Reaktion #946255

Reaktionsgleichung

PCC

benzyl alcohol

4-(diethoxyphosphorylmethyl)benzoic acid

ethyl ether

borane THF

4-(diethoxyphosphorylmethyl)benzoic acid

→

oil

Ausbeute 77.0%

4-(Diethoxyphosphorylmethyl)benzaldehyde

Ausbeute 77.0%

Lösungsmittel

CH2Cl2

CH2Cl2

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeThe reaction was quenched by slow addition of water
2. 2
   EinengenThe mixture was concentrated
3. 3
   Sonstigethe residue was partitioned between water (100 mL) and CH2Cl2 (100 mL)
4. 4
   WaschenThe aqueous layer was washed with CH2Cl2
5. 5
   WaschenThe combined organic layers were washed with water
6. 6
   Trocknendried (MgSO4)
7. 7
   Einengenconcentrated
8. 8
   Sonstigeto give a yellow oil
9. 9
   workup.WAITAfter 2 h
10. 10
    Sonstigethe organic solution was decanted from the tarry residue
11. 11
    WaschenThe residue was washed with ethyl ether (3×50 mL)
12. 12
    FiltrationThe combined organic solution was filtered through Florisil
13. 13
    Einengenconcentrated to a brown oil
14. 14
    workup.DISTILLATIONKugelrohr distillation (190° C. @ 0.05 Torr)

Vorschrift

Triethylphosphite (9.28 mL, 53.3 mmol) and α-bromo-p-toluic acid (10.4 g, 48.4 mmol) were suspended in toluene (25 mL) and the mixture was heated to reflux for 18 h. The mixture was cooled to room temperature. After 12 h, the resulting white solid was collected by suction filtration, washed with petroleum ether and dried to yield 4-(diethoxyphosphorylmethyl)benzoic acid as a white solid (10.2 g, 77%): mp 117–120° C; 1H NMR δ 1.26 (t, J=6.8 Hz, 6H), 3.24 (d, J=25.6 Hz, 2H), 4.06 (m, 4H), 7.38–7.40 (m, 2H), 8.02 (d, J=7.6 Hz, 2H), 11.4 (br s, 1H); 13C NMR δ 16.5, 16.6, 33.4, 34.8, 62.8, 62.9, 129.1, 129.2, 130.00, 130.05, 130.10, 130.48, 130.51, 137.3, 137.4, 170.1; FABMS obsd 273.0896, calcd 273.0892; Anal. Calcd. for C12H17O5P: C, 52.94; H, 6.29; Found: C, 52.92; H, 6.28. A suspension of 4-(diethoxyphosphorylmethyl)benzoic acid (9.99 g, 36.7 mmol) in anhydrous THF (40 mL) at 0° C. was treated dropwise over 10 min with borane-THF complex (40.3 mL, 40.3 mmol, 1.0 M in THF). The reaction mixture was stirred at room temperature for 4 h. The reaction was quenched by slow addition of water. The mixture was concentrated and the residue was partitioned between water (100 mL) and CH2Cl2 (100 mL). The aqueous layer was washed with CH2Cl2. The combined organic layers were washed with water, dried (MgSO4), and concentrated to give a yellow oil. Analysis by TLC and 1H NMR spectroscopy showed starting material (˜10%) and the desired benzyl alcohol. The latter (9.56 g) was dissolved in CH2Cl2 and rapidly added to a sample of PCC (10.8 g, 50.1 mmol) in CH2Cl2 (50 mL) with rapid stirring. After 2 h, ethyl ether (150 mL) was added and the organic solution was decanted from the tarry residue. The residue was washed with ethyl ether (3×50 mL). The combined organic solution was filtered through Florisil and concentrated to a brown oil. Kugelrohr distillation (190° C. @ 0.05 Torr) afforded a clear, colorless oil (6.54 g, 77%): 1H NMR δ 1.24 (t, J=7.2 Hz, 6H), 3.21 (d, J=22.4 Hz, 2H), 4.03 (m, 4H), 7.45–7.48 (m, 2H), 7.83 (d, J=7.6 Hz, 2H), 9.99 (s, 1H); 13C NMR δ 16.1, 16.2, 33.0, 34.9, 62.1, 62.2, 77.2, 129.49, 129.53, 129.6, 129.66, 129.71, 130.2, 130.2, 138.8, 138:9, 191.61, 191.63; 31P NMR δ 25.4, 25.9; FABMS obsd 257.0949, calcd 257.0943 (C12H17PO4).

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