2-bromo-7-iodo-3-(trifluoromethoxy)-9H-xanthen-9-one → 2-bromo-7-iodo-9-methyl-3-(trifluoromethoxy)-9H-xanthen-9-ol

HRID 335946

反応式

HRID 335946 の反応式
[Br:1][C:2]1[C:15]([O:16][C:17]([F:20])([F:19])[F:18])=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([I:21])=[CH:9][CH:10]=3)[C:5](=[O:22])[C:4]=2[CH:3]=1.[CH3:23][Mg]Cl.BrC1C=CC2OC3C(=NC(Cl)=CC=3F)C(=C)C=2C=1>C1COCC1>[Br:1][C:2]1[C:15]([O:16][C:17]([F:18])([F:20])[F:19])=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([I:21])=[CH:9][CH:10]=3)[C:5]([CH3:23])([OH:22])[C:4]=2[CH:3]=1

参加物

5

反応物 3

HCID 674359492-bromo-7-iodo-3-(trifluoromethoxy)-9H-xanthen-9-oneHCID 866584728-bromo-2-chloro-4-fluoro-10-methylene-10H-chromeno[3,2-b]pyridineHCID 178418332HCID 178418332、化合物

生成物 1

HCID 674395142-bromo-7-iodo-9-methyl-3-(trifluoromethoxy)-9H-xanthen-9-ol収率 100.2%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

A RBF was charged with 2-bromo-7-iodo-3-(trifluoromethoxy)-9H-xanthen-9-one (2.94 g, 6.06 mmol) and THF (33.7 mL). The black suspension was cooled to −78° C. using an i-PrOH/dry ice bath. Methylmagnesium chloride (3.0 M in THF, 4.45 mL, 13.34 mmol) was added dropwise. After 2 h, LCMS showed olefin product. The whole was quenched with satd' aq NH4Cl (20 mL) at 0° C., water (50 mL) and diluted with EtOAc (100 mL). The product was extracted with EtOAc (3×50 mL). The organic layer was separated, dried over MgSO4, filtered, and concentrated to afford yellow oil. 1H NMR confirmed the tertiary alcohol, 2-bromo-7-iodo-9-methyl-3-(trifluoromethoxy)-9H-xanthen-9-ol (3.04 g, 6.07 mmol, 100% yield). LCMS (ESI) calcd for C15H9BrF3IO3: [M]+=500. Found [M−H2O+H]+=483. Dehydration took place on LCMS to give the olefin, 2-bromo-7-iodo-9-methylene-3-(trifluoromethoxy)-9H-xanthene). This material was carried on to the next step.

後処理

  1. customThe whole was quenched with satd' aq NH4Cl (20 mL) at 0° C.
  2. additionwater (50 mL) and diluted with EtOAc (100 mL)
  3. extractionThe product was extracted with EtOAc (3×50 mL)
  4. customThe organic layer was separated
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto afford yellow oil

出典と根拠

ORDレコード
ord-2b57d64cb3e64d8593bb940f65c347c7
出典データセット
uspto-grants-2014_11
特許番号
US08883782B2

関連ノート

読み込み中…