446
A.A. Kalinin et al. / Dyes and Pigments 147 (2017) 444e454
Fig. 2. First hyperpolarizability values of chromophores FTC, CLD, OLD and their indolizine analogues, calculated at the B3LYP/6-31G(d)//M06-2X/aug-cc-pVDZ0 level [32].
Scheme 1. Chemical structures and synthesis of chromophore (MPI-1)-V-TCF. Reagents and Conditions: (i) Br2, rt, CHCl3; (ii) picoline, acetone, 65 ꢀC, 30 h; (iii) NaHCO3, H2O, reflux
30 min; (iv) DMF, POCl3, 45 min 35e40 ꢀC; (v) TCF, EtOH, reflux 14 h or AcOH/Py, 50 ꢀC, 14 h.
Scheme 2. Chemical structures and synthesis of chromophore (MPI-3)-V-TCF. Reagents and Conditions: (i) Br2, rt, CHCl3; (ii) picoline, acetone, 65 ꢀC, 8 h; (iii) NaHCO3, H2O, reflux
30 min; (iv) DMF, POCl3, 45 min 35e40 ꢀC; (v) TCF, EtOH, reflux 14 h or AcOH/Py, 50 ꢀC, 14 h.
2.2.1.2. (E)-2-(3-(1-methyl-2-phenylindolizinyl)-vinyl)-3-cyano-5,5-
dimethylfuran-2(5H)-ylidene)-malononitrile
((MPI-3)-V-TCF).
Yield 12% (a), 85% (b). Green powder, m.p.: 284e286 ꢀC. MALDI-
TOF: 417 [MH]þ, 439 [MþNa]þ, 455 [MþK]þ. IR (nmax, cmꢁ1, KBr):
2217, 1585, 1557, 1516, 1463, 1447, 1425, 1387, 1353, 1286, 1269,
1230, 1197, 1153, 1134, 1062, 1024, 921, 843, 768, 755. 1H NMR
Scheme 3. Chemical structures and synthesis of chromophore DMA-V-TCF. Reagents
and Conditions: (i) TCF, EtOH, reflux 14 h.
(400 MHz, DMSO-d6)
d
9.00 (d, J ¼ 7.0 Hz, 1H), 8.06 (d, J ¼ 15.0 Hz,
1H), 7.88 (d, J ¼ 8.6 Hz, 1H), 7.63 (dd, J ¼ 8.6, 7.0 Hz, 1H), 7.56 (dd,
J ¼ 7.5, 7.0 Hz, 2H), 7.48e7.53 (m, 1H), 7.38 (dd, J ¼ 7.5, 1.4 Hz, 2H),
7.32 (ddd, J ¼ 7.0, 7.0, 1.1 Hz, 1H), 6.03 (d, J ¼ 15.0 Hz, 1H), 2.17 (s,
2129, 1594, 1557, 1522, 1474, 1441, 1362, 1293, 1268, 1237, 1205,
1154, 1105, 1081, 1072, 928, 823, 752, 705. 1H NMR (400 MHz,
3H), 1.58 (s, 6H). 1H NMR (600 MHz, CDCl3)
d 8.35e8.55 (br, 1H),
8.46 (d, J ¼ 6.9 Hz, 1H), 7.59 (d, J ¼ 8.6 Hz, 1H), 7.57 (dd, J ¼ 7.4,
7.0 Hz, 2H), 7.52 (dd, J ¼ 7.3, 7.3 Hz, 1H), 7.40 (dd, J ¼ 8.6, 7.3 Hz, 1H),
7.36 (d, J ¼ 7.3 Hz, 2H), 7.13 (dd, J ¼ 7.3, 7.0 Hz, 1H), 5.57e5.77 (br,
DMSO-d6)
d
8.56 (d, J ¼ 6.6 Hz, 1H), 8.26 (d, J ¼ 8.8 Hz, 1H), 8.20 (d,
J ¼ 15.1 Hz, 1H), 7.69 (dd, J ¼ 8.8, 7.6 Hz, 1H), 7.55 (dd, J ¼ 7.3, 7.1 Hz,
2H), 7.49 (dd, J ¼ 7.3 Hz, 1H), 7.39 (d, J ¼ 7.1 Hz, 2H), 7.35 (ddd,
J ¼ 7.6, 6.6 Hz, 1H), 6.15 (d, J ¼ 15.1 Hz, 1H), 2.39 (s, 3H), 1.56 (s, 6H).
1H), 2.23 (s, 3H), 1.29 (s, 6H), 13C NMR (150 MHz, CDCl3)
d 177.22,
173.00, 141.21, 138.23, 133.85, 130.15, 129.67, 129.19, 128.78, 127.44,
126.07, 122.27, 118.33, 116.25, 114.39, 113.78, 112.97, 103.80, 95.90,
51.33, 26.13, 8.98.
1H NMR (600 MHz, CDCl3)
d
8.46e8.26 (br, 1H), 8.01 (d, J ¼ 6.8 Hz,
1H), 7.91 (d, J ¼ 8.7 Hz, 1H), 7.53 (dd, J ¼ 7.3, 7.1 Hz, 2H), 7.49 (dd,
J ¼ 7.1, 7.1 Hz, 1H), 7.42 (dd, J ¼ 8.7, 7.3 Hz, 1H), 7.34 (d, J ¼ 7.3 Hz,
2H), 7.11 (dd, J ¼ 7.3, 6.8 Hz,1H), 6.08e5.88 (br,1H), 2.41 (s, 3H),1.35
(s, 6H), 13C NMR (150 MHz, CDCl3)
d 177.18, 173.99, 140.17, 138.05,
2.2.1.3. (E)-2-(4-(N,N-dimethylaminophenyl)-vinyl)-3-cyano-5,5-
dimethylfuran-2(5H)-ylidene)malononitrile (DMA-V-TCF). Yield 83%
(a). Dark blue powder, m.p.: 317e319 ꢀC (lit. 290e292 ꢀC [37]).
MALDI-TOF: 331 [MH]þ, 353 [MþNa]þ, 369 [MþK]þ.
133.59, 130.27, 129.75, 128.97, 128.48, 126.49, 125.25, 124.81, 118.29,
115.63, 113.57, 113.30, 112.70, 111.51, 106.58, 96.01, 52.03, 26.26,
9.82.