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3.57 (s, 4H, H17); 6.68 (d, J ¼ 8.33 Hz, 4H, H11); 6.90 (d, J ¼
7.14 Hz, 4H, H10); 6.98 (d, J ¼ 7.36 Hz, 4H, H7); 7.50 (d, J ¼
7.39 Hz, 4H, H6); 7.54 (d, J ¼ 7.41 Hz, 4H, H3); 7.59 (d, J ¼
6.91 Hz, 4H, H2). 13C NMR (CDCl3, d, ppm): ꢁ2.30 (C13); 116.24
(C11); 117.36 (C7); 121.24 (C10); 126.24 (C3); 128.22 (C6); 134.67
(C2); 134.89 (C5); 136.41 (C1); 141.34 (C4); 142.84 (C12), 148.38
(C9); 158.67 (C8). 29Si NMR (CDCl3, d, ppm): ꢁ8.09. Elem. anal.
calcd for C38H34N2O2Si; (578.83): C, 78.84%; H, 5.93%; N,
4.84%. Found: C, 78.81%; H, 5.89%, N, 4.81%.
Bꢀis(4-(4-formylphenyl)phenyl)dimethylsilane (9). Mp
¼
230 C to 233 C. FT-IR (KBr, n, cmꢁ1): 3013, 3030, 3047, 3070
(C–H arom.); 2957 (C–H aliph.); 2737, 2823 (C–H ald.); 1694 (C]
O); 1604, 1572 (C]C); 1387 (Si–CH3); 1166, 1111 (Si–Ph); 813
(arom. p-subst.). 1H NMR (DMSO-d6, d, ppm): 0.64 (s, 6H, H10);
7.70 (d, J ¼ 8.07 Hz, 4H, H2); 7.74 (d, J ¼ 8.04 Hz, 4H, H3); 7.86
(d, J ¼ 8.16 Hz, 4H, H6); 7.97 (d, J ¼ 8.23 Hz, 4H, H7); 10.08 (s,
2H, H9). 13C NMR (DMSO-d6, d, ppm): ꢁ3.48 (C10); 125.72 (C3);
126.55 (C6); 129.08 (C7); 133.83 (C2); 134.98 (C8); 137.55 (C1),
139.12 (C4); 145.14 (C5); 191.12 (C9). 29Si NMR (DMSO-d6, d,
ppm): ꢁ7.85. Elem. anal. calcd for C28H24O2Si; (420.61): C,
79.95%; H, 5.76%. Found: C, 79.91%; H, 5.70%.
ꢀ
Bis(4-(4-(4-aminophenoxy)phenyl)phenyl)diphenylsilane (8).
Mp ¼ 163 ꢀC to 164 ꢀC. FT-IR (KBr, n, cmꢁ1): 3370, 3444 (N–H);
3011, 3039, 3065 (C–H arom.); 1486, 1505, 1597 (C]C); 1235 (C–
O–C); 1111 (Si–Ph); 816 (arom. p-subst.). 1H NMR (CDCl3, d,
ppm): 3.49 (s, 4H, H17); 6.68 (d, J ¼ 8.61 Hz, 4H, H11); 6.90 (d, J
¼ 8.62 Hz, 4H, H10); 6.99 (d, J ¼ 8.56 Hz, 4H, H7), 7.39 (m, 4H,
H15); 7.44 (m, 2H, H16); 7.52 (d, J ¼ 8.58 Hz, 4H, H6); 7.56 (d, J
¼ 7.88 Hz, 4H, H3), 7.62 (d, J ¼ 6.26 Hz, 4H, H14); 7.64 (d, J ¼
7.62 Hz, 4H, H2). 13C NMR (CDCl3, d, ppm): 116.26 (C11); 117.40
(C7); 121.27 (C10); 126.24 (C3); 127.93 (C15); 128.25 (C6); 129.64
(C16); 132.42 (C1); 134.28 (C13); 134.74 (C5); 136.41 (C14);
136.87 (C2); 141.71 (C4); 142.83 (C12); 148.41 (C9); 158.78 (C8).
29Si NMR (CDCl3, d, ppm): ꢁ14.52. Elem. anal. calcd for
Bis(4-(4-formylphenyl)phenyl)diphenylsilane (10). Mp
¼
272 C to 275 C. FT-IR (KBr, n, cmꢁ1): 3015, 3049, 3068 (C–H
arom.); 2733, 2821 (C–H ald.); 1700 (C]O); 1572, 1604 (C]C);
1111, 1429 (Si–Ph); 810 (arom. p-subst.). 1H NMR (CDCl3, d,
ppm): 7.42 (d, J ¼ 7.17 Hz, 4H, H12); 7.48 (m, 2H, H13); 7.63 (d, J
¼ 7.28 Hz, 4H, H11); 7.67 (d, J ¼ 7.79 Hz, 4H, H3); 7.72 (d, J ¼
7.64 Hz, 4H, H2); 7.78 (d, J ¼ 7.88 Hz, 4H, H6); 7.96 (d, J ¼
7.85 Hz, 4H, H7); 10.06 (s, 2H, H9). 13C NMR (CDCl3, d, ppm):
126.84 (C3); 127.72 (C6); 128.09 (C12); 129.92 (C13); 130.32 (C7);
133.60 (C10); 134.50 (C1); 135.44 (C8); 136.38 (C11); 137.05 (C2);
140.86 (C4); 146.81 (C5); 191.83 (C9). 29Si NMR (CDCl3, d, ppm):
ꢁ14.36. Elem. anal. calcd for C38H28O2Si; (544.75): C, 83.78%;
H, 5.19%. Found: C, 83.72%; H, 5.13%.
ꢀ
ꢀ
C
48H38N2O2Si; (698.93): C, 82.48%; H, 4.91%; N, 4.01%. Found:
C, 82.42%; H, 4.85%, N, 3.96%.
Bis(4-(4-formylphenyl)phenyl)di-R-silane (R ¼ methyl (9),
phenyl (10)). To a mixture of dibromo compound (1 or 2) (18.50
mmol), bis(triphenylphosphine) palladium(II) dichloride
(0.55 g, 0.784 mmol) and 4-formylyphenylboronic acid (6.935 g,
46.25 mmol) a solution containing K2CO3 (16.50 g) dissolved in
126 mL of a water–1,4-dioxane mixture (1 : 1 vol/vol) was added;
then, the mixture was heated at 85 ꢀC for 12 hours. Then, water
was added, and a dark brown solid was obtained which was
ltered under vaccum. This product was treated with THF, and
the remaining solids were removed by ltration through celite.
The obtained solution was dried and concentrated to obtain
a black solid, which was puried by column chromatography
(silica/petroleum ether–chloroform, 1 : 1 vol/vol) and subse-
quent recrystallization from ethyl acetate. Following this
procedure, 9 and 10 were obtained as white solids in yields of
56% and 51%, respectively.
Silylated oligomeric poly(ether-azomethine)s synthesis
A mixture of dialdehyde (9 or 10), anhydrous calcium chloride,
p-toluenesulfonic acid (p-TsOH) and anhydrous DMAc was
placed under a nitrogen atmosphere with vigorous stirring and
heated until reux. When the dialdehyde was dissolved, a solu-
tion containing the diamine (7 or 8) in anhydrous DMAc
prepared under nitrogen ow was slowly added; the reaction
was then maintained under reux for 24 hours. Then, the
mixture was added to methanol under stirring and the obtained
solid was ltered, extensively washed with hot methanol, and
dried at 100 ꢀC under vacuum for 24 hours.
PAM-I. Yield: 79%, FT-IR (KBr, n, cmꢁ1): 3063, 3032, 3013 (C–
H arom.); 2954 (C–H aliph.); 2877 (CO–H); 1698 (C]O); 1624
(C]N); 1603, 1496, 1487 (C]C); 1244 (C–O–C); 1114 (Si–Ph);
1
872 (Si–CH3); 810 (arom. p-subst.). H NMR (DMAc, acetone-d6
internal reference (int. ref.), d, ppm): 0.47 (m, 12H, H22, H23);
7.14 (d, J ¼ 7.25 Hz, 4H, H7), 7.29 (m, 4H, H10); 7.55 (m, 8H,
H11, H20); 7.61–7.84 (m, 16H, H2, H3, H6, H19); 7.97 (m, 8H,
H15, H16); 8.80 (s, 2H, H13). 13C NMR (DMAc, acetone-d6 int.
ref., d, ppm): ꢁ3.333; ꢁ3.329 (C22, C23); 121.55 (C7); 122.82
(C10); 126.36 (C3); 126.46 (C19); 127.46, 127.56, 127.79 (C6, C11,
C16); 129.04 (C15); 132.13 (C5); 133.21; 133.22 (C2, C20); 133.61,
1300 | RSC Adv., 2018, 8, 1296–1312
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