472
Bull. Chem. Soc. Jpn. Vol. 83, No. 5 (2010) BCSJ AWARD ARTICLE
removed under reduced pressure. The residue was separated by
GPLC to afford 1,2-diphosphacyclohex-4-ene derivative 29
(37.9 mg, 40.1 ¯mol, 67%). 29: yellow crystals, mp: 198 °C
After heating at 120 °C for 6 h, the reaction mixture was filtered
through Celiteµ with toluene. The solvent of the filtrate was
removed under reduced pressure, and then the residue was
separated by GPLC to afford N-phenylmaleimide adduct 31b
(53.7 mg, 51.7 ¯mol, 86%). 31b: orange crystals, mp: 232 °C
1
(decomp.). H NMR (400 MHz, C6D12, 50 °C): ¤ ¹0.33 (br s,
18H), 0.15 (s, 18H), 0.23 (s, 27H), 1.65 (d, J = 2.9 Hz, 3H),
2.10 (s, 3H), 2.40 (dt, J = 12.6, 10.2 Hz, 1H), 2.51 (dd, J =
15.4, 2.8 Hz, 1H), 3.19-3.31 (m, 1H), 3.36 (br s, 2H), 3.41-
1
(decomp.). H NMR (400 MHz, C6D6, r.t.): ¤ 0.348 (s, 18H),
3
0.356 (s, 18H), 0.45 (s, 27H), 2.976 (dd, JHH = 8.5, 3.1 Hz,
3.45 (m, 1H), 6.71 (s, 2H), 7.26-7.35 (m, 4H), 7.82 (d, 3JHH
=
1H), 2.982 (s, 2H), 4.60 (br d, JHH = 8.5 Hz, 1H), 4.79 (d,
3
8.5 Hz, 2H), 8.29 (s, 1H), 9.39 (d, 3JHH = 8.0 Hz, 2H);
13C{1H} NMR (100 MHz, C6D12, 50 °C): ¤ 1.83 (CH3), 2.24
(CH3), 5.93 (CH3), 20.03 (CH3), 21.40 (CH3), 22.95, 29.76 (d,
3JHH = 3.1 Hz, 1H), 6.71-6.74 (m, 2H), 6.81-6.91 (m, 3H),
3
6.96-7.03 (m, 3H), 7.14 (d, JHH = 7.5 Hz, 1H),66 7.16 (dd,
3JHH = 7.0 Hz, 4JHH = 1.4 Hz, 1H),66 7.23 (ddd, 3JHH = 7.5,
3
3
3JCP = 9.1 Hz, CH), 29.96 (d, JCP = 9.1 Hz, CH), 31.74 (dd,
7.5 Hz, 4JHH = 1.3 Hz, 1H), 7.25 (s, 2H), 7.92 (d, JHH
=
1JCP = 22.3 Hz, 2JCP = 9.1 Hz, CH2), 33.24 (dd, 1JCP = 20.6
7.5 Hz, 1H), 7.94 (d, 3JHH = 7.5 Hz, 1H); 13C{1H} NMR
2
Hz, JCP = 4.9 Hz, CH2), 125.12 (CH), 125.48 (CH), 127.80
(100 MHz, C6D6, r.t.): ¤ 1.83 (CH3), 1.88 (CH3), 5.68 (CH3),
(dd, 2JCP = 4.5 Hz, 3JCP = 2.1 Hz), 128.14 (CH), 128.57 (d,
1JCP = 21.0 Hz, 2JCP = 2.9 Hz), 129.51 (CH), 130.43 (dd,
3JCP = 20.2 Hz, 4JCP = 14.4 Hz, CH), 130.81 (d, 2JCP = 4.9
22.52, 33.18 (CH), 47.21 (CH), 49.36 (CH), 52.57 (d, JCP
=
2
1
13.2 Hz, CH), 57.05 (d, JCP = 64.3 Hz), 124.68 (CH), 125.72
(d, JCP = 19.0 Hz, CH), 125.81 (CH), 126.10 (CH), 126.51
3
3
4
Hz), 131.24 (CH), 132.86 (dd, JCP = 2.0 Hz, JCP = 2.0 Hz),
(CH), 127.06 (CH), 127.19 (CH © 2), 127.26 (br, CH), 127.62
1
2
3
1
133.03 (d, JCP = 28.0 Hz), 138.03 (dd, JCP = 9.5 Hz, JCP
=
(CH), 128.27 (CH), 128.57 (CH), 132.29, 135.74 (d, JCP
=
4.5 Hz), 146.75, 153.52; 31P NMR (121 MHz, C6D6, r.t.): ¤
¹58.2, ¹57.4 (AB quartet, 1JPP = 208 Hz). HRMS (FAB) m/z,
found: 945.4689 ([M + H]+), calcd for C50H87P2Si7 ([M +
H]+): 945.4668. Anal. Found: C, 63.38; H, 9.38%. Calcd for
C50H86P2Si7: C, 63.50; H, 9.17%.
Reaction of BbtP=P(9-Anth) (1b) with Maleic Anhydride
(30a). A C6D6 suspension (0.9 mL) of BbtP=P(9-Anth) (1b,
51.8 mg, 60.0 ¯mol) and maleic anhydride (30a, 17.8 mg,
0.182 mmol) was degassed and sealed in an NMR tube. After
heating at 120 °C for 14 h, the reaction mixture was filtered
through Celiteµ with toluene. The solvent of the filtrate was
removed under reduced pressure, and the residue was separated
by GPLC to afford maleic anhydride adduct 31a (49.1 mg,
51.1 ¯mol, 85%). 31a: orange crystals, mp: 235 °C (decomp.).
1H NMR (400 MHz, C6D6, r.t.): ¤ 0.368 (s, 18H), 0.370 (s,
18H), 0.45 (s, 27H), 2.76 (dd, 3JHH = 9.1, 3.3 Hz, 1H), 2.85 (s,
27.2 Hz), 139.84, 141.58 (d, JCP = 4.9 Hz), 143.39, 144.53,
146.42, 146.91, 174.55, 174.61; 31P NMR (121 MHz, C6D6,
r.t.): ¤ 525.8, 564.3 (AB quartet, 1JPP = 577 Hz). HRMS (FAB)
m/z, found: 1036.4352 ([M + H]+), calcd for C54H84NO2P2Si7
([M + H]+): 1036.4362. Anal. Found: C, 62.63; H, 8.09; N,
1.40%. Calcd for C54H83NO2P2Si7: C, 62.56; H, 8.07; N,
1.35%. UV-vis (hexane): -max 484 (¾ 390), 369 (sh, 2300),
328 nm (6400).
3
Reaction of BbtP=P(9-Anth) (1b) with 30 equiv of
Fumaronitrile (30c).
A C6D6 suspension (0.9 mL) of
BbtP=P(9-Anth) (1b, 51.8 mg, 60.0 ¯mol) and fumaronitrile
(30c, 141 mg, 1.81 mmol) was degassed and sealed in an NMR
tube. After heating at 120 °C for 13 h, the starting material 1b
and fumaronitrile adduct 31c were observed in the ratio of 3:97
1
as judged by the H NMR spectra together with maleonitrile
(30d).67 After the reaction mixture was filtered through Celiteµ
with toluene, the solvent of the filtrate was removed under
reduced pressure. The residue was separated by GPLC and then
PTLC (eluent: benzene, Rf = 0.5) to afford fumaronitrile
adduct 31c (47.1 mg, 50.0 ¯mol, 83%) 31c: orange crystals,
3
3
2H), 4.53 (d, JHH = 3.3 Hz, 1H), 4.55 (br d, JHH = 9.1 Hz,
3
4
1H), 6.77 (ddd, JHH = 7.5, 7.3 Hz, JHH = 1.2 Hz, 1H), 6.84
(ddd, 3JHH = 7.5, 7.3 Hz, 4JHH = 1.5 Hz, 1H), 6.92 (ddd,
3JHH = 7.3, 7.3 Hz, JHH = 1.0 Hz, 1H), 6.97 (dd, JHH = 7.3
Hz, JHH = 1.5 Hz, 1H), 7.06 (dd, JHH = 7.3 Hz, JHH = 1.2
Hz, 1H), 7.14 (ddd, JHH = 7.8, 7.3 Hz, JHH = 1.5 Hz, 1H),66
4
3
5
3
4
1
mp: 210 °C (decomp.). H NMR (400 MHz, C6D6, r.t.): ¤ 0.29
3
4
(s, 18H), 0.35 (s, 18H), 0.42 (s, 27H), 2.59 (s, 2H), 2.67 (dd,
3
3
3
7.26 (s, 2H), 7.74 (d, JHH = 7.8 Hz, 1H), 7.84 (d, JHH = 7.3
Hz, 1H); 13C {1H} NMR (100 MHz, C6D6, r.t.): ¤ 1.83 (CH3),
1.88 (CH3), 5.67 (CH3), 22.61, 33.53 (CH), 46.55 (CH), 49.94
(CH), 52.85 (d, 2JCP = 15.7 Hz, CH), 56.78 (d, 1JCP = 66.8
Hz), 124.60 (CH), 125.60 (d, 3JCP = 23.9 Hz, CH), 125.90
(CH), 126.28 (CH), 127.00 (CH), 127.32 (CH), 127.68
(CH © 2), 127.86 (CH), 134.85 (br d, 1JCP = 34.6 Hz),
138.85, 141.13 (br d, 2JCP = 10.7 Hz), 142.58, 143.98,
146.39, 147.36, 169.79; 31P NMR (121 MHz, C6D6, r.t.): ¤
3JHH = 4.1, 2.7 Hz, 1H), 3.92 (d, JHH = 2.7 Hz, 1H), 4.46 (d,
3JHH = 4.1 Hz, 1H), 6.89-7.02 (m, 4H), 7.10-7.16 (m, 2H),
3
7.20 (s, 2H), 7.65 (d, 3JHH = 7.5 Hz, 1H), 7.89 (d, JHH
=
7.5 Hz, 1H); 13C{1H} NMR (100 MHz, C6D6, r.t.): ¤ 1.84
(CH3), 1.89 (CH3), 5.63 (CH3), 22.65, 34.11 (CH), 38.13 (CH),
2
1
42.48 (d, JCP = 26.4 Hz, CH), 46.94 (CH), 56.68 (d, JCP
=
63.5 Hz), 118.29, 118.98, 125.19 (CH), 126.19 (br, CH),
126.24 (CH), 126.43 (br d, 3JCP = 26.4 Hz, CH), 127.06 (CH),
127.67 (CH), 127.71 (CH © 2), 128.20 (CH), 133.74 (d, 1JCP
=
1
2
520.3, 571.2 (AB quartet, JPP = 583 Hz). HRMS (FAB) m/z,
30.5 Hz), 139.65, 140.17, 140.42 (d, JCP = 9.1 Hz), 142.62,
146.40, 147.79; 31P NMR (121 MHz, C6D6, r.t.): ¤ 518.8, 579.4
(AB quartet, 1JPP = 592 Hz); HRMS (FAB) m/z, found:
941.4102 ([M + H]+), calcd for C48H79N2P2Si7 ([M + H]+):
941.4103. Anal. Found: C, 61.07; H, 8.36; N, 3.07%. Calcd for
C48H78N2P2Si7: C, 61.22; H, 8.35; N, 2.97%. UV-vis (hexane):
found: 961.3905 ([M + H]+), calcd for C48H79O3P2Si7
([M + H]+): 961.3889. Anal. Found: C, 59.67; H, 8.42%.
Calcd for C48H78O3P2Si7: C, 59.95; H, 8.18%. UV-vis
(hexane): -max 487 (¾ 420), 370 (sh, 2100), 323 nm (6900).
Reaction of BbtP=P(9-Anth) (1b) with N-Phenylmale-
imide (30b). A C6D6 suspension (0.9 mL) of BbtP=P(9-Anth)
(1b, 51.8 mg, 60.0 ¯mol) and N-phenylmaleimide (30b, 31.2
mg, 0.180 mmol) was degassed and sealed in an NMR tube.
-
490 (¾ 450), 369 (1900), 317 nm (7700).
max
Reaction of BbtP=P(9-Anth) (1b) with 30 equiv of
Maleonitrile (30d). A C6D6 suspension (0.9 mL) of