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

HRID 1191968Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1191968
[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

Komponenten

6

Edukt 2

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

Produkt 1

HCID 582885584-Tetrahydropyranyloxy-4'-trifluormethyltolan

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 7912DiisopropylamineLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-dc120c2229c945e49e99189186c7034d
Quelldatensatz
uspto-grants-2014_03
Patentnummer
US08680142B2

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