N,N,N',N'-Tetramethylethylenediamine → 1-phenyl-2-(4-methylphenyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide

HRID 2058903Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2058903
C([Li])CCC.CN(C)CCN(C)C.[CH2:14]([NH:21][C:22]1[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][CH:23]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[C:29]1([P:35](Cl)(Cl)=[O:36])[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>CCCCCC.C1CCCCC1>[C:29]1([P:35]2(=[O:36])[C:20]3[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=3[CH2:14][N:21]2[C:22]2[CH:23]=[CH:24][C:25]([CH3:28])=[CH:26][CH:27]=2)[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1

Komponenten

7

Edukt 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 69990Phenylphosphonic dichlorideHCID 79403N-benzyl-4-methylanilineHCID 178418339Butyllithium

Produkt 1

HCID 130375031-phenyl-2-(4-methylphenyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxideAusbeute 20 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8058HexaneLösungsmittelHCID 8078CyclohexaneLösungsmittel3×

Reaktionsbedingungen

Temperatur
26 °C

Versuchsvorschrift

Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (3.9 g, 0.061 mol) in hexane was added to a solution of tetramethylethylenediamine (1.8 g, 0.0155 mol) in 30 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-benzyl-4-toluidine (5.9 g, 0.03 mol) in 30 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. The suspension containing the dilithio compound was stirred for 4 hours at 26° C. and then cooled to 0° C. A solution of phenylphosphonic dichloride (6.25 g, 0.032 mol) in 30 ml. of anhydrous cyclohexane was added dropwise to the suspension and the resulting mixture was stirred for 1.5 hours at 26° C. The reaction was quenched with the rapid addition of 6 ml. of acetic acid. The mixture was concentrated in vacuo and the resulting residue partitioned in methylene chloride and water. The layers were separated and the methylene chloride layer was washed with 5% hydrochloric acid, then water, dried over sodium sulfate and concentrated in vacuo to yield a brown-green glass. The brown-green glass was crystallized from ethyl acetate to yield light green plates which were recrystallized from toluene to yield 1-phenyl-2-(4-methylphenyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (1.9 g, 20% yield) as white crystals having a melting point of 197°-199° C. and the following analysis:

Aufarbeitung

  1. temperatureWhile maintaining
  2. customthe temperature of the reaction at 0° C.
  3. customto produce a suspension
  4. temperaturecooled to 0° C
  5. stirringthe resulting mixture was stirred for 1.5 hours at 26° C
  6. customThe reaction was quenched with the rapid addition of 6 ml
  7. concentrationThe mixture was concentrated in vacuo
  8. customthe resulting residue partitioned in methylene chloride
  9. customThe layers were separated
  10. washthe methylene chloride layer was washed with 5% hydrochloric acid
  11. dry with materialwater, dried over sodium sulfate
  12. concentrationconcentrated in vacuo
  13. customto yield a brown-green glass
  14. customThe brown-green glass was crystallized from ethyl acetate
  15. customto yield light green plates which
  16. customwere recrystallized from toluene

Quellen und Nachweise

ORD-Eintrag
ord-c77b0227f06744df86aa4e598282cefa
Quelldatensatz
uspto-grants-1982_03
Patentnummer
US04319913

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