8
Tetrahedron
–
1
Yellow-orange solid; mp : 135.9 °C; yield 52 %; IR (ATR,
Yellow solid; mp : 135.2 °C; yield 37 %; IR (ATR, ν/cm ):
ACCEPTED MANUSCRIPT
–1
ν/cm ): 3099, 2980, 2872, 1697, 1649, 1510, 1232, 1159, 1097,
3092, 2974, 2918, 2198, 1616, 1510, 1423, 1261, 1107, 817, 732,
1
1
9
72, 812, 763, 752; H-NMR (400 MHz, CDCl , δ): 1.29 (3H, t,
711; H-NMR (400 MHz, CDCl , δ): 2. 32 (3H, s), 3.48 (1H, d,
3
3
J=7.2 Hz), 2.31 (3H, s), 2.37 (3H, t, J=1.6 Hz), 3.35 (1H, dd,
J=14.0, 1.6 Hz), 3.67 (1H, dd, J=14.0, 1.6 Hz), 4.03 (1H, d, J=1.2
Hz), 4.16-4.22 [10H (2H, O-CH -CH ; 8H, Ferrocene C-H), m],
J=14.4 Hz), 3.79 (1H, d, J=14.0 Hz), 4.07-4.08 (1H, m), 4.16-
4.17 (6H, m), 4.21-4.22 (2H, m), 7.12 (2H, d, J=7.6 Hz), 7.18
(1H, dd, J=5.2, 3.6 Hz), 7.24 (2H, d, J=8.0 Hz), 7.54 (1H, dd,
2
3
13
13
7
.09 (2H, d, J=8.0 Hz), 7.22 (2H, d, J=8.4 Hz); C-NMR (100
J=5.2, 1.2 Hz), 7.98 (1H, dd, J=3.6, 0.8 Hz); C-NMR (100
MHz, CDCl , δ): 14.29(CH ), 14.51(CH ), 20.99(CH CO),
MHz, CDCl , δ): 21.01(CH ), 46.45(C4), 66.63(CH), 66.65(CH),
3
3
3
3
3
3
4
6
1
1
4.92(C4), 59.54(CH ), 66.25(CH), 67.01(CH), 67.84(CH),
68.18(CH), 68.63(CH), 68.89(CH*5), 91.94(C3), 93.70(C5),
117.31(CN), 124.74(CH*2), 128.26(CH), 128.87(CH*2),
129.63(CH), 129.88(CH), 130.21(C), 137.58(C), 141.60(C),
2
8.42(CH), 68.78(CH*5), 89.40(C), 95.26(C5), 101.45(C3),
24.81(CH*2), 128.68(CH*2), 136.95(C), 143.19(C), 166.06(C),
+
+
+
66.47(C); LC-MS m/z (%) : 430 (M , % 82), 431 (MH , %
160.86(C2); HRMS (m/z): C H FeNOS calculated for [M+H] :
26
21
+
1
00); HRMS (m/z): calculated for C H FeO [M] : 430.12314;
452.0766; found: 452.07951.
25
26
3
found: 430.12770.
5
-[3-(Ferrocenyl)-3-(p-tolyl)allyliden]-1,3-dimethyl-
2
-Ferrocenyl-2-(4-methyl-phenyl)-6,6-dimethyl-2,3,6,7-
tetrahydrobenzofuran-4(5H)-one (19)
Yellow solid; mp : 167.5 °C; yield 50 %; IR (ATR, ν/cm ):
pyrimidin-2,4,6(1H,3H,5H)-trione (23)
Purple solid, mp : 274-275 °C; yield 17 %; IR (ATR, ν/cm ):
–
1
–
1
3101, 2960, 2926, 1716, 1656, 1539, 1409, 1303, 1222, 1083,
1
1
3
103, 2927, 2866, 1624, 1508, 1402, 1236, 812, 738; H-NMR
821, 785, 750; H-NMR (400 MHz, CDCl , δ): 2.43 (3H, s), 3.31
3
(
2
400 MHz, CDCl , δ): 1.14 (3H, s), 1.19 (3H, s), 2.29 (2H, s),
.32 (3H, s), 2.44 (2H, s), 3.38 (1H, d, J= 14.0 Hz), 3.67 (1H, dt,
(3H, s), 3.40 (3H, s), 4.20 (5H, s), 4.63-4.64 (2H, m), 4.66-4.67
(2H, m), 7.20 (2H, d, J=8.4 Hz), 7.26 (2H, d, J=7.6 Hz), 8.01
(1H, d, J=12.8 Hz), 8.48 (1H, d, J=13.2 Hz) ; C-NMR (100
3
13
J= 14.0, 1.6 Hz), 3.94-3.95 (1H, m), 4.15 (5H, s), 4.18-4.22 (3H,
m), 7.11 (2H, d, J=8.0 Hz), 7.22 (2H, d, J=8.0 Hz); C-NMR
13
MHz, CDCl , δ): 21.39(CH Ph), 27.92(NCH ), 28.43(NCH ),
3
3
3
3
(
100 MHz, CDCl , δ): 21.00(CH Ph), 28.84(CH *2), 34.10(C6),
70.50(CH*2), 70.99(CH*5), 73.16(CH*2), 83.28(C), 110.22(C),
121.70(CH), 128.86(CH*2), 129.68(CH*2), 134.09(C),
139.53(C), 151.75(C), 154.35(CH), 162.34(C), 163.08(C),
3
3
3
3
6
1
1
8.03(C7), 40.99(C3), 50.97(C5), 66.13(CH), 67.38(CH),
8.13(CH), 68.79(CH), 68.85(CH*5), 94.27(C), 94.36(C),
11.34(C), 124.94(CH/2), 128.75(CH*2), 137.34(C), 142.13(C),
+
+
171.32(C); LC-MS m/z (%) : 468 (M , %100), 469 (MH , %65);
Anal. Calcd for C H FeN O : C % 66.68, H 5.17, N 5.98;
+
74.81(C), 194.74(CO); LC-MS m/z (%) : 440 (M , % 44), 441
26
24
2
3
+
+
(MH , % 100); HRMS (m/z): calculated for C H FeO [M+H]
found: C % 66.61, H 5.13, N 6.12.
27
28
2
:
441.15115; found: 441.15551.
1
-[5-Ferrocenyl-2-methyl-5-(4-fluoro-phenyl)-4,5-
2
-Ferrocenyl-2-(4-methyl-phenyl)-2,3,6,7-
dihydrofuran-3-yl]ethanone (24)
tetrahydrobenzofuran-4(5H)-one (20)
Yellow solid; mp : 140-141 °C; yield 41 %; IR (ATR, ν/cm ):
Yellow-orange solid; mp : 74.9-76.0 °C; yield 55 %; IR (ATR,
ν/cm ): 3019, 1620, 1605, 1244, 1215, 934, 821; H-NMR (400
–1
–1
1
1
3
101, 2974, 2870, 1625, 1510, 1402, 1180, 815, 752; H-NMR
MHz, CDCl , δ): 2.28 (3H, s), 2.41 (3H, t, J=1.2 Hz), 3.38 (1H,
3
(
400 MHz, CDCl , δ): 2.09-2.15 (2H, m), 2.32 (3H, s), 2.42 (2H,
dd, J=14.0; 1.2 Hz), 3.74 (1H, dd, J=14.0; 1.2 Hz), 4.01 (1H, d,
J=1.6 Hz), 4.13 (1H, d, J=1.6 Hz), 4.15 (5H, s), 4.19-4.21 (2H,
m), 6.96-7.01 (2H, m), 7.28-7.32 (2H, m); C-NMR (100 MHz,
3
td, J=6.4; 2.8 Hz), 2.58 (2H, t, J=6.4 Hz), 3.38 (1H, d, J=14.0
Hz), 3.66 (1H, dt, J=14.0; 2.0 Hz), 3.95-3.96 (1H, m), 4.14 (5H,
s), 4.17-4.19 (2H, m), 4.21-4.23 (1H, m), 7.11 (2H, d, J=8.4 Hz),
7
2
6
9
1
13
CDCl , δ): 15.19(CH ), 29.48(CH CO), 45.68(C4), 66.15(CH),
3
3
3
13
.22 (2H, d, J=8.0 Hz);
C-NMR (100 MHz, CDCl , δ):
66.87(CH), 68.06(CH), 68.65(CH), 68.78(CH*5), 89.20(C),
3
2
1.00(C6), 21.89(CH3), 24.14(C7), 36.50(C5), 41.06(C3),
6.09(CH), 67.34(CH), 68.11(CH), 68.78(CH), 68.81(CH*5),
3.98(C), 94.38(C), 112.93(C), 124.98(CH*2), 128.75(CH*2),
94.79(C5), 112.20(C3), 114.86 (CH*2, d, J=21.3 Hz), 126.65
3
4
(CH*2, d, J=8.4 Hz), 141.65 (C, d, J=3.9 Hz), 161.93 (C, d,
1
19
J=245.3 Hz), 165.93(C2), 194.05(CO); F-NMR (376 MHz,
CDCl , δ): -115.20; HRMS (m/z): C H FFeO calculated for
[M+H] : 405.09478; found: 405.09600.
37.36(C), 142.17(C), 175.86(C), 195.47(CO); HRMS (m/z):
3
23 21
2
+
+
C H FeO calculated for [M+H]
:
413.11985; found:
25
24
2
4
13.12185.
Ethyl
5-ferrocenyl-5-(4-fluoro-phenyl)-2-methyl-4,5-
5
-Ferrocenyl-2-phenyl-5-(4-methyl-phenyl)-4,5-
dihydrofuran-3-carboxylate (25)
Yellow solid; mp : 97.5 °C; yield 57 %; IR (ATR, ν/cm ): 3095,
–
1
dihydrofuran-3-carbonitrile (21)
–
Yellow-orange solid; mp : 145.8 °C; yield 46 %; IR (ATR, ν/cm
2970, 2928, 1697, 1645, 1508, 1271, 1155, 1146, 1085, 1072,
1
1
)
: 3089, 3026, 2964, 2922, 2200, 1625, 1575, 1259, 1103, 1026,
968, 833, 808, 754; H-NMR (400 MHz, CDCl , δ): 1.31 (3H, t,
3
1
8
12, 759; H-NMR (400 MHz, CDCl , δ): 2.32 (3H, s), 3.52
J=7.2 Hz), 2.39 (3H, s), 3.32 (1H, dd, J=14.4, 1.6 Hz), 3.69 (1H,
dd, J=14.4, 1.6 Hz), 4.03 (1H, d, J=1.6 Hz), 4.14-4.24 [10H (2H,
O-CH -CH ; 8H, Ferrocene C-H), m], 6.94-7.00 (2H, m), 7.28-
3
(1H, d, J=14.4 Hz), 3.85 (1H, d, J=14.8 Hz), 4.07-4.08 (1H, m),
4
.16 (5H, s), 4.22-4.24 (3H, m), 7.12 (2H, d, J=8.0 Hz), 7.24 (2H,
2
3
13
13
d, J=7.6 Hz), 7.50-7.53 (3H, m), 8.10-8.13 (2H, m); C-NMR
7.33 (2H, m);
C-NMR (100 MHz, CDCl , δ): 14.26(CH ),
3
3
(
100 MHz, CDCl , δ): 21.03(CH ), 46.73(C4), 66.38(CH),
14.50(CH ), 45.05(C4), 59.65(CH ), 66.17(CH), 66.90(CH),
3
3
3
2
6
9
1
1
6.79(CH), 68.14(CH), 68.70(CH), 68.87(CH*5), 78.64(C),
0.97(C5), 94.04(C3), 117.69(CN), 124.75(CH*2),
27.15(CH*2), 128.11(C), 128.85(CH*2), 128.91(CH*2),
67.96(CH), 68.55(CH), 68.79(CH*5), 89.02(C), 94.94(C5),
2
101.49(C3), 114.79 (CH*2, d, J=21.4 Hz), 126.66 (CH*2, d,
3
4
1
J=7.6 Hz), 141.97 (C, d, J=3.1 Hz), 161.89 (C, d, J=244.6 Hz),
19
31.45(CH), 137.60(C), 141.97(C), 165.52(C2); HRMS (m/z):
165.92(C), 166.28(C); F-NMR (376 MHz, CDCl , δ): -115.45;
LC-MS (m/z): 434.30 (M , % 100); Anal. Calcd for C H FFeO
3
+
+
C H FeNO calculated for [M+H]
:
446.12018; found:
28
23
24 23
3
4
46.12274.
: C % 66.38, H 5.34; found: C % 66.38, H 5.034
5
-Ferrocenyl-5-(4-methyl-phenyl)-2-(thien-2-yl)-4,5-
2-Ferrocenyl-2-(4-fluoro-phenyl)-6,6-dimethyl-2,3,6,7-
tetrahydrobenzofuran-4(5H)-one (26)
dihydrofuran-3-carbonitrile (22)