Benzene, 1-bromo-4-(trifluoromethyl)- → 4-Tetrahydropyranyloxy-4'-trifluormethyltolan

HRID 1020514ノート

反応式

HRID 1020514 の反応式
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]#[CH:15])=[CH:10][CH:9]=1.Br[C:17]1[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][CH:18]=1>C(NC(C)C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][C:8]1[CH:9]=[CH:10][C:11]([C:14]#[C:15][C:17]2[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][CH:18]=2)=[CH:12][CH:13]=1

参加物

6

反応物 2

HCID 67872Benzene, 1-bromo-4-(trifluoromethyl)-HCID 11310191P-[Tetrahydropyran-2-yloxy]phenylacetylene

生成物 1

HCID 582885584-Tetrahydropyranyloxy-4'-trifluormethyltolan

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 7912Diisopropylamine溶媒

反応条件

温度
80 °C

実験手順

A solution of 3 (12.1 g, 60 mmol) and 4-bromobenzotriflouride (14.85 g, 66 mmol) in diisopropylamine (250 ml) was heated to 30° C. under nitrogen, and the solution was degassed. Then Pd(PPh3)2Cl2 (210 mg, 0.3 mmol) and copper(I) iodide (114 mg, 0.6 mmol) were added to this clear solution. The reaction mixture was stirred for 2 hours at 80° C., and then cooled to room temperature. The salt formed during the reaction procedure was filtered off and washed well with ethyl acetate. The filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (10 ml), water (100 ml) and crushed ice (50 g), then extracted with ethyl acetate. The combined organic paste was washed with brine and dried over MgSO4. The solvent was removed in vacuo and the residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1) to give a pale yellow crystals of 4. Yield 16.6 g (80%); mp 112˜113° C.; δH(CDCl3, 300 MHz): 7.59 (s, 4H, Ar—H), 7.48 (d, J=8.7, 2H, Ar—H), 7.04 (d, J=8.7, 2H, Ar—H), 5.46 (t, J=3.1, 1H, OCHO), 3.89 (m, 1H, THP), 3.62 (m, 1H, THP), 1.86˜1.62 (m, 6H, THP).

後処理

  1. customthe solution was degassed
  2. temperaturecooled to room temperature
  3. customThe salt formed during the reaction procedure
  4. filtrationwas filtered off
  5. washwashed well with ethyl acetate
  6. customThe filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (10 ml), water (100 ml)
  7. customcrushed ice (50 g)
  8. extractionextracted with ethyl acetate
  9. washThe combined organic paste was washed with brine
  10. dry with materialdried over MgSO4
  11. customThe solvent was removed in vacuo
  12. customthe residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1)
  13. customto give a pale yellow crystals of 4

出典と根拠

ORDレコード
ord-fb1cdaf54db14de0bca10ac6ab6e342e
出典データセット
uspto-grants-2014_05
特許番号
US08716355B2

反応ノート

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