4-Bromotriphenylamine → Diphenyl-(4-(4,4,5,5-tetramethyl-(1,3,2)dioxaborolan-2-yl)-phenyl)-amine

HRID 917252

Reaktionsgleichung

Reaktionsgleichung von HRID 917252
C([Li])CCC.CC(C)=O.C(=O)=O.Br[C:14]1[CH:32]=[CH:31][C:17]([N:18]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:16][CH:15]=1.C(O[B:37]1[O:41][C:40]([CH3:43])([CH3:42])[C:39]([CH3:45])([CH3:44])[O:38]1)(C)C>C1COCC1>[C:19]1([N:18]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:17]2[CH:31]=[CH:32][C:14]([B:37]3[O:41][C:40]([CH3:43])([CH3:42])[C:39]([CH3:45])([CH3:44])[O:38]3)=[CH:15][CH:16]=2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Komponenten

6

Edukt 4

HCID 6428384-BromotriphenylamineHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 18522661Acetone cardiceHCID 178418339Butyllithium

Produkt 1

HCID 11639307Diphenyl-(4-(4,4,5,5-tetramethyl-(1,3,2)dioxaborolan-2-yl)-phenyl)-amineAusbeute 72,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

Following the general procedure of arylboronic ester synthesis as reported in Ranger et al., Chem. Commun. 1597-1598 (1997), incorporated herein by reference, n-butyllithium was added dropwise via syringe to a −78° C. (acetone-dry ice cooling bath) solution of 4-bromo-N,N-diphenylaniline (24 g, 0.074 mole) in 175 ml dry THF. Stirring was continued at −78° C. for an hour and then at −50° C. for an hour. The mixture was cooled to −78° C. and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17.22 g, 0.0925 mole) added via syringe in one portion. The temperature was maintained at −78° C. for three hours. The cooling bath was removed and the reaction left to warm to room temperature while standing for 12 hours. The reaction mixture was poured into saturated ammonium acetate and extracted with ether. The ether layer was dried over magnesium sulfate and concentrated to give a viscous oil. Purification by column chromatography (silica gel eluting with hexane:toluene mixtures of increasing gradient from 100% hexane to 40% hexane) gave N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline as an oil (19.9 g, 72.8% yield), which slowly crystallized to a solid on standing.

Aufarbeitung

  1. waitwas continued at −78° C. for an hour
  2. waitat −50° C. for an hour
  3. temperatureThe temperature was maintained at −78° C. for three hours
  4. customThe cooling bath was removed
  5. waitthe reaction left
  6. temperatureto warm to room temperature
  7. additionThe reaction mixture was poured into saturated ammonium acetate
  8. extractionextracted with ether
  9. dry with materialThe ether layer was dried over magnesium sulfate
  10. concentrationconcentrated
  11. customto give a viscous oil
  12. customPurification
  13. temperatureby column chromatography (silica gel eluting with hexane:toluene mixtures of increasing gradient from 100% hexane to 40% hexane)

Quellen und Nachweise

ORD-Eintrag
ord-45b42224fb4842c9994d198baa87230d
Quelldatensatz
uspto-grants-2007_09
Patentnummer
US07271406B2

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