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2 of 17
UCHIYAMA et Al.
|
1
0-n-Butyl-9-ethyl-2,3,6,7,14,15-hexamethyl-9-phos-
9-Ethyl-2,3,6,7,14,15-hexamethyl-9-phosphonio-
phonio-10-stannatriptycene iodide 12: white solid [de-
10-bismatriptycene iodide 16: pale yellow solid [m.p.
1
1
comp. 153~158°C], H NMR (600 MHz, CDCl ) δ = 1.15
293~295°C (decomp.)], H NMR (600 MHz, CDCl )
3
3
3
3
3
(
3H, t, J = 7.2 Hz), 1,70-1.75 (2H, m), 2.12 (3H, dt,
δ = 2.13 (3H, dt,
J
= 17.6 Hz,
(9H, s), 2.29 (9H, s), 3.81 (2H, dq,
J
= 7.52 Hz), 2.27
HH
PH
HH
3
3
2
J
= 18.6 Hz,
J
= 7.2 Hz), 2.18-2.21 (2H, m), 2.26
J
= 13.5 Hz,
PH
HH
PH
3
3
4
3
(
9H, s), 2.33 (9H, s), 2.43 (2H, t, J = 7.2 Hz), 4.09
J
= 7.59 Hz), 8.11 (3H, d, J = 10.2 Hz), 8.29 (3H, d,
HH
HH PH
2
3
13
1
(
2H, dq,
J
= 13.2 Hz,
J
= 7.2 Hz), 7.61 (3H, d,
J
= 3.0 Hz), C{ H} NMR (151 MHz, CDCl ) δ = 7.67
PH
HH
PH
3
3
4
3
3
2
J
= 3.6 Hz, J = 46.2 Hz), 7.93 (3H, d, J = 12.0 Hz,
(p, J = 5.74 Hz), 10.6 (s, J = 49.7 Hz), 19.73 (p), 19.92
PH
SnH
PH
PC
PC
4
13
1
1
2
JSnH = 15.0 Hz),
C{ H} NMR (151 MHz, CDCl )
(p), 122.8 (t,
J
= 94.6 Hz), 131.6(q,
J
= 14.3 Hz),
3
PC
PC
2
1
3
3
δ = 8.28 (p, J = 5.89 Hz), 9.05 (s, J = 50.0 Hz), 10.9
138.2 (q, J = 12.2 Hz), 139.2 (t, J = 12.2 Hz), 142.3
PC
PC
PC
PC
4
4
31
(
s, J = 3.17 Hz), 13.7 (t), 19.8 (p), 19.9 (p), 27.7 (s),
(q, J = 3.62 Hz), 159.0 (q), P NMR (162 MHz, CDCl )
PC
P
C
3
1
3
2
8.7 (s), 126.0 (q, J = 85.2 Hz), 132.3 (t, J = 12.8 Hz,
δ = 54.4 (s), ESI-MS [CH CN]: Found: m/z 581.1807, Calcd
PC
PC
3
3
2
J
= 26.4 Hz), 137.6 (t,
J
= 13.0 Hz), 138.5 (q,
for C H Bi: 581.1805.
SnC
SnC
26 29
3
2
3
JPC = 13.0 Hz), 140.7 (q, JPC = 3.17 Hz), 146.1 (q,
JPC = 10.3 Hz),
31
1
P
{ H} NMR (243 MHz, CDCl )
3
4
.4
Data of 2,3,6,7,14,15-Hexamethyl-9-
3
119
1
|
δ = −7.37 (t, J = 237.9 Hz), Sn{ H} NMR (224 MHz,
SnP
phospha-10-heteratriptycene 9-oxide
3
CDCl ) δ = −232.3 (d, J = 257.4 Hz), ESI-MS [CH CN]:
3
SnP
3
Found: m/z 549.1734, Calcd for C H PSn: 549.1728.
Phosphaheteratriptycene oxides were purified from the crude
materials, which were obtained by Wittig reactions of non-
stabilized phosphonium ylides bearing a phosphaheteratrip-
tycene skeleton with benzaldehyde, by the following method.
The crude materials were obtained by evaporation of THF
as a reaction solvent and filtrated with a membrane together
with 3 mL of CHCl . The CHCl solution was introduced to
3
0
38
9
-Ethyl-2,3,6,7,14,15-hexamethyl-9-phosphonio-
1
0-phosphphatriptycene iodide 13: Pale yellow solid
1
[
(
(
(
m.p.342.5~343.5°C], H NMR (600 MHz, CDCl ) δ = 2.15
3
3
3
3H, dt, J = 19.8 Hz, J = 7.2 Hz), 2.28 (9H, s), 2.35
PH
HH
2
3
9H, s), 4.29 (2H, dq, J = 9.00 Hz, J = 7.8 Hz), 7.80
PH
HH
3
4
3
3H, dd, J = 6.6 Hz, J = 4.2 Hz), 8.04 (3H, d, J =
PH
HH
PH
3
3
1
3
1
1
1.4 Hz), C{ H} NMR (151 MHz, CDCl ) δ = 7.49 (p,
a 908 gel permeation chromatography (GPC) and separated
a few fraction to get a fraction containing a target phosphine
oxide with a retention time at 45-50 min. The obtained frac-
tion was separated by preparative thin layer chromatography
(PTLC) to get a pure target phosphine oxide.
3
2
1
J
= 7.35 Hz), 7.90 (s,
J
= 46.3 Hz), 19.7 (p), 19.8
PC
PC
1
2
(
p), 124.8 (q, J = 74.7 Hz), 132.1 (t, J = 11.1 Hz),
PC
PC
2
3
1
36.8 (t,
J
= 33.7 Hz,
J
= 8.55 Hz), 139.4 (q,
PC
PC
3
1
2
J
= 12.3 Hz), 140.7 (q, J = 21.1 Hz, J = 10.2 Hz),
PC
PC
PC
3
31
1
1
41.6 (q, J = 13.4 Hz), P { H}NMR (243 MHz, CDCl )
2,3,6,7,14,15-Hexamethyl-10-phenyl-9-phospha-10-
silatriptycene 9-oxide 33: compound 33 decomposed during
its purification because of unstable in the air.
PC
3
δ = −2.56 (s), −59.8 (s), ESI-MS [CH CN]: Found: m/z
3
4
03.1742, Calcd for C H P : 403.1739.
26 29 2
9
-Ethyl-2,3,6,7,14,15-hexamethyl-9-phosphonio-
2,3,6,7,14,15-Hexamethyl-10-phenyl-9-phospha-10-
1
0-arsatriptycene iodide 14: Pale yellow solid [m.p.
germatriptycene 9-oxide 34: Pale yellow solid [decomp.
1
1
3
31~334°C], H NMR (600 MHz, CDCl ) δ = 2.17 (3H, dt,
313.0~314.5°C], H NMR (600 MHz, CDCl ) δ = 2.20
3
3
3
3
4
J = 19.2 Hz, J = 7.8 Hz), 2.28 (9H, s), 2.36 (9H, s),
(9H, s), 2.25 (9H, s), 7.48 (3H, d, J = 3.6 Hz), 7.69-
PH
HH
PH
2
3
2
4
.27 (2H, dq, J = 13.8 Hz, J = 7.2 Hz), 7.79 (3H, d,
7.74 (3H, m), 8.04 (3H, d, J = 12.0 Hz), 8.07-8.09
PH
HH
PH
4
3
13
1
13
1
J = 4.2 Hz), 8.05 (3H, d, J = 10.8 Hz), C{ H} NMR
(2H, m), C{ H} NMR (151 MHz, CDCl ) δ = 19.5 (p),
PH
PH
3
2
4
(
151 MHz, CDCl ) δ = 7.62 (p, J = 5.74 Hz), 8.34 (s,
19.7 (p), 127.4 (q, J = 3.17 Hz), 129.4 (t), 130.8 (t),
3
PC
PC
1
1
2
3
J
= 47.4 Hz), 19.8 (p), 19.9 (p), 122.1 (q, J = 91.7 Hz),
131.0 (t, J = 7.7 Hz), 133.0 (t, J = 12 Hz), 134.5
PC
PC
PC PC
2
3
1
1
32.2 (t, J = 12.8 Hz), 135.9 (t, J = 9.21 Hz), 139.3
(q), 135.94 (t), 135.97 (q, J = 100.1 Hz), 136.8 (q,
PC
PC
PC
3
4
3
4
2
(
q, J = 12.1 Hz), 141.5 (q, J = 2.57 Hz), 143.8 (q,
J
= 11.5 Hz), 137.7 (q, J = 2.3 Hz), 142.2 (q, J
PC
PC
PC PC PC
2
31
1
31
1
J
= 6.95 Hz), P { H}NMR (243 MHz, CDCl ) δ = 1.32
=12.4 Hz), P{ H} NMR (243 MHz, CDCl ) δ = 1.65
PC
3
3
(
s), ESI-MS [CH CN]: Found: m/z 447.1214, Calcd for
(s), ESI-MS [CH CN]: Found: m/z 511.1241, Calcd for
3
3
C H AsP: 447.1217.
C H GeOP+H: 511.1241.
2
6
29
30 29
9
-Ethyl-2,3,6,7,14,15-hexamethyl-9-phosphonio-
2,3,6,7,14,15-Hexamethyl-10-phenyl-9-phospha-
1
0-stibatriptycene iodide 15: Pale yellow solid [m.p.
10-stannatriptycene 9-oxide 35: White solid [m.p
1
7]
1
1
2
38~341°C, lit m.p. 237~241°C], H NMR (600 MHz,
305.1~307.9°C], H NMR (600 MHz, CDCl ) δ = 2.21
3
3
3
4
CDCl ) δ = 2.16 (dt, J = 18.6 Hz, J = 7.2 Hz, 3H,
(9H, s), 2.26 (9H, s), 7.54 (3H, d,
J
= 3.60 Hz),
3
PH
HH
PH
H ), 2.27 (s, 9H, H ), 2.36 (s, 9H, H ), 2.36 (s, 9H, H ),
7.64-7.69 (3H, m), 7.94-7.75 (2H, m), 8.14 (3H, d,
Et
Me
Me
Me
2
3
3
4
13
1
4
.20 (dq, J = 13.2 Hz, J = 7.6 Hz, 2H, H ), 7.85 (d,
J
= 11.4 Hz,
J = 19.8 Hz),
SnH
C{ H}
NMR
PH
HH
Et
PH
4
3
J
= 3.6 Hz, 3H, 4,5,16-H), 8.01 (d, J = 10.8 Hz, 3H,
(151 MHz, CDCl ) δ = 19.48 (p), 19.54 (p), 129.8 (t), 130.8
3
PH
PH
3
1
1
2
3
1
,8,13-H), P{ H} NMR (243 MHz, CDCl ) δ = 12.2 (s).
(t), 131.9 (t, J = 8.15 Hz), 136.00 (t, J = 13.4 Hz),
PC PC
3