Crownꢀcontaining polythiophenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
973
3J = 15.8 Hz); 7.14 (d, 1 H, H(5´), 3J = 5.0 Hz). 13C NMR
(CDCl3), δ: 69.06, 69.20, 69.59, 69.63, 70.53, 70.57 (C(3), C(5),
C(6), C(8), C(9), C(11)); 71.10, 71.12 (C(2), C(12)); 111.74,
114.03 (C(14), C(17)); 120.14, 120.18, 123.82, 125.42, 127.51,
128.15 (C=C, C(3´), C(4´), C(5´), C(16)); 130.63 (C(15));
143.09 (C(2´)); 149.11, 149.28 (C(13a), C(17a)). MS (EI, 70 eV),
m/z (Irel (%)): 376 [M+] (100), 288 (16), 244 (65), 188 (8), 171
(10), 160 (8), 122 (7), 115 (4), 86 (5), 45 (18).
69.57, 70.48, 70.07 (2 C each, CH2O); 111.41, 113.75 (C(14),
C(17)); 119.81, 120.31, 124.24 (2 C), 125.98, 126.66 (C=C,
C(3´), C(4´), C(14), C(16), C(17)); 130.35 (C(2″), C(5″));
133.80, 135.21, 142.29 (C(2´), C(5´), C(15)); 149.18, 149.23
(C(13a), C(17a)). MS (ESI), m/z: 871 [M + K]+, 855 [M + Na]+.
UV (MeCN), λmax/nm: 451.
15ꢀ[(E)ꢀ2ꢀ(2,2´:5´,2″ꢀTetrathienylꢀ5ꢀyl)vinyl]ꢀ1,4,7,10,13ꢀ
pentaoxabenzocyclopentadecane (4c), red crystals, m.p. 294 °C.
Found (%): C, 61.89; H, 5.05. C28H28O5S3. Calculated (%):
15,15´ꢀ{2,2´ꢀDithienylꢀ5,5´ꢀbis[(E)ꢀetheneꢀ2,1ꢀdiyl]}bisꢀ
1,4,7,10,13ꢀpentaoxabenzocyclopentadecane (4a). Bromide 3a
(0.22 g, 0.49 mmol), bis(pinacolato)diboron (0.14 g, 0.54 mmol),
and potassium acetate (0.14 g, 1.5 mmol) were dissolved in
anhydrous DMF (7 mL). The resulting solution was degassed by
three sequential freeze—pump—thaw cycles. The reaction vesꢀ
sel was filled with dry argon, charged with PdCl2(dppf) (0.012 g,
0.015 mmol), and heated while stirring the reaction mixture at
75 °C for 2 h. On cooling, bromide 3a (0.44 g, 1 mmol),
PdCl2(dppf) (0.012 g, 0.015 mmol), and Na2CO3 (0.26 g,
2.44 mmol) in water (1.2 mL) were added under argon and the
mixture was heated at 75 °C for 10 h. The major part of the
solvent was removed and the resulting suspension was filtered.
The precipitate was washed with acetone and ether, dissolved in
CH2Cl2, washed with water, and dried over MgSO4. Evaporaꢀ
tion gave the target product 4a (0.35 g, 70%) as a bright yellow
solid, m.p. 242—243 °C. Found (%): C, 63.98; H, 6.17.
C40H46O10S2. Calculated (%): C, 64.01; H, 6.05. 1H NMR
(CDCl3), δ: 3.73 (s, 8 H, H(5), H(6), H(8), H(9)); 3.89 (m, 4 H,
H(3), H(11)); 4.16 (m, 4 H, H(2), H(12)); 6.79 (d, 1 H,
CH=CH, 3J = 16.2 Hz); 6.84 (d, 1 H, H(17), 3J = 8.1 Hz); 6.92
1
C, 62.20; H, 5.22. H NMR (CDCl3), δ: 3.76 (s, 8 H, H(5),
H(6), H(8), H(9)); 3.92 (m, 4 H, H(3), H(11)); 4.17 (m, 4 H,
H(2), H(12)); 6.84 (d, 1 H, CH=CH, 3J = 15.4 Hz); 6.99—7.29
(m, 11 H, H arom., H of thiophene, CH=CH). MS (ESI), m/z:
579 [M + K]+, 563 [M + Na]+, 558 [M + NH4]+, 541 [M + H]+.
UV (MeCN), λmax/nm: 422.
15,15´ꢀ{2,2´:5´,2″:5″,2″′ꢀTetrathienylꢀ5,5″′ꢀbis[(E)ꢀetheneꢀ
2,1ꢀdiyl]}bisꢀ1,4,7,10,13ꢀpentaoxabenzocyclopentadecane (4d),
dark red crystals, m.p. 273 °C. Found (%): C, 62.93; H, 5.38.
C48H50O10S4. Calculated (%): C, 63.00; H, 5.51. 1H NMR
(CDCl3), δ: 3.75 (s, 8 H, H(5), H(6), H(8), H(9)); 3.91 (m, 4 H,
H(3), H(11)); 4.16 (m, 4 H, H(2), H(12)); 6.81 (d, 1 H,
CH=CH, 3J = 15.4 Hz); 6.83 (d, 1 H, H(17), 3J = 7.9 Hz); 6.92
3
3
(d, 1 H, H(3´), J = 3.4 Hz); 6.99 (m, 2 H, H(14), H(16), J =
8.9 Hz); 7.01 (d, 1 H, CH=CH, 3J = 15.6 Hz); 7.02 (d, 1 H,
3
H(4´), J = 3.2 Hz); 7.07 (m, 4 H, H(3″), H(4″) of thiophene).
MS (ESI), m/z: 937 [M + Na]+, 488 [M + Na + K]2+, 480
[M + 2 Na]2+. UV (MeCN), λmax/nm: 458.
This work was financially supported by the INTAS
(Grant 03ꢀ51ꢀ4696) and the Russian Foundation for Baꢀ
sic Research (Project No. 07ꢀ03ꢀ00724).
3
(d, 1 H, H(4´), J = 3.8 Hz); 7.00 (d, 1 H, H(16), 3J = 8.1 Hz);
7.01 (s, 1 H, H(14)); 7.02 (d, 1 H, CH=CH, 3J = 16.2 Hz); 7.04
(d, 1 H, H(3´), 3J = 3.8 Hz). 13C NMR (CDCl3), δ: 68.80, 68.96
(1 C each), 69.45, 70.37, 70.96 (2 C each, CH2O); 111.30,
113.66 (C(14), C(17)); 119.86, 120.26, 123.94, 126.67, 128.13
(C=C, C(3´), C(4´), C(16)); 130.35, 135.69, 142.08 (C(2´),
C(5´), C(15)); 149.07, 149.23 (C(13a), C(17a)). MS (ESI),
m/z (Irel (%)): 789 [M + K]+ (100), 773 [M + Na]+ (28),
768 [M + NH4]+ (59), 751 [M + 1]+ (46). UV (MeCN),
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kis(triphenylphosphine)palladium (1 mol.% with respect to the
amount of 5a,b) was added under argon to a solution of the
starting compounds in an appropriate dry solvent (30—40 mL
per millimole of 3a). The reaction mixture was stirred for a
period of time specified in Table 1; the reaction was accompaꢀ
nied by the formation of a precipitate. The major part of the
solvent was removed and the resulting suspension was filtered.
The precipitate was washed with acetone and ether, dissolved in
chloroform or dichloromethane, washed with water, and dried
over MgSO4. Evaporation gave the target product as crystals.
15,15´ꢀ{2,2´:5´,2″ꢀTrithienylꢀ5,5″ꢀbis[(E)ꢀetheneꢀ2,1ꢀ
diyl]}bisꢀ1,4,7,10,13ꢀpentaoxabenzocyclopentadecane (4b),
brickꢀcolored crystals, m.p. 252 °C. Found (%): C, 63.01;
H, 5.83. C44H48O10S3. Calculated (%): C, 63.44; H, 5.81.
1H NMR (CDCl3), δ: 3.75 (s, 8 H, H(5), H(6), H(8), H(9));
3.91 (m, 4 H, H(3), H(11)); 4.15 (m, 4 H, H(2), H(12)); 6.78
(d, 1 H, CH=CH, 3J = 15.4 Hz); 6.81 (d, 1 H, H(17), 3J =
8.3 Hz); 6.89 (d, 1 H, H(3´), 3J = 3.8 Hz); 6.97 (m, 2 H, H(14),
H(16), 3J = 8.9 Hz); 7.00 (d, 1 H, CH=CH, 3J = 15.4 Hz); 7.01
(d, 1 H, H(4´), 3J = 3.8 Hz); 7.05 (s, 2 H, H(3″), H(4″) of
thiophene). 13C NMR (CDCl3), δ: 68.89, 69.07 (1 C each),
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