NJC
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obtained in 90% as colorless powder (softens and slowly purified by column chromatography on aluminium oxide using
decomposes above 200 1C). 1H NMR (CDCl3): 1.34 (2H, m, CH2Cl2/hexane (3 : 2).
CH2); 1.62 (3H, s, CH3); 2.23 (2H, m, CH2); 3.04 (2H, t,
Methyl 6-(3-(2,7-di(9H-carbazol-9-yl)-9-methyl-9H-fluoren-9-
J = 6.5 Hz, CH2); 7.34 (6H, m, CH); 7.48 (5H, m, CH); 7.54 yl)propoxy)-2,2-diphenyl-2H-benzo[h]chromene-5-carboxylate (2a).
(2H, ddd, J1 = 8.0, J2 = 1.9 Hz, CH); 7.61 (3H, m, CH); 7.98 (2H, Yield: 0.11 g (50%), slightly orange powder, m.p. 171–173 1C.
d, J = 7.7 Hz, CH); 8.11 (2H, ddd, J1 = 7.7, J2 = 0.9 Hz, CH); 8.23 1H NMR (CDCl3): 1.39 (2H, m, CH2); 1.66 (3H, s, CH3); 2.31 (2H,
(1H, d, J = 1.9 Hz, CH); 8.27 (1H, d, J = 1.9 Hz, CH). EA: m, CH2); 3.70 (3H, s, COOCH3); 3.83 (2H, t, J = 6.0 Hz, CH2); 6.17
calculated C 72.57, H 4.60, N 4.13; C41H31IN2; Found C 72.41, (1H, d, J = 10.1 Hz, CH); 6.67 (1H, d, J = 10.1 Hz, CH); 7.29 (14H, m,
H 4.72, N 3.98.
The same procedure afforded (3-iodopropyl)benzene (9b) 7.65 (2H, d, J = 1.4 Hz, CH); 7.79 (1H, m, CH); 8.01 (2H, d, J =
identical to the commercially available sample in 95% yield. 8.0 Hz, CH); 8.09 (2H, d, J = 8.2 Hz, CH); 8.23 (2H, dd, J1 = 13.2, J2 =
arom); 7.44 (10H, m, arom); 7.58 (2H, dd, J1 = 8.1, J2 = 1.8 Hz, CH);
A general procedure for compounds 1. A solution of N-(3- 1.9 Hz, CH); 8.31 (1H, d, J = 8.3 Hz, CH). HRMS (m/z): calculated
dimethylaminopropyl)-N0-ethylcarbodiimide hydrochloride (EDC) for [M + NH4]+ 976.4109; found 976.4109. EA: calculated C 85.15,
(0.19 g, 1 mmol) in anhydrous CH2Cl2 (10 ml) was slowly added to H 5.25, N 2.92; C68H50N2O4; found C 84.99, H 5.35, N 2.88.
a solution of an appropriate alcohol R-OH (1 mmol), derivative 4
Methyl 2,2-diphenyl-6-(3-phenylpropoxy)-2H-benzo[h]chromene-
(0.39 g, 1 mmol) and 4-dimethylaminopyridine (DMAP) (0.12 g, 5-carboxylate (2b). Yield: 0.21 g (80%), yellowish powder, m.p. 138–
1
1 mmol) in anhydrous CH2Cl2 (10 ml) at 0 1C. The mixture was 140 1C. H NMR (CDCl3): 2.15 (2H, dd, J1 = 6.8, J2 = 6.4 Hz CH2);
stirred at room temperature for 48 h. The resulting solution was 2.85 (2H, t, J = 7.8 Hz, CH2); 3.93 (3H, s, COOCH3); 4.04 (2H, t,
added to water (30 ml) and extracted with CH2Cl2 (3 ꢁ 30 ml). The J = 6.4 Hz, CH2); 6.19 (1H, d, J = 10.0 Hz, CH); 6.74 (1H, d, J =
combined organic phase was washed with water (2 ꢁ 30 ml), dried 10.0 Hz, CH); 7.27 (10H, m, arom); 7.48 (7H, m, arom); 7.99 (1H,
over MgSO4, filtered and the solvent was evaporated. The product dd, J1 = 7.3, J2 = 1.6 Hz, CH); 8.34 (1H, dd, J1 = 7.5, J2 = 1.6 Hz, CH).
was purified by column chromatography on a silica gel using a HRMS (m/z): calculated for [M + H]+ 527.2217; found 527.2217. EA:
mixture of CH2Cl2/hexane (2 : 1) as the eluent.
calculated C 82.11, H 5.74; C36H30O4; found C 82.16, H 5.76.
3-(2,7-Di(9H-carbazol-9-yl)-9-methyl-9H-fluoren-9-yl)propyl
Methyl 6-(3-(2,7-di(9H-carbazol-9-yl)-9-methyl-9H-fluoren-9-
8-methyl-2,2-diphenyl-2H-benzo[h]chromene-5-carboxylate (1a). yl)propoxy)-2-phenyl-2-(4-(piperidin-1-yl)phenyl)-2H-
Yield 0.23 g (50%), yellowish powder, colorless after crystal- benzo[h]chromene-5-carboxylate (3a). Yield: 0.18 g (35%),
1
lization from acetonitrile, m.p. 181–183 1C. 1H NMR(CDCl3): slightly violet powder, m.p. 211–213 1C. H NMR (CDCl3): 1.39
1.42 (2H, m, CH2); 1.68 (3H, s, CH3); 2.30 (2H, ddd, J1 = 8.1, J2 = (2H, m, CH2); 1.55 (4H, m, C5H10N); 1.66 (3H, s, CH3); 1.69 (2H,
7.9, J3 = 3.8 Hz, CH2); 2.39 (3H, s, CH3); 4.17 (2H, t, J = 6.5 Hz, m, C5H10N); 2.30 (2H, m, CH2); 3.13 (4H, m, C5H10N); 3.71 (3H,
CH2); 6.09 (1H, d, J = 10.1 Hz, CH); 7.26 (11H, m, CH); 7.42 (9H, s, COOCH3); 3.83 (2H, t, J = 6.6 Hz, CH2); 6.12 (1H, d, J = 10.0
m, CH); 7.50 (4H, d, J = 8.2 Hz, CH); 7.51 (1H, d, J = 10.1 Hz, CH); Hz, CH); 6.64 (1H, d, J = 10.0 Hz, CH); 6.88 (1H, m, arom); 7.31
7.64 (2H, dd, J1 = 8.1, J2 = 1.9 Hz, CH); 7.73 (2H, d, J = 1.8 Hz, CH); (13H, m, arom); 7.43 (9H, m, arom); 7.57 (1H, d, J = 1.2 Hz, CH);
7.84 (1H, br s, CH); 8.07 (2H, d, J = 8.0 Hz, CH); 8.16 (4H, d, J = 7.7 7.63 (3H, dd, J1 = 10.6, J2 = 1.5 Hz, CH); 7.80 (1H, d, J = 8.1 Hz,
Hz, CH); 8.23 (1H, d, J = 8.5 Hz, CH). HRMS (m/z): calculated for CH); 8.01 (2H, d, J = 8.1 Hz, CH); 8.10 (1H, d, J = 7.5 Hz, CH);
[M + NH4]+ 960.4160; found 960.4160. EA: calculated C 86.60, H 8.24 (2H, dd, J1 = 13.4, J2 = 1.9 Hz, CH); 8.29 (2H, d, J = 8.5 Hz,
5.34, N 2.97; C68H50N2O3; found C 86.53, H 5.44, N 2.88.
CH). HRMS (m/z): calculated for [M + NH4]+ 1059.4844; found
3-Phenylpropyl 8-methyl-2,2-diphenyl-2H-benzo[h]chromene- 1059.4845. EA: calculated C 84.12, H 5.71, N 4.03; C73H59N3O4;
5-carboxylate (1b). Yield 0.40 g (78%), beige powder, colorless found C 84.07, H 5.88, N 4.11.
after crystallization from acetonitrile, m.p. 105–107 1C. 1H
Methyl 2-phenyl-6-(3-phenylpropoxy)-2-(4-(piperidin-1-yl)phenyl)-
NMR(CDCl3): 2.13 (2H, q, J = 8.1 Hz, CH2); 2.50 (3H, s, CH3); 2H-benzo[h]chromene-5-carboxylate (3b). Yield: 0.14 (47%),
g
2.82 (2H, t, J = 8.1 Hz, CH2); 4.36 (2H, t, J = 6.5 Hz, CH2); 6.22 (1H, slightly violet powder, m.p. 146–148 1C. 1H NMR (CDCl3): 1.58
d, J = 10.1 Hz, CH); 7.16–7.34 (10H, m, CH); 7.40 (1H, dd, J1 = 8.6, (2H, m, C5H10N); 1.76 (4H, m, C5H10N); 2.15 (2H, dd, J1 = 7.7, J2 =
J2 = 1.7 Hz, CH); 7.52 (5H, m, CH); 7.57 (1H, br s, CH); 7.66 (1H, 6.4 Hz CH2); 2.84 (2H, dd, J1 = 8.1, J2 = 7.5 Hz, CH2); 3.17 (4H, m,
d, J = 10.1 Hz, CH); 7.96 (1H, s, CH); 8.28 (1H, d, J = 8.5 Hz, CH). C5H10N); 3.92 (3H, s, COOCH3); 4.04 (2H, t, J = 6.4 Hz, CH2); 6.15
HRMS (m/z): calculated for [M + H]+ 511.2268; found 511.2269. (1H, d, J = 10.0 Hz, CH); 6.71 (1H, d, J = 10.0 Hz, CH); 7.01 (2H, m,
EA: calculated C 84.68, H 5.92; C36H30O3; found C 84.56, H 5.83. arom); 7.27 (9H, m, arom); 7.48 (5H, m, arom); 7.99 (1H, dd, J1 = 7.0,
A general procedure for compounds 2 and 3. To a solution of J2 = 1.8 Hz, CH); 8.32 (1H, dd, J1 = 7.0, J2 = 1.8 Hz, CH). HRMS (m/z):
derivatives 5 or 6 (0.5 mmol) in 10 ml of acetonitrile, potassium calculated for [M + H]+ 610.2652; found 610.2651. EA: calculated
hydroxide (2.0 mmol) was added. The resulting mixture was C 80.76, H 6.45, N 2.30; C36H30NO4; found C 80.68, H 6.63, N 2.33.
stirred at room temperature for 0.5 h. Then the corresponding
R-I (9a or b) (0.6 mmol) was added and the stirring was
continued at the same temperature for 16–24 h. Acetonitrile
was removed in vacuum and the resulting mixture was treated
References
with water and extracted with dichloromethane (3 ꢁ 50 ml).
The extract was washed with water and dried over MgSO4. All
volatiles were removed in vacuum and the crude product was
1 J. C. Crano and R. J. Guglielmetti, Organic Photochromic
and Thermochromic Compounds, Plenum Press, New York,
1999, vol. 1.
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New J. Chem.