Reaction of acetylferrocene with dimethylformamide dimethyl acetal and some transformations of the reaction product

Article abstract of DOI:10.1134/S1070363211030133

1-Dimethylamino-3-ferrocenyl-3-oxoprop-1-ene was synthesized by the reaction of acetylferrocene with dimethylformamide dimethyl acetal. Its reactivity in the reactions with mononucleophilic (sodium salts of phenol, thiophenol, benzenesulfinate, diethylphosphorous acid) and binucleophilic reagents (hydrazine hydrate, hydroxylamine, amidines, 1,2-diaminobenzene, 2-aminophenol, 2-aminothiophenol) and methyl iodide was studied. As a result, we obtained new ferrocene-containing α-keto-unsaturated compounds and heterocycles of pyrazole, isoxazole, pyrimidine, and benzazepine series. In the reaction with CH₃I formed ferrocenoylacetylene which in the presence of dicarbonyl-bis(triphenylphosphine)nickel catalyst easily trimerized to give a mixture of 1,2,4- and 1,3,5-triferrocenoylbenzene.

Full text of DOI:10.1134/S1070363211030133

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 3, pp. 521–528. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.I. Moskalenko, A.V. Boeva, V.I. Boev, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 3, pp. 425–432.
Reaction of Acetylferrocene
with Dimethylformamide Dimethyl Acetal
and Some Transformations of the Reaction Product
A. I. Moskalenko, A. V. Boeva, and V. I. Boev
Lipetsk State Pedagogical University, ul. Lenina 42, Lipetsk, 398020 Russia
e-mail: kaf_himii@lspu.lipetsk.ru
Received March 23, 2010
Abstract—1-Dimethylamino-3-ferrocenyl-3-oxoprop-1-ene was synthesized by the reaction of acetylferrocene
with dimethylformamide dimethyl acetal. Its reactivity in the reactions with mononucleophilic (sodium salts of
phenol, thiophenol, benzenesulfinate, diethylphosphorous acid) and binucleophilic reagents (hydrazine hydrate,
hydroxylamine, amidines, 1,2-diaminobenzene, 2-aminophenol, 2-aminothiophenol) and methyl iodide was
studied. As a result, we obtained new ferrocene-containing α-keto-unsaturated compounds and heterocycles of
pyrazole, isoxazole, pyrimidine, and benzazepine series. In the reaction with CH I formed ferrocenoylacetylene
3
which in the presence of dicarbonyl-bis(triphenylphosphine)nickel catalyst easily trimerized to give a mixture
of 1,2,4- and 1,3,5-triferrocenoylbenzene.
DOI: 10.1134/S1070363211030133
Studies in the chemistry of ferrocene and its
derivatives attracted attention in connection with a
number of unusual and unique properties of these
compounds [1, 2], including a wide range of biological
activity. Most interesting with respect to the biological
effects are heterocyclic derivatives of ferrocene [3, 4],
whose activity depends on the nature of functional groups
and the nature of the heterocycle in their molecules.
The methods for obtaining these ferrocene derivatives
play an important role, for they stimulate the research
on new heterocyclic compounds of the ferrocene series
with potential practically useful properties.
reactive reagents in organic synthesis [10–12] of
compounds of various types, including heterocycles.
Therewith, the greater lability of the substrate
hydrogen atoms, the easier proceeds its condensation
with acetal I [7–9]. In this regard, we can expect a low
reactivity of acetylferrocene in the reaction with acetal
I, since the acidity of the hydrogen atoms of acetyl
groups is significantly reduced by the influence of
electron-donating ferrocenyl core [1]. Indeed, we
found that acetylferrocene poorly reacted with acetal I:
only on prolonged (52 h) boiling in a large excess of
the latter in an inert atmosphere. Even in these
conditions, only 26% of acetylferrocene reacted with
compound I to form enamine II in quantitative yield
with respect to the converted acetylferrocene. The
more prolonged reflux of the reaction mixture led to its
darkening due to the decomposition of ferrocene-
containing components, and the yield of the desired
product II decreased.
Here we report on the first examined reaction of
acetylferrocene with dimethylformamide dimethyl
acetal I, which is known [5–9] to be able to react with
compounds containing labile hydrogen atoms. In the
reaction two moles of methanol were released and the
corresponding enamines were formed, the highly
o
(
CH O) CHN(CH ) 105 C, 52 h
3 2 3 2,
I
Fc
C
O
CH3
Fc
C
O
CH CH N(CH3)2
−
2 CH OH
3
II
Fc = C
5
H
5 5 4
FeC H .
5
21

5
22
MOSKALENKO et al.
Table 1. Yields, melting points, TLC, elemental analysis, and chromato-mass-spectral data of compounds III–XXI
Mass-
spectrum,
m/z [M + 1]
284
Found, %
Fe
Calculated, %
Fe
Comp. Yield,
no.
mp,
R
f
Formula
M
calc
%
°С
(system)
C
H
N
C
H
N
+
а
II
99.2 169–170 0.55 (B)
63.38 5.89 19.73 4.87 C15
61.64 4.81 21.93 10.94 C13
61.40 4.28 22.07 5.54 C13
60.03 4.48 19.89 14.93 C14
61.67 5.41 15.93 11.86 C18
66.75 6.33 16.28 12.18 C19
60.64 4.46 14.85 11.17 C19
67.81 4.19 15.73 11.74 C20
69.63 4.55 16.83 8.42 C19
69.45 4.31 16.94 4.09 C19
65.82 4.24 16.18 3.88 C19
66.96 6.38 17.27 4.25 C18
69.63 5.48 16.19 3.95 C20
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
17FeNO 63.60 6.01 19.75 4.95 383
61.90 4.76 22.22 11.12 252
11FeNO 61.66 4.35 22.13 5.53 253
b
III
IV
V
99.2 151–152 0.65 (А)
253
12FeN
2
b
72.0 110–112 0.72 (А)
254
52.0 174–175 0.48 (А)
64.2 158–159 0.73 (А)
86.5 152–154 0.54 (А)
86.7 181–182 0.59 (А)
89.2 208–209 0.51 (B)
73.0 138–139 0.77 (C)
71.4 118–120 0.64 (C)
84.2 133–134 0.71 (C)
59.0 174–175 0.68 (B)
67.5 184–186 0.47 (B)
70.8 128–129 0.38 (C)
79.5 136–137 0.44 (C)
75.4 184–185 0.36 (C)
280
13FeN
19FeN
15FeN
17FeN
15FeN
16FeN
3
3
3
3
3
2
60.22 4.66 20.07 15.05 279
61.89 5.44 16.05 12.03 349
66.86 6.58 16.42 12.32 341
60.80 4.53 14.93 11.20 375
67.99 4.25 15.86 11.90 353
69.51 4.88 17.07 8.54 328
VI
350
O
O
VII
342
VIII
IX
376
2
354
X
329
XI
330
15FeNO 69.30 4.56 17.02 4.26 329
15FeNS 66.09 4.35 16.23 4.06 345
XII
XIII
XIV
XV
346
324
21FeNO 66.87 6.50 17.34 4.33 323
19FeNO 69.57 5.51 16.23 4.06 345
346
333
68.79 4.61 16.74
65.51 4.47 16.23
59.84 4.18 14.86
54.36 5.68 14.73
65.42 4.17 23.38
65.24 4.09 23.61
C
C
C
C
C
C
19
19
19
17
13
39
16FeO
16FeOS
2
68.67 4.82 16.87
65.52 4.60 16.09
60.00 4.21 14.74
54.26 5.59 14.89
65.55 4.20 23.53
65.55 4.20 23.53
332
348
380
376
238
714
XVI
XVII
XVIII
XIX
349
381
16FeO
21FeO
10FeO
3
S
P
70.5 108–109 0.72 (C)
377
4
b
81.0 78–80
0.81 (А)
239
c
XX+XXI 84.0 218–220 0.56 (А)
715
30Fe
3
O
3
a
b
o
c
With respect to the converted acetylferrocene. Published data [13] mp: 148–153 C (III); 110–112°C (IV); 78–80°C (XIX). Two peaks
with the integral intensities ratio 1:3.
1
Table 2. IR and Н NMR spectral data for compounds III–XXI
–
1
IR spectrum, ν, cm
Comp.
no.
1
Н NMR spectrum, δ, ppm
Ferrocene core
Aromatic system Functional groups
II
2997, 1596, 1418, 1101,
1668 (C=O),
1624 (C=C)
2.98 s (6H, 2CH
3
), 4.15 s (5H, C
), 5.36 d (1H, C=СН, J 16.2 Hz), 7.69 d
1H, C=СН–N, J 16.2 Hz)
3.98 s (5H, C ), 4.23 m (2H, C
), 6.48 d (1Н, Het), 7.54 d (1Н, Het)
4.08 s (5H, C ), 4.35 m (2H, C ), 4.78 m (2H,
), 6.05 d (1Н, Het), 7.97 d (1Н, Het)
4.10 s (5H, C ), 4.52–4.76 m (6H, C
(1Н, Het), 8.46 d (1Н, Het)
3.28–3.49 m (4H, 2 NCH ), 3.76–3.98 m (4H, 2 OCH
4.08 s (5H, C ), 4.56 m (2H, C ), 4.81 m (2H,
), 6.18 d (1Н, Het), 8.44 d (1Н, Het)
4.12 s (5H, C ), 4.58 m (2H, C ), 4.78 m (2H,
), 7.53–8.79 m (6Н, Het)
1.24 t (3H, CH ), 4.12 s (5H, C
4.50 m (2H, C ), 4.77 m (2H, C
.52 s (1Н, Het), 8.55 d (1Н, Het)
5 5 5 2
H ), 4.36 m (2H, C H ),
1
000, 807
5 2
4.76 m (2H, C H
(
III
IV
V
3005, 1563, 1460, 1098, 1605, 1502, 1431 3423 (N–H)
002, 812
3002, 1560, 1462, 1100, 1602, 1501, 1426
000, 810
3000, 1564, 1456, 1102, 1608, 1505, 1428 3420, 3392 (NH
005, 816
3005, 1568, 1448, 1101, 1606, 1501, 1430
98, 812
5
H
5
5 2
H ), 4.62 m (2H,
1
5 2
C H
5
H
5
5 2
H
1
5 2
C H
2
)
5
H
5
5 4 2
H , NH ), 6.08 d
1
VI
2
2
),
9
5
H
5
5 2
H
5 2
C H
VII
3000, 1584, 1447, 1107, 1611, 1598, 1523,
000, 818
1503, 1428
3006, 1584, 1462, 1102, 1604, 1506, 1438 1689 (C=O)
001, 821
5
H
5
5 2
H
1
5 2
C H
VIII
3
5
H
5
), 4.31 q (2H, OCH
2
),
1
5
H
2
5 2
H ), 6.51 d (1Н, Het),
7
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

REACTION OF ACETYLFERROCENE
523
Table 2. (Contd.)
–
1
IR spectrum, ν, cm
Comp.
no.
1
Н NMR spectrum, δ, ppm
Ferrocene core
Aromatic system Functional groups
IX
X
3000, 1592, 1419, 1102, 1603, 1598, 1520,
98, 819
1500, 1438
3004, 1582, 1418, 1100, 1602, 1560, 1450, 3428 (NH),
003, 819
1436
1622 (C=N),
612 (C=C)
3002, 1580, 1418, 1100, 1604, 1563, 1452, 1622 (C=N),
002, 818
1432
1610 (C=C)
3000, 1586, 1420, 1102, 1602, 1568, 1454, 1621 (C=N),
000, 823
1430
1612 (C=C)
2998, 1592, 1418, 1100, 1608, 1561, 1456, 1669 (C=O),
003, 810
1430
1624 (C=C)
4.04 s (5H, C
5
H
5
), 4.51 m (2H, C
5
H
2
), 4.73 m (2H,
9
5 2 6 4
C H ), 6.24 d (1Н, Het), 7.03–7.24 m (4Н, С Н ), 8.07 d
(1Н, Het)
1
4.07 s (5H, C
5
H
5
), 4.38 m (2H, C
5
H
2
), 4.66 m (2H,
),
1
C
5
H
2
), 6.72 d (1Н, С=СН), 7.00–7.18 m (4Н, С
8.12 d (1Н, С=СН–N)
4.11 s (5H, C ), 4.42 m (2H, C
), 6.83 d (1Н, С=СН), 7.03–7.24 m (4Н, С
8.26 d (1Н, С=СН–O)
4.10 s (5H, C ), 4.40 m (2H, C
), 6.72 d (1Н, С=СН), 7.01–7.25 m (4Н, С
.18 d (1Н, С=СН–S)
1.38–1.84 m (6H, 3 CH
4.12 s (5H, C ), 4.38 m (2H, C
), 5.38 d (1H, C=СН, J 16.4 Hz), 7.71 d (1H,
C=СН–N, J 16.4 Hz)
4.02 s (5H, C ), 4.36 m (2H, C
, NCH ), 5.41 d (1H, C=СН, J 16.2 Hz), 6.98–7.11
m (5Н, С ), 7.74 m (1H, C=СН–N)
4.13 s (5H, C ), 4.42 m (2H, C
6 4
Н
XI
1
5
H
5
5
H
2
), 4.78 m (2H,
),
XII
C
5
H
2
6 4
Н
1
XIII
5
H
5
5
H
2
), 4.80 m (2H,
),
1
C
5
H
2
6 4
Н
8
XIV
XV
3000, 1589, 1420, 1104, 1602, 1571, 1453, 3426 (NH),
002, 810
1436
1668 (C=O),
624 (C=C)
2998, 1576, 1422, 1100, 1603, 1562, 1452, 1671 (C=O),
000, 812
1429
1618 (C=C)
2
), 3.16–3.42 m (4H, 2NCH
2
),
1
5
H
5
5 2
H
), 4.78 m (2H,
1
5 2
C H
1
5
H
5
5 2
H ), 4.75–4.98 m (4H,
C
5
H
2
2
XVI
XVII
XVIII
2999, 1578, 1426, 1103, 1605, 1560, 1453, 1668 (C=O),
6 5
Н
1
001, 816
1420
1620 (C=C)
5
H
5
5 2
H ), 4.78 m (2H,
C
5
H
2
), 5.73 d (1H, C=СН, J 15.8 Hz), 7.08–7.38 m (5Н,
), 8.29 d (1H, C=СН–О, J 15.8 Hz)
3002, 1569, 1428, 1102,
000, 817
1681 (C=O),
1628 (C=C),
С
6
Н
5
1
5 5 5 2
4.12 s (5H, C H ), 4.40 m (2H, C H ), 4.72 m (2H,
1
332, 1152 (SO
2
)
C
5
H
2
), 5.64 d (1H, C=СН, J 16.1 Hz), 7.06–7.43 m (5Н,
), 8.16 d (1H, C=СН–S, J 16.1 Hz)
3000, 1573, 1426, 1100,
002, 818
1678 (C=O),
1624 (C=C),
С
6
Н
5
1
4.10 s (5H, C
), 5.83 d (1H, C=СН, J 16.2 Hz), 7.28–7.64 m
(5Н, С ), 8.54 d (1H, C=СН–SO , J 16.2 Hz)
1.24 t (3H, CH ), 4.08 s (5H, C ), 4.28 q (4H, 2OCH
4.40 m (2H, C ), 4.71 m (2H, C ), 5.79 d (1H,
HH 16.0 Hz), 7.86–8.03 m (1H, C=СН–P, JHH
5 5 5 2
H ), 4.42 m (2H, C H ), 4.72 m (2H,
1
262 (P=O),
156 (P–O)
5 2
C H
1
6
Н
5
2
XIX
3008, 1584, 1418, 1103,
000, 820
2148 (C≡C),
3
H
5 5
2
),
1
1665 (C=O)
5
H
2
5 2
H
XX+XXI 3002, 1582, 1428, 1100, 1608, 1564, 1552, 1702, 1694 (C=O) C=СН,
J
2
1
000, 816
1438, 1406
16.0 Hz, JPH 17.2 Hz )
.17 s (5H, C ), 4.36–4.48 m (3H, C
m (2H, C
4
5
H
5
5 2
H , ≡СН), 4.69
5
2
H )
5 5 5 2
4.18 s (15H, 3C H ), 4.49 m (6H, 3 C H ), 4.76 m (6H,
3
C
5
H
2
), 7.65–8.07 m (3Н, С Н )
6 3
–
1
–1
The composition and structure of compound II are
3086 cm , carbonyl C=O group at 1668 cm , and
–
1
confirmed by elemental analysis, GC–MS (Table 1),
double C=C bond at 1624 cm .
1
IR and H NMR spectral data (Table 2), as well as by a
1
In the H NMR spectrum of compound II the
variety of chemical transformations.
signals of HC=CH groups appear as doublets at 5.36
and 7.69 ppm with the coupling constant 16.2 Hz,
indicating trans-configuration of substituents at the
carbon atoms at the double bond. The spectrum also
The IR spectrum of ketoenamine II contains
characteristic absorption bands of stretching vibrations
of C–H bond of the cyclopentadienyl rings at 3100–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

5
24
MOSKALENKO et al.
contains singlets at 2.98 and 4.15 ppm, respectively,
relating to the six protons of the dimethylamino group
and to the five protons of С Н , and multiplets at 4.36
and 4.76 ppm characteristic of the four protons of
substituted cyclopentadienyl ring.
ethyl 5-amino-1H-pyrazolo-4-carboxylic acid, and 1H-
benzimidazole-2-amine. These reagents react with
enamine II in the suitable reaction conditions to form
ferrocene-containing pyrimidine V–IX in yields of 72–
85%.
5
5
The study of enamine II reactivity showed that it is
a valuable reagent in the synthesis of various ferrocene
derivatives. Thus, it reacts readily with binucleophilic
reagents to form five-, six- and seven-membered
heterocyclic ferrocene-containing compounds III–XII.
The synthesis of the seven-membered heterocyclic
compounds was carried out by the condensation of
enamine II with 1,2-disubstituted aromatic binucleo-
philes, 1,2-diaminobenzene, 2-aminophenol, and 2-
aminothiophenol, at heating the equimolar amounts of
reactants in anhydrous ethanol in the presence of
sodium ethoxide. As a result, the corresponding 5-ferro-
cenyl-substituted benzazepines X–XII containing two
heteroatoms in the ring were obtained in the yield of
In particular, refluxing enamine II with an excess
of hydrazine hydrate in ethanol affords 3-ferro-
cenylpyrazol III in nearly quantitative yield, and the
reaction with hydroxylamine produces 3-ferrocenyl-
oxazol IV, but in lower (72%) yield.
6
8–73%.
H N
2
X
NH NH2 H O
EtONa
2
2
II +
NH
−HNMe , −H O
2
2
o
Fc
EtOH, 78 C
N
HX
II
N
X−XII
Fc
X = HN (X), O (XI), S (XII).
It should be noted the high regioselectivity of the
III
−
HNMe , −H O
2
2
H NOH HCl, NaHCO3
2
O
Fc
N
IV
For the synthesis of six-membered heterocycles on
the basis of enamine II, we used the reagents
containing amidine group (NH=C–NH ): guanidine,
morpholino-1-carboxamidine, pyridine-4-carboxamidine,
above mentioned heterocyclization reactions involving
enamine II due to the specificity of the structure of
binucleophilic reagents. The latter in the reaction are
preferably condensed with carbonyl group of the
substrate II due to the presence in them of the primary
amino groups. Then the subsequent elimination of
dimethylamino group of substrate II or intermediate
formed in the presence of a strong base leads to the
closure of the heterocycle to give the end products III–
XII.
2
NH
R
C
N
NH2
R
N
N
V−VII
Fc
EtOOC
We also investigated the reaction of enamine II
with some mononucleophilic reagents proceeding
through the substitution of dimethylamino group.
Thus, reflux in toluene of equimolar amounts of
compound II with piperidine and benzylamine gives
rise to amines XIII and XIV. On heating with the
sodium salts of phenol, thiophenol, and benzene-
sulfinate, and diethylphosphorous acid in ethanol the
nucleophilic substitution proceeds to afford com-
pounds XV–XVIII as a result of the formation of new
C–O, C–S, and C–P bonds.
N
N
H N
N
2
H
II
−
HNMe2,
H O
N
Fc
−
2
COOEt
VIII
N
NH2
N
N
H
N
It is known [10] that enamines, as the bases, are
able to react with electrophilic reagents. In particular,
we studied the reaction of enamine II with methyl
iodide as the electrophilic reagent. It was unexpectedly
found that on reflux of reagents in anhydrous
Fc
IX
R = NH (V),
N
O (VI),
N (VII).
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

REACTION OF ACETYLFERROCENE
525
HY
Fc
Fc
Fc
C
O
CH CH Y
XV, XVI
HSO2
EtONa
II
C
O
CH CH SO2
−
HNMe2
XVII
O
HP(OEt)2
−
HNMe2
C
O
CH CH PO(OEt)2
XVIII
HN
PhCH NH
2 2
Fc
C
O
CH CH
N
Fc
C
O
CH CH NH CH2
Ph
XIII
XIV
X = O (XV), S (XVI).
acetonitrile the quaternary trimethylammonium salt A
is not formed, but formed 3-ferrocenylpropyn-3-one
XIX previously described in [13]. The formation of
this compound in 81% yield can probably be explained
by the formation in the first stage of the reaction of
easily decomposing iodomethylate A:
MeCN
+
−
II + MeI
Fc
C
O
CH CH N Me I
Fc
C
O
C
CH
3
+
−
−
HN Me I
3
A
XIX
Elimination of the trimethylammonium hydroiodide
from the salt A is caused of course by the high acidity
of the α-hydrogen atom owing to the electron-with-
drawing effect of the neighboring carbonyl group as
well as trimethylammonium group, whose negative
inductive effect is conjugated with the π-electrons of
the double bond.
conditions [13] affords, respectively, pyrazol III and
oxazole IV, previously obtained from enamine II.
Also it was found that under heating in benzene in
the presence of a catalytic amount of dicarbonyl-bis
(
triphenylphosphine)nickel the compound XIX under-
goes trimerization to form a mixture of 1,2,4- and
,3,5-triferrocenoylbenzenes XX and XXI, which is a
1
Compound XIX synthesized reacted with hydrazine
hydrate and hydroxylamine under the reaction
characteristic transformation for acetylene and its
derivatives.
O
Fc
O
C
O
C
C
O
C
(
CO) Ni(PPh )
2 3 2
Fc
Fc
Fc
XIX
+
C
Fc
XX
C
O
O
Fc
XXI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

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26
MOSKALENKO et al.
The composition and structure of compounds III–
XXI are confirmed by analytical and spectroscopic
acetylferrocene with ethylacetate and then the target
product II with acetone. After the solvent removal the
unreacted acetylferrocene (8.39 g, 73.6%) and enamine
II (3.71 g, 99.2%, with respect to the converted
acetylferrocene) were isolated.
data given in Tables 1 and 2. It should be noted that in
1
the H NMR spectrum of compound XIV the
fragments CH=CH, CH appear as doubled signals
2
with the integral intensity ratio ~3:7, due, as we think,
to the existence of two isomers B and C.
3
-Ferrocenylpyrazol (III). A mixture of 0.5 g of
enamine II and 0.5 ml of hydrazine hydrate in 3 ml of
ethanol was refluxed with stirring for 2 h, the solvent
was removed in a vacuum. The mixture was mixed
with 30 ml of water and extracted with ethyl acetate
Ph
H C
2
H
CH Ph
2
N
N
H
O
(
2×30 ml). The organic layer was washed with water
O
and dried over anhydrous sodium sulfate. After the
removal of solvent in a vacuum, 0.45 g (99.2%) of
compound III was obtained, which was crystallized
from benzene.
Fc
Fc
B
C
3
-Ferrocenyloxazol (IV). To a solution of 0.5 g of
Moreover, the signal of the NH proton of isomer B
is located in the weak field at 8.10 ppm, whereas the
same proton in isomer C resonates in a strong field at
enamine II in 5 ml of ethanol was added aqueous
solution of hydroxylamine prepared from 0.63 g of
HONH ·HCl and 0.84 g of NaHCO in 5 ml of water,
the mixture was refluxed under stirring for 5 h, cooled,
mixed with 50 ml of water, and extracted with ethyl
acetate (2×50 ml). The organic layer was dried over
anhydrous sodium sulfate. After distilling off the
solvent in a vacuum, the residue was purified by
chromatography eluting with the ethyl acetate–hexane
2
3
5
.38 ppm with the same ratio of the integral intensities.
The formation of such isomers has previously been
noted in [9].
1
By GC–MS and H NMR spectral data, the ratio of
structural isomers XX and XXI in a mixture is 1:3.
Thus, based on accessible acetylferrocene we
developed a convenient method of obtaining 1-
dimethylamino-3-ferrocenyl-3-oxoprop-1-ene II, which
can be widely used in the synthesis of various ferro-
cene derivatives of the scientific and practical interest.
(
4:1) mixture. Yield 0.33 g (72%) of compound IV,
which was crystallized from aqueous ethanol (1:1).
Compound XII was obtained similarly.
2
-Amino-4-ferrocenylpyrimidine (V). A mixture
of 0.5 g of enamine II, 0.52 g of guanidine dihydro-
EXPERIMENTAL
chloride, and 1.24 g of K CO in 5 ml of DMSO was
2
3
stirred at 80–90°C under argon for 1.5 h, cooled,
diluted with 50 ml of water, and extracted with ethyl
acetate (3×70 ml). The organic layer was washed with
water and dried over anhydrous sodium sulfate. After
distilling off the solvent in a vacuum the residue was
purified by chromatography eluting with the ethyl
acetate–chloroform mixture (5:1). Yield 0.26 g (52%)
of azine V, which was crystallized from aqueous
methanol (2:1).
Commercial reagents (Acros) were used. The IR
spectra were recorded on a UR-20 spectrometer from
KBr pellets. The H NMR spectra were registered on a
1
Varian Mercury Plus-400 spectrometer (400 MHz) in
CDCl with internal reference HMDS. GC–MS spectra
3
were recorded on a Thermo Finnigan Surveyor MSQ
(
USA) instrument by chemical ionization at
atmospheric pressure. Identity and purity of the
compounds obtained was monitored by TLC on Silufol
UV-254 plates, eluents ethyl acetate–chloroform, 4:1
Compound VI was obtained similarly.
(
A), acetone (B), ethyl acetate–hexane, 1:1 (C).
-Dimethylamino-3-ferrocenyl-3-oxoprop-1-ene
II). A mixture of 11.4 g of acetylferrocene and 200 ml
2
-(Pyridin-4-yl)-4-ferrocenylpyrimidine (VII). A
1
mixture of 0.57 g of enamine II, 0.77 g of pyridine-4-
carboxamidine dihydrochloride, and 1.12 g of potas-
sium tert-butoxide in 10 ml of anhydrous ethanol was
refluxed with stirring under argon for 2 h, cooled,
diluted with 100 ml of water, and extracted with ethyl
acetate (3×80 ml). The organic layer was washed with
(
of dimethylformamide dimethyl acetal I was refluxed
under inert atmosphere for 52 h at stirring. Excess of
acetal I was removed in a vacuum. The residue was
subjected to chromatography eluting the starting
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REACTION OF ACETYLFERROCENE
527
water and dried over anhydrous sodium sulfate. After
distilling off the solvent in a vacuum the residue was
purified by chromatography eluting with the ethyl
acetate–chloroform mixture (5:1). Yield 0.59 g (86.5%)
of compound VII, which was crystallized from
aqueous methanol (2:1).
aqueous solution was extracted with 60 ml of ethyl
acetate. The combined organic solutions were washed
with water, dried over anhydrous sodium sulfate, and
concentrated. The residue was purified by chromato-
graphy eluting with the ethyl acetate–hexane mixture
(5:1). Yield 0.77 g (81%) of compound XIX, which
was crystallized from a mixture of benzene and hexane
Compounds VIII–IX were obtained similarly.
(
1:3).
5
-Ferrocenyl-1H-benzo[a]-1,4-diazepine (X). To
Trimerization of compound (XIX). To a solution
a solution of 2 mmol of sodium ethoxide in 5 ml of
anhydrous ethanol was added 2 mmol of 1,2-diamino-
benzene. The mixture was stirred under argon for
0 minutes. Then 2 mmol of enamine II was added,
and the mixture was refluxed for 3 h, cooled, diluted
with 50 ml of water and extracted with ethyl acetate
of 0.5 g of compound XIX in 5 ml of anhydrous
benzene was added 0.05 g of dicarbonyl-bis(triphenyl-
phosphine)nickel [15], and the mixture was stirred at
3
7
0–75ºC in an argon atmosphere for 5 h to complete
consumption of the starting compounds (TLC
monitoring), was filtered and concentrated. The
residue was crystallized from the hexane–methylene
chloride mixture (2:1). Yield 0.42 g (84%) of a
mixture of compounds XX and XXI.
(
3×60 ml). The organic layer was washed with water,
dried over anhydrous sodium sulfate, and concentrated.
The residue was purified by chromatography eluting
with the ethyl acetate–hexane mixture (2:1). Yield
0
.48 g (73%) of compound X, which was crystallized
REFERENCES
from ethyl acetate–hexane mixture (1:1).
1
. Perevalova, E.G., Reshetova, M.D., and Grandberg, K.I.,
Metody elementoorganicheskoi khimii. Zhelezoorga-
nicheskie soedineniya. Ferrotsen (Methods of Organo-
elemental Chemistry. Organoiron Compounds. Ferro-
cene), Moscow: Khimiya, 1983.
Compounds XI and XII were synthesized similarly.
1-Piperidino-3-ferrocenyl-3-oxoprop-1-ene (XIII).
A mixture of 0.57 g of enamine II and 0.2 ml of
piperidine in 3 ml of anhydrous toluene was refluxed
with stirring for 5 h. Then the solvent was removed on
a rotary evaporator and the residue was crystallized
from ethyl acetate–hexane, 1:1. Yield 0.38 g (59%).
2. Staveren, D.R., and Metzler-Nolte, N., Chem. Rev.,
2004, vol. 104, no. 12, p. 5931.
3. Zora, M. and Gormen, M., J. Organomet. Chem., 2007,
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Compound XIV was obtained similarly.
4
. Snegur, L.V., Nekrasov, Yu.S., Sergeeva, N.S., Zhili-
na, Zh.V., Gumenyuk, V.V., Starikova, Z.A., Simenel, A.A.,
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Organometal. Chem., 2008, vol. 22, p. 139.
1-(o-Phenoxy)-3-ferrocenyl-3-oxoprop-1-ene (XV).
To a solution of 2 mmol of EtONa in 5 ml of an-
hydrous ethanol under an argon atmosphere was added
mmol of phenol. The mixture was stirred for 30 min,
2
5. Effenberger, F. and Simchen, G., Chem. Ber., 1963,
vol. 96, no. 4, p. 1350.
then 2 mmol of enamine II was added and the mixture
was refluxed under stirring for 3 h to complete con-
sumption of the starting compounds (TLC monitor-
ing). After the removal of solvent, the residue was
dissolved in 100 ml of ethyl acetate, washed with
water, dried over anhydrous sodium sulfate, the
solvent was removed on a rotary evaporator, and the
residue was crystallized from aqueous ethanol (1:1).
Yield 0.47 g (70.8%).
6
7
. Bredereck, H., Chem. Ber., 1968, vol. 101, no. 1, p. 41.
. Hengartner, V., Batcho, A.D., Blount, J.F., Leimgruber, W.,
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and Bren’, V.A., Zh. Org. Khim., 2008, vol. 44, no. 4,
p. 608.
8
9
Compounds XVI–XVIII were synthesized similarly.
1
1
0. Shmushkovich, J., Enaminy (Enamines), in Uspekhi
organicheskoi khimii (Advances of Organic Chemistry),
Knunyants, I.L., Ed., Moscow: Mir, 1966, vol. 4, pp. 5–
123.
3
-Ferrocenylpropyn-3-one (XIX). A mixture of
1
.13 g of enamine II and 3 ml of CH I in 10 ml of
3
anhydrous acetonitrile was refluxed with stirring for
h. Then 50 ml of water and 100 ml of ethyl acetate
were added. The organic layer was separated and the
8
1. Bredereck, H., Sell, R., and Effenberger, F., Chem. Ber.,
1964, vol. 97, no. 11, p. 3407.
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1
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1
5. Dzhemilev, U.M., Popod’ko, N.R., and Kozlova, E.V.,
1
1
3. Schlögl, K. and Monar, A., Monatsh. Chem., 1962,
Metallokompleksnyi kataliz v organicheskom sinteze
vol. 93, no. 4, p. 861.
(
Metal Complex Catalysis in Organic Synthesis),
4. Reutov, O.A., Kurts, A.L., and Butin, K.P., Organi-
Moscow: Khimiya, 1999, pp. 60–61.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011