PHOTOCHROMIC DIHYDROINDOZILINE: TOWARD NANOTECHNOLOGY APPLICATIONS
(dd, J ¼ 7.20, J ¼ 7.60 Hz, 2H, CH-arom.), 7.40–7.43 (d, 6H,
J ¼ 8.72 Hz), 7.32–7.36 (d, 2H, J ¼ 8.60 Hz), 7.16–7.19 (d, 2H,
J ¼ 8.60 Hz), 7.05–7.09 (m, 2H, CH-arom.), 5.68–5.72 (m, 1H, 70-CH),
5.11–5.17 (dt, J ¼ 8.00 Hz, J ¼ 2.00 Hz, 80-CH), 4.50–4.53 (q, 6H,
J ¼ 7.12 Hz), 3.94 (s, 3H, 30-CH3), 3.49 (s, 3H, 20-CH3), 2.19 (two
overlapping, s, 12H), 2.12 (s, 3H, 60-CH3), 1.62 (s, 3H, 80-CH3), 1.42 (t,
1H, CH-arom.), 8.32–8.36 (d, 12H, J ¼ 8.72 Hz), 8.12–7.15 (d,
J ¼ 8.00 Hz, 2H, CH-arom.), 7.67–7.70 (d, J ¼ 7.20 Hz, 2H,
CH-arom.), 7.51–7.54 (dd, J ¼ 7.20, J ¼ 7.60 Hz, 3H, CH-arom.),
7.61–7.64 (d, 12H, J ¼ 8.72 Hz), 7.26–7.32 (d, 2H, J ¼ 8.60 Hz),
7.10–7.13 (d, 2H, J ¼ 8.60 Hz), 7.06–7.08 (m, 2H, CH-arom.),
5.88–5.92 (m, 1H, 70-CH), 5.18–5.23 (dt, J ¼ 8.00 Hz, J ¼ 2.00 Hz,
80-CH), 4.49–4.53 (q, 12H, J ¼ 7.12 Hz), 3.86 (s, 3H, 30-CH3), 3.44 (s,
3H, 20-CH3), 2.17 (two overlapping, s, 24H), 2.16 (s, 3H, 60-CH3), 1.53
(s, 3H, 80-CH3), 1.47 (t, 18H, J ¼ 7.12 Hz), ppm. 13CNMR (400 MHz,
CDCl3) d 166.43 (30-CO), 165.98 (20-CO), 164.16 (CO-ethyl ester),
153.94, 150.18, 148.79, 148.32, 148.47, 144.31, 143.63, 141.79,
140.36, 138.74, 138.30, 136.18, 136.03, 134.46, 133.74, 132.30,
131.79, 130.62, 127.50, 125.67, 123.16, 122.48, 122.00, 121.32,
118.38, 117.57, 112.21, 105.89, 93.47 (acetylenic-C), 89.35
(acetylenic-C), 88.67, 65.32 (80a-C), 63.52 (spiro-C), 61.64, 52.51
(30-CH3), 51.97 (20-CH3), 46.53, 40.28, 31.64, 26.31, 24.70, 23.18,
22.65 (60-CH3), 22.28, 21.16 (80-CH3), 14.85, 12.34, ppm; IR (KBr):
n ¼ 3100–3032 (C—H, arom.), 2910–2997 (C—H, aliph.), 2216
13
9H, J ¼ 7.12 Hz) ppm. CNMR (400 MHz, CDCl3) d 167.65 (30-CO),
165.35 (20-CO), 163.28 (CO-ethyl ester), 152.99, 150.34, 148.65,
148.79, 147.56, 142.62, 142.37, 139.63, 138.68, 138.67, 136.10,
136.85, 133.63, 133.47, 131.22, 130.19, 129.85, 128.64, 127.78,
124.61, 124.10, 124.02, 123.75, 122.18, 121.87, 121.46, 118.76,
117.26, 112.50, 105.81, 93.76 (acetylenic-C), 89.79 (acetylenic-C),
88.28, 65.41 (80a-C), 63.40 (spiro-C), 61.87, 52.41 (30-CH3), 51.23
(20-CH3), 46.89, 39.65, 30.18, 26.17, 24.85, 23.64, 22.37, 22.76
(60-CH3), 22.43, 21.13 (80-CH3), 14.13, 12.58, ppm; IR (KBr):
n ¼ 3069ꢁ3021 (C—H, arom.), 2895–2976 (C—H, aliph.), 2228
0
0
—
—
—
(acetylenic bond), 1748 (3 -C O), 1702 (CO-ester), 1687 (2 -C
—
—
—
O), 1586 (C N), 1450 (C C), 1379, 1261, 1175, 1136, 950, 887,
—
—
746 cmꢁ1; HR-MS m/e (%) 1092.46 [Mþ]; Elemental Analysis for
C70H64N2O10: C, 76.90; H, 5.90; N, 2.56; Found %: C, 76.89; H, 5.94;
N, 2.58.
(acetylenic bond), 1742 (3 -C O), 1713 (CO-ester), 1685 (2 -C
0
0
—
—
—
—
—
—
O), 1567 (C N), 1452 (C C), 1355, 1261, 1185, 1134, 947, 868,
—
—
751 cmꢁ1; HR-MS m/e (%) 1770.75 [Mþ]; Elemental Analysis for
115H106N2O16: C, 77.94; H, 6.03; N, 1.58; Found %: C, 77.93; H, 6.05;
N, 1.57.
Dimethyl
2,7-((bis(ethynylphenyl)-3,5,7-tris(4-carboethoxy)
C
adamanty)l-4a0H-spiro[fluorene-9,50-pyrrolo[1,2-b]pyridazine]-60,70-
—
—
—
H, method A,
—
dicarboxylate 14c: From DHI 11c; R1
R
2
yield ¼ 18%, mp ¼ 146 8C; method B, yield ¼ 14%, mp ¼ 147 8C;
Acknowledgements
—
—
—
H,
—
method C, yield ¼ 23%, mp ¼ 146 8C; from DHI 11g: R1
R
2
The author is highly indebted to Alexander von Humboldt
foundation (AvH) and Taibah University for financial support of
this work. He also thanks Prof. Dr Heinz Du¨rr (University of
Saarland, Saarbru¨cken, Germany), Prof. Dr Henri Bouas-Laurent,
and Prof. Dr Jean-Luc Pozzo (University of Bordeaux, France) for
their continuous helpful discussions and measurements.
method A, yield ¼ 29%, mp ¼ 145 8C; method B, yield ¼ 37%,
mp ¼ 146 8C; method C, yield ¼ 69%, mp ¼ 145 8C; method D,
yield ¼ 10%, mp ¼ 146 8C; method E, yield ¼ 12%, mp ¼ 145 8C.
1H NMR (400 MHz, CDCl3) d 8.22–8.24 (d, J ¼ 8.00 Hz, 1H,
CH-arom.), 8.10–8.14 (d, 12H, J ¼ 8.72 Hz), 8.04–7.07 (d,
J ¼ 8.00 Hz, 2H, CH-arom.), 7.60–7.63 (d, J ¼ 7.20 Hz, 2H,
CH-arom.), 7.49–7.55 (dd, J ¼ 7.20, J ¼ 7.60 Hz, 3H, CH-arom.),
7.46–7.9 (d, 12H, J ¼ 8.72 Hz), 7.20–7.26 (d, 2H, J ¼ 8.60 Hz),
7.02–7.05 (d, 2H, J ¼ 8.60 Hz), 7.08–7.14 (m, 2H, CH-arom.),
6.99–7.01 (dd, J ¼ 1.76, J ¼ 1.76, 1H, 60-CH), 5.72–5.73 (m, 1H,
70-CH), 5.36–5.40 (t, J ¼ 2.2 Hz, 1H, 80-CH), 5.06–5.08 (dt,
J ¼ 8.00 Hz, J ¼ 2.00 Hz, 8a0-CH), 4.42-4.48 (q, 12H, J ¼ 7.12 Hz),
3.92 (s, 3H, 30-CH3), 3.40 (s, 3H, 20-CH3), 2.19 (two overlapping, s,
24H), 1.48 (t, 18H, J ¼ 7.12 Hz) ppm. 13CNMR (400 MHz, CDCl3) d
166.98 (30-CO), 165.76 (20-CO), 164.01 (CO-ethyl ester), 153.91,
150.02, 148.95, 148.64, 148.02, 144.35, 143.67, 141.68, 140.27,
138.95, 138.20, 136.11, 136.11, 134.03, 133.87, 132.16, 131.64,
129.90, 128.84, 127.50, 125.67, 124.78, 123.05, 122.48, 121.17,
121.02, 118.24, 117.36, 112.13, 105.78, 93.87 (acetylenic-C), 89.01
(acetylenic-C), 88.46, 65.34 (80a-C), 63.57 (spiro-C), 61.43, 52.46
(30-CH3), 51.47 (20-CH3), 46.87, 40.21, 31.64, 26.38, 24.78, 23.34,
22.78, 22.24, 14.67, 12.29 ppm; IR (KBr): n ¼ 3117ꢁ3041 (C—H,
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ar0om.), 2887–2981 (C—H, aliph.), 2209 (acetylenic bond), 1748
0
—
—
—
—
(3 -C O), 1711 (CO-ester), 1685 (2 -C O), 1567 (C N), 1450
—
—
(C C), 1354, 1268, 1178, 1106, 949, 887, 751 cmꢁ1; HR-MS m/e
—
—
(%) 1742.72 [Mþ]; Elemental Analysis for C113H102N2O16: C, 77.82;
H, 5.89; N, 1.61; Found %: C, 77.81; H, 5.88; N, 1.62.
Dimethyl
2,7-((bis(ethynylphenyl)-3,5,7-tris(4-carboethoxy)
adamanty)l-20,4a0-dimethyl-4a0H-spiro[fluorene-9,50-pyrrolo[1,2-b]
pyridazine]-60,70-dicarboxylate 14d: From DHI 11d; R1
R
—
—
—
CH ,
—
2
3
method A, yield ¼ 14%, mp ¼ 126 8C; method B, yield ¼ 22%,
mp ¼ 126 8C; method C, yield ¼ 25%, mp ¼ 127 8C; from DHI 11h:
—
—
—
—
R1
R
CH , method A, yield ¼ 25%, mp ¼ 126 8C; method B,
2
3
yield ¼ 36%, mp ¼ 125 8C; method C, yield ¼ 64%, mp ¼ 126 8C;
method D, yield ¼ 8%, mp ¼ 126 8C; method E, yield ¼ 11%,
mp ¼ 125 8C. 1H NMR (400 MHz, CDCl3) d 8.22–8.24 (d, J ¼ 8.00 Hz,
J. Phys. Org. Chem. 2011, 24 173–184
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