Ethyl phosphorochloridite → Diethyl 2-[di(1-naphthyl)phosphino]phenylphosphonite

HRID 1168637

Reaktionsgleichung

Reaktionsgleichung von HRID 1168637
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[P:8]([C:19]1[C:28]2[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH:22]=[CH:21][CH:20]=1)[C:9]1[C:18]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH:12]=[CH:11][CH:10]=1.[P:29](Cl)([O:33][CH2:34][CH3:35])[O:30][CH2:31][CH3:32]>O1CCCC1>[C:9]1([P:8]([C:19]2[C:28]3[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=3)[CH:22]=[CH:21][CH:20]=2)[C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[P:29]([O:33][CH2:34][CH3:35])[O:30][CH2:31][CH3:32])[C:18]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH:12]=[CH:11][CH:10]=1

Komponenten

4

Edukt 2

HCID 68530Ethyl phosphorochloriditeHCID 11201532(2-Bromophenyl)[di(1-naphthyl)]phosphine

Produkt 1

HCID 11488538Diethyl 2-[di(1-naphthyl)phosphino]phenylphosphoniteAusbeute 81 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

Into a four-neck flask was weighed 10.00 g (22.7 mmol) of (2-bromophenyl)[di(1-naphthyl)]phosphine (6). The atmosphere of the reaction vessel fitted with a thermometer, a condenser tube, and a dropping funnel with a pressure-equalizing tube was completely replaced with nitrogen, and 100 mL of anhydrous tetrahydrofuran (hereinafter referred to as THF) was added thereto. Thereto was added dropwise 14.8 mL (23.8 mmol) of n-butyllithium-hexane (1.6 M) solution at −78° C. over a period of 30 minutes, followed by 1 hour of stirring at the same temperature. The resulting mixed solution was cooled to −78° C. and thereto was added dropwise a 10 mL THF solution of 3.92 g (23.8 mmol) of diethyl chlorophosphite (manufactured by Aldrich) over a period of 30 minutes. After the dropwise addition, a cooling bath was removed and the whole was further stirred at room temperature for 15 hours. After the completion of the reaction, THF was removed by evaporation, the residue was dissolved in 50 mL of diethyl ether, and insoluble matter was removed by filtration. The solvent was removed by evaporation and the residue was purified by active alumina column chromatography (eluent: hexane/ethyl acetate={fraction (4/1)}) to obtain the title compound (8.83 g, a pale yellow solid). Yield 81.0%.

Aufarbeitung

  1. customInto a four-neck flask was weighed
  2. customThe atmosphere of the reaction vessel fitted with a thermometer, a condenser tube, and a dropping funnel with a pressure-equalizing tube
  3. additionwas added
  4. additionThereto was added dropwise 14.8 mL (23.8 mmol) of n-butyllithium-hexane (1.6 M) solution at −78° C. over a period of 30 minutes
  5. additionThe resulting mixed solution
  6. additionAfter the dropwise addition, a cooling bath
  7. customwas removed
  8. stirringthe whole was further stirred at room temperature for 15 hours
  9. customAfter the completion of the reaction, THF
  10. customwas removed by evaporation
  11. dissolutionthe residue was dissolved in 50 mL of diethyl ether
  12. custominsoluble matter was removed by filtration
  13. customThe solvent was removed by evaporation
  14. customthe residue was purified by active alumina column chromatography (eluent: hexane/ethyl acetate={fraction (4/1)})

Quellen und Nachweise

ORD-Eintrag
ord-4bb78ea8d0d44d76be487f718ce63aa5
Quelldatensatz
uspto-grants-2003_09
Patentnummer
US06624320B2

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