1986 Bull. Chem. Soc. Jpn., 76, No. 10 (2003)
Syntheses of 1,3-Diphenyldisiloxanes
Fig. 4. Unit-cell structure of 8.
127.6, 130.8, 133.0, 133.9; 29Si NMR (79.3 MHz) ꢀ ꢁ58:5; MS
m=z 427 (Mþ ꢁ 15). Found: Si, 12.5%. Calcd for C20H28Cl2-
O3Si2: Si, 12.6%.
Synthesis of 1,3-Di-t-butoxy-1,3-diisocyanato-1,3-diphenyl-
disiloxane (5b). A solution of t-butyl alcohol (2.96 g, 0.04
mol) and triethylamine (0.40 g, 0.004 mol) in THF (50 mL) was
ꢂ
added to a rapidly stirred cold (0 C) solution of 2 (7.89 g, 0.02
mol) in THF (80 mL). The reaction mixture was refluxed for 2
h, filtered, and distilled to give 5b.
5b Yield: 35%. Bp 161.0–162.0 ꢂC/107 Pa. IR 1078, 1131,
Fig. 5. Projection of the c axis of 8.
1
1189, 1244, 1430, 2283, 2979, 3067 cmꢁ1; H NMR (400 MHz)
reaction mixture was refluxed for 2 h, filtered, and distilled to
give 3.
ꢀ 1.34(s, 18H), 7.34(m, 4H,
m-C6H5), 7.39 (m, 2H, p-C6H5),
7.65 (m, 4H, o-C6H5); 13C NMR (100.4MHz) ꢀ 31.5, 75.6,
123.2, 128.1, 131.0, 132.0, 133.8; 29Si NMR (79.3 MHz) ꢀ
ꢁ76:2.
3 Yield: 81%. Bp 167.1–168.2 ꢂC/373 Pa. IR 1047, 1100,
1126, 1381, 1430, 2973 cmꢁ1 1H NMR (400 MHz) ꢀ 1.18 (d,
;
24H), 4.29 (m, 4H), 7.29–7.72 (m, 10H); 13C NMR (100.4
MHz) ꢀ 25.1, 64.8, 127.8, 130.3, 133.0, 134.7; 29Si NMR (79.3
MHz) ꢀ ꢁ68:1(s); MS m=z 403 (Mþ ꢁ 59). Found: Si, 12.4%.
Calcd for C24H38O5Si2: Si, 12.2%.
Synthesis of 1,1,3,3-Tetrakis(diethylamino)-1,3-diphenyldi-
siloxane (6). A solution of ethyl bromide (23.97 g, 0.22 mol)
in diethyl ether was added to a rapidly stirred suspension of mag-
nesium (5.35 g, 0.22 mol) in diethyl ether (100 mL) at 20 ꢂC, and
the mixture was refluxed for 2 h. A solution of diethylamine
(16.06 g, 0.22 mol) was added to the mixture being stirred at 20
ꢂC, and the mixture was refluxed for 2 h. A solution of 1
(20.24g, 0.055 moꢂl) in benzene (50 mL) was added to the mixture
being stirred at 0 C, refluxed, filtered, and distilled to give 6.
6 Yield: 40%. Bp 182.6–183.5 ꢂC/160 Pa. IR 1031, 1099,
Synthesis
of
1,3-Diisocyanato-1,3-diisopropoxy-1,3-di-
phenyldisiloxane (4). A solution of 2-propanol (2.40 g, 0.04
ꢂ
mol) in THF (50 mL) was added to a rapidly stirred cold (0 C)
solution of 2 (7.89 g, 0.02 mol) in THF (80 mL). The reaction
mixture was refluxed for 2 h, filtered, and distilled to give 4.
ꢂ
4 Yield: 72%. Bp 153–155 C/26ꢁ71Pa. IR 1029, 1383, 1174,
1593, 2291, 2895, 2975, 3074cm
.
1H NMR (300 MHz) ꢀ
1209, 1430, 2868, 2969 cmꢁ1 1H NMR (400 MHz) ꢀ 0.97 (t,
;
1.26–1.15 (m, 12H, J ¼ 6:3 Hz), 4.39–4.20 (m, 2H, J ¼ 6:3
Hz), 7.41–7.31 (m, 4H, m-C6H5, J ¼ 2:1 Hz), 7.49–7.43 (m,
2H, p-C6H5, J ¼ 2:1 Hz), 7.70–7.62 (m, 4H, o-C6H5, J ¼ 2:1
Hz); 13C NMR (75.5 MHz) ꢀ 25.2, 25.3, 25.4, 65.9, 66.9, 67.2,
127.8, 128.0, 128.2, 130.3, 130.4, 131.0, 131.4, 133.9, 134.0,
134.6; 29Si NMR (59.6 MHz) ꢀ ꢁ70:6.
24H), 2.89 (q, 16H), 7.27–7.71 (m, 10H); 13C NMR (100.4
MHz) ꢀ 14.7, 38.8, 127.8, 130.7, 132.8, 134.6; 29Si NMR (79.3
MHz) ꢀ ꢁ37:6; MS m=z 514(M þ). Found: Si, 11.0%. Calcd
for C28H50N4O1Si2: Si, 10.9%.
Synthesis of 1,3-Di-t-butoxy-1,3-diphenyldisiloxane-1,3-diol
(7). A solution of water (0.72 g, 0.04mol) and triethylamine
(4.04 g, 0.04 mol) was added to a rapidly stirred cold (0 ꢂC) solu-
tion of 5a or 5b (0.02 mol), and the mixture was refluxed for 2 h,
filtered, and evaporated to give the crude 7. Recrystallization
from pentane (5 mL) afforded pure 7.
7 Yield : 26% (from 5a) and 52% (from 5b). Mp 67.5–69.5 ꢂC
(decomp). IR 1043, 1105, 1370, 1430, 3345 cmꢁ1; 1H NMR (400
MHz) ꢀ 1.22 (s, 18H), 4.38 (s, 2H), 7.20–7.60 (m, 10H); 13C NMR
(100.4MHz) ꢀ 31.7, 74.0, 127.6, 130.0, 134.0, 134.5; 29Si NMR
(79.3 MHz) ꢀ ꢁ67:9; MS m=z 391 (Mþ ꢁ 15). Found: Si,
13.7%. Calcd for C20H30O5Si2: Si, 13.8%.
Synthesis of 1,3-Di-t-butoxy-1,3-dichloro-1,3-diphenyldi-
siloxane (5a). A solution of t-butyl alcohol (2.96 g, 0.04mol)
and pyridine (6.33 g, 0.04mol) in THF (50 mL) was added to a
rapidly stirred cold (0 ꢂC) solution of 1 (7.36 g, 0.02 mol) in
THF (80 mL). The reaction mixture was refluxed for 2 h, filtered,
and distilled to give 5a.
5a Yield: 82%. Bp 144.3–145.6 ꢂC/200 Pa. IR 542, 1090,
;
1100, 1186, 1244, 1430, 2279 cmꢁ1 1H NMR (400 MHz) ꢀ
1.35 (s, 18H), 7.30 (m, 4H, m-C6H5), 7.32 (m, 2H, p-C6H5),
7.70 (m, 4H, o-C6H5); 13C NMR (100.4MHz) ꢀ 31.4, 76.4,