LETTER
TsCl as Catalyst for the Synthesis of a-Aminophosphonates
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(17) TsCl (1 mmol, 0.18 g) was added to a stirred mixture of
diethyl phosphite (0.012 mol) in CH2Cl2 (10 mL) at r.t.
Imine (0.01 mol) was added to the reaction mixture and the
mixture was stirred for 2–4 h at r.t. H2O (50 mL) was added
to the reaction mixture and the organic layer was extracted
with EtOAc (4 × 50 mL), dried with CaCl2, and the solvent
was evaporated to give the crude product. Chromatography
on silica gel with EtOAc–n-hexane (1:9 → 5:5) and
evaporation of the solvent under reduced pressure gave the
pure products in 65–85% yields. All the products gave
satisfactory spectral data in accordance with the assigned
structures and literature reports.12a,16b
Diethyl[phenyl(phenylamino)methyl]phosphonate (2a):
1H NMR (250 MHz, CDCl3): d = 1.13 (t, J = 7.0 Hz, 3 H),
1.29 (t, J = 7.0 Hz, 3 H), 3.60–3.75 (m, 1 H), 3.85–4.01 (m,
1 H), 4.03–4.22 (m, 2 H), 4.76 (d, JHP = 24.2 Hz, 1 H), 6.59
(d, J = 8.5 Hz, 2 H), 6.69 (t, J = 7.2 Hz, 1 H), 7.11 (t, J = 8.3
Hz, 2 H), 7.22–7.52 (m, 5 H). 31P NMR (101.2 MHz, CDCl3,
H3PO4): d = 23.31. 13C NMR (62.9 MHz, CDCl3): d = 16.2
(d, JPC = 6.3 Hz), 16.4 (d, JPC = 6.3 Hz), 56.1 (d, JPC = 150.3
Hz), 63.1, 63.2, 113.8, 118.3, 127.9 (d, JPC = 5.7 Hz), 128.5
(d, JPC = 2.5 Hz), 129.2, 136.0 (d, JPC = 2.5 Hz), 146.3 (d,
JPC = 14.5 Hz).
Synlett 2008, No. x, A–C © Thieme Stuttgart · New York