◦
1
1
1
2
58–160 C. H NMR (300 MHz, CDCl
3
): d 7.66 (d, J = 7.5 Hz,
fluorene (1a) (5.00 Kg, 15.43 mol), KOH (0.87 Kg, 15.43 mol)
H), 7.57 (d, J = 8.0 Hz, 1H), 7.50 (s, 1H), 7.47 (d, J = 8.0 Hz,
H), 7.33 (t, 1H), 7.25 (t, 1H). C NMR (75.5 MHz, CDCl ):
d 192.6, 146.2, 143.1, 141.5, 135.2, 134.5, 132.5, 130.2, 129.2,
25.5, 124.8, 121.3, 120.6. Analysis calculated for (%) C13 ClO:
C, 72.74; H, 3.29. Found C, 72.91; H, 3.31.
and THF (25 L). The reaction mixture was stirred at room
temperature while the solution was kept lower than the snorkel,
and air was introduced for 5 min every 30 min to ensure there was
sufficient oxygen with minimal loss of solvent. At the completion
of the reaction, the reaction mixture was filtered to remove KOH
and the filtrate was concentrated to obtain the crude product.
The crude product was washed with water (3 ¥ 50 L), dried
to give 5.11 Kg of 2,7-dibromofluorenone, yield: 98%. KOH
1
3
3
1
H
7
Synthesis of 2-fluorofluorenone (2k)
Application of the above procedure to 2-fluorofluorene (1k)
0.921 g, 5 mmol), KOH (0.280 g, 5 mmol) and THF (15 mL)
afforded compound 2k (0.941 g, 95%) as a yellow solid: mp
(0.65 Kg, 75%) and THF (20 L, 75%) were recycled.
(
◦
1
1
7
7
1
1
15–117 C. H NMR (300 MHz, CDCl
3
): d 7.66–7.69 (m, 1H),
Acknowledgements
.45–7.49 (m, 3H), 7.33–7.36 (m, 1H), 7.27–7.31 (m, 1H), 7.14–
.18 (m, 1H). C NMR (75.5 MHz, CDCl ): d 192.4, 165.9,
61.1, 143.8, 140.1, 140.0, 136.3, 136.2, 135.0, 134.3, 128.7,
24.5, 121.8, 121.7, 121.2, 120.8, 120.1, 112.1, 111.9. Analysis
calculated for (%) C13
H, 3.54.
1
3
This work was supported by Research Project Supported by
Shanxi Scholarship Council of China (No. 200817) and The
Science and Technology Project for the Higher Educational
Institutes of Shanxi Province of China (No. 20080001).
3
7
H FO: C, 78.78; H, 3.56. Found C, 78.59;
Notes and references
Synthesis of 3-fluorofluorenone (2l)
1
(a) A. A. Gouda, Talanta, 2009, 80, 151–157; (b) W.-Y. Wong, G.-L.
Lu, K.-H. Choi and Y.-H. Guo, J. Organomet. Chem., 2005, 690,
Application of the above procedure to 3-fluorofluorene (1l)
1
77–186; (c) J. Wang, M.-Q. Wu, W.-B. Liu, S.-W. Yang, J.-W. Bai,
(
0.921 g, 5 mmol), KOH (0.280 g, 5 mmol) and THF (15 mL)
Q.-Q. Ding and Y. Li, Eur. Polym. J., 2010, 46, 1024–1031; (d) L.
Oldridge, M. Kastler and K. M u¨ llen, Chem. Commun., 2006, 885;
afforded compound 2l (0.924 g, 93%) as a yellow solid: mp 123–
◦
1
1
25 C. H NMR (300 MHz, CDCl
3
): d 7.68 (t, 2H), 7.50–7.53
(
e) D. Cao, Z. Liu, Y. Deng, G. Li and G. Zhang, Dyes Pigm., 2009,
(
(
1
1
m, 2H), 7.33–7.37 (m, 1H), 7.22 (d, J = 5.5 Hz, 1H), 6.94–6.98
83, 348–353; (f) E. W. Reinheimer, J. R. Gal a´ n-Mascar o´ s and K. R.
Dunbar, Synth. Met., 2009, 159, 45–51; (g) A. Baheti, P. Singh and
K. R. Justin Thomas, Dyes Pigm., 2011, 88, 195–203; (h) S. Song, D.
Ju, J. Li, D. Li, Y. Wei, C. Dong, P. Lin and S. Shuang, Talanta, 2009,
77, 1707–1714; (i) X. Zeng, C. Wang, A. S. Batsanov, M. R. Bryce, J.
Gigon, B. Urasinska-Wojcik and G. J. Ashwell, J. Org. Chem., 2010,
1
3
m, 1H). C NMR (75.5 MHz, CDCl
3
): d 192.2, 168.5, 166.4,
47.8, 147.7, 142.9, 134.9, 134.8, 130.5, 130.0, 126.8, 126.7,
24.5, 120.5, 116.0, 115.9, 108.8, 108.6. Analysis calculated for
FO: C, 78.78; H, 3.56. Found C, 78.61; H, 3.55.
(
%) C13
H
7
7
5, 130–136; (j) X. Xu, H. Zhang, X. Liu, Q. Zhuang and Z. Han, Eur.
Polym. J., 2010, 46, 528–534; (k) Y. Lu, M. Li, Y. Zhang, D. Hu, L. Ke
and W. Xu, Thermochim. Acta, 2010, 515, 32–37; (l) N. Agarwal, Dyes
Pigm., 2009, 83, 328–333; (m) A. Farcas, N. Jarroux, V. Harabagiu
and P. Gu e´ gan, Eur. Polym. J., 2009, 45, 795–803; (n) D. Hadjipavlou-
Litina, G. E. Magoulas, M. Krokidis and D. Papaioannou, Eur. J.
Med. Chem., 2010, 45, 298–310; (o) J. Kim, Y. Jin, S. Song, S. H.
Kim, S. H. Park, K. Lee and H. Suh, Macromolecules, 2008, 41,
Synthesis of 2-methylfluorenone (2m)
Application of the above procedure to 2-methylfluorene (1m)
(
0.901 g, 5 mmol), KOH (0.420 g, 7.5 mmol) and THF (15 mL)
afforded compound 2m (0.874 g, 90%) as a yellow solid: mp 91–
◦
1
9
7
2
1
1
2 C. H NMR (300 MHz, CDCl
3
): d 7.62 (d, J = 7.2 Hz, 1H),
8
324–8331; (p) K. Takagi, S. Sugimoto, M. Mitamura, Y. Yuki, S.-I.
.44–7.47 (m, 3H), 7.38 (d, J = 7.6 Hz, 1H), 7.23–7.28 (m, 2H),
Matsuoka and M. Suzuki, Synth. Met., 2009, 159, 228–233; (q) K.
Chupungars, P. Rerngsamran and S. Thaniyavarn, Int. Biodeterior.
Biodegrad., 2009, 63, 93–99; (r) Y. Lu, Y. Zhou, Y.-W. Quan, Q.-
M. Chen, R.-F. Chen, Z.-Y. Zhang, Q.-L. Fan, W. Huang and J.-F.
Ding, Org. Lett., 2011, 13, 200–203; (s) M. E. El-Khouly, Y. Chen,
X. Zhuang and S. Fukuzumi, J. Am. Chem. Soc., 2009, 131, 6370–
1
3
.36 (s, 3H). C NMR (75.5 MHz, CDCl
41.3, 138.8, 135.0, 134.4, 134.1, 134.0, 128.5, 124.7, 123.9,
21.8, 119.5, 21.1. Analysis calculated for (%) C14 10O: C, 86.57;
3
): d 194.1, 144.3,
H
H, 5.19. Found C, 86.69; H, 5.20.
6
371; (t) X. Zhang, J.-B. Han, P.-F. Li, X. Ji and Z. Zhang, Synth.
Commun., 2009, 39, 3804–3815; (u) P. V. Ivchenko, I. E. Nifant’ev,
V. A. Ezersky and A. V. Churakov, J. Organomet. Chem., 2011, 696,
Synthesis of 3-methylfluorenone (2n)
1
931–1934; (v) K. M. Omer, S.-Y. Ku, K.-T. Wong and A. J. Bard,
Application of the above procedure to 3-methylfluorene (1n)
0.901 g, 5 mmol), KOH (0.420 g, 7.5 mmol) and THF (15 mL)
afforded compound 2n (0.884 g, 91%) as a yellow solid: mp 67–
J. Am. Chem. Soc., 2009, 131, 10733–10741; (w) Y. Wei, S. Samori,
S. Tojo, M. Fujitsuka, J.-S. Lin, C.-T. Chen and T. Majima, J. Am.
Chem. Soc., 2009, 131, 6698–6707; (x) E. Kaya, A. Balan, D. Baran,
A. Cirpan and L. Toppare, Org. Electron., 2011, 12, 202–209; (y) K.
M. Omer, S.-Y. Ku, Y.-C. Chen, K.-T. Wong and A. J. Bard, J. Am.
Chem. Soc., 2010, 132, 10944–10952; (z) H. S. Oh, S. Liu, H. Jee,
A. Baev, M. T. Swihart and P. N. Prasad, J. Am. Chem. Soc., 2010,
(
◦
1
6
7
7
(
1
9 C. H NMR (300 MHz, CDCl
3
): d 7.66 (d, J = 7.5 Hz, 1H),
.57 (d, J = 7.5 Hz, 1H), 7.46–7.51 (m, 2H), 7.35 (s, 1H), 7.28–
1
3
.30 (m, 1H), 7.10 (d, J = 8.0 Hz, 1H), 2.46 (s, 3H). C NMR
): d 194.0, 146.3, 145.3, 144.8, 135.2, 135.1,
32.4, 130.0, 129.5, 124.7, 124.6, 121.7, 120.5, 22.1. Analysis
1
32, 17346–17348; (aa) Y.-M. Jeon, J.-W. Kim, C.-W. Lee and M.-S.
75.5 MHz, CDCl
3
Gong, Dyes Pigm., 2009, 83, 66–71; (bb) J.-C. Tsai, M. Kumar and
J.-G. Lin, J. Hazard. Mater., 2009, 164, 847–855.
calculated for (%) C14
H, 5.21.
H
10O: C, 86.57; H, 5.19. Found C, 86.74;
2 (a) H. P. Rathnayake, A. Cirpan, F. E. Karasz, M. Y. Odoi, N. I.
Hammer, M. D. Barnes and P. M. Lahti, Chem. Mater., 2007, 19,
3
265–3270; (b) N. Chidambaram and S. Chandrasekaran, J. Org.
Chem., 1987, 52, 5048–5051; (c) R. Rangarajan and E. J. Eisenbraun,
J. Org. Chem., 1985, 50, 2435–2438; (d) W.-F. Jiang, H.-L. Wang,
A.-G. Wang and Z.-Q. Li, Synth. Commun., 2008, 38, 1888–1895;
Pilot-scale study for synthesis of 2,7-dibromofluorenone
Into a 50 L four-necked flask equipped with a mechanical stirrer,
a snorkel and an air condenser were charged 2,7-dibromo-9-
(
e) R. Grisorio, P. Mastrorilli, G. Ciccarella, G. P. Suranna and C. F.
Nobile, Tetrahedron Lett., 2008, 49, 2078–2082; (f) J. G. Rodr ´ı guez,
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Green Chem., 2011, 13, 1891–1896 | 1895