A. R. Katritzky et al.
FULL PAPER __________________________________________________________________________
13C NMR (CDCl3): δ/ppm = 52.5, 94.8, 110.3, 115.8 (d, J =
21.7 Hz), 120.2, 123.9, 127.1 (d, J = 8.7 Hz), 127.2, 128.9 (d,
J = 3.2 Hz), 131.8, 147.0, 151.5, 163.6 (d, J = 250.6 Hz).
C23H15F2N3O calcd.: C 71.31 H 3.91 N 10.85
4-(4-Iodobutyl)-2,6-diphenylpyrylium Perchlorate (15a)
Yield 40%, m.p. 177–180 °C. – 1H NMR (CDCl3/CF3CO2D):
δ/ppm = 1.90–2.08 (m, 4H), 3.10–3.20 (m, 2H), 3.22–3.30
(m, 2H), 7.64–7.75 (m, 4H), 7.79 (d, J = 7.5Hz, 2H), 8.22 (d,
J = 7.8 Hz, 4H), 8.26 (s, 2H). – 13C NMR (CDCl3/CF3CO2D):
δ/ppm = 5.5, 29.6, 32.4, 36.5, 118.7, 128.0, 128.5, 130.4,
136.1, 171.1, 176.9. – HRMS: calcd. for C21H20IO: 415.0559
(M–ClO4); found: 415.0558.
(387.39)
found: C 71.08 H 3.73 N 10.87.
1-(3,11-Dimethoxy-5,7,8,9-tetrahydro-6H-dibenzo [c,h]
xanthen-7-yl)-1H-1,2,3-benzotriazole (24)
Yield 65%, m.p. 164–166 °C. – 1H NMR (CDCl3): δ/ppm =
1.76–2.00 (m, 2H), 2.31–2.48 (m, 2H), 2.50–2.67 (m, 2H),
2.72–2.87 (m, 2H), 3.83 (s, 6H), 6.38 (s, 1H), 6.69 (s, 2H),
6.87 (d, J = 8.7 Hz, 2H), 7.27 (t, J = 2.1 Hz, 2H), 7.42 (d, J =
6.9 Hz, 1H), 7.80 (d, J = 8.7 Hz, 2H), 8.05 (d, J = 6.9 Hz,
1H). – 13C NMR (CDCl3): δ/ppm = –23.4, 27.8, 55.3, 59.9,
101.8, 110.5, 111.5, 113.5, 119.9, 122.0, 123.3, 123.9, 127.1,
131.5, 138.3, 145.3, 146.9, 160.0.
4-n-Butyl-2,6-diphenylpyrylium Perchlorate (16a)
Yield 32%, m.p. 203 °C. – 1H NMR (CDCl3/CF3CO2D):
δ/ppm = 1.00 (t, J = 7.2 Hz, 3H), 1.45–1.57 (m, 2H), 1.79–
1.90 (m, 2H), 3.13 (t, J = 7.8 Hz, 2H), 7.68–7.74 (m, 4H),
7.78–7.84 (m, 2H), 8.17–8.25 (m, 6H). – 13C NMR (CDCl3/
CF3CO2D): δ/ppm = 13.4, 22.5, 31.3, 37.7, 118.7, 128.0,
128.4, 130.4, 136.1, 171.1, 178.1.
C29H25N3O3 calcd.: C 75.14 H 5.45
(463.54) found: C 74.99 H 5.48
N 9.07
N 9.07.
C21H21ClO5 calcd.: C 64.87 H 5.44
(388.85)
found: C 65.16 H 5.40.
4-Hexyl-2,6-diphenylpyrylium Perchlorate (17a)
Preparation of the Salts 12–19 (General Procedure)
Yield 57%, m.p. 149–153 °C. – 1H NMR (CDCl3/CF3CO2D):
δ/ppm = 0.89 (t, J = 6.6 Hz, 3H), 1.25–1.40 (m, 4H), 1.42–
1.54 (m, 2H), 1.78–1.92 (m, 2H), 3.07–3.18 (m, 2H), 7.65–
7.74 (m, 4H), 7.74–7.82 (m, 2H), 8.21 (d, J = 5.1 Hz, 4H),
8.22 (s, 1H). – 13C NMR (CDCl3/CF3CO2D): δ/ppm = 13.8,
22.3, 29.0, 29.2, 31.3, 38.0, 116.8, 128.0, 128.4, 130.4, 135.9,
170.9, 178.1.
To a solution of the 2,6-diphenyl-4H-(1H-benzotriazol-1-
yl)pyran (7) (1.25 mmol) in dry THF (30 mL), at –78 °C, was
added n-BuLi (0.78 mL, 1.25 mmol, 1.6M in hexane). The
solution was stirred at –78 °C for 0.5 h, before adding the
electrophile (1.25 mmol) as a solution in dry THF (10 mL).
The reaction mixture was stirred overnight and allowed to
warm up to rt, before being quenched with saturated aqueous
NH4Cl-solution (40 mL), and extracted with diethyl ether
(2 × 30 mL). The combined organic extract was washed with
brine and water and dried with MgSO4. The solvent was re-
moved in vacuo and to the resulting oil, acetic acid (20 mL)
and HClO4 (0.4 mL, 70%) added. The precipitate separating
after addition of water (50 mL) is filtered off and recrystal-
lized from glacial acetic acid/nitromethane (10/1, v/v).
C23H25ClO5 calcd.: C 66.26 H 6.06
(416.91)
found: C 66.31 H 5.83.
4-Dodecyl-2,6-diphenylpyrylium Perchlorate (18a)
Yield 44%, m.p. 128–132 °C (from ethanol/ether). –1H NMR
(CDCl3/CF3CO2D): δ/ppm = 0.89 (t, J = 6.2 Hz, 3H), 1.10–
1.50 (m, 16H), 1.57–1.75 (m, 2H), 1.78–1.93 (m, 2H), 3.19
(t, J = 6.7 Hz, 2H), 7.62–7.90 (m, 6H), 8.27 (d, J = 7.0 Hz,
4H), 8.37 (s, 2H). – 13C NMR (CDCl3/CF3CO2D): δ/ppm =
14.0, 22.6, 29.2, 29.3, 29.4, 29.5, 29.6, 29.7, 31.9, 38.0, 118.8,
128.0, 128.4, 130.3, 135.9, 170.8, 178.1.
4-Methyl-2,6-diphenylpyrylium Perchlorate (12a)
Yield 28%, m.p. 288 °C (lit. [12] 268 °C). –1H NMR (CDCl3/
CF3CO2D): δ/ppm = 2.89 (s, 3H), 7.67–7.74 (m, 4H), 7.77–
7.84 (m, 2H), 8.17–8.24 (m, 6H). – 13C NMR (CDCl3/
CF3CO2D): δ/ppm = 24.1, 120.0, 127.9, 128.4, 130.5, 136.1,
170.9, 180.0.
C29H37ClO5 calcd.: C 69.51 H 7.46
(501.07)
found: C 69.30 H 7.45.
4,4'-(1,4-Butyliden)-bis-2,6-diphenylpyrylium bis-Perchlo-
C18H15ClO calcd.: C 62.35 H 4.36
rate (19a)
(346.77)
found: C 62.47 H 4.27.
1
Yield 56%, m.p. 252.7–254 °C. – H NMR (CDCl3/
4-Benzyl-2,6-diphenylpyrylium Perchlorate (13a)
CF3CO2D): δ/ppm = 2.06–2.22 (m, 4H), 3.08–3.35 (m, 4H),
7.57–7.71 (m, 8H), 7.71–7.82 (m, 4H), 8.22 (d, J = 7.5 Hz,
8H), 8.35 (s, 4H). – 13C NMR (CDCl3/CF3CO2D): δ/ppm =
28.7, 37.2, 119.1, 128.0, 128.5,130.3, 135.9, 171.1, 176.9.
C38H32Cl2O10 calcd.: C 63.42 H 4.49
Yield 81%, m.p. 218 °C (lit. [5] 220 °C). – 1H NMR (CDCl3/
CF3CO2D): δ/ppm = 4.45 (s, 2H), 7.31–7.42 (m, 5H), 7.62–
7.69 (m, 4H), 7.72–7.78 (m, 2H), 8.11–8.16 (m, 6H). –
13C NMR (CDCl3/CF3CO2D): δ/ppm = 43.2, 118.7, 127.9,
128.4, 128.5, 129.7, 130.3, 134.1, 136.0, 171.2, 175.6.
C24H19ClO5 calcd.: C 68.17 H 4.53
(719.58)
found: C 63.51 H 4.56.
(422.86):
found: C 67.96 H 4.44.
Transformation of the 4-(1H-Benzotriazol-1-yl)-2,6-di-
arylpyrans to 10a–c and 25 (General Procedure)
4-(4-Chlorobutyl)-2,6-diphenylpyrylium Perchlorate (14a)
1
To a solution of 4H-(1H-benzotriazol-1-yl)-2,6-diarylpyran
(0.63 mmol) in THF (15 mL) was added n-BuLi (0.45 mL,
1.41M solution in hexane, 0.63 mmol) at –78 °C under argon.
After 30 minutes, the reaction mixture was allowed to warm
up to rt and stirred overnight, quenched with water, extracted
with ethyl acetate and dried over MgSO4. The solvent was
removed, and the residue was washed with diethyl ether to
give pure product.
Yield 60%, m.p. 174 – 175.5 °C. – H NMR (CDCl3/
CF3CO2D): δ/ppm = 1.90–2.20 (m, 4H), 3.18–3.30 (m, 2H),
3.60–3.72 (m, 2H), 7.70–7.90 (m, 6H), 8.35 (d, J = 7.5 Hz,
4H), 8.63 (s, 2H). – 13C NMR (CDCl3/CF3CO2D) : δ/ppm =
25.7, 31.1, 36.0, 43.7, 118.6, 127.5, 127.9, 129.6, 135.0, 169.9,
176.4.
C21H20Cl2O5 calcd.: C 59.59 H 4.76
(423.29)
found: C 59.52 H 4.70.
156
J. Prakt. Chem. 1999, 341, No. 2