0 ml, 230 mmol) was added dropwise over 18 min, keeping the temperature below 6° C. The mixture was then stirred at 0-3° C. under nitrogen for 85 min. The mixture was then diluted with dichloromethane (150 ml) and washed with water (200 ml). The organic layer was dried (Na2SO4) and evaporated in vacuo. The residue was purified by flash chromatography (silica gel, 20-40% EtOAc/hexane) to afford 7.67 g (83%) of the title compound as a white solid; 1H NMR (360 MHz, CDCl3) δ0.48 (9H, s), 7.30 (1H. dd, Jd=10.1 and 8.8 Hz), 7.36 (1H. td, J=7.6 and 1.1 Hz), 7.58 (1H, m). 7.90 (1H, td. J=7.3 and 1.8 Hz), 8.30 (1H, s); MS (ES+) m/e 321/323 [MH]+.

후처리

  1. additionwas added portionwise, over 21 min
  2. customthe temperature below 5° C
  3. customthe temperature below 6° C
  4. stirringThe mixture was then stirred at 0-3° C. under nitrogen for 85 min
  5. washwashed with water (200 ml)
  6. dry with materialThe organic layer was dried (Na2SO4)
  7. customevaporated in vacuo
  8. customThe residue was purified by flash chromatography (silica gel, 20-40% EtOAc/hexane)

출처 및 근거

ORD 기록
ord-c58552c8d08641668f8982050cf90adc
출처 데이터셋
uspto-grants-2003_06
특허 번호
US06579875B1

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