at 150 1C for 20 min. The solution was neutralized by an
aqueous 6 N NaOH solution and extracted with dichloro-
methane (3 Â 3 mL). The organic layers were dried over MgSO4
and evaporated. The residue was purified using column chro-
matography (eluent: petroleum ether/diethyl ether: 7/3).
2 (a) R. G. Sherrill, J. M. Berman, L. Birkemo, D. K. Croom,
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General procedure for ferrocenyl benzodiazepine synthesis.
To a solution of benzodiazepines 7–9 (0.636 mmol) in freshly
distilled DMF (10 mL) was added t-BuOK (0.713 g,
0.636 mmol) at 0 1C. After stirring for 30 min at 0 1C,
ferrocenylmethyltrimethyl ammonium iodide 10 (0.169 g,
0.438 mmol) in DMF (5 mL) was added to the mixture at
20 1C. The solution was heated at 150 1C for 4 h under N2. 1 M
HCl solution was then added until neutralization and the
mixture was extracted by CH2Cl2 (3 Â 15 mL). The organic
layers were dried over MgSO4 and evaporated. The residue
was purified using column chromatography (eluent: ethyl
acetate/petroleum ether: 5/5).
7-Chloro-1,3-dihydro-1-ferrocenylmethyl-5-phenyl-2H-1,4-
benzodiazepin-2-one (11). Yield 68%. Mp 184 1C. dH
(300 MHz, CDC13) 7.37 (3H, m, ArH), 7.27 (4H, m,
ArH), 7.06 (1H, m, ArH), 5.12 (1H, d, J 14.0 Hz, CH2Fc),
4.70 (1H, d, J 10.3 Hz, CH2), 4.41 (1H, d, J 14.0 Hz,
CH2Fc), 4.09 (5H, s, Cp’), 3.97 (4H, m, Cp), 3.64 (1H, d,
J 10.3 Hz, CH2); dC (75.5 MHz, CDC13) 169.1, 168.2, 140.7,
138.2, 132.0, 131.0, 130.5, 129.5, 129.4, 128.2, 124.4, 69.4,
68.6, 67.9, 56.9, 46.2. rtLCMS 3.58 MS 368.9. Found: C,
66.35; H, 4.57; N, 5.96%. C26H21ClFeN2O requires C,
66.62; H, 4.52; N, 5.98%.
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7-Chloro-1,3-dihydro-1-ferrocenylmethyl-5-(-2-fluorophenyl)-
2H-1,4-benzodiazepin-2-one (12). Yield 78%. Mp 110 1C. dH
(300 MHz, CDC13) 7.37–7.30 (3H, m, ArH), 7.29 (1H, td,
J 9.1 and 3.0 Hz, ArH), 7.10 (1H, td, J 7.1 and 3.0 Hz, ArH),
6.99 (1H, s, ArH), 6.97–6.95 (1H, m, ArH), 5.05 (1H, d,
J 14.2 Hz, CH2Fc), 4.78 (1H, d, J 10.5 Hz, CH2), 4.61 (1H,
d, J 14.1 Hz, CH2Fc), 4.07–3.96 (3H, m, Cp), 4.05 (5H, s, Cp’),
3.98 (2H, m, Cp), 3.67 (1H, d, J 10.5 Hz, CH2); dC (75.5 MHz,
CDC13) 168.1, 165.8, 140.1, 132.2, 1322, 131.5, 131.1, 130.0,
128.4, 124.3, 124.1, 116.4, 116.1, 69.7, 69.1, 68.7, 68.1, 57.0,
46.6. rtLCMS 3.51 MS 486.9. Found: C, 63.99; H, 4.13; N,
5.65%. C26H20ClFFeN2O requires C, 64.16; H, 4.14;
N, 5.76%.
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1,3-Dihydro-1-ferrocenylmethyl-5-phenyl-2H-1,4-benzodiazepin-
2-one (13). Yield 84%. Mp 215 1C. dH (300 MHz, CDC13) 7.49
(2H, m, ArH), 7.42–7.31 (5H, m, ArH), 7.28 (2H, m, ArH),
5.20 (1H, d, J 15.0 Hz, CH2Fc), 4.70 (1H, d, J 10.1 Hz, CH2),
4.53 (1H, d, J 15.0 Hz, CH2Fc), 4.16 (5H, s, Cp’), 3.90 (4H, m,
Cp), 3.67 (1H, d, J 10.2 Hz, CH2); dC (75.5 MHz, CDC13) 172.2,
171.2, 139.4, 138.8, 131.7, 131.3, 130.3, 129.7, 128.7, 127.2, 123.3,
121.2, 69.7, 69.1, 68.7, 68.7, 68.1, 57.0, 55.7. rtLCMS 3.31 MS
434.9. Found: C, 71.12; H, 5.23; N, 6.33%. C26H22FeN2O
requires C, 71.40; H, 5.11; N, 6.45%.
14 J. Safaei-Ghomi and A. Hatami, Synth. Commun., 2008, 38,
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c
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