4040
C. Fehér et al. / Journal of Organometallic Chemistry 694 (2009) 4036–4041
104–105 °C. Anal. Calc. for C19H14FeO (314.16): C, 72.64; H, 4.49.
Found: C, 72.51; H, 4.56%. Yield: 91%.
4.5.9. 3-Ferrocenyl-5-n-hexyl-1-methyl-5-pyrazole (8d)
1H NMR (400 MHz, CDCl3) d: 6.04 (s, 1H); 4.62 (brs, 2H); 4.23
(brs, 2H); 4.05 (s, 5H); 3.74 (s, 3H); 2.57 (t, J = 7.4 Hz, 2H); 1.65
(t, J = 7.4 Hz, 2H); 1.28–1.40 (m, 6H); 0.88 (t, J = 7.4 Hz, 3H). 13C
NMR (CDCl3) d: 149.2; 144.1; 102.1; 79.4; 69.6; 68.4; 66.6; 36.1;
31.8; 29.2; 28.6; 25.9; 22.8; 14.3. MS (m/z/rel. int.): 350 (M+)/
100; 278/15; 213/7; 140/10; 121/9; 56/5. Anal. Calc. for
C20H26FeN2 (350.29): C, 68.58; H, 7.48; N, 8.00. Found: C, 68.43;
H, 7.56; N, 7.89%. Yield: 70%. (Contains 2% of 9d).
4.5.2. 1-Ferrocenyl-2-heptyn-1-one (3b)
1H NMR (400 MHz, CDCl3) d: 4.89 (brs, 2H); 4.55 (brs, 2H); 4.23
(s, 5H); 2.44 (t, J = 7.5 Hz, 2H); 1.45–1.70 (m, 4H); 0.97 (t, J = 7.5 Hz,
3H). IR (cmÀ1): 2206; 1613. 13C NMR (CDCl3) d:181.8; 93.0; 80.8;
80.7; 73.2; 70.7; 70.6; 30.2; 22.2; 19.0; 13.7. MS (m/z/rel. int.):
294 (M+)/100; 265/5; 251/2; 237/4; 223/10; 200/8; 121/20; 56/
15. Red oil. Anal. Calc. for C17H18FeO (294.17): C, 69.41; H, 6.17.
Found: C, 69.60; H, 6.09%. Yield: 65%.
4.5.10. 1,3-Diphenyl-5-ferrocenyl-pyrazole (11a)
1H NMR (400 MHz, CDCl3) d: 7.94 (dd, J = 1.2 Hz, 8.4 Hz, 2H);
7.34–7.46 (m, 8H); 6.84 (s, 1H); 4.21 (brs, 2H); 4.15 (brs, 2H);
4.10 (s, 5H). 13C NMR (CDCl3) d: 151.7; 143.1; 140.5; 133.2;
128.8; 128.6; 128.1; 127.8; 126.3; 125.8; 103.8; 74.9; 69.8; 68.7;
68.6. MS (m/z/rel. int.): 404 (M+)/100; 339/6; 281/4; 254/4; 235/
8; 202/5; 180/5; 152/5; 121/12; 77/8; 56/10. Anal. Calc. for
C25H20FeN2 (404.29): C, 74.27; H, 4.98; N, 6.93. Found: C, 74.12;
H, 5.07; N, 7.05%. Yield: 78%. (Contains 4% of 10a).
4.5.3. 4,4-Dimethyl-1-ferrocenyl-2-pentyn-1-one (3c)
1H NMR (400 MHz, CDCl3) d: 4.90 (brs, 2H); 4.60 (brs, 2H); 4.25
(s, 5H); 1.39 (s, 9H). 13C NMR (CDCl3) d: 181.8; 93.1; 81.0; 79.2;
73.1; 70.8; 70.7; 30.6; 28.1. IR (cmÀ1): 2222; 1621. MS (m/z/rel.
int.): 294 (M+)/100; 251/27; 200/13; 121/22; 56/9. Red solid.
M.p.: 89–90 °C. Anal. Calc. for C17H18FeO (294.17): C, 69.41; H,
6.17. Found: C, 69.07; H, 6.35%. Yield: 65%.
4.5.11. 2-Amino-6-ferrocenyl-4-phenyl-pyrimidine (14a)
4.5.4. 1-Ferrocenyl-2-nonyn-1-one (3d)
1H NMR (400 MHz, CDCl3) d: 7.99–8.03 (m, 2H); 7.45–7.51 (m,
3H); 7.12 (s, 1H); 5.06 (brs, 2H); 4.96 (t, J = 1.9 Hz, 2H); 4.45 (t,
J = 1.9 Hz, 2H); 4.09 (s, 5H). 13C NMR (CDCl3) d: 169.7; 164.9;
163.6; 138.2; 130.4; 128.9; 127.2; 104.2; 81.4; 70.9; 70.2; 68.2.
MS (m/z/rel. int.): 355 (M+)/100; 290/16; 207/11; 177/9; 145/11;
121/8; 89/6; 56/8. Dark red solid. M.p.: 159–160 °C. Anal. Calc.
for C20H17FeN3 (355.22): C, 67.62; H, 4.82; N, 11.83. Found: C,
67.49; H, 4.70; N, 11.95%. Yield: 50%.
1H NMR (400 MHz, CDCl3) d: 4.85 (brs, 2H); 4.58 (brs, 2H); 4.25
(s, 5H); 2.42 (t, J = 7.6 Hz, 2H); 1.22–1.70 (m, 8H); 0.88 (t, J = 7.6 Hz,
3H). 13C NMR (CDCl3) d: 181.8; 93.1; 80.8; 80.7; 73.2; 70.7; 70.6;
31.5; 28.8; 28.2; 22.8; 19.3; 14.3. IR (cmÀ1): 2212; 1627. MS (m/
z/rel. int.): 322 (M+)/100; 223/5; 121/18; 56/7. Red oil. Anal. Calc.
for C19H22FeO (322.23): C, 70.82; H, 6.88. Found: C, 71.05; H,
6.65%. Yield: 60%.
4.5.5. 4-Acetoxy-1-ferrocenyl-2-butyn-1-one (3e)
4.5.12. 2-Amino-4-n-butyl-6-ferrocenyl-pyrimidine (14b)
1H NMR (400 MHz, CDCl3) d: 6.60 (s, 1H); 5.02 (brs, 2H); 4.85
(brs, 2H); 4.41 (brs, 2H); 4.04 (s, 5H); 2.58 (t, J = 7.4 Hz, 2H); 1.70
(quintet, J = 7.4 Hz, 2H); 1.41 (sextet, J = 7.4 Hz, 2H); 0.98 (t,
J = 7.4 Hz, 3H). 13C NMR (CDCl3) d: 171.1; 168.1; 163.1; 106.7;
81.2; 70.8; 70.1; 68.1; 37.8; 31.1; 22.7; 14.1. MS (m/z/rel. int.):
335 (M+)/100; 293/65; 228/7; 147/17; 121/13; 56/7. Dark red so-
lid. M.p.: 114–115 °C. Anal. Calc. for C18H21FeN3 (335.23): C,
64.49; H, 6.31; N, 12.53. Found: C, 64.53; H, 6.57; N, 12.22%. Yield:
41%.
1H NMR (400 MHz, CDCl3) d: 4.95 (s, 2H); 4.91 (brs, 2H); 4.62
(brs, 2H); 4.28 (s, 5H); 2.15 (s, 3H). 13C NMR (CDCl3) d: 180.5;
170.2; 84.9; 83.9; 80.0; 73.7; 70.9; 70.8; 52.0; 20.8. IR (cmÀ1):
2219; 1749; 1627. MS (m/z/rel. int.): 310 (M+)/100; 268/7; 240/
12; 158/21; 121/18; 56/15. Red solid. M.p.: 100–101 °C. Anal. Calc.
for C16H14FeO3 (310.13): C, 61.97; H, 4.55. Found: C, 62.16; H,
4.78%. Yield: 20%.
4.5.6. 3-Ferrocenyl-1-methyl-5-phenyl-pyrazole (8a)
1H NMR (400 MHz, CDCl3) d: 7.39–7.48 (m, 5H); 6.36 (s, 1H);
4.69 (brs, 2H); 4.27 (brs, 2H); 4.11 (s, 5H); 3.87 (s, 3H). 13C NMR
(CDCl3) d: 149.7; 144.5; 130.8; 128.7; 128.6; 128.4; 103.7; 78.7;
69.4; 68.3; 66.5; 37.4. IR (cmÀ1): 1565; 1478. MS (m/z/rel. int.):
342 (M+)/100; 277/10; 221/4; 171/9; 121/8; 56/7. Orange solid.
M.p.: 132–134 °C. Anal. Calc. for C20H18FeN2 (342.22): C, 70.19;
H, 5.30; N, 8.19. Found: C, 70.31; H, 5.42; N, 8.25%. Yield: 90%.
4.5.13. 2-(4-Benzoylamino-4-ethoxycarbonyl-butyl-amino)-6-
ferrocenyl-4-phenyl-pyrimidine (15a)
1H NMR (400 MHz, CDCl3) d: 8.00–8.03 (m, 2H); 7.76–7.79 (m,
2H); 7.36–7.50 (m, 6H); 7.04 (s, 1H); 6.75 (d, J = 7.6 Hz, 1H); 5.18
(t, J = 7.1 Hz, 1H); 4.94–4.95 (m, 2H); 4.85–4.91 (m, 1H); 4.41
(brs, 2H); 4.21 (q, J = 7.1 Hz, 2H); 4.06 (s, 5H); 3.59 (q, J = 6.7 Hz,
2H); 2.10–2.20 (m, 1H); 1.90–2.03 (m, 1H); 1.74–1.87 (m, 2H);
1.26 (t, J = 7.2 Hz, 3H). 13C NMR (CDCl3) d: 172.8; 169.0; 167.3;
164.3; 162.9; 138.4; 134.2; 131.9; 130.3; 129.2; 128.8; 127.3;
127.2; 103.0; 81.9; 70.7; 70.1; 68.2; 61.9; 52.7; 41.4; 30.6; 26.0;
14.4. MS (m/z/rel. int.): 603 ([M+H]+)/100. Dark red solid. M.p.:
66–67 °C. Anal. Calc. for C34H34FeN4O3 (602.51): C, 67.78; H,
5.69; N, 9.30. Found: C, 67.61; H, 5.75; N, 9.42%. Yield: 40%.
4.5.7. 5-n-Butyl-3-ferrocenyl-1-methyl-pyrazole (8b)
1H NMR (400 MHz, CDCl3) d: 6.02 (s, 1H); 4.62 (brs, 2H); 4.21
(brs, 2H); 4.02 (s, 5H); 3.71 (s, 3H); 2.55 (t, J = 7.2 Hz, 2H); 1.65
(quintet, J = 7.2 Hz, 2H); 1.42 (sextet, J = 7.2 Hz, 2H); 0.97 (t,
J = 7.2 Hz, 3H). 13C NMR (CDCl3) d: 149.2; 144.0; 102.0; 79.5;
69.6; 68.4; 66.6; 36.1; 30.8; 25.6; 22.6; 14.0. MS (m/z/rel. int.):
322 (M+)/100; 278/20; 257/7; 213/9; 140/10; 56/5. Anal. Calc. for
C18H22FeN2 (322.23): C, 67.09; H, 6.88; N, 8.69. Found: C, 67.28;
H, 6.56; N, 8.89%. Yield: 98%. (Contains 3% of 9b).
4.5.14. 2-(4-Benzoylamino-4-ethoxycarbonyl-butyl-amino)-4-n-
butyl-6-ferrocenyl-pyrimidine (15b)
1H NMR (400 MHz, CDCl3) d: 7.78–7.82 (m, 2H); 7.48–7.51 (m,
1H); 7.41–7.44 (m, 2H); 6.80 (d, J = 7.7 Hz, 1H); 6.48 (s, 1H); 5.12
(brs, 1H); 4.89 (brs, 2H); 4.85–4.90 (m, 1H); 4.38 (brs, 2H); 4.22
(q, J = 6.5 Hz, 2H); 4.04 (s, 5H); 3.52 (q, J = 7.0 Hz, 2H); 2.54 (t,
J = 8.0 Hz, 2H); 1.74–2.20 (m, 4H); 1.72 (quintet, J = 8.0 Hz, 2H);
1.39 (sextet, J = 8.0 Hz, 2H); 1.28 (t, J = 6.5 Hz, 3H); 0.96 (t,
J = 8.0 Hz, 3H). 13C NMR (CDCl3) d: 172.8; 170.9; 168.2; 167.8;
162.9; 134.2; 132.0; 128.8; 127.3; 105.9; 82.1; 70.5; 70.0; 68.1;
61.9; 52.6; 40.7; 37.8; 31.1; 30.5; 26.1; 22.6; 14.2; 14.1. MS (m/
4.5.8. 5-t-Butyl-3-ferrocenyl-1-methyl-pyrazole (8c)
1H NMR (400 MHz, CDCl3) d: 6.03 (s, 1H); 4.63 (brs, 2H); 4.25
(brs, 2H); 4.09 (s, 5H); 3.94 (s, 3H); 1.40 (s, 9H). 13C NMR (CDCl3)
d: 151.8; 148.1; 101.3; 79.8; 69.5; 68.3; 66.4; 39.2; 31.1; 29.7.
MS (m/z/rel. int.): 322 (M+)/100; 305/34; 292/11; 241/7; 140/10;
56/3. Orange solid. M.p.: 96–98 °C. Anal. Calc. for C18H22FeN2
(322.23): C, 67.09; H, 6.88; N, 8.69. Found: C, 66.85; H, 6.71; N,
8.95%. Yield: 56%.