New quaternary phosphonium salt as multi-site…
(
300 MHz, CDCl ) d 8.26 (d, J = 6 Hz, 1H), 8.21 (s, 1H), 7.79 (d, J = 6 Hz, 2H),
3
7
.41 (s, 3H), 2.02 (t, J = 6 Hz, 4H), 1.20 – 1.03 (m, 24H), 0.81 (t, J = 4.5 Hz, 6H);
C NMR (75 MHz, CDCl ) d: 152.33, 151.98, 147.67, 147.14, 138.74, 129.28,
1
3
3
1
2
27.39, 123.28, 123.22, 121.21, 119.79, 118.25, 55.69, 40.06, 31.74, 29.87, 29.18,
9.16, 23.74, 22.58, 14.06.
Synthesis of 2-bromo-7-nitro-9,9-dioctyl-9H-fluorene (6b)
To a stirred solution of 2-bromo-7-nitro-fluorene 4b (1 g, 3.4 mmol) in DMSO,
2
5 % aq. sodium hydroxide solution added dropwise over a period of 10 min under
nitrogen gas purging, then catalyst 3 (10 mol %) was added and followed by
-bromooctane 5a (1.33 g, 6.8 mmol), then the reaction mass was stirred at room
1
temperature. Reaction completion was confirmed by TLC, then extracted with ethyl
acetate, washed with water, dried over sodium sulfate and evaporated under reduced
1
pressure, to obtain a white solid with 95 % yield. H NMR (300 MHz, CDCl ) d
3
8
.26-8.19 (m, 1H), 7.80-7.76 (m, 1H), 7.65 (d, J = 3 Hz, 1H), 7.58 (d, J = 27 Hz,
H), 7.53–7.37 (m, 1H), 2.07–1.95 (m, 4H), 1.25–1.05 (m, 24H), 0.82 (t,
1
13
J = 4.5 Hz, 6H); C NMR (75 MHz, CDCl ) d: 154.40, 151.63, 147.41, 146.46,
3
1
37.73, 130.74, 126.58, 123.44, 122.49, 119.92, 118.30, 118.24, 56.02, 39.95,
1.72, 29.78, 29.14, 23.70, 22.57, 14.05.
3
Synthesis of 2,7-dibromo-9,9-dioctyl-9H-fluorene (6c)
To a stirred solution of 2,7-dibromofluorene 4c (1 g, 3.0 mmol) in DMSO, 25 % aq.
sodium hydroxide solution added dropwise over a period of 10 min under nitrogen
gas purging, then the catalyst 3 (10 mol %) was added followed by 1-bromooctane
5
with ethyl acetate, washed with water, dried over sodium sulfate and evaporated
a (1.19 g, 6.1 mmol). Reaction completion was confirmed by TLC, then extracted
1
under reduced pressure, to obtain a white solid with 96 % yield. H NMR
(
300 MHz, CDCl ) d: 7.53–7.43 (m, 6H), 1.92–1.88 (m, 4H), 1.20–1.05 (m, 20H),
3
13
0
1
2
.85 (t, J = 6 Hz, 6H), 0.59 (d, J = 6 Hz, 4H); C NMR (75 MHz, DMSO) d:
52.54, 139.05, 130.14, 126.16, 121.47, 121.09, 55.67, 40.14, 31.75, 29.85, 29.16,
9.14, 23.61, 22.59, 14.07.
Synthesis of 9,9-dihexyl-9H-fluorene (6d)
To a stirred solution of fluorene 4d (1 g, 6.0 mmol) in DMSO, 25 % aq. sodium
hydroxide solution added dropwise over a period of 10 min under nitrogen gas
purging, then catalyst 3 (10 mol %) was added, followed by 1-bromohexane 5b
(
1.98 g, 12.0 mmol). Reaction completion was confirmed by TLC, then extracted
with ethyl acetate, washed with water, dried over sodium sulfate and evaporated
1
under reduced pressure, to obtain a colourless viscous liquid with 98 % yield. H
NMR (300 MHz, CDCl ) d: 7.88–7.86 (m, 2H), 7.53–7.43 (m, 6H), 2.19–2.14 (m,
3
1
H), 1.33–1.23 (m, 12H), 0.94 (t, J = 6 Hz, 6H), 0.85–0.78 (m, 4H); C NMR
3
4
(
75 MHz, CDCl ) d: 145.58, 136.25, 122.05, 121.79, 117.71, 114.72, 50.03, 35.66,
3
2
6.62, 24.90, 18.82, 17.69, 9.06.
123