10.1002/ejoc.201800101
European Journal of Organic Chemistry
FULL PAPER
sulfate, evaporation of the solvent in vacuo and column chromatography
(silica, cyclohexane/ethyl acetate (3:1), Rf = 0.21), 57 mg (51 µmol, 46 %)
of an orange colored solid remained, m. p. 110 °C. 1H-NMR (600 MHz,
CDCl3): δ = 8.39 (s, 2 H, ArCONH), 8.04 (d, 3J = 7.8 Hz, 2 H, Py-H-3), 8.02
(d, 3J = 8.4 Hz, 2 H, Py-H-5), 7.98 (br. s, 1 H, Ar-H-2), 7.78 (br. t, 3J = ~8
Hz, 2 H, Py-H-4), 7.92 (br. s, 2 H, CONHCH), 7.62 (d, 4J = 1.2 Hz, 2 H, Ar-
H-4,6), 7.05 (s, 2 H, thio-H-4), 4.13 (t, 3J = 5.4 Hz, 2 H, OCH2), 3.73 (t, 3J
= 6.3 Hz, 2 H, OCH2CH2CH2CH2), 2.17 (mc, 2 H, COCH), 1.93 (s, 6 H, thio-
CH3), 1.92-1.87 (m, 4 H, OCH2CH2CH2), 1.77-1.70 (m, 2 H, CHCHaHbCH3),
1.72-1.67 (m, 2 H, CHCHaHbCH2), 1.63-1.56 (m, 2 H, CHCHaHbCH3), 1.56-
1.50 (m, 2 H, CHCHaHbCH2), 1.36-1.30 (m, 8 H, CH2CH2CH3), 0.97 (t, 3J
= 7.4 Hz, 6 H, CHCH2CH3), 0.89 (t, 3J = 6.9 Hz, 6 H, CH2CH2CH3) ppm.
13C-NMR (150 MHz, CDCl3): δ = 175.0 (s, NHCOCH), 170.4 (s, pyrrol-CO),
164.3 (s, ArCONH), 160.0 (s, Ar-C-5), 149.9 (s, Py-C-2), 149.4 (s, Py-C-
6), 143.4 (s, thio-C-2), 141.2 (d, Py-C-4), 136.4 (s, Ar-C-1,3), 132.4 (s, thio-
C-3), 131.0 (d, thio-C-4), 127.3 (s, pyrrol-C-3,4), 117.7 (d, Ar-C-2), 117.2
(d, Ar-C-4,6), 110.4 (d, Py-C-5), 109.8 (d, Py-C-3), 109.6 (s, thio-C-5), 68.2
(t, OCH2), 51.1 (d, COCH), 38.4 (t, OCH2CH2CH2CH2), 32.7 (t,
CHCH2CH2), 30.0 (t, CH2CH2CH3), 26.7 (t, OCH2CH2CH2), 26.3 (t,
CHCH2CH3), 25.5 (t, OCH2CH2), 23.0 (t, CH2CH2CH3), 15.2 (q, thio-CH3),
14.2 (q, CH2CH2CH3), 12.3 (q, CHCH2CH3) ppm. MS (EI, 70 eV): m/z =
(d, Ar2-C-6), 129.5 (d, Ar2-C-5), 127.1 (s, pyrrol-C-3,4), 123.8 (s, Ar2-C-4),
122.6 (s, Ar2-C-1), 121.3 (s, thio-C-5), 117.7 (d, Ar1-C-2), 117.2 (d, Ar1-C-
4,6), 110.4 (d, PyC-5), 109.8 (d, Py-C-3), 107.0 (s, Ar2-C≡C-SiiPr3), 92.79*
(s, Ar2-C≡C-SiiPr3), 92.75* (s, thio-C≡C-Ar2), 87.4 (s, thio-C≡C-Ar2), 68.2
(t, Ar1OCH2), 51.0 (d, NHCOCH), 38.4 (t, OCH2CH2CH2CH2), 32.7 (t,
CHCH2CH2), 30.0 (t, CH2CH2CH3), 26.7 (t, OCH2CH2), 26.3 (t,
CHCH2CH3), 25.5 (t, OCH2CH2CH2), 23.0 (t, CH2CH2CH3), 20.7 (q, Ar2-
CH3), 18.9 (q, Si(CH(CH3)2)), 15.3 (q, thio-CH3), 14.2 (q, CH2CH2CH3),
12.3 (q, CHCH2CH3), 11.5 (d, Si(CH(CH3)2)) ppm. For
a better
discrimination between the signal, the ppm values have been listed with
an additional decimal digit. MS (MALDI-TOF, CI-CCA): m/z = 1548 [M]•+.
IR (ATR): ꢀꢁ = 2957, 2941, 2892, 2864 (aliph. C-H valenz), 2179, 2145
(C≡C valenz), 1769, 1703 (C=O valenz, imide), 1584, 1498 (C=C valenz,
arom.), 1444 (C-H def.), 800 (2,6-disubst. pyridine) cm-1. Elemental
analysis: C92H113N7O7S2Si2 (1549.23) calcd. C 71.32 H 7.35 N 6.33 S 4.14;
C92H113N7O7S2Si2 . 2 H2O (1585.27) calcd. C 69.70 H 7.44 N 6.18 S 4.05;
found C 69.89 H 7.35 N 6.22 S 3.86.
5-{4-[(3,4-Bis{2-methyl-5-[2-methyl-4-
(tris[methylethyl]silylethynyl)phenyl]ethynyl}thiophen-3-yl)]-2,5-
dioxo-1H-pyrrol-1-yl}-N,N‘-bis[6-(2-ethylhexanoylamino)pyrid-2-yl]-
1,3-benzenedicarboxamide (25)
1115 (4), 1117 (10), 1119 (5) [M]•+, 1036 (5), 1038 (8) [M-Br]+. HRMS (EI):
12
C
1H5979Br214N716O732S2
calcd. 1115.2284, found 1115.2268 (Δ: 1.43
1H5979Br181Br114N716O732S
2 calcd. 1117.2264, found 1117.2258
52
12
C
52
ppm).
(Δ: 0.47 ppm).
Sequentially and under nitrogen, dry triethylamine (300 µL) and 4-methyl-
1-(tris[methylethyl]silylethynyl)-4-ethynylbenzene (5, 60.0 mg (203 µmol),
dissolved in dry tetrahydrofuran (1.7 mL), were dropped into a suspension
of 5-{4-[(3,4-bis{5-bromo-2-methylthiophen-3-yl})-2,5-dioxo-1H-pyrrol-1-
yl]-N,N‘-bis[6-(2-ethylhexanoylamino)pyrid-2-yl]-1,3-
12
C
52
1H5981Br214N716O732S2
calcd. 1119.2243, found
IR (ATR): ꢀꢁ = 3413, 3312 (N-H valenz, amide),
1119.2254 (Δ: 1.00 ppm).
2959, 2929, 2857 (aliph. C-H valenz), 1698 (C=O valenz, imide), 1677
(C=O valenz, amide), 1583, 1503 (C=C valenz, arom.), 1241 (C-O valenz,
ether), 800 (2,6-disubst. pyridine) cm-1. Elemental analysis:
C52H59Br2N7O7S2 (1118.01)
benzenedicarboxamide (20, 98 mg, 94 µmol)), bis(triphenylphosphine)-
palladium(II) dichloride (4.0 mg, 5.7 µmol), copper(I) iodide (2.0 mg,
11 µmol) and triphenylphosphine (5.0 mg, 19 µmol) in dry tetrahydrofuran
(3 mL). After stirring at 50 °C for 3 d, the mixture was cooled to room temp.
and the solvent was removed. in vacuo. Column chromatography (silica
gel, cyclohexane/ethyl acetate (5:1), Rf = 0.09) gave 13 mg (8.8 µmol, 9 %)
of a yellow solid, m. p. 188 °C. 1H-NMR (500 MHz, CDCl3): δ = 8.51 (br. s,
2 H, Py-NHCOCH), 8.30 (s, 2 H, Ar1-H-4,6), 8.19 (s, 1 H, Ar1-H-2), 8.09
(br. s, 2 H, Ar1-CONH), 8.02 (d, 3J = 8.0 Hz, 2 H, Py-H-3), 7.97-7.92 (m, 2
H, Py-H-5), 7.71 (br. t, 3J = ~8 Hz, 2 H, Py-H-4), 7.37 (d, 3J = 7.5 Hz, 2 H,
Ar2-H-6), 7.32 (mc, 4 H, thio-H-4, Ar2-H-3), 7.26 (d, 3J = 7.5 Hz, 2 H, Ar2-
H-5), 2.43 (s, 6 H, Ar2-CH3), 2.27-2.16 (m, 2 H, COCH), 2.04 (s, 6 H, thio-
CH3), 1.79-1.54 (m, 4 H, CHCHaHbCH2, CHCHaHbCH3), 1.63-1.57 (m, 2 H,
CHCHaHbCH3), 1.54-1.47 (m, 2 H, CHCHaHbCH2), 1.36-1.28 (m, 8 H,
CH2CH2CH3), 1.14-1.12 (m, 42 H, CH(CH3)2), 0.96 (t, 3J = 7.3 Hz, 6 H,
CHCH2CH3), 0.88-0.84 (m, 6 H, CH2CH2CH3) ppm. 13C-NMR (125 MHz,
CDCl3): δ = 175.3 (s, Py-NHCOCH), 168.7 (s, pyrrol-C-2,5), 163.7 (s,
Ar1CONH), 150.1 (s, Py-C-2), 149.3 (s, Py-C-6), 144.5 (s, thio-C-2), 141.2
(d, Py-C-4), 141.1 (s, Ar2-C-2), 136.0 (s, Ar1-C-5), 133.4 (s, Ar1-C-1,3),
133.2 (d, thio-C-4, Ar2-C-3), 129.7 (s, thio-C-3), 129.5 (d, Ar2-C-5), 128.3
(d, Ar1-C-2), 127.5 (d, Ar1-C-4,6), 126.5 (s, pyrrol-C-3,4), 124.3 (s, Ar2-C-
4), 123.9 (d, Ar2-C-6), 122.5 (s, Ar2-C-1), 121.7 (s, thio-C-5), 110.6 (d, Py-
C-3), 109.9 (d, Py-C-5), 107.0 (s, Ar2-C≡C-SiiPr3), 106.7 (s, thio-C≡C-Ar2),
93.1 (s, thio-C≡C-Ar2), 92.9 (s, Ar2-C≡C-SiiPr3), 50.8 (d, COCH), 32.7 (t,
CHCH2CH2), 30.0 (t, CH2CH2CH3), 26.3 (t, CHCH2CH3), 23.0 (t,
CH2CH2CH3), 18.9 (d, Si(CH(CH3)2), 15.4 (q, thio-CH3), 14.2 (q,
CH2CH2CH3), 12.3 (q, CHCH2CH3) 11.5 (d, Si(CH(CH3)2) ppm. MS
(MALDI-TOF, CI-CCA): m/z = 1499 [M+Na]+, 1476 [M]•+, 1433 [M-C3H7]+.
IR (ATR): ꢀꢁ = 2958, 2939, 2927, 2863 (aliph. C-H valenz), 2177, 2148
(C≡C valenz), 1773, 1699 (C=O valenz, imide), 1583, 1500 (C=C valenz,
arom.), 1443 (C-H deform.), 800 (2,6-disubst. pyridine) cm-1. Elemental
analysis*: C88H105N7O6S2Si2 (1477.12) calcd. C 71.55 H 7.16 N 6.64 S
4.34, C88H105N7O6S2Si2 . 1.5 CH2Cl2 (1604.52) calcd. C 66.66 H 6.78 N
5-{4-[(3,4-Bis{2-methyl-5-[(2-methyl-4-
{tris[methylethyl]silylethynyl}phenyl)ethynyl]thiophen-3-yl})-2,5-
dioxo-1H-pyrrol-1-yl]-butoxy}-N,N’-bis[6-(2-
ethylhexanoylamino)pyrid-2-yl]-1,3-benzenedicarboxamide (24)
5-{4-[(3,4-Bis{5-bromo-2-methylthiophen-3-yl})-2,5-dioxo-1H-pyrrol-1-yl]-
butoxy}-N,N‘-bis[6-(2-ethylhexanoylamino)pyrid-2-yl]-1,3-
benzenedicarboxamide
(21,
59
mg,
53
µmol),
bis(triphenylphosphine)palladium dichloride (4.0 mg, 5.7 µmol), copper(I)
iodide (2.0 mg, 11 µmol), and triphenylphosphine (5.0 mg, 19 µmol) were
suspended in dry tetrahydrofuran (3 mL). Under nitrogen, first dry
triethylamine (300 µL) and then 4-methyl-1-(tris[methylethyl]silylethynyl)-
4-ethynylbenzene (5, 50.0 mg, 169 µmol), dissolved in dry tetrahydrofuran
(1.5 mL), were added dropwise. After stirring for 3 d at 50 °C, the mixture
was cooled to room temp. and the solvent was evaporated in vacuo.
Column chromatography [silica gel, cyclohexane/ethyl acetate (3:1), Rf =
0.24] yielded 32 mg (21 µmol, 40 %) of a green solid, m. p. 138-139 °C.
1H-NMR (500 MHz, CDCl3): δ = 8.42 (br. s, 2 H, Ar1CONH), 8.02 (d, 3J =
3
8.0 Hz, 2 H, Py-H-3), 8.01 (d, J = 8.0 Hz, 2 H, Py-H-5), 7.98 (br. s, 1 H,
Ar1-H-2), 7.79 (br. s, 2 H, NHCOCH), 7.75 (t, 3J = 8.0 Hz, 2 H, Py-H-4),
7.62 (d, 4J = 1.4 Hz, 2 H, Ar1-H-4,6), 7.37 (d, J = 8.0 Hz, 2 H, Ar2-H-6),
3
7.33 (br. s, 2 H, Ar2-H-3), 7.28 (s, 2 H, thio-H-4), 7.26 (dd, 3J = 8.0 Hz, 4J
= 1.5 Hz, 2 H, Ar2-H-5), 4.12 (t, 3J = 5.5 Hz, 2 H, OCH2), 3.75 (t, 3J = 6.0
Hz, 2, H, OCH2CH2CH2CH2), 2.43 (s, 6 H, Ar2-CH3), 2.17 (mc, 2 H, COCH),
1.99 (s, 6 H, thio-CH3), 1.94-1.87 (m, 4 H, OCH2CH2CH2), 1.75-1.65 (m, 4
H, CHCHaHbCH2, CHCHaHbCH3), 1.61-1.54 (2 H, CHCHaHbCH3), 1.54-
1.49 (m, 2 H, CHCHaHbCH2), 1.36-1.28 (m, 8 H, CH2CH2CH3), 1.15-1.11
3
3
(m, 42 H, CH(CH3)2), 0.96 (t, J = 7.4 Hz, 6 H, CHCH2CH3), 0.87 (t, J =
7.0 Hz, CH2CH2CH3) ppm. 13C-NMR (125 MHz, CDCl3): δ = 175.0 (s,
NHCOCH), 170.6 (s, pyrrol-C-2,5), 164.3 (s, Ar1CONH), 160.0 (s, Ar1-C-
5),
149.9
(s,
Py-C-2),
149.4
(s,
Py-C-6),
6.06 S 3.97, found
spectroscopic investigations, 25 was recycled by dissolvation in
C 66.70 H 6.67 N 6.16 S 3.86. *After the
143.7 (s, thio-C-2), 141.2 (d, Py-C-4), 140.1 (s, Ar2-C-2), 136.4 (s, Ar1-C-
1,3), 133.24* (d, thio-C-4), 133.15* (d, Ar2-C-3), 132.9 (s, thio-C-3), 131.6
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