ORDER
REPRINTS
ORGANOPHOSPHORUS CHEMISTRY. III
3381
heat the vessel, but to absorb the reaction mixture if the vessel were to
shatter. The vessel and crystallizing dish are then placed in the microwave
oven and heated for the appropriate time on high power (1100 Watt).
Once the heating cycle is complete and the crystallizing dish and
vessel have cooled to ambient temperature, the vessel is opened and the
mixture purified by fractional distillation or rotary evaporation as
necessary.
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8
Methyltriphenylphosphonium iodide (3a): mp 228–231 C, Lit mp
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13
1
2
3
1
30–234 C. H NMR d: 7.83–7.76 (m, 6H), 7.72–7.67 (m, 4H), 3.33 (d,
H, J ¼ 13.3). C NMR d: 135.01 (d, J ¼ 3.0 Hz), 133.13 (d, J ¼ 10.7 Hz),
30.32 (d, J ¼ 12.9 Hz), 118.92 (d, J ¼ 88.7 Hz), 10.76 (d, J ¼ 57.0 Hz).
3
1
P NMR d: 21.5.
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(
Ethoxycarbonylmethyl)triphenylphosphonium bromide (3b): mp 153 C
ꢀ
4
1
(
(
4
dec), Lit mp 151 C (dec). H NMR d: 7.95–7.88 (5H, m), 7.82–7.77
3H, m), 7.71–7.64 (5H, m), 7.35–7.28(2H, m), 5.58(2H, d, J ¼ 13.8Hz),
1
3
.04 (2H, q, J ¼ 7.1 Hz), 1.07 (3H, t, J ¼ 7.2). C NMR d: 164.39 (d,
J ¼ 3.5 Hz), 135.16 (d, J ¼ 2.9 Hz), 133.95 (d, J ¼ 10.6 Hz), 130.25 (d,
J ¼ 13.1 Hz), 117.91 (d, J ¼ 89.0 Hz), 62.83, 33.18 (d, J ¼ 56.3 Hz), 13.71.
3
1
P NMR d: 20.7.
Benzyltriphenylphosphonium bromide (3c): mp 283–285 C, Lit mp
ꢀ
4
ꢀ
1
2
87–291 C. H NMR d: 7.79–7.71 (8H, m), 7.67–7.60 (5H, m), 7.41–7.29
(
2H, m), 7.25–7.20 (1H, m), 7.14–7.08(4H, m), 5.40 (2H, d, J ¼ 14.4 Hz).
1
3
C NMR d: 134.96 (d, J ¼ 2.9 Hz), 134.35 (d, J ¼ 9.9 Hz), 131.47 (d,
J ¼ 5.7 Hz), 130.11 (d, J ¼ 12.5 Hz), 128.78 (d, J ¼ 3.5 Hz), 128.36
d, J ¼ 3.9 Hz), 127.08(d, J ¼ 8.6 Hz), 117.75 (d, J ¼ 85.8 Hz), 30.83 (d,
(
3
1
J ¼ 46.8Hz). P NMR d: 23.0.
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9
ꢀ
1
Diethyl methylphosphonate (5a): bp 190 C, Lit bp 194 C. H NMR d:
1
3
4
6
.10 (m, 4H), 1.46 (d, 3H, J ¼ 17.6 Hz), 1.33 (t, 6H, J ¼ 7.1 Hz). C NMR d:
3
1
1.14 (d, J ¼ 6.3 Hz), 16.10 (d, J ¼ 6.3 Hz), 10.88 (d, J ¼ 144.2 Hz). P NMR
d: 30.3.
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9
Triethyl phosphonoacetate (5b): bp 174–176 C, (20 mmHg), Lit bp
1
1
1
(
(
42–145 (9 mmHg). H NMR d: 4.18(m, 6H), 2.97 (d, 2H, J ¼ 21.6 Hz),
1
3
.35 (t, 6H, J ¼ 7.1 Hz), 1.29 (t, 3H, J ¼ 6.1 Hz). C NMR d: 165.51
d, J ¼ 5.9 Hz), 62.37 (d, J ¼ 6.3 Hz), 61.25, 34.07 (d, J ¼ 134.2 Hz), 16.04
3
1
d, J ¼ 6.2 Hz), 13.81. P NMR d: 19.7.
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9
Diethyl benzylphosphonate (5c): bp 168–170 C (20 mmHg), Lit bp
1
1
06–108(1 mmHg). H NMR d: 7.35 (m, 5H), 4.03 (m, 4H), 3.15 (d, 2H,
1
3
J ¼ 21.6 Hz), 1.23 (t, 6H, J ¼ 7.0 Hz). C NMR d: 131.34 (d, J ¼ 9.1 Hz),
1
29.51 (d, J ¼ 6.5 Hz), 128.25 (d, J ¼ 3.0 Hz), 126.59 (d, J ¼ 3.5 Hz), 61.83
3
1
(
d, J ¼ 6.8Hz), 33.49 (d, J ¼ 138.0 Hz), 16.10 (d, J ¼ 5.9 Hz). P NMR
d: 26.3.