Acetic Anhydride → 2-(3-Furyl)-4-(trifluoromethyl)phenyl acetate

HRID 1692370

Reaktionsgleichung

Reaktionsgleichung von HRID 1692370
I[C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][C:3]=1[OH:12].[C:13]([O-])(=[O:15])[CH3:14].[K+].[O:18]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19]1.C(N(CC)CC)C.C(OC(=O)C)(=O)C>CC1CCCO1.COC(C)(C)C.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:13]([O:12][C:3]1[CH:4]=[CH:5][C:6]([C:8]([F:11])([F:10])[F:9])=[CH:7][C:2]=1[C:20]1[CH:21]=[CH:22][O:18][CH:19]=1)(=[O:15])[CH3:14]

Komponenten

9

Edukt 5

HCID 7918Acetic AnhydrideHCID 8471TriethylamineHCID 517044Potassium AcetateHCID 2734358Furan-3-boronic acidHCID 115728162-Iodo-4-(trifluoromethyl)phenol

Produkt 1

HCID 594366072-(3-Furyl)-4-(trifluoromethyl)phenyl acetateAusbeute 86,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 73012-MethyltetrahydrofuranLösungsmittelHCID 15413tert-Butyl methyl etherLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

2-Iodo-4-(trifluoromethyl)phenol (9.9 g, 0.0344 mol) was dissolved in 2-methyl tetrahydrofuran (100 mL) then potassium acetate (11.8 g, 0.12 mol) and 3-furylboronic acid (5.0 g, 0.0447 mol) was added and the reaction degasses 3 times before bis(tri-tert-butylphosphine)palladium (0) (1.0 g, 0.00196 mol) was added and the reaction degassed 3 more times. The reaction was then stirred at 90° C. under nitrogen for 18 hours. The reaction was then cooled and partitioned between EtOAc (50 mL) and water (50 mL), the organic layer was separated and dried in vacuo to give a brown oil. This was dissolved in tert-butyl methyl ether (50 mL), triethylamine (7.2 mL, 0.051 mol) added then acetic anhydride (4.7 mL, 0.051 mol) and stirred for 2 hours at room temperature. The reaction was then partitioned between EtOAc (30 ml) and water (30 ml) then organic layer was dried in vacuo to give a brown oil which crystallised upon standing. This was triturated with heptane to give the title product as a pale brown solid (8.04 g, 86.6%). LCMS Rt=1.70 min. 1H NMR (400 MHz, CDCl3): δ 2.34(s, 3H), 6.67(s, 1H) 7.26(m, 1H) 7.51 (s, 1H), 7.57(d, 1H), 7.76(m 2H)

Aufarbeitung

  1. additionwas added
  2. customthe reaction degassed 3 more times
  3. temperatureThe reaction was then cooled
  4. custompartitioned between EtOAc (50 mL) and water (50 mL)
  5. customthe organic layer was separated
  6. customdried in vacuo
  7. customto give a brown oil
  8. customThe reaction was then partitioned between EtOAc (30 ml) and water (30 ml)
  9. customorganic layer was dried in vacuo
  10. customto give a brown oil which
  11. customcrystallised
  12. customThis was triturated with heptane

Quellen und Nachweise

ORD-Eintrag
ord-f95a583c83fe43d58fa2fb2af71b22f5
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08153814B2

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