154
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
Vedernikov et al.
Calculated (%): C, 68.28; H, 6.28; N, 3.79. 1H NMR (25 C),
: 3.62 (m, 8 H, 4 CH2O); 3.77 (m, 4 H, 2 CH2CH2OAr); 4.09
(m, 4 H, 2 CH2OAr); 7.01 (d, 1 H, H(5´), J = 8.2 Hz); 7.16 (d, 1 H,
H(2´), J = 1.9 Hz); 7.18 (dd, 1 H, H(6´), J = 8.2 Hz, J = 1.9 Hz);
7.48 (d, 2 H, H(3), H(5), J = 5.8 Hz); 8.61 (d, 2 H, H(2), H(6),
J = 5.8 Hz). 13C NMR (23 C), : 68.23 (CH2OAr); 68.44
(CH2CH2OAr); 68.55 (CH2OAr); 68.62 (CH2CH2OAr); 69.56
(CH2O); 69.61 (CH2O); 70.45 (2 CH2O); 85.26 (CCPy); 94.26
(CCPy); 113.07 (C(1´)); 113.25 (C(5´)); 116.22 (C(2´)); 125.06
(C(3), C(5)); 125.43 (C(6´)); 130.48 (C(4)); 148.23 (C(3´));
149.80 (C(2), C(6)); 149.98 (C(4´)). UV (MeCN, C =
= 5•10–5 mol L–1), max/nm (): 315 (23 000), 293 (18 500),
242 (17 000). MS, m/z (Irel (%)): 369 [M]+ (14), 238 (12), 237 (100),
111 (13), 101 (16), 98 (31), 77 (19), 57 (32), 56 (25), 53 (21).
4ꢀ(2,3,5,6,8,9,11,12,14,15ꢀDecahydroꢀ1,4,7,10,13,16ꢀbenzoꢀ
hexaoxacyclooctadecinꢀ18ꢀylethynyl)pyridine (4d) was syntheꢀ
sized in 35% yield as a slightly yellowish substance with m.p.
118—120 C (from hexane). Found (%): C, 66.60; H, 6.54; N, 3.20.
C23H27NO6. Calculated (%): C, 66.81; H, 6.58; N, 3.39.
1H NMR (23 C), : 3.53 (s, 4 H, 2 CH2O); 3.56 (m, 4 H, 2 CH2O);
3.62 (m, 4 H, 2 CH2O); 3.76 (m, 4 H, 2 CH2CH2OAr); 4.14
(m, 4 H, 2 CH2OAr); 7.03 (d, 1 H, H(5´), J = 8.1 Hz); 7.17 (br.s,
1 H, H(2´)); 7.18 (dd, 1 H, H(6´), J = 8.1 Hz, J = 1.8 Hz); 7.50
(d, 2 H, H(3), H(5), J = 6.0 Hz); 8.61 (d, 2 H, H(2), H(6),
J = 6.0 Hz). 13C NMR (30 C), : 68.09 (CH2OAr); 68.15
(CH2OAr); 68.44 (CH2CH2OAr); 68.49 (CH2CH2OAr); 69.63
(2 CH2O); 69.71 (2 CH2O); 69.81 (2 CH2O); 85.22 (CCPy);
94.29 (CCPy); 112.83 (C(5´)); 112.96 (C(1´)); 115.63 (C(2´));
125.02 (C(3), C(5)); 125.24 (C(6´)); 130.48 (C(4)); 147.90
(C(3´)); 149.62 (C(4´)); 149.76 (C(2), C(6)). UV (MeCN,
C = 5•10–5 mol L–1), max/nm (): 320 (21 500), 293 (16 300),
243 (16 400). MS, m/z (Irel (%)): 413 [M]+ (42), 325 (45), 237 (100),
222 (88), 210 (85), 181 (76), 152 (60), 111 (61), 73 (57), 71 (50).
2ꢀ[(3,4ꢀDimethoxyphenyl)ethynyl]ꢀ1,3ꢀbenzothiazole (5) was
synthesized in 53% yield as a slightly yellowish substance with
m.p. 91—93 C (from hexane). Found (%): C, 69.16; H, 4.32;
N, 4.62. C17H13NO2S. Calculated (%): C, 69.13; H, 4.44;
N, 4.74. 1H NMR (30 C), : 3.83 (s, 6 H, 2 MeO); 7.06 (d, 1 H,
H(5´), J = 8.3 Hz); 7.27 (d, 1 H, H(2´), J = 1.6 Hz); 7.31 (dd, 1 H,
H(6´), J = 8.3 Hz, J = 1.6 Hz); 7.53 (m, 1 H, H(6)); 7.59
(m, 1 H, H(5)); 8.05 (d, 1 H, H(4), J = 8.1 Hz); 8.13 (d, 1 H,
H(7), J = 7.7 Hz). 13C NMR (30 C), : 55.53 (MeO); 55.60
(MeO); 81.35 (CCHet); 96.47 (CCHet); 111.46 (C(1´));
111.86 (C(5´)); 114.59 (C(2´)); 122.05 (C(7)); 122.91 (C(4));
125.79 (C(6´)); 126.27 (C(6)); 126.88 (C(5)); 134.60 (C(7a));
147.84 (C(2)); 148.65 (C(3´)); 150.93 (C(4´)); 152.48 (C(3a)).
UV (MeCN, C = 5•10–5 mol L–1), max/nm (): 348 (24 000),
336 (25 900). MS, m/z (Irel (%)): 295 [M]+ (100), 280 (75), 252 (69),
237 (41), 224 (49), 223 (58), 209 (34), 183 (40), 147 (34), 69 (48).
4ꢀ[(2ꢀBromoꢀ4,5ꢀdimethoxyphenyl)ethynyl]quinoline (6).
A solution of bromine (83 mg, 0.52 mmol) in CHCl3 (1.1 mL)
was added to a solution of styrylquinoline 3 (50 mg, 0.17 mmol)
in CHCl3 (5 mL), and the mixture was kept for 4 days at ~20 C
in the dark. Chloroform (10 mL) was added to the mixture,
which was washed with a 2% aqueous solution of Na2SO3 (5 mL),
and the organic solvent was thoroughly evaporated in vacuo.
A solution of ButOK (0.76 g, 6.8 mmol) in absolute ButOH
(10 mL) was added to the dry residue (103 mg), and the mixture
was heated for 3 h with stirring at 80 C. Water (0.5 mL) was
added to the reaction mixture, the solvent was evaporated
in vacuo, and the residue was chromatographed on SiO2, using
as an eluent a gradient benzene—EtOAc mixture to 50% of the
latter. One fraction (43 mg) containing a mixture of the comꢀ
pounds was collected (1H NMR monitoring) and crystallized by
the slow evaporation of the solution in a hexane—CHCl3 mixꢀ
ture at ~20 C. Compound 6 was obtained in a yield of 19 mg
(30%) as yellowish spherulites with m.p. 105—107 C. Found (%):
C, 61.74; H, 3.85; N, 3.74. C19H14BrNO2. Calculated (%):
C, 61.97; H, 3.83; N, 3.80. 1H NMR (27 C), : 3.85 (s, 3 H,
5´ꢀMeO); 3.87 (s, 3 H, 4´ꢀMeO); 7.36 (s, 1 H, H(3´)); 7.41
(s, 1 H, H(6´)); 7.74 (d, 1 H, H(3), J = 4.5 Hz); 7.78 (m, 1 H,
H(6)); 7.87 (m, 1 H, H(7)); 8.10 (d, 1 H, H(8), J = 8.5 Hz); 8.51
(d, 1 H, H(5), J = 8.8 Hz); 8.95 (d, 1 H, H(2), J = 4.5 Hz).
13C NMR (25 C), : 55.92 (5´ꢀMeO); 56.09 (4´ꢀMeO); 87.42
(CCHet); 97.38 (CCHet); 114.68 (C(1´)); 115.47 (C(3´));
115.84 (C(6´)); 116.76 (C(2´)); 123.51 (C(3)); 125.72 (C(5));
126.58 (C(4a)); 127.71 (C(6)); 128.23 (C(4)); 129.51 (C(8));
130.21 (C(7)); 147.51 (C(8a)); 148.17 (C(5´)); 150.10 (C(2));
150.90 (C(4´)). UV (MeCN, C = 5•10–5 mol L–1), max/nm ():
352 (21 500), 340 (21 300), 256 (17 700), 239 (29 400). MS, m/z
(Irel (%)): 369 [M]+ with 81Br (100), 367 [M]+ with 79Br (98),
245 (35), 230 (11), 202 (16), 185 (10), 175 (30), 101 (14),
83 (9), 59 (15).
1ꢀMethylꢀ4ꢀ[(4ꢀmethoxyphenyl)ethynyl]pyridinium iodide
(7a). Methyl iodide (47 L, 0.75 mmol) was added to a solution
of compound 4a (31 mg, 0.15 mmol) in CH2Cl2 (1 mL), and the
mixture was kept for 6 days at ~20 C. The solvent was evaporatꢀ
ed in vacuo, and the residue was triturated in benzene (3 mL),
filtered off, washed with benzene (2×3 mL), and dried in air.
Dye 7a was obtained in a yield of 52 mg (100%) as a yellowishꢀ
green powder with m.p. 188—190 C (from MeCN—benzene).
Found (%): C, 51.48; H, 4.01; N, 3.97. C15H14INO. Calculatꢀ
ed (%): C, 51.30; H, 4.02; N, 3.99. 1H NMR (28 C), : 3.84
(s, 3 H, MeO); 4.30 (s, 3 H, MeN); 7.10 (d, 2 H, H(3´), H(5´),
J = 8.8 Hz); 7.67 (d, 2 H, H(2´), H(6´), J = 8.8 Hz); 8.18 (d, 2 H,
H(3), H(5), J = 6.6 Hz); 8.94 (d, 2 H, H(2), H(6), J = 6.6 Hz).
13C NMR (28 C), : 47.54 (MeN); 55.47 (MeO); 84.92 (CCPy);
103.17 (CCPy); 111.46 (C(1´)); 114.78 (C(3´), C(5´)); 128.34
(C(3), C(5)); 134.36 (C(2´), C(6´)); 138.61 (C(4)); 145.22 (C(2),
C(6)); 161.32 (C(4´)). UV (MeCN, C = 5•10–5 mol L–1),
max/nm (): 363 (28 200), 247 (27 500).
1ꢀEthylꢀ4ꢀ[(4ꢀmethoxyphenyl)ethynyl]pyridinium perchlorate
(7b). A mixture of compound 4a (40 mg, 0.19 mmol) and ethyl
pꢀtoluenesulfonate (115 mg, 0.57 mmol) was heated for 4 h at
90 C (oil bath). The resulting mixture was triturated with benzꢀ
ene (2×5 mL) at ~20 C and then heated at 80 C with 10 mL of
benzene. The undissolved yellow substance was separated by
decantation and dissolved in MeOH (2 mL). Then 70% perꢀ
chloric acid (33 L, 0.38 mmol) was added, and the mixture was
cooled to –10 C. The precipitate formed was rapidly filtered
off, washed with benzene (2×5 mL), and dried in air. Dye 7b was
obtained in a yield of 31 mg (47%) as a yellow powder with m.p.
136—138 C (from MeOH). Found (%): C, 58.30; H, 4.60;
N, 4.15. C16H16ClNO5•0.15C6H6. Calculated (%): C, 58.08;
H, 4.87; N, 4.01. 1H NMR (30 C), : 1.54 (t, 3 H, MeCH2,
J = 7.3 Hz); 3.85 (s, 3 H, MeO); 4.58 (q, 2 H, MeCH2, J = 7.3 Hz);
7.10 (d, 2 H, H(3´), H(5´), J = 8.6 Hz); 7.68 (d, 2 H, H(2´),
H(6´), J = 8.6 Hz); 8.20 (d, 2 H, H(3), H(5), J = 6.7 Hz); 9.05
(d, 2 H, H(2), H(6), J = 6.7 Hz).
Betaine 3ꢀ{4ꢀ[(4ꢀmethoxyphenyl)ethynyl]pyridinioꢀ1ꢀyl}ꢀ
propaneꢀ1ꢀsulfonate (7c). 1,3ꢀPropane sultone (37 L, 0.42 mmol)
was added to a solution of compound 4a (59 mg, 0.28 mmol) in