1,2-Dimethoxyethane → 3'-Chloro-2-fluoro-6-methoxy-3-(4-nitro-benzyl)-biphenyl

HRID 1632029ノート

反応式

HRID 1632029 の反応式
Br[CH2:2][C:3]1[C:4]([F:18])=[C:5]([C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([Cl:17])[CH:12]=2)[C:6]([O:9][CH3:10])=[CH:7][CH:8]=1.[N+:19]([C:22]1[CH:27]=[CH:26][C:25](B(O)O)=[CH:24][CH:23]=1)([O-:21])=[O:20].P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(COC)OC>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(O)C>[Cl:17][C:13]1[CH:12]=[C:11]([C:5]2[C:6]([O:9][CH3:10])=[CH:7][CH:8]=[C:3]([CH2:2][C:25]3[CH:26]=[CH:27][C:22]([N+:19]([O-:21])=[O:20])=[CH:23][CH:24]=3)[C:4]=2[F:18])[CH:16]=[CH:15][CH:14]=1

参加物

7

反応物 4

HCID 80711,2-DimethoxyethaneHCID 62657Potassium Phosphate, TribasicHCID 27735524-Nitrophenylboronic acidHCID 577037013-Bromomethyl-3'-chloro-2-fluoro-6-methoxy-biphenyl

生成物 1

HCID 580201863'-Chloro-2-fluoro-6-methoxy-3-(4-nitro-benzyl)-biphenyl収率 76%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 702Ethanol溶媒

反応条件

温度
60 °C

実験手順

In a 40 mL vial equipped with a stir bar was placed 3-bromomethyl-3′-chloro-2-fluoro-6-methoxy-biphenyl (I-33, 400 mg, 1.21 mmol), 4-nitrophenylboronic acid (420 mg, 1.45 mmol), potassium phosphate (tribasic) (514 mg, 2.42 mmol), dimethoxyethane (3.5 mL) and 50% aqueous ethanol (3.5 mL). After degassing with nitrogen for 15 minutes, tetrakis(triphenylphosphine)palladium(0) (140 mg, 0.121 mmol) was added. The mixture was heated to 60° C. for 18 hours and then the palladium catalyst was removed by filtering through Celite. To the filtrate were added water (50 mL) and a saturated ammonium chloride solution (50 mL). After extracting with ethyl acetate (3×50 mL), the organic portions were combined, washed with brine (75 mL), dried (MgSO4) and concentrated. The crude material was purified by silica gel chromatography utilizing 20% ethyl acetate/hexanes as eluent to produce 342 mg (76%) of 3′-chloro-2-fluoro-6-methoxy-3-(4-nitro-benzyl)-biphenyl (I-34) as a yellow solid. MS (APCI−): 370.1 (M−1).

後処理

  1. customIn a 40 mL vial equipped with a stir bar
  2. customAfter degassing with nitrogen for 15 minutes
  3. customthe palladium catalyst was removed
  4. filtrationby filtering through Celite
  5. additionTo the filtrate were added water (50 mL)
  6. extractionAfter extracting with ethyl acetate (3×50 mL)
  7. washwashed with brine (75 mL)
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated
  10. customThe crude material was purified by silica gel chromatography

出典と根拠

ORDレコード
ord-8468ac35d8634dceb4a5a52c0da83393
出典データセット
uspto-grants-2014_07
特許番号
US08791267B2

反応ノート

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