1,2-Dibromo-1,1,2,2-tetrafluoroethane → 7-Bromo-6-chloro-3-(2-fluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine

HRID 2306596노트

반응식

HRID 2306596 반응식
[Cl:1][C:2]1[C:3]([Si](C)(C)C)=[CH:4][C:5]2[N:6]([C:8]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=3[F:17])=[N:9][N:10]=2)[N:7]=1.[Br:22]C(F)(F)C(F)(F)Br>CCCC[N+](CCCC)(CCCC)CCCC.C1C=CC([Sn-](F)(F)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1COCC1.ClCCl>[Br:22][C:3]1[C:2]([Cl:1])=[N:7][N:6]2[C:8]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=3[F:17])=[N:9][N:10]=[C:5]2[CH:4]=1

참가 물질

6

반응물 2

HCID 313011,2-Dibromo-1,1,2,2-tetrafluoroethaneHCID 154861756-Chloro-3-(2-fluorophenyl)-7-(trimethylsilyl)-[1,2,4]triazolo[4,3-b]pyridazine

생성물 1

HCID 154861767-Bromo-6-chloro-3-(2-fluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine수율 88%

시약·촉매·용매 3

HCID 1784490421-Butanaminium, N,N,N-tributyl-, (TB-5-11)-difluorotriphenylstannate(1-) (1:1)촉매HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매

실험 절차

Tetrabutylammonium difluorotriphenylstannate (6.8 g, 10.8 mmol) was added to a suspension of 6-chloro-3-(2-fluorophenyl)-7-(trimethylsilyl)-1,2,4-triazolo[4,3-b]pyridazine (3.17 g, 9.88 mmol), prepared as in Example 25 Step c), and 1,2-dibromotetrafluoroethane (6.0 ml, 50 mmol) in anhydrous THF (75 ml) and-the mixture was stirred at room temperature under nitrogen for 18 h. The mixture was diluted with dichloromethane (100 ml), filtered and the filtrate was concentrated. Flash column chromatography on silica gel, eluting with 50-100% EtOAc-hexane, gave 7-bromo-6-chloro-3-(2-fluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine (2.84 g, 88%) as an off-white solid; 1H NMR (360 MHz, CDCl3) δ 7.31 (1H, dd, J=10 and 10 Hz), 7.36 (1H, ddd, J=8, 8 and 1 Hz), 7.57-7.63 (1H, m), 7.87 (1H, ddd, J=7, 7 and 2 Hz), 8.49 (1H, s); MS (ES+) m/e 327/329/331 [MH]+.

후처리

  1. filtrationfiltered
  2. concentrationthe filtrate was concentrated
  3. washFlash column chromatography on silica gel, eluting with 50-100% EtOAc-hexane

출처 및 근거

ORD 기록
ord-aac454a7aaa745d1a8cd96a9ae6472b5
출처 데이터셋
uspto-grants-2004_12
특허 번호
US06828322B2

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