Ferrocenyl-substituted α,β-unsaturated ketones in synthesis of tetrahydropyrimidinones

Article abstract of DOI:10.1007/s11176-005-0096-2

Ferrocenyltetrahydropyrimidin-2-ones were prepared by reactions of linear and cyclic α,β-unsaturated ketones of the ferrocene series with urea in i-PrOH in the presence of t-BuOK. The structures of the compounds prepared were studied by ¹H and

Full text of DOI:10.1007/s11176-005-0096-2

Russian Journal of General Chemistry, Vol. 74, No. 11, 2004, pp. 1757 1762. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004,
pp. 1887 1893.
Original Russian Text Copyright
2004 by E. Klimova, Lorez, T. Klimova, Garcia, Hernandez, Ramirez.
Ferrocenyl-Substituted , -Unsaturated Ketones in Synthesis
of Tetrahydropyrimidinones
E. I. Klimova, E. A. Vazquez Lopez, T. Klimova, M. Martinez Garcia,
Ortega S. Hernandez, and L. Ruiz Ramirez
National Autonomous University of Mexico, Mexico City, Mexico
Institute of Chemistry, National Autonomous University of Mexico, Mexico City, Mexico
Received November 12, 2002
Abstract Ferrocenyltetrahydropyrimidin-2-ones were prepared by reactions of linear and cyclic , -un-
saturated ketones of the ferrocene series with urea in i-PrOH in the presence of t-BuOK. The structures of the
1
compounds prepared were studied by H and 13C NMR and IR spectroscopy, and also by single crystal X-ray
diffraction.
Urea, thiourea, and their derivatives are used in
synthesis of pyrimidine derivatives, which are compo-
nents of many biologically active substances and
nucleic acids [1]. In the metallocene series, the reac-
tions of thiourea [2 6] and phenylthiourea [6] with
ferrocenyl-substituted chalcones have been reported,
but there is no unambiguous opinion on the structure
of the products. The reactions were performed in al-
cohol in the presence of sodium alcoholates with
refluxing [3, 4, 6] or under ultrasonic treatment [5].
The products of condensation with thiourea were iden-
tified as tetrahydropyrimidinethiones I with the C=C
double bond at the 4,5 position, and the products of
condensation with phenylthiourea, as tetrahydropyri-
midinethiones II with the C=C double bond at the 3,4
position (Scheme 1).
With urea and its derivatives, the related condensa-
tions were not performed. The prospects for applying
the expected products, e.g., as physiologically active
substances make it interesting to prepare ferrocenyl-
substituted tetrahydropyrimidinones and to study in
detail their structure and chemical behavior.
In this work we studied the reactions of urea with
, -unsaturated linear and cyclic ketones containing
the ferrocenyl substituent.
We found that urea reacts with chalcones IIIa IIId
on refluxing in absolute isopropyl alcohol in the pres-
ence of t-BuOK to give 1,2,3,6-tetrahydropyrimidin-2-
ones IVa IVd, respectively, in 70 80% yields
(Scheme 2).
Scheme 2
Scheme 1.
H
H
Ar
O
R1
O
Ar
N
O
NH2CONH2
R1
R2
N
S
+ NH2CSNH2
N
C R
N
R3
R2
H
CH
R3
H
R
Fc
Fc
I
IIIa IIId
IVa IVd
NH2CSNHPh
R = H, A = 4-CH3OC6H4 (a); R = H, Ar = 4-BrC6H4 (b);
R = H, Ar = Fc (c); R = CH3, Ar = Fc (d).
R1
R2
N
S
The isolated pyrimidin-2-ones IVa IVd are the
only reaction products. These are finely crystalline
pale yellow substances stable in storage in the solid
state. In common organic solvents (CHCl3, CH2Cl2,
CH3COCH3, CH3COOEt, C6H6, etc.), they rapidly
decompose, but in basic solvents (pyridine, morpho-
line, dimethylformamide, etc.) they are stable.
N
H
R3
II
R1 = Fc, R2 = H, R3 = Ar; R1 = Ar, R2 = H, R3 = Fc;
R1, R2 = FcCH=C(CH2)3; R3 = Fc, Fc = C5H5FeC5H4.
1070-3632/04/7411-1757 2004 MAIK Nauka/Interperiodica

1758
KLIMOVA et al.
Table 1. 1H NMR data for the compounds prepared, , ppm (J, Hz)
Comp.
no.
C5H5 (s)
C5H4 (m)
CH3, CH2
CH
NH
Ar
IVaa
4.18 (5H) 4.14 (2H), 4.19 3.81 (3H)
(1H), 4.23 (1H)
4.94 d.d (1H, J 2.0, 6.63 br.s (1H), 6.92 d (2H, J 8.7),
4.4), 5.12 m (1H, J 8.20 s (1H)
7.49 d (2H, J 8.7)
4.4)
IVba
IVca
IVda
VIaa
4.19 (5H) 4.17 (3H), 4.23
(1H)
4.18(5H), 4.14 (2H), 4.27
4.21 (5H) (2H), 4.71 (4H)
4.17(5H), 4.13 (2H), 4.32 1.78 (3H)
4.24 (5H) (2H), 4.69 (4H)
5.01 d (1H, J 0.9), 6.15 br.s (1H), 7.43 d (2H, J 8.3),
5.16 d (1H, J 0.9) 8.15 s (1H)
3.8 4.72 br.s (1H), 6.91 br.s (1H),
5.14 d (1H, J 0.9 ) 8.01 s (1H)
4.80 br.s (1H),
5.17 s (1H)
7.52 d (2H, J 8.3)
6.99 br.s (1H)
8.20 s (1H)
4.22 (5H) 4.12 (3H), 4.16 2.24 t (2H, J 7.5), 4.64 br.s (1H)
6.85 br.s (1H), 7.15 m (3H),
(1H)
2.72 d.t (2H, J 7.5,
8.41 s (1H)
7.50 m (1H)
15.0)
VIba
VIcb
VIdc
4.21 (5H) 4.12 (3H), 4.16 2.20 t (2H, J 8.1), 4.62 d (1H, J 1.0) 6.82 br.s (1H),
6.91 m (1H),
7.15 m (2H)
(1H)
2.66 t (2H, J 8.1),
3.76 (3H)
3.62 (5H) 3.50 (3H), 3.55 2.08 2.25 m (4H), 4.11 br.s (1H)
(1H) 3.14 (3H)
8.41 s (1H)
6.13 br.s (1H),
7.90 br.s (1H)
6.16 d (1H, J 8.8),
6.98 d (1H, J 8.8),
7.36 s (1H)
4.22 (5H) 4.12 (3H), 4.15 2.21 t (2H, J 7.8), 4.64 d (1H, J 1.2) 6.84 br.s (1H),
6.70 d.d (1H, J 2.1,
8.4), 7.05 d (1H, J
8.4), 7.12 d (1H,
J 2.1)
6.81 s (1H), 7.23 s
(1H)
(1H)
2.63 q (2H, J 7.8),
3.73 (3H)
8.58 s (1H)
VIea,b 4.19 (5H) 4.07 (2H), 4.11 2.14 m (2H), 2.58 m 4.63 br.s (1H)
6.76 br.s (1H),
8.29 s (1H)
(1H), 4.14 (1H) (2H), 2.17 (3H), 2.81
(3H)
VIIIaa,c 4.20 (5H) 4.11 (1H), 4.12 1.25 m (1H), 1.45 m 4.42 d (1H, J 2.4 ) 5.87 d (1H, J 2.4),
(2H), 4.13 (1H) (3H), 1.63 m (2H),
1.93 2.22 m (4H)
7.79 s (1H)
VIIIba,c 4.12 (5H), 4.11 (1H), 4.14 1.24 m (2H), 1.69 m 4.39 d (1H, J 3.0), 6.68 d (1H, J 3.0),
4.22 (5H) (3H), 4.26 (1H), (3H), 2.24 m (3H) 6.36 s (1H)
7.72 s (1H)
4.29 (2H), 4.43
(1H)
VIIIcc 4.12(5H), 4.14 (1H), 4.23 1.63 2.38 m (6H) 4.98 d (1H, J 0.9), 6.40 br.s (1H),
4.25 (5H) (2H), 4.33 (2H),
4.41 (1H), 4.51
6.07 s (1H)
7.92 s (1H)
(1H), 4.56 (1H)
VIIIdd 4.12(5H), 4.18 (2H), 4.34 2.40 m (1H), 2.54 m 5.11 s (1H), 6.70 s 6.97 s (1H), 9.92 s
4.28 (5H) (2H), 4.46 (4H) (1H), 2.74 m (2H) (1H)
VIIIea,b 4.12 (5H), 4.10 (2H), 4.16 2.24 (3H), 2.71 d (2H, 4.56 d (1H, J 0.8), 6.69 d (1H, J 0.8),
4.23 (5H) (2H), 4.20 (2H), J 8.5 ), 2.86 d (2H, J 6.59 s (1H) 8.29 s (1H)
4.25 (2H) 8.5)
4.19 (5H) 4.07 (2H), 4.10 1.40 2.00 m (8H) 2.38 m (1H), 4.63 d 6.55 d (1H, J 1.8),
(1H), 4.17 (1H) (1H, J 1.8) 8.30 s (1H)
XIIa,b 3.76 (5H), 3.77 (2H), 3.87 1.80 m (2H), 2.10 m 3.63 m (1H), 3.70 m 6.83 br.s (1H),
(1H)
Xa,b
3.97 (5H) (2H), 3.89 (2H), (2H), 2.16 (3H)
(1H), 4.26 br.s (1H), 8.32 s (1H)
6.71 s (1H)
3.93 (1H), 4.10
(1H)
1
a
b
c
d
Note: The H NMR spectra were recorded in the following solvents: (CD ) CO, DCON(CD ) , CDCl , and C D N.
3 2
3 2
3
5 5
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

FERROCENYL-SUBSTITUTED , -UNSATURATED KETONES IN SYNTHESIS
1759
Table 2. 13C NMR data for IVb, IVc, VIa, VIc VIe, VIIIa, and VIIIb (75 MHz); VIIIc, VIIIe, X, and XII (9.0 kHz,
solid state)], C, ppm
Comp.
C5H5
68.6
C5H4
C
ipsoFc CH2, CH3
C
CH= CH C=O
CN
Ar
no.
IVba
IVca
65.3, 65.4,
67.15, 67.2
65.3, 65.4,
65.7, 66.8, 67.4, 92.7
67.5, 68.7, 68.8
91.3
121.5, 127.6 98.1 50.3 134.2 132.7 126.3, 130.7
94.2 49.8 153.3 134.2
68.4,
69.2
79.8,
VIaa
VIcb
VIda
VIea,b
68.6
68.2
68.5
68.5
65.2, 66.1, 67.1, 92.9 24.4, 27.8,
108.9, 127.5,
128.9
53.4 154.2 135.5 121.1, 126.3,
127.4, 127.5
53.8 158.7 127.7 106.2, 110.3,
113.6
53.5 158.2 130.0 107.1, 109.3,
112.9
53.7 154.3 134.5 119.9, 129.9
67.5
64.8, 66.1, 66.8, 93.1 24.1, 28.1,
67.2 55.3
65.2, 66.1, 67.1, 92.8 24.8, 26.9,
67.5 55.3
65.2, 66.2, 67.1, 93.1 19.0, 20.5,
67.4 23.4, 24.2
54.5
121.8, 121.9,
121.95, 153.5
127.2, 127.6,
128.2, 154.2
108.2, 127.8,
128.8, 130.5,
134.2
VIIIaa,c 68.6
66.9, 67.0, 69.2, 78.5 24.1, 25.4,
107.5
54.2 152.7 131.6
69.6
28.4, 29.9,
30.1
VIIIba,c 66.5,
63.3, 64.2, 64.9, 78.8, 23.8, 24.1,
65.5, 66.2, 66.4, 91.3 27.6, 28.2
123.7, 129.5 107.9 53.9 152.0 131.9
67.0
66.8,
68.2
VIIIcd 68.1,
69.2
63.0 75.0
82.8, 23.7, 25.0,
93.1 26.5
83.3, 47.4, 52.2,
92.9 54.0
107.6, 127.5 113.0 55.9 156.9 128.3
118.4, 126.1 114.5 55.1 156.7 127.4
52.2, 157.1 122.7,
VIIIdd 70.1,
70.4
65.2 75.0
64.2, 67.8
65.0 76.0
Xd
69.8
95.4
25.0 32.0
53.9
135.9
XIId
68.5,
69.9
82.8, 32.5, 33.4,
92.6 36.2
121.5, 125.6 112.0 52.9, 157.5 127.9
58.9,
69.5
13
a
b
c
d
The C NMR spectra were recorded in the following solvents: (CD ) SO, DCON(CD ) , CDCl , and neat sample, solid phase.
3 2
3 2
3
Table 3. IR data (KBr) for the compounds prepared
Comp.
no.
1
, cm
IVa
IVb
IVc
IVd
VIa
VIb
VIc
VId
VIe
769, 800, 1027, 1180, 1246, 1295 1459, 1513, 1613, 1681, 2836, 2962, 3096, 3220, 3330, 3462
748, 816, 1005, 1149, 1297, 1467, 1561, 1620, 1684, 2923, 3091, 3230, 3423
701, 749, 813, 999, 1103, 1160, 1288, 1436, 1482, 1584, 1693, 2843, 2942, 3093, 3224, 3429
689, 759, 817, 1002, 1105, 1241,1290, 1437, 1573, 1673, 2828, 2920, 2976, 3090, 3255, 3367
723, 768, 808, 820, 1028, 1108, 1269, 1294, 1390, 1450, 1481, 1560, 1681, 2832, 2934, 3098, 3223, 3331, 3426
750, 789, 823, 1035, 1111,1218, 1263, 1295, 1344, 1432, 1468, 1577, 1680, 2835, 2934, 3090, 3230, 3428
769, 814, 1001, 1037, 1125, 1156, 1252, 1276,1378, 1426, 1467, 1592, 1647, 1680, 2835, 2933, 3091, 3223, 3433
772, 819, 1033, 1120, 1220, 1295, 1473, 1484, 1578, 1607, 1679, 2831, 2936, 3093, 3231, 3430
767, 811, 1008, 1027, 1106, 1228, 1298, 1395, 1462, 1480, 1654, 1678, 2830, 2923, 3101, 3226, 3429
VIIIa 763, 775, 820, 1027, 1075, 1214, 1301, 1393, 1443, 1481, 1647, 1684, 2846, 2921, 3097, 3254, 3342
VIIIb 672, 750, 812, 997, 1104, 1220, 1298, 1325, 1458, 1470, 1656, 1682, 2851, 2925, 3091, 3234, 3428
VIIIc 670, 769, 819, 997, 1105, 1220, 1296, 1330, 1423, 1467, 1637, 1681, 2830, 2933, 3093, 3240, 3433
VIIId 679, 754, 816, 1001, 1104, 1293, 1351, 1414, 1458, 1630, 1677, 2847, 2923, 3092, 3214, 3438
VIIIe 689, 756, 818, 893, 1001, 1067, 1129, 1293, 1370, 1465, 1623, 1681, 2767, 2938, 3091, 3252, 3430
X
762, 814, 957, 1027, 1106, 1197, 1236, 1369, 1451, 1475, 1624, 1681, 2868, 2939, 3099, 3257, 3327
XI
695, 745, 830, 1002, 1157, 1220, 1262, 1287, 1324, 1402, 1463, 1627, 1680, 2180, 2866, 2932, 3092, 3344, 3440
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

1760
KLIMOVA et al.
C26
C25
C22
O1
C24
C23
Fe2
C1
C3
N1
N6
C27
C20
C12
C17
C4
C21
C5
C13
Fe1
C16
C19
C18
C7
C11
C8
C15
C9
C10
Molecular structure of IVd.
1
The compounds were characterized by IR and H
and 13C NMR spectroscopy and by elemental analysis
(Tables 1 4); the data obtained confirm the suggested
structures. In particular, the H NMR spectrum of
each of compounds IVa IVd contains two NH proton
at 5.14 ppm), H6 signal (compounds IVa IVc), and
cyclopentadienyl proton signals.
1
The structure of IVd was determined by single
crystal X-ray diffraction. The required crystal was
obtained by crystallization from morpholine. It was
found that compound IVd, indeed, has the structure
of 6-methyl-4,6-diferrocenyl-1,2,3,6-tetrahydropyrimi-
signals, characteristic signals of olefinic protons at
3
5
6
5.12, 5.16, and 5.14 ppm with JH H 4.4, 1.2, and
0.9 Hz for IVa IVc, respectively (for IVd, a singlet
Table 4. Yields, melting points, and elemental analyses of IVa IVd, VIa VIe, VIIIa VIIIe, X, and XII
Found, % Calculated, %
Comp. Yield,
mp,
C
Formula
no.
%
C
H
Fe
N
C
H
Fe
N
IVa
IVb
IVc
IVd
VIa
VIb
VIc
71
68
75
80
92
87
91
86
92
91
94
90
87
88
89
85
233 234
191 193
181 182
255 256
264 265
282 284
266 267
313 314
293 295
291 293
295 297
263 265
278 280
257 259
284 286
295 297
64.81
55.10
64.78
62.61
68.54
66.84
66.73
66.51
69.98
64.97
66.08
65.67
64.76
63.79
62.97
63.83
5.43
3.84
4.92
5.09
5.39
5.23
5.49
5.52
6.02
6.45
5.37
5.21
4.87
5.23
5.74
5.94
14.17
12.91
24.12
23.20
14.68
13.24
13.70
13.58
13.72
16.08
20.28
21.04
21.69
20.27
7.05
6.23
5.83
5.71
7.41
6.54
6.44
6.53
6.93
8.12
5.26
5.11
5.23
7.80
C21H20FeN2O2
C20H17BrFeN2O 54.94
64.97
5.20
3.92
4.76
5.04
5.25
5.35
5.35
5.35
6.10
6.33
5.53
5.30
5.06
5.34
5.83
6.14
14.38
12.78
23.97
23.26
14.53
13.49
13.49
13.49
13.51
15.95
20.45
20.99
21.55
20.41
7.21
6.40
6.00
5.83
7.23
6.76
6.76
6.76
6.78
8.00
5.13
5.26
5.40
7.67
C24H22Fe2N2O
C25H24Fe2N2O
C22H20FeN2O
C23H22FeN2O2
C23H22FeN2O2
C23H22FeN2O2
C24H25FeN2O
C19H22FeN2O
C30H30Fe2N2O
C29H28Fe2N2O
C28H26Fe2N2O
C29H29Fe2N3O
C19H21FeN3O
C20H23FeN3O
64.84
62.53
68.77
66.68
66.68
66.68
69.74
65.16
65.96
65.44
64.90
63.65
62.83
63.68
VId
VIe
VIIIa
VIIIb
VIIIc
VIIId
VIIIe
X
15.28 11.72
14.71 10.92
15.37 11.56
14.80 11.13
XII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

FERROCENYL-SUBSTITUTED , -UNSATURATED KETONES IN SYNTHESIS
1761
din-2-one. The general view of the molecule of IVd is
shown in the figure; the main geometric parameters
are given in Table 5 and do not require special com-
ments.
Table 5. Selected bond lengths d and bond angles in the
molecule of IVd
Bond
d,
Bond angle
, deg
We studied the behavior in this reaction of a series
of mono- and bisferrocenalacetones of the carbo- and
heterocyclic series (compounds Va Ve, VIIa VIIe,
IX, XI) and found that, in all the cases, the reactions
are fast and give polycyclic ferrocenyltetrahydropyri-
midin-2-ones VIa VIe, VIIIa VIIIe, X, and XII, re-
spectively, in high yields (Scheme 3).
O1 C1
C1 N1
C1 N6
N1 C3
C11 C14
C3 C4
1.230(4)
1.354(5)
1.360(4)
1.474(5)
1.519(16)
1.512(5)
1.524(5)
1.333(5)
1.407(4)
1.469(5)
1.410(5)
1.414(5)
1.422(5)
1.412(5)
1.522(5)
2.046(4)
O1C1N1
O1C1N6
C1N1C3
N1C3C4
N1C3C7
C4C3C7
C5C4C3
C4C5N6
C1N6C5
N1C3C27
C4C3C27
C8C7C11
C8C7C3
C11C7C3
C8C7Fe1
C5C17Fe34
123.5(4)
114.5(4)
126.4(3)
106.8(3)
110.3(3)
109.0(3)
123.2(4)
117.6(4)
124.5(4)
108.5(3)
110.0(3)
106.3(4)
126.7(4)
126.4(4)
69.7(2)
C3 C7
C4 C5
Scheme 3.
C5 N6
C5 C17
C7 C8
O
H
H
C17 C18
C17 C21
C7 C11
C3 C27
C7 Fe1
N
N
O
H
R3
R2
R3
R2
Fc
Fc
NH2CONH2
R1
R1
122.1(3)
VIa VIe
Va Ve
R1 = R2 = R3 = H (a); R1 = CH3O, R2 = R3 = H (b); R1 =
R3 = H, R2 = CH3O (c); R1 = R2 = H, R3 = CH3O (d);
R1 = R3 = CH3, R2 = H (e).
(Tables 1 4). The position of the C=C double bond
in the tetrahydropyrimidin-2-one ring is confirmed by
the multiplicity and position of the proton signals of
the substituted cyclopentadienyl ring of the Fc moiety
[7]; all or some of them are shifted upfield relative to
the C5H5 singlet, as in products IVa IVd. The signals
of the quaternary carbon atoms in the 13C NMR spec-
tra additionally confirm the suggested structures.
O
H
H
N
N
X
O
X
H
R
R
Fc
NH2CONH2
Fc
)
(
)
(
The regioselectivity of formation of VIa VIe,
VIIIa VIIIe, X, and XII is very high. All these com-
pounds were isolated as single isomers. The content
of possible alternative isomers was too low for their
reliable detection and identification.
VIIa VIIe
VIIIa VIIIe
R = H, X = (CH2)4 (a); R = FcCH=, X = (CH2)4 (b); R =
FcCH=, X = (CH2)3 (c); R = FcCH=, X = (CH2)2 (d); R =
FcCH=, X = CH2N(CH2)CH2 (e).
H
EXPERIMENTAL
O
N
O
NH2CONH2
The IR spectra were taken on a Specord IR-75
1
spectrometer in KBr. The H and 13C NMR spectra
H
N
H
N
N
of solutions were measured on a Varian Unity-Inova
spectrometer [300 and 75 MHz, respectively; solvents
CDCl3, (CD3)2SO, DCON(CD3)2, and C5D5N; inter-
nal reference Me4Si]. The 13C NMR spectra of solid
Fc
Fc
IX
X
NH2CONH2
N
CH3
N
VIIIc, VIIIe, X, and XII were taken on a Bruker
CH3
Fc
H
1
DMX-500 spectrometer (9.3 kHz). The H and 13C
CHFc
FcCH
FcCH
NMR and IR data are given in Tables 1 3. For the
chromatography of the starting chalcones, we used
columns packed with Al2O3 (Brockmann grade III);
the eluent was hexane ether, 1 : 2 (by volume).
O
N
N
H
O
XI
XII
The structures of IVa IVe, VIIIa VIIIe, X, and
The following chemicals (Aldrich) were used: fer-
rocenecarbaldehyde, 99%; cyclohexanone, 99%; cy-
cloheptanone, 99%; 1-methyl-4-piperidone, 97%;
1
XII were unambiguously proved by IR and H and
13C NMR spectra, and also by elemental analysis
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004

1762
KLIMOVA et al.
Table 6. Crystallographic data and parameters of X-ray
diffraction experiment for IVd
the direct method and refined by the least-squares
method in the full-matrix anisotropic approximation
for nonhydrogen atoms.
Parameter
Value
, -Unsaturated ketones IIIa IIId, Va Ve,
VIIc VIIe, IX, and XI were prepared from ferrocene-
carbaldehyde and the corresponding ketones in
aqueous-alcoholic alkali [8]. Compounds VIIa and
VIIb were prepared by condensation of cyclohepta-
none with ferrocenecarbaldehyde in benzene in the
presence of t-BuOK [9].
Formula
C22H24Fe2N2O
480.16
291(2)
Monoclinic
C2/c
22.3342(15)
14.7506(10)
14.6421(10)
90.0
123.21
90.0
1
Molecular weight, g mol
Temperature, K
Crystal system
Space group
a,
b,
c,
Synthesis of 6-ferrocenyl-1,2,3,6-tetrahydropyr-
imidin-2-ones IVa IVd, VIa VIe, VIIIa VIIIe, X,
and XII. A mixture of 10 mmol of chalcone IIIa
IIId, Va Ve, VIIc VIIe, IX, or XI, 25 mmol of urea,
20 mmol of t-BuOK, and 150 ml of i-PrOH was re-
fluxed with stirring for 3 5 h until the bright red color
of the chalcone disappeared and a yellow solution
formed. This solution was quickly poured into 200 ml
of water. The precipitate was filtered off, washed with
water on the filter, and vacuum-dried. The finely crys-
talline products obtained were virtually pure ferro-
cenyltetrahydropyrimidinones, yields 70 90%. For
additional purification, they were recrystallized from
morpholine.
, deg
, deg
, deg
3
V,
4035.9(5)
8
1.580
1.458
1984
Z
3
dcalc, g cm
1
Absorption coefficient, mm
F(000)
Radiation
MoK
,
0.71073
Graphite
1.76 24.99
16354
Monochromator
, deg
Total number of reflections
Number of unique reflec-
tions with I > 2 (I)
R1
ACKNOWLEDGMENTS
3552
0.0479
0.0591
0.0755
272
The study was financially supported by DGAPA-
UNAM (grant no. IN203599). The authors are grate-
ful to O.S.J. Mun~ os for measuring the NMR spectra.
WR2
Rint
Number of refined
parameters
Weight scheme
REFERENCES
w = 1/[ 2(Fo2) +
(0.1693P)2 + 10.77P],
where P = (Fo2 + 2Fc)/3
0.908
1. Ulbricht, T.I.V., Purines, Pyrimidines and Nucleotides,
New York: MacMillan, 1964, pp. 46 50.
2. Shvekhgeimer, M.-G.A., Usp. Khim., 1996, vol. 65,
no. 1, p. 43.
Goodness of fit (full-matrix
least-squares method on F2)
Residual electron density,
0.386/0.733
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ko, D.P., J. Organomet. Chem., 1993, vol. 456, p. 235.
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1972, vol. 10, P. 79.
3
e
,
/
min max
4-methoxybenzaldehyde, 98%; acetylferrocene, 95%;
4-bromobenzaldehyde, 99%; 3-quinuclidinone hydro-
chloride, 97%; tropinone, 99%; cyclopentanone, 99%;
-tetralone, 98%; 5-methoxy-1-tetralone, 97%; urea,
99%; 6-methoxy-1-tetralone, 99%; 7-methoxy-1-tetra-
lone, 99%; 5,7-dimethyl-1-tetralone, 97%; potassium
tert-butylate, 95%.
8. Nesmeyanov, A.N., Postnov, V.N., Klimova, E.I., and
Sazonova, V.A., Izv. Akad. Nauk SSSR, Ser. Khim.,
1979, no. 2, p. 239.
9. Klimova, E.I., Martinez, G.M., Klimova, T., and Men-
dez, S.J.M., J. Organomet. Chem., 2000, vol. 602,
p. 105.
The unit cell parameters and reflection intensities
were measured on a Bruker-Smart APEX-CCD dif-
fractometer. The crystallographic data and parameters
of the X-ray diffraction experiment and refinement are
given in Table 6. The structure of IVd was solved by
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 11 2004