Reaktionsgleichung
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([CH:10](O)[CH3:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].[P:13]([Cl:16])(Cl)Cl.[CH:17]([N:20]([Si](C)(C)C)[CH:21]([CH3:23])[CH3:22])([CH3:19])[CH3:18].CC[O:30]CC>>[Cl:16][P:13]([N:20]([CH:21]([CH3:23])[CH3:22])[CH:17]([CH3:19])[CH3:18])[O:30][CH2:11][CH2:10][C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1Komponenten
Versuchsvorschrift
p-Nitrophenylethanol (4.16 g; 25 mmole) was added portion wise to a solution of freshly distilled PCl3 (14 ml; 0.16 mole) in absolute ether (40 ml) at -30° C. under a nitrogen atmosphere within 45 min. The reaction mixture was stirred at r.t. for 1.5 h and the solvent and excess PCl3 were then removed in vacuo at 0° C. The residue was treated with N,N-diisopropyl-trimethylsilylamine (Preparation 5a) (4.33 g; 25 mmole) at 0° C. under a nitrogen atmosphere for 30 min and then at r.t. for 20 h. The resulting trimethylsilyl chloride was removed under high vacuum at r.t. to yield a syrupy pale yellow product (7.1 g; 85%) which crystallized upon storage at -20° C. This material was then used for the subsequent phosphitylation reactions. 1H-NMR (CDCl3): 8.1-8.2 (m, 2H, o to NO2); 7.39-7.43 (m, 2H, m to NO2); 4.04-4.18 (m, 2H, P--O--CH2); 3.63-3.79 (m, 2H, N--CH); 3.07-3.13 (t, 2H, P--O--C--CH2); 1.14-1.27 (2d, 12H, N--C--CH3). 31P-NMR (CDCl3): 181.60 ppm.
Aufarbeitung
- customthe solvent and excess PCl3 were then removed in vacuo at 0° C
- waitat r.t. for 20 h
- customThe resulting trimethylsilyl chloride was removed under high vacuum at r.t.
- customto yield a syrupy pale yellow product (7.1 g; 85%) which
- customcrystallized upon storage at -20° C
Quellen und Nachweise
- ORD-Eintrag
- ord-13eb5aae9ad342ff8cf802195bed0431
- Quelldatensatz
- uspto-grants-1999_01
- Patentnummer
- US05863905
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