Synthesis and spectroscopic and structural studies of cross-conjugated dienones derived from cyclic ketones and aromatic aldehydes

Article abstract of DOI:10.1007/s11172-006-0397-6

Cross-conjugated dienones were synthesized by the reactions of cyclic ketones with two equivalents of aromatic aldehydes under basic conditions. An NMR spectroscopic study and X-ray diffraction analysis demonstrated that all reaction products are formed as E,E isomers. Spontaneous photochemical trans-cis isomerization of cross-conjugated dienones under the scattered light in solution was observed for the first time. The degree of isomerization depends mainly on the nature of the central fragment of the dienone molecule. The previously unknown product of photochemical [2+2]-cycloaddition of 2,5-bis[(E)-(3-pyridyl)methylidene]cyclopentanone was synthesized and characterized by spectroscopic methods and X-ray diffraction. Under the conditions used, only one isomer of the cyclobutane adduct was obtained. Springer Science+Business Media, Inc. 2006.

Full text of DOI:10.1007/s11172-006-0397-6

1
184
Russian Chemical Bulletin, International Edition, Vol. 55, No. 7, pp. 1184—1194, July, 2006
Synthesis and spectroscopic and structural studies of
crossꢀconjugated dienones derived from cyclic ketones
and aromatic aldehydes
S. Z. Vatsadze,aꢀ M. A. Manaenkova, N. V. Sviridenkova, N. V. Zyk, D. P. Krut´ko,
a
a
a
a
b
c
d
e
A. V. Churakov, M. Yu. Antipin, J. A. K. Howard, and H. Lang
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 932 8846. Eꢀmail: szv@org.chem.msu.ru
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
1
b
3
1 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 952 1279. Eꢀmail: churakov@igic.ras.ru
c
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
8 ul. Vavilova, 119991 Moscow, Russian Federation.
2
Fax: +7 (495) 135 5085. Eꢀmail: mꢀantipin@yahoo.com
d
Department of Chemistry, University of Durham,
South Road, Durham DH1 3LE, UK.
Department of Inorganic Chemistry, Institute of Chemistry,
e
Chemnitz University of Technology, Dꢀ09111 Chemnitz, Germany*
Crossꢀconjugated dienones were synthesized by the reactions of cyclic ketones with two
equivalents of aromatic aldehydes under basic conditions. An NMR spectroscopic study and
Xꢀray diffraction analysis demonstrated that all reaction products are formed as E,E isomers.
Spontaneous photochemical trans—cis isomerization of crossꢀconjugated dienones under the
scattered light in solution was observed for the first time. The degree of isomerization depends
mainly on the nature of the central fragment of the dienone molecule. The previously unknown
product of photochemical [2+2]ꢀcycloaddition of 2,5ꢀbis[(E)ꢀ(3ꢀpyridyl)methylidene]cycloꢀ
pentanone was synthesized and characterized by spectroscopic methods and Xꢀray diffraction.
Under the conditions used, only one isomer of the cyclobutane adduct was obtained.
Key words: crossꢀconjugated dienones, ketones, aromatic aldehydes, Xꢀray diffraction
analysis, photoisomerization, [2+2]ꢀcycloaddition.
Crossꢀconjugated dienones of the bisꢀarylidenecycloꢀ
The dienone derivatives of cyclopentanone, cyclohexꢀ
anone, and cycloheptanone have been synthesized and
reliably characterized. Substituted benzaldehydes containꢀ
ing chlorine, bromine, methyl, methoxy, phenoxy, and/or
nitro groups in different positions of the benzene ring of
aldehydes, as well as heteroaromatic 2ꢀthiopheneꢀ and
2ꢀfuranaldehydes, were used as the aldehyde component.
Dienones derived from Nꢀmethylꢀ and Nꢀbutylꢀ4ꢀpiꢀ
peridones and tropanones are much less in number. The
synthesis of tropanone derivatives based on 4ꢀ and
alkanone series (hereinafter, dienones) are generally synꢀ
thesized by the reactions of cyclic ketones with two equivaꢀ
lents of aromatic aldehydes. These compounds are used
1
,2
for the construction of polymers, crystals with the nonꢀ
3
—5
6
linear optical properties,
and dyes, as well as for the
synthesis of numerous condensed systems based on hydrꢀ
azine, thioureas, cyanoacetamide, guanidine derivatives,
7
—12
and many other compounds.
Both dienones and their
heterocyclization products have various biological activiꢀ
1
1
13,14
18
ties, such as antiviral, antimicrobial,
and antiꢀ
3ꢀpyridinealdehydes was documented.
1
5,16
20
inflammatory
activities, and can be used as anesthetꢀ
ics, cholagogues,18 and contraceptives.
Recently, it has been suggested to use pyridineꢀconꢀ
1
7
19
taining dienones as exodentate ligands, which can react
with metal ions to form soꢀcalled coordination polymers,
viz., infinite ensembles (M—L)n (M is metal and L is
ligand). In the present study, we examined a series of
pyridineꢀ and thiopheneꢀcontaining bisꢀarylidene derivaꢀ
*
Technische Universität Chemnitz, Fakultät für Naturwissenꢀ
schaften, Institut für Chemie, Lehrstuhl Anorganische Chemie,
Straße der Nationen 62, Dꢀ09111 Chemnitz, Germany.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1141—1150, July, 2006.
066ꢀ5285/06/5507ꢀ1184 © 2006 Springer Science+Business Media, Inc.
1

Crossꢀconjugated dienones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
1185
tives of cycloalkanones suitable for the preparation of
supramolecular complexes. In addition, dienones based
on substituted benzaldehydes were studied as model comꢀ
pounds. Some of these compounds were described in the
literature. However, in most cases, no spectroscopic, steꢀ
reochemical, and photochemical studies were performed.
Scheme 1
Results and Discussion
Z
Ar
Product
Yield (%)
(
CH2)2
Ph
4ꢀMeOC H4
1
2
3
4
5
6
7
8
87
65
25
88
96
50
73
69
90
38
60
68
86
98
76
50
44
16
64
68
50
51
48
18
78
82
90
50
37
75
33
30
In the present study, we performed aldolꢀcrotonic conꢀ
densation of carbocyclic cyclopentanone and cyclohexꢀ
anone and heterocyclic 1ꢀmethylꢀ, 1ꢀbenzylꢀ, 1ꢀethylꢀ,
and 1ꢀisopropylꢀ4ꢀpiperidones with aromatic and heteroꢀ
aromatic aldehydes. Several methods have been develꢀ
oped for performing this reaction, which differ in the
nature of the catalyst and the solvent. The classical method
is based on condensation of ketones and aldehydes in
6
4
2
2
4
ꢀMeNC H
6
4
a
ꢀFur
b
ꢀTh
ꢀPy
c
3ꢀPy
ꢀPy
Ph
ꢀMeOC H4
2
(CH2)3
9
4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
6
2ꢀFur
5ꢀMe(C4H2O)
2ꢀTh
d
an alcoholic or aqueous medium in the presence of a
base.2
1—27
Acetic acid in the presence of HCl was used
4
3
ꢀPy
ꢀPy
only for the synthesis of dienones from Nꢀbutylpiperiꢀ
done.18 In recent years, transition metalꢀbased catalysts,
CH N(Me)CH2
Ph
2
2
8
4ꢀMeOC H4
for example, Cp ZrCl2 in the presence of NiCl ,
6
2
2
2
9
4ꢀMeNC6H4
TiCl (SO CF ) under solventꢀfree conditions, RuCl3
in a sealed tube under solventꢀfree conditions, and in
ionic liquids in the presence of FeCl •6H O (see Ref. 31),
3
3
3
2
4
ꢀTh
ꢀPy
30
3ꢀPy
Ph
3
2
CH N(Ph)CH2
have found use. It should be noted that not nearly all of
the aboveꢀmentioned conditions are suitable for the reacꢀ
tions with heteroaromatic, particularly, pyridine aldeꢀ
hydes. In the present study, we used basic catalysis in
2
4
4
2
ꢀMeOC H4
6
ꢀMe NC H
6 4
2
ꢀFur
5ꢀMe(C4H2O)
2ꢀTh
6
21
aqueous or aqueousꢀalcoholic media as the simplest
and most universal conditions.
4
3
ꢀPy
ꢀPy
Dienones were synthesized according to Scheme 1.
Generally, condensation occurs in good yield. For
example, the reactions with 2ꢀthiophenecarbaldehyde proꢀ
duce dienone derivatives in yields from 64 to 96%. 4ꢀDiꢀ
methylaminobenzaldehyde proved to be least reactive. The
reactions with the latter compound afforded target prodꢀ
ucts in yields of, at most, 30% because it was accompaꢀ
nied by polymerization. The reactions with 1ꢀmethylꢀ4ꢀ
piperidone also proceeded with difficulty. We failed to
prepare products of its condensation with 2ꢀfurancarbꢀ
aldehyde and 2ꢀfuranꢀ5ꢀmethylcarbaldehydes. The lower
reactivity of 1ꢀmethylꢀ4ꢀpiperidone in such reactions
compared to cyclohexanone is unlikely to be attributed
exclusively to the inclusion of the heteroatom into the
carbocycle because related 1ꢀbenzylꢀ4ꢀpiperidone is reꢀ
active under analogous conditions and is involved in conꢀ
densation with all used aldehydes to form the correspondꢀ
ing dienones.
2ꢀPy
3ꢀPy
3ꢀPy
CH N(Et)CH
CH N(Pr )CH
2
2
i
2
2
a
d
Fur is furyl. b Th is thienyl. c Py is pyridyl.
5ꢀMethylfuranꢀ2ꢀyl.
confirmed by the chemical shifts of the carbonyls in the
1
3
C NMR spectra (δ ≈ 190).
Dienone derivatives of cyclic ketones can exist in E,E,
Z,Z, or Z,E configurations.
The structures of the resulting condensation products
1
13
were established by H and C NMR and IR spectrosꢀ
copy. The IR spectra of all compounds show two characꢀ
teristic bands in the 1720—1670 and 1620—1590 cm–1
regions, which is indicative of the presence of the carboꢀ
nyl group conjugated with the double bonds. This is also
In all reactions, we obtained only the E,E isomer. In
the spectra of all compounds, the signals for the protons

1
186
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
Vatsadze et al.
of the CH= group appear at δ 7.30—7.90. It is known32
that the Z isomers are characterized by the chemical shifts
at δ ~6.8, whereas the signals for the E isomers should
appear at higher field than 7.2 ppm.
ing mean planes and the lengths of the double bonds
(C=C and C=O) and the adjacent bonds are given in
Table 2.
Cyclopentane dienone molecule 6 is rather planar unꢀ
like the sixꢀmembered analogs, in which the presence of
the additional methylene or Nꢀalkylamino group causes
the deviation of the latter from the plane formed by three
trigonal and two methylene carbon atoms of the ring.
The structures of compounds 6, 13, 14, and 31 were
additionally confirmed by Xꢀray diffraction (Table 1,
Table 2, Fig. 1). The structure of compound 15 has been
established earlier.2 It should be noted that data on the
structures of dienones containing heterocyclic substituꢀ
ents are lacking in the literature.
0
33
In the recent study concerned with the nonlinear
optical properties of crystals of dibenzylidenecycloꢀ
alkanones, it has been demonstrated that the intermoꢀ
lecular C—H...O bond (or several such bonds) between
the carbonyl oxygen atom and the hydrogen atom of the
methylene group is an important factor responsible for
the crystal structure of these compounds. Among the crysꢀ
tals under study, the shortest C—H...O contact (2.42(1) Å)
was found in the structure of cyclopentanone derivative 6.
A common structural feature of pyridineꢀcontaining
molecules is the presence of the following three planar
fragments: the central dienone group including the oxyꢀ
gen and carbon atoms of the carbonyl group and the carꢀ
bon atoms of the adjacent double bonds (hereinafter deꢀ
noted as Cen) and two heterocyclic fragments including
1
six atoms of the pyridine ring (hereinafter denoted as Het
2
33
and Het ). The dihedral angles between the correspondꢀ
As in the structure of phenyl analog 1, the oxygen atom
Table 1. Crystallographic data, details of Xꢀray data collection, and characteristics of the structure refinement of compounds 6, 13,
4, 31, and 33
1
Compound
6
13
14
31
33
Molecular formula
C H N O
C16H OS
C H N O
C H N O C35.50H28.39Cl N O
1
7
14
2
14
2
18 16
2
19 19
3
6
4
2.19
Molecular weight
262.30
286.39
276.33
305.37
758.83
Crystal dimensions/mm
0.40×0.20×0.20
Monoclinic
C2/c
6.0078(2)
11.6896(4)
18.5325(6)
90
95.807(1)
90
1294.84(7)
4
0.30×0.20×0.20
Monoclinic
0.50×0.40×0.40
Monoclinic
0.40×0.20×0.20
0.20×0.10×0.10
Crystal system
Space group
a/Å
b/Å
c/Å
α/deg
β/deg
γ/deg
V/Å3
Triclinic
Triclinic
–
–
P2 /c
P2 /c
P1
P1
1
1
15.000(9)
11.982(8)
7.608(7)
90
95.87(6)
90
1360(2)
4
1.398
0.379
600
8.309(9)
9.261(5)
18.824(15)
90
100.94(8)
90
1422(2)
4
1.290
6.010(5)
8.942(2)
15.190(7)
98.30(3)
97.97(5)
98.60(5)
787.9(8)
2
13.2251(4)
15.9387(4)
16.9422(5)
83.847(1)
79.893(2)
79.163(1)
3443.0(2)
4
Z
–
3
dcalc/g cm
µ/mm
F(000)
1.346
0.085
552
1.287
0.082
324
1.464
0.540
1556
–
1
0.081
584
Diffractometer
T/K
θ Scan range
Ranges of indices
of reflections
«Bruker SMART» «Nonius CAD 4»
«Nonius CAD 4»
293(2)
«Nonius CAD 4» «Bruker SMART»
110(2)
293(2)
2.18—24.99
–17 ≤ h ≤ 17
0 ≤ k ≤ 14
–9 ≤ l ≤ 5
3899
293(2)
2.34—24.97
–7 ≤ h ≤ 7
–10 ≤ k ≤ 10
–18 ≤ l ≤ 18
5538
100(2)
3.49—26.99
–7 ≤ h ≤ 7
–13 ≤ k ≤ 14
23 ≤ l ≤ 22
5059
2.20—24.97
–9 ≤ h ≤ 6
0 ≤ k ≤ 10
–22 ≤ l ≤ 22
4501
1.22—25.50
–16 ≤ h ≤ 15
–19 ≤ k ≤ 19
–18 ≤ l ≤ 20
22724
–
Number of measured
reflections
Number of independent
reflections
1418
(0.0287)
121
2318
(0.1607)
172
2486
(0.0363)
255
2769
(0.0317)
285
12723
(0.0375)
857
(
Rint)
Number of parameters
in refinement
R (I ≥ 2σ(I ))
0.0357
0.1033
1.061
0.0928
0.2409
1.063
0.0430
0.1121
0.993
0.0371
0.0971
0.990
0.1264
0.3401
2.008
1
wR (based on all reflections)
2
2
Goodnessꢀofꢀfit on F
Residual electron density
0.306/–0.135
0.476/–0.449
0.224/–0.183
0.168/–0.125
3.320/–1.550
–
3
(
max/min)/e Å

Crossꢀconjugated dienones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
1187
Table 2. Selected geometric parameters (interplanar angles and bond lengths) in the molecular structures of comꢀ
pounds 6, 13—15, and 31
Comꢀ
pound
Angle/deg
Cen/Het2
Bond lengths/Å
C=C (O)C—C(=C) (C=)C—Het
Cen/Het1
Het /Het
1
2
C=O
6
5.95(5)
21.3(2)
5.95(5)
24.9(2)
11.88(5)
36.4(2)
1.224(2)
1.221(7)
1.345(1)
1.337(8)
1.491(1)
1.494(8)
1.486(8)
1.496(2)
1.505(3)
1.505(2)
1.505(2)
1.481(2)
1.492(2)
1.464(1)
1.453(8)
1.444(8)
1.465(2)
1.465(3)
1.475(2)
1.468(2)
1.461(2)
1.451(2)
1
1
1
3
3
4
5
1
1
.336(8)
1.338(3)
.341(2)
1.345(2)
.354(2)
1.337(2)
.338(2)
37.5(1)
54.99(5)
46.34(7)
23.9(1)
39.95(5)
9.8(1)
22.2(1)
38.10(7)
39.06(8)
1.219(2)
1.230(2)
1.229(2)
1
1
1
Note: Cen is the fragment consisting of six atoms and including the carbonyl group and conjugated double bonds and
Het is the fragment including the atoms of the heterocyclic substituent.
of one molecule forms two hydrogen bonds with the meꢀ
thylene hydrogen atoms of two translationally related
molecules. In the reference molecule, one hydrogen atom
of each methylene group is also involved in the formation
of analogous bonds with two adjacent molecules, resultꢀ
ing in networks consisting of dimers (Fig. 2). Within these
networks, molecules 6 are arranged in a headꢀtoꢀtail
fashion.
When studying the structure of ligand 15,20 we found
intermolecular C—H...O contacts (2.57(2) and 2.61(2) Å),
O(1)
O(1)
C(9)
C(6)
C(1)
C(6A)
C(5A)
C(1)
C(14) C(12)
C(7)
C(4A)
C(4)
C(7)
C(15)
C(16)
C(7A)
C(5)
N(1)
C(8)
S(1)
C(10)
C(11)
C(2)
C(3)
C(13)
C(2A)
C(8A)
C(9A)
C(2)
C(6)
C(3)
C(5)
N(1A)
C(3A)
C(8) C(9)
S(2)
C(4)
6
13
O(1)
C(11)
C(13)
O(1)
C(1)
C(23)
C(17)
C(7)
C(16)
C(14)
C(16) C(13) C(1)
C(26)
C(12)
C(22)
C(21)
C(18)
N(1)
C(12)
N(2) C(11)
C(8)
C(17)
C(10)
C(9)
C(24)
C(2)
C(3)
C(6)
C(5)
C(27)
C(28)
C(14)
C(18)
C(15)
N(1)
C(15)
N(2)
C(25)
C(4)
C(2)
1
4
15
O(1)
C(12) C(1)
C(28)
N(1)
C(16)
C(22)
N(2)
C(26)
C(18)
C(13)
C(23)
C(11)
C(21)
C(20)
C(14)
C(10)
C(25)
C(15)
C(24)
N(3)
C(2)
C(3)
3
1
Fig. 1. Molecular structures of compounds 6, 13—15, and 31.

1
188
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
Vatsadze et al.
dimers are packed in stacks along the crystallographic
axis a.
In the crystal structure of thiophene dienone 13, the
stacking motif is analogous to that found in cyclohexane
analogs 14 and 15 (Fig. 3). The molecules in the stack are
arranged in a headꢀtoꢀtail fashion along the crystalloꢀ
graphic axis c. In 13, the shortest intermolecular contact
is formed between the O(1) atom and the thiophene
α proton H(16) from the adjacent stack (2.46 Å).
In the crystal structure of piperidone derivative 31,
there is an interaction between the O(1) atom and the
α proton H(28) of the pyridine ring of the centrosymꢀ
metric molecule (2.42(2) Å), resulting in the formation
of dimers packed in stacks along the crystallographic
axis a (Fig. 4).
Analysis of the crystal structures of compounds 13, 6,
1
4, 31, and 15 demonstrated the absence of π—πꢀstacking
interactions between the heteroaromatic rings.
When attempting to grow single crystals of 2,5ꢀbis[(E)ꢀ
(
3ꢀpyridyl)methylidene]cyclopentanone (7) in the light
Fig. 2. Molecular packing in the crystal structure of 6.
from a MeCN—CCl4 mixture during one month, we
obtained crystals, which appeared to be (Xꢀray diffracꢀ
tion data) not the target dienone but its dimerization prodꢀ
uct at the C=C double bond, viz., dispirododecane 33
(Fig. 5). This [2+2]ꢀcycloaddition could afford four isoꢀ
mers A—D. However, we observed the formation of only
isomer B.
which correspond to interactions between the carbonyl
oxygen atom and the methylene protons and the α proꢀ
tons of the pyridine rings, respectively. The former interꢀ
action results in the formation of chiral headꢀtoꢀtail
dimers, which are packed in stacks along the crystalloꢀ
graphic axis b. The adjacent stacks are linked to each
other by interactions of the latter type. Analogous interꢀ
molecular contacts resulting in a similar threeꢀdimenꢀ
sional arrangement of molecules were found in the
crystal structure of isomeric compound 14. The nearest
centrosymmetric molecules are linked to each other by
two contacts through the O(1) atoms and the axial hydroꢀ
gen atoms at the C(5) atom (2.63(2) Å). The resulting
1
The H NMR spectrum (CDCl ) of dimer 33 shows a
3
characteristic singlet for two equivalent protons of the
cyclobutane ring at δ 4.63. The signals of two types of the
pyridine rings are also well distinguished. The methylene
protons of the cyclopentane rings and the vinyl protons
bound to these groups appear as a characteristic ABCDX
system (multiplets at δ 2.80, 2.60, 2.30, and 1.50 for
the cyclopentane protons) and a broadened triplet at
Fig. 3. Molecular packing in the crystal structure of 13.

Crossꢀconjugated dienones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
1189
Fig. 4. Molecular packing in the crystal structure of 31.
N(2)
C(25)
C(24)
C(27)
C(16)
C(15)
C(17)
N(1)
O(12)
C(23)
C(22)
C(26)
C(10)
C(12)
C(14)
C(28)
C(11)
C(21)
C(13)
C(38) C(33)
C(32)
C(18)
C(31)
C(41)
C(42)
C(45)
C(46)
C(47)
C(36)
C(34)
C(30)
O(11)
C(43)
C(37)
N(3)
C(35)
C(44)
C(48)
N(4)
Fig. 5. Molecular structure of compound 33. Only one of two
independent molecules is presented for clarity. The hydrogen
atoms and the CCl and water solvent molecules are omitted.
4
CH= groups and two nonequivalent pyridine rings, and
an AA´BB´ system of the methylene protons of cycloꢀ
pentanone. In the reaction mixture, the E,Eꢀ7 : E,Zꢀ7 : 33
ratio was 3.0 : 1.0 : 1.5.
δ 7.52 (CH=). The chemical shifts of these signals,
except for the signals for aromatic protons, are virtually
equal to those of the phenyl analog, viz., photocycloꢀ
dimerization product of dienone 1 in a dichloromethane
solution.3
This observation stimulated us to study in detail staꢀ
bility of dienones in solution by NMR spectroscopy. We
found that compounds 1, 6, 7, 9, 14, 15, 20, and 21, 28,
32 in DMSOꢀd undergo changes associated with the acꢀ
6
4
tion of light on solutions of the samples. It appeared that
the composition and nature of the products depend on
the type of the central ring.
It was also found34 that an isomer of type B was generꢀ
ated in a mixture of two other photoproducts, whose forꢀ
mation was not observed in our experiments. To the conꢀ
For example, when an ampoule with a solution of
compound 1 was protected from light, no changes in the
1
trary, analysis of the H NMR spectra demonstrated that,
1
after heating of dienone 7 in a MeCN—CCl solution in
H NMR spectrum were observed during several days.
4
the light, the reaction mixture contained, along with the
starting compound 7 and dimer 33, a product whose specꢀ
troscopic characteristics correspond to the E,Z isomer of
compound 7. This assumption was supported by the presꢀ
ence of the signals for the protons of two nonequivalent
However, after exposure of the sample to scattered dayꢀ
light for ~8 h, the spectrum shows additional signals,
which can be assigned to the E,Z isomer.
It should be noted that the ratio of signals of two
products remains unchanged in the course of further storꢀ

1
190
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
Vatsadze et al.
a
a
8
.5
8.0
7.5
7.0
δ
9
.0
8.5
8.0
7.5
7.0
δ
b
E,E + E,Z
b
E,E + E,Z
E,E + E,Z
E,E + E,Z
E,Z
8.5
Fig. 7. Fragments of the 1H NMR spectra of compound 15
DMSOꢀd , aromatic region): storage in the dark for 3 days (a)
8.0
7.5
7.0
δ
E,Z
E,Z
E,Z
E,Z
(
6
and then in the light for 3 days (b).
9
.0
8.5
8.0
7.5
7.0
δ
Fig. 6. Fragments of the 1H NMR spectra of compound 7
DMSOꢀd , aromatic region): storage in the dark for 3 days (a)
(
Table 3. Isomer ratios of dienones after the establishment of the
6
and then in the light for 3 days (b). The assignments of the
signals of the starting compound (E,E) and the photoisoꢀ
merization product (E,Z ) are given.
photochemical equilibrium
Ringa Comꢀ
Ratio of stereoisomers
poꢀ
und
E,E
E,Z *
Z,Z
age in the light. The solvent has no effect on the process,
because the same signals are also observed in a solution
Y
δ
Y
δ
Y
δ
of 1 in CDCl . Analogous phenomena were observed for
compounds 6 and 7 (Fig. 6).
С5
С6
1
6
7
9
1
1
74 7.46 26
63 7.42 37
71 7.50 29
13 7.63 61
12 7.54 45
12 7.62 38
7.34, 6.99
7.28, 7.03
7.37, 7.05
—
—
—
26
43
50
0.38
20
—
—
—
6.61
6.68
6.70
6.75
6.61
3
For cyclohexanone derivatives 9, 14, and 15 containꢀ
ing the phenyl or pyridine substituents, processes in soluꢀ
tion exposed to light occur in time in a more complex way
than those with cyclopentanones. In the first step, prodꢀ
ucts corresponding to E,Z isomers are rapidly (~1 day)
formed, and these products are then slowly transformed
into symmetric Z,Z isomers. The final mixtures contain
all possible isomers in a ratio that depends on the nature
of the arylidene substituent (Fig. 7, Table 3).
b
— , 6.73
b
4
5
— , 6.78
7.40, 6.80
b
1.0c
b
c
С7
С8
34
35
—
7.26
— , 6.61
16 6.96 64
7.56, 6.51
Note. Y (%) is the percentage of the stereoisomer, δ are the
chemical shifts of the olefinic protons. For the E,Z isomer, the
first chemical shift belongs to the proton at the double bond in
the E configuration.
In addition, we demonstrated that 2,7ꢀdibenzylideneꢀ
cycloheptanone (34) and 2,8ꢀdibenzylidenecyclooctanone
a
The size of the central ring.
The precise position was not determined because of overlapꢀ
b
(
35) are also photolabile compounds. In the light, both
ping of the signals.
c
dienones undergo transformations analogous to those
found for compound 9 (see Table 3).
Since the precise percentage of the E,E isomer was not deterꢀ
mined because of overlapping of the signals, the ratio of the E,Z
to Z,Z isomers is given.
Photochemical transformations of pyridine derivatives
of piperidones 20, 21, 28, and 32 are complicated by
oxidative processes involving the aliphatic nitrogen atom.
Nevertheless, the initial step of these transformations also
involves trans—cis photoisomerization.
To summarize, we demonstrated that the reactions of
cyclic ketones with aromatic aldehydes under basic conꢀ
ditions produce crossꢀconjugated dienones as E,E isoꢀ

Crossꢀconjugated dienones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
1191
1
mers. It was found for the first time that this series of
compounds can undergo photochemical equilibrium
trans—cis isomerization in solution under the scattered
light. The extent of isomerization is primarily determined
by the nature of the central fragment of the dienone molꢀ
ecule. The ketones under study are able to undergo photoꢀ
chemical [2+2]ꢀcycloaddition, as was exemplified by the
reaction of 2,5ꢀbis[(E)ꢀ(3ꢀpyridyl)methylidene]cycloꢀ
pentanone.
(C=O), 1615 (C=C). H NMR, δ: 3.06 (s, 4 H, C(3)H2, C(4)H2);
6
6
.52 (dd, 2 H, βꢀH (C H O), J = 3.5 Hz, Jβ—β´ = 1.8 Hz);
β—α
.68 (d, 2 H, β´ꢀH (C H O), J = 1.8 Hz); 7.30 (s, 2 H,
β´—β
CH=); 7.57 (d, 2 H, αꢀH (C H O), J
δ: 25.8 (CH ); 112.6, 115.9, 119.8, 135.9, 145.0, 152.8,
95.3 (C=O).
,5ꢀBis[(E)ꢀ(2ꢀthienyl)methylidene]cyclopentanone (5) (see
Ref. 36), yield 96%, m.p. 222 °C. Found (%): C, 66.14; H, 4.44.
C H OS . Calculated (%): C, 66.01; H, 4.39. IR, ν/cm–1:
4
3
4
3
= 3.5 Hz). 1 C NMR,
3
4
3
α—β
2
1
2
15
12
2
1
1685 (C=O), 1600 (C=C). H NMR, δ: 3.02 (s, 4 H, C(3)H ,
2
C(4)H ); 7.15 (dd, 2 H, βꢀH (C H S), J
β—α
= 4.9 Hz, Jβ—β´ =
2
4
3
3
2
.6 Hz); 7.38 (d, 2 H, β´ꢀH (C H S), J
= 3.6 Hz); 7.55 (d,
β´—β
4
3
Experimental
13
H, αꢀH (C H S), J = 4.9); 7.78 (s, 2 H, CH=). C NMR,
α—β
4
3
δ: 26.0 (CH ); 126.2, 128.1 130.3, 132.6, 135.8, 140.4,
2
The course of the reactions was monitored and the purity of
the compounds was checked by thinꢀlayer chromatography
194.4 (C=O).
2,6ꢀBis[(E)ꢀphenylmethylidene]cyclohexanone (9) (see
Ref. 29), yield 90%, m.p. 118 °C. IR, ν/cm : 1660 (C=O),
1630 (C=C). H NMR, δ: 1.90 (m, 2 H, C(4)H , J
5.4 Hz); 3.35 (t, 4 H, C(3)H , C(5)H , J
7.36—7.56 (m, 10 H, Ph); 7.63 (s, 2 H, CH=).
2,6ꢀBis[(E)ꢀ(4ꢀmethoxyphenyl)methylidene]cyclohexanone
(10) (see Ref. 29), yield 38%, m.p. 142 °C. IR, ν/cm : 1665
–
1
(
TLC) on a fixed silica gel layer (Silufol plates).
1
The IR spectra were measured on an URꢀ20 instrument (in
=
2
4—3,5
1
13
Nujol mulls). The H and C NMR spectra were recorded on a
= 5.4 Hz);
3,5—4
2
2
1
VarianꢀVXRꢀ400 instrument (400 MHz for H and 100 MHz
for C). The chemical shifts are given on the δ scale relative to
HMDS as the internal standard ( H) or the signal of the deuterꢀ
ated solvent ( C). Photoisomerization of dienones was studied
13
1
–1
13
1
(C=O), 1590 (C=C). H NMR, δ: 1.79 (tm, 2 H, C(4)H2,
by NMR spectroscopy on a Bruker Avance 250 instrument
J4—3,5 = 5.4 Hz); 2.89 (t, 4 H, C(3)H , C(5)H , J
3.82 (s, 6 H, OMe); 6.94 (d, 4 H, H(3´), H(5´) (4ꢀOMeꢀC H ),
= 5.9 Hz);
2
2
3,5—4
1
(
250.130 MHz for H NMR spectra and 62.860 MHz for
6 4
1
3
1
C{ H} spectra) in DMSOꢀd .
J3´,5´—2´,6´ = 9.2 Hz); 7.45 (d, 4 H, H(2´), H(6´) (4ꢀOMeꢀC H ),
6 4
6
13
The solvents were purified and dried according to proceꢀ
J2´.6´—3´.5´ = 9.2 Hz); 7.81 (s, 2 H, CH=). C NMR, δ: 22.9
dures published in the handbook.3 The melting points were
determined in open capillary tubes on a heating block and
are uncorrected. Elemental analysis was carried out on a
CarloꢀErba CHN analyzer. 2,7ꢀDibenzylidenecycloheptanone
5
(C(4)H ); 28.5 (C(3)H , C(5)H ); 55.2 (OMe); 113.8, 128.7,
2
2
2
132.2, 134.3, 136.4, 159.8, 190.1 (C=O).
2,6ꢀBis[(E)ꢀ(2ꢀfuryl)methylidene]cyclohexanone (11) (see
Ref. 36), yield 60%, m.p. 140 °C. Found (%): C, 75.68; H, 5.57.
–
1
(
34) and 2,8ꢀdibenzylidenecyclooctanone (35) were prepared
C H O . Calculated (%): C, 75.58; H, 5.55. IR, ν/cm : 1660
16 14 3
2
2,27
1
according to known procedures.
(C=O), 1590 (C=C). H NMR, δ: 1.89 (tm, 2 H, C(4)H2,
Synthesis of α ,βꢀdiarylidene derivatives of cyclic ketones.
Method A (see Ref. 21). A mixture of ketone (0.01 mol) and
aldehyde (0.02 mol) was dissolved in 95% ethanol (15 mL), and
a sodium hydroxide solution (0.04 g) in a minimum amount of
water was added. The solution was magnetically stirred (TLC
monitoring). The precipitate that formed was filtered off and
recrystallized from ethanol.
J4—3,5 = 5.2 Hz); 2.99 (t, 4 H, C(3)H , C(5)H , J
= 5.2 Hz);
3.89 (s, 6 H, OMe); 6.49 (dd, 2 H, βꢀH (C H O), J = 3.5 Hz,
β—α
2
2
3,5—4
4
3
Jβ—β´ = 1.4 Hz); 6.64 (d, 2 H, β´ꢀH (C H O), J = 1.4 Hz);
4
3
β´—β
1
3
7.53 (m, 4 H, αꢀH (C H O), CH=)). C NMR, δ: 21.7
4
3
(C(4)H ); 28.0 (C(3)H , C(5)H ); 112.3, 116.0, 123.3, 133.0,
2
2
2
144.5, 152.8, 189.0 (C=O).
2,6ꢀBis[(E)ꢀ(5ꢀmethylꢀ2ꢀfuryl)methylidene]cyclohexanone
(12), yield 68%, m.p. 106 °C. Found (%): C, 76.45; H, 6.48.
2
,5ꢀBis[(E)ꢀphenylmethylidene]cyclopentanone (1) (see
–
1
–1
Ref. 29), yield 87%, m.p. 196 °C. IR, ν/cm : 1690 (C=O),
610 (C=C). 1H NMR, δ: 3.11 (s, 4 H, C(3)H , C(4)H );
C H O . Calculated (%): C, 76.57; H, 6.43. IR, ν/cm : 1660
1
8
18
3
1
1
7
(C=O), 1600 (C=C). H NMR, δ: 1.86 (tm, 2 H, C(4)H2,
J4—3,5 = 5.7 Hz); 2.36 (s, 6 H, Me (5ꢀMeꢀC H O)); 2.97
2
2
.35—7.50 (m, 10 H, Ph); 7.60 (s, 2 H, CH=).
,5ꢀBis[(E)ꢀ(4ꢀmethoxyphenyl)methylidene]cyclopentanone
4
2
2
(t, 4 H, C(3)H , C(5)H , J
= 5.7 Hz); 6.11 (d, 2 H,
3,5—4
2
2
–
1
(
2) (see Ref. 29), yield 65%, m.p. 198 °C. IR, ν/cm : 1700
βꢀH (5ꢀMeꢀC H O), J
= 3.3 Hz); 6.56 (d, 2 H,
β—β´
4
2
1
(
C=O), 1610 (C=C). H NMR, δ: 2.98 (s, 4 H, C(3)H , C(4)H );
β´ꢀH (5ꢀMeꢀC H O), J
= 3.3 Hz); 7.49 (s, 2 H, CH=).
β´—β
2
2
4
2
3
.76 (s, 6 H, OMe); 6.85 (d, 4 H, H(3´), H(5´) (4ꢀOMeꢀC H ),
2,6ꢀBis[(E)ꢀ(2ꢀthienyl)methylidene]cyclohexanone (13) (see
Ref. 36), yield 86%, m.p. 169 °C. Found (%): C, 66.99; H, 4.89.
6
4
J3´,5´—2´,6´ = 7.9 Hz); 7.16 (s, 2 H, CH=); 7.46 (d, 4 H, H(2´),
H(6´) (4ꢀOMeꢀC H ), J = 7.9 Hz).
,5ꢀBis[(E)ꢀ(4ꢀdimethylaminophenyl)methylidene]cycloꢀ
pentanone (3), yield 25%, m.p. 298 °C. Found (%): C, 79.50;
H, 7.50; N, 7.98. C H N O. Calculated (%): C, 79.73; H, 7.56;
–
1
C H OS . Calculated (%): C, 67.09; H, 4.94. IR, ν/cm
1660 (C=O), 1590 (C=C). H NMR, δ: 1.97 (tm, 2 H, C(4)H ,
:
6
4
2´,6´—3´,5″
16 14
2
1
2
2
J4—3,5 = 5.71 Hz); 2.95 (t, 4 H, C(3)H , C(5)H , J
=
=
2
2
3,5—4
5.71 Hz); 7.14 (dd, 2 H, βꢀH (C H S), J
= 5.1 Hz, Jβ—β´
2
3
26
2
4
3
β—α
–
1
1
N, 8.09. IR, ν/cm : 1690 (C=O), 1600 (C=C). H NMR, δ:
3.7 Hz); 7.37 (d, 2 H, β´ꢀH (C H S), J
= 3.7 Hz); 7.53 (d,
β´—β
4
3
3
4
.01 (s, 12 H, NMe ); 4.24 (s, 4 H, C(3)H , C(4)H ); 6.72 (d,
2 H, αꢀH (C H S), J
= 5.1 Hz); 7.99 (s, 2 H, CH=).
α—β
2
2
2
4
3
H, H(3´), H(5´) (4ꢀNMe) ꢀC H ), J
= 9.2 Hz); 7.51
1ꢀMethylꢀ3,5ꢀbis[(E)ꢀphenylmethylidene]ꢀ4ꢀpiperidone (16)
2
6
4
3´,5´—2´,6´
–
1
(
d, 4 H, H(2´), H(6´) ((4ꢀ(NMe) C H ), J = 9.2 Hz);
(see Ref. 11), yield 50%, m.p. 118 °C. IR, ν/cm : 1680 (C=O),
2
6
4
2´,6´—3´,5″
1
7
.53 (s, 2 H, CH=).
,5ꢀBis[(E)ꢀ(2ꢀfuryl)methylidene]cyclopentanone (4) (see
Ref. 36), yield 88%, m.p. 164 °C. Found (%): C, 74.93; H, 4.99.
1630 (C=C). H NMR, δ: 2.43 (s, 3 H, Me); 3.74 (s, 4 H,
2
C(2)H , C(6)H ); 7.38—7.40 (m, 10 H, Ph); 7.80 (s, 2 H, CH=).
2
2
1ꢀMethylꢀ3,5ꢀbis[(E)ꢀ(4ꢀmethoxyphenyl)methylidene]ꢀ4ꢀ
piperidone (17) (see Ref. 11), yield 44%, m.p. 198 °C. IR, ν/cm :
–
1
–1
C H O . Calculated (%): C, 74.99; H, 5.03. IR, ν/cm : 1690
15
12
3

1
192
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
Vatsadze et al.
1
1
3
670 (C=O), 1605 (C=C). H NMR, δ: 2.50 (s, 3 H, NMe);
C(6)H ); 62.0 (PhCH ); 127.5, 127.8, 128.3, 128.4, 129.2, 130.4,
130.5, 133.1, 137.1, 138.7, 186.6 (C=O).
2
2
.79 (s, 4 H, C(2)H , C(6)H ); 3.90 (s, 6 H, OMe); 6.95 (d, 4 H,
2
2
H(3´), H(5´) (4ꢀOMeꢀC H ), J = 7.2 Hz); 7.40 (d,
1ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(4ꢀpyridyl)methylidene]ꢀ4ꢀpiperidone
6
4
3´,5´—2´,6´
–
1
4
H, H(2´), H(6´) (4ꢀOMeꢀC H ), J = 7.2 Hz); 7.69
(28) (see Ref. 37), yield 50%, m.p. 171 °C. IR, ν/cm : 1680
6
4
2´,6´—3´,5″
1
(
s, 2 H, CH=).
ꢀMethylꢀ3,5ꢀbis[(E)ꢀ(4ꢀdimethylaminophenyl)methylidene]ꢀ
ꢀpiperidone (18) (see Ref. 11), yield 16%, m.p. 232 °C. IR,
(C=O), 1620 (C=C). H NMR, δ: 3.72 (s, 2 H, PhCH ); 3.83
2
1
(br.s, 4 H, C(2)H , C(6)H ); 7.17 (d, 4 H, H(2´), H(6´)
2
2
4
(C H N), J
= 5.1 Hz); 7.26 (m, 5 H, Ph); 7.68
5
4
2´,6´—3´,5´
–
1
1
ν/cm : 1680 (C=O), 1610 (C=C). H NMR, δ: 2.49 (s, 3 H,
(s, 2 H, CH=); 8.64 (br.d, 4 H, H(3´), H(5´) (C H N),
5 4
NMe); 3.02 (s, 12 H, NMe ); 3.79 (s, 4 H, C(2)H , C(6)H );
J3´,5´—2´,6´ = 5.1 Hz).
2
2
2
6
9
.72 (d, 4 H, H(3´), H(5´) (4ꢀNMe ꢀC H ), J
.0 Hz); 7.34 (d, 4 H, H(2´), H(6´) (4ꢀNMe ꢀC H ),
=
1ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(3ꢀpyridyl)methylidene]ꢀ4ꢀpiperidone
(29), yield 37%, m.p. 166 °C. Found (%): C, 78.56; H, 5.84;
N, 11.38. C H N O. Calculated (%): C, 78.45; H, 5.76;
2
6
4
3´,5´—2´,6´
2 6 4
J2´,6´—3´,5″ = 9.0 Hz); 7.76 (s, 2 H, CH=).
24
21
3
–
1
1
1
ꢀMethylꢀ3,5ꢀbis[(E)ꢀ(2ꢀthienyl)methylidene]ꢀ4ꢀpiperidone
N, 11.44. IR, ν/cm : 1675 (C=O), 1620 (C=C). H NMR, δ:
–
1
(
19) (see Ref. 11), yield 68%, m.p. 118 °C. IR, ν/cm : 1665
3.71 (s, 2 H, PhCH ); 3.84 (s, 4 H, C(2)H , C(6)H ); 7.24 (m,
2
2
2
1
(
C=O), 1610 (C=C). H NMR, δ: 2.57 (s, 3 H, Me); 3.78 (s,
5 H, Ph); 7.31 (dd, 2 H, H(5´) (C H N), J
= 7.9 Hz,
= 7.9 Hz);
5
4
5´—4´
4
4
3
2
1
H, C(2)H , C(6)H ); 7.12 (dd, 2 H, βꢀH (C H S), J
=
=
J5´—6´ = 4.9 Hz); 7.62 (d, 2 H, H(4´) (C H N), J
2
2
4
3
β—α
5 4 4´—5´
.9 Hz, Jβ—β´ = 3.5 Hz); 7.30 (d, 2 H, β´ꢀH (C H S), J
7.75 (s, 2 H, CH=); 8.56 (d, 2 H, H(6´) (C H N), J
=
4
3
β´—β
5
4
6´—5´
.5 Hz); 7.52 (d, 2 H, αꢀH (C H S), J
H, CH=). C NMR, δ: 46.0 (Me); 56.6 (CH ); 127.9, 128.2,
= 4.9 Hz); 7.90 (s,
4.9 Hz); 8.62 (br.s, 2 H, H(2´) (C H N)).
4
3
α—β
5 4
13
1ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(2ꢀpyridyl)methylidene]ꢀ4ꢀpiperidone
(30) (see Ref. 37), yield 75%, m.p. 125 °C. Found (%): C, 78.13;
H, 5.71; N, 11.48. C24H N O. Calculated (%): C, 78.45;
2
30.4, 133.0, 138.7, 186.1 (C=O).
1
ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ1ꢀphenylmethylidene]ꢀ4ꢀpiperidone
21
3
–1
–
1
(
(
(
(
22) (see Ref. 37), yield 51%, m.p. 158 °C. IR, ν/cm : 1680
C=O), 1620 (C=C). H NMR, δ: 3.69 (s, 2 H, PhCH ); 3.85
s, 4 H, C(2)H , C(6)H ); 7.31—7.38 (m, 15 H, Ph); 7.80
s, 2 H, CH=).
ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(4ꢀmethoxyphenyl)methylidene]ꢀ4ꢀ
H, 5.76; N, 11.44. IR, ν/cm : 1680 (C=O), 1620 (C=C).
1
1
H NMR, δ: 3.78 (s, 2 H, PhCH ); 4.24 (s, 4 H, C(2)H ,
2
2
2
C(6)H ); 7.13—7.33 (m, 7 H, H(5´) (C H N), Ph); 7.39 (d,
2
2
2
5
4
2 H, H(3´) (C H N), J
= 7.6 Hz); 7.60 (s, 2 H, CH=);
3´—4´
5
4
1
7.64 (dt, 2 H, H(4´) (C H N), J
= J4´—5´ = 7.6 Hz,
4´—3″
5
4
–
1
piperidone (23) (see Ref. 37), yield 48%, m.p. 162 °C. IR, ν/cm
1
3
:
J4´—6´ = 6.0 Hz); 8.61 (dd, 2 H, H(6´) (C H N), J
= 6.0 Hz,
6´—4´
5
4
1
675 (C=O), 1600 (C=C). H NMR, δ: 3.70 (s, 2 H, PhCH );
J6´—5´ = 5.8 Hz).
2
.73 (s, 4 H, C(2)H , C(6)H ); 3.84 (s, 6 H, OMe); 6.88 (d, 4 H,
Method B (see Ref. 6). A mixture of aldehyde (0.02 mol) and
ketone (0.01 mol) in water (40 mL) was stirred with cooling
to 5 °C, and a 10% sodium hydroxide solution (2 mL) was
added. The mixture was stirred at 25 °C for 10 h and then
neutralized with a dilute hydrochloric acid solution. The preꢀ
cipitate was filtered off and recrystallized from ethanol.
2
2
H(3´), H(5´) (4ꢀOMeꢀC H ), J = 8.8 Hz); 7.23—7.31
6
4
3´,5´—2´,6´
(
m, 9 H, H(2´), H(6´) (4ꢀOMeꢀC H ), Ph); 7.44 (s, 2 H, CH=).
6 4
1
ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(4ꢀdimethylaminophenyl)methylidene]ꢀ
4
ꢀpiperidone (24) (see Ref. 37), yield 18%, m.p. 208 °C. IR,
–
1
1
ν/cm : 1660 (C=O), 1600 (C=C). H NMR, δ: 2.99 (s, 12 H,
NMe ); 3.72 (s, 2 H, PhCH ); 3.87 (s, 4 H, C(2)H , C(6)H );
2,5ꢀBis[(E)ꢀ(4ꢀpyridyl)methylidene]cyclopentanone (6) (see
2
2
2
2
–
1
6
.72 (d, 4 H, H(3´), H(5´) (4ꢀNMe ꢀC H ), J
=
Ref. 6), yield 50%, m.p. 239 °C, 50%. IR, ν/cm : 1670 (C=O),
2
6
4
3´,5´—2´,6´
1
5
.8 Hz); 7.23—7.29 (m, 9 H, H(2´), H(6´) (4ꢀNMe ꢀC H ),
1630 (C=C). H NMR, δ: 3.16 (s, 4 H, CH ); 7.42 (d, 4 H,
2
6
4
2
Ph); 7.73 (s, 2 H, CH=).
H(2´), H(6´) (C H N), J
= 5.9 Hz); 7.49 (s, 2 H,
2´,6´—3´,5´
5
4
1
ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(2ꢀfuryl)methylidene]ꢀ4ꢀpiperidone
CH=); 8.70 (d, 4 H, H(3´), H(5´) (C H N), J
=
5
4
3´,5´—2´,6´
–
1
13
(
(
25) (see Ref. 37), yield 78%, m.p. 138 °C. IR, ν/cm : 1670
C=O), 1620 (C=C). H NMR, δ: 3.74 (s, 2 H, PhCH ); 3.92
5.9 Hz). C NMR, δ: 26.3 (CH ); 124.1, 131.5, 140.4, 142.4,
2
1
150.4, 195.3 (C=O).
2
(
5
3
s, 4 H, C(2)H , C(6)H ); 6.42 (dd, 4 H, βꢀH (C H O), J
=
=
2,5ꢀBis[(E)ꢀ(3ꢀpyridyl)methylidene]cyclopentanone (7), yield
73%, m.p. 216 °C. Found (%): C, 77.65; H, 5.44; N, 10.56.
C H N O. Calculated (%): C, 77.84; H, 5.38; N, 10.68. IR,
2
2
4
3
β—α
.2 Hz, Jβ—β´ = 3.3 Hz); 6.53 (d, 2 H, β´ꢀH (C H O), J
4 3
β´—β
.3 Hz); 7.22—7.32 (m, 5 H, Ph); 7.50—7.59 (m, 4 H,
17
14
–1
2
13
1
αꢀH (C H O), CH=). C NMR, δ: 54.1 (C(2)H , C(6)H );
6
1
ν/cm : 1670 (C=O), 1610 (C=C). H NMR, δ: 3.16 (s, 4 H,
CH ); 7.33 (dd, 2 H, H(5´) (C H N), J = 7.8 Hz, J5´—6´
4
3
2
2
1.6 (PhCH ); 112.4, 116.8, 122.0, 127.2, 128.3, 129.1, 130.3,
=
2
2
5
4
5´—4´
37.7, 145.0, 152.1, 186.9 (C=O).
5.0 Hz); 7.57 (s, 2 H, CH=); 7.87 (d, 2 H, H(4´) (C H N),
5 4
1
ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(5ꢀmethylꢀ2ꢀfuryl)methylidene]ꢀ4ꢀpiꢀ
J4´—5´ = 7.8 Hz); 8.59 (d, 2 H, H(6´) (C H N), J
= 5.0 Hz);
6´—5´
5
4
–
1
peridone (26) (see Ref. 37), yield 82%, m.p. 168 °C. IR, ν/cm
665 (C=O), 1610 (C=C). 1H NMR, δ: 2.29 (s, 6 H, Me
MeC H O)); 3.77 (s, 2 H, PhCH ); 3.94 (s, 4 H, C(2)H ,
C(6)H ); 6.08 (d, 2 H, βꢀH (5ꢀMeꢀC H O), J
:
8.85 (br.s, 2 H, H(2´) (C H N)).
5 4
1
(
2,5ꢀBis[(E)ꢀ(2ꢀpyridyl)methylidene]cyclopentanone (8) (see
–
1
Ref. 6), yield 69%, m.p. 195 °C. IR, ν/cm : 1690 (C=O), 1610
4
2
2
2
1
= 3.4 Hz);
(C=C). H NMR, δ: 3.35 (s, 4 H, CH ); 7.21 (dd, 2 H, H(5´)
2
4
2
β—β´
2
6
.50 (d, 2 H, β´ꢀH (5ꢀMeꢀC H O), J
= 3.4 Hz); 7.25—7.38
(C H N), J
= 7.9 Hz, J5´—6´ = 4.7 Hz); 7.51 (d, 2 H, H(3´)
= 7.9 Hz); 7.54 (s, 2 H, CH=); 7.72 (dt, 2 H,
4
2
β´—β
5
4
5´—4´
3´—4´
(
m, 5 H, Ph); 7.44 (s, 2 H, CH=).
ꢀBenzylꢀ3,5ꢀbis[(E)ꢀ(2ꢀthienyl)methylidene]ꢀ4ꢀpiperidone
(C H N), J
5
4
1
H(4´) (C H N), J
= J4´—5´ = 7.9 Hz, J4´—6´ = 1.7 Hz); 8.74
5
4
4´—3´
–
1
(
(
27) (see Ref. 37), yield 90%, m.p. 168 °C. IR, ν/cm : 1660
C=O), 1610 (C=C). H NMR, δ: 3.80 (s, 2 H, PhCH ); 3.83
(dd, 2 H, H(6´) (C H N), J
= 1.7 Hz, J6´—5´ = 4.7 Hz).
6´—4´
5
4
1
13
C NMR, δ: 27.2 (CH ); 122.7, 127.1 131.5, 136.2 141.8, 150.0,
2
2
(
s, 4 H, C(2)H , C(6)H ); 7.06 (dd, 2 H, βꢀH (C H S), J
=
=
155.1, 198.3 (C=O).
2
2
4
3
β—α
5
3
.2 Hz, Jβ—β´ = 3.7 Hz); 7.26 (d, 2 H, β´ꢀH (C H S), J
2,6ꢀBis[(E)ꢀ(4ꢀpyridyl)methylidene]cyclohexanone (14) (see
4
3
β´—β
–
1
.7 Hz); 7.28—7.37 (m, 5 H, Ph); 7.48 (d, 2 H, αꢀH (C H S),
Ref. 6), yield 98%, m.p. 150 °C. IR, ν/cm : 1670 (C=O), 1630
4
3
Jα—β = 5.2 Hz); 7.90 (s, 2 H, CH=). 13C NMR, δ: 54.1 (C(2)H2,
(C=C). H NMR, δ: 1.80 (tm, 2 H, C(4)H , J
1
= 5.20 Hz);
2
4—3,5

Crossꢀconjugated dienones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
1193
2
.90 (t, 4 H, C(3)H , C(5)H , J
= 5.20 Hz); 7.25 (d, 4 H,
= 5.8 Hz); 7.64 (s, 2 H,
Xꢀray diffraction analysis. Experimental intensities of comꢀ
pounds 6, 13, 14, 31, and 33 were measured on automated
Bruker SMART 1000 and EnrafꢀNonius CAD 4 diffractometers
using MoꢀKα radiation (λ = 0.71073 Å, graphite monochromaꢀ
tor). Absorption corrections 13, 14, and 31 were ignored. Abꢀ
sorption corrections for 6 and 33 were applied based on intensiꢀ
ties of equivalent reflections.3 The structures were solved by
direct methods (SHELXꢀ86).39 All nonhydrogen atoms were
2
2
3,5—4
H(2´), H(6´) (C H N), J
CH=); 8.64 (d, 4 H, H(3´), H(5´) (C H N), J =
5
1
5
4
2´,6´—3´,5´
5
4
3´,5´—2´,6´
13
.8 Hz). C NMR, δ: 22.4 (C(4)H ); 28.2 (C(3)H , C(5)H );
2
2
2
23.8, 134.2, 143.0, 149.9, 150.1, 189.2 (C=O).
2
,6ꢀBis[(E)ꢀ(3ꢀpyridyl)methylidene]cyclohexanone (15) (see
8
Ref. 20), yield 72%, m.p. 139 °C. Found (%): C, 78.40; H, 6.00;
N, 10.15. C18H N O. Calculated (%): C, 78.22; H, 5.85;
16
2
–
1
1
2
N, 10.14. IR, ν/cm : 1670 (C=O), 1610 (C=C). H NMR, δ:
.83 (m, 2 H, C(4)H ); 2.92 (m, 4 H, C(3)H , C(5)H ); 7.33
refined by the fullꢀmatrix leastꢀsquares method against F
4
0
1
(SHELXLꢀ97) except for the disordered CCl and water solꢀ
2
2
2
4
(
7
dd, 2 H, H(5´) (C H N), J = 7.5 Hz, J5´—5´ = 5.2 Hz);
vent molecules in the structure of 33. All hydrogen atoms in
compounds 6, 13, 14, and 31 were located in difference electron
density maps and refined isotropically. The hydrogen atoms in
the structure of 33 were placed in calculated positions and reꢀ
fined using a riding model. Large final values of the R factors
and high residual electron densities for the structure of 33 are
associated, on the one hand, with a poor quality of the crystals
and, on the other hand, with the presence of a large amount of
disordered solvent molecules in the structure.
5
4
5´—4´
.74 (m, 4 H, H(4´) (C H N), CH=); 8.55 (d, 2 H, H(6´)
5 4
(
C H N), J
= 5.2 Hz); 8.70 (br.s, 2 H, H(2´) (C H N)).
6´—5´ 5 4
5
4
1
3
C NMR, δ: 22.6 (C(4)H ); 28.2 (C(3)H , C(5)H ); 123.2,
2
2
2
1
31.5, 133.5, 136.9, 137.6, 149.2, 151.0, 189.1 (C=O).
ꢀMethylꢀ3,5ꢀbis[(E)ꢀ(4ꢀpyridyl)methylidene]ꢀ4ꢀpiperidone
20) (see Ref. 11), yield 68%, m.p. 150 °C. Found (%): C, 73.99;
H, 6.00; N, 14.35. C18H N O. Calculated (%): C, 74.19;
1
(
17
3
–
1
H, 5.89; N, 14.35. IR, ν/cm : 1680 (C=O), 1625 (C=C).
1
H NMR, δ: 2.43 (s, 3 H, Me); 3.71 (s, 4 H, C(2)H , C(6)H );
2
2
7
7
.22 (d, 4 H, H(2´), H(6´) (C H N), J = 4.6 Hz);
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 06ꢀ03ꢀ
33077).
5
4
2´,6´—3,5´
.65 (s, 2 H, CH=); 8.66 (d, 4 H, H(3´), H(5´) (C H N),
5 4
J3´,5´—2´,6´ = 4.6 Hz).
1
ꢀMethylꢀ3,5ꢀbis[(E)ꢀ(3ꢀpyridyl)methylidene]ꢀ4ꢀpiperidone
–
1
(
21) (see Ref. 37), yield 72%, m.p. 139 °C. IR, ν/cm : 1675
References
1
(
C=O), 1620 (C=C). H NMR, δ: 2.43 (s, 3 H, Me); 3.72 (s,
4
2
H, C(2)H , C(6)H ); 7.33 (m, 2 H, H(5´) (C H N)); 7.66 (d,
2 2 5 4
H, H(4´) (C H N), J = 6.7 Hz); 7.72 (s, 2 H, CH=); 8.55
4´—5´
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4
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5 4 5 4
1
C NMR, δ: 45.8 (Me); 56.8 (CH ); 123.4, 130.9, 132.8, 134.6,
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1
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(
19
3
–
1
1
N, 13.76. IR, ν/cm : 1700 (C=O), 1610 (C=C). H NMR, δ:
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1
2
(
s, 4 H, C(2)H , C(6)H ); 7.36 (m, 2 H, H(5´) (C H N));
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7
2
.69 (d, 2 H, H(4´) (C H N), J
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4´—5´
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4
H, CH=); 8.56 (m, 2 H, H(6´) (C H N)); 8.62 (br.s, 2 H,
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4
1
ꢀIsopropylꢀ2,5ꢀbis[(E)ꢀ(3ꢀpyridyl)methylidene]ꢀ4ꢀpiperiꢀ
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21
3
–
1
1
N, 13.16. IR, ν/cm : 1695 (C=O), 1610 (C=C). H NMR, δ:
.12 (d, 6 H, Me, J = 6.9 Hz); 2.97 (m, 1 H, CH); 3.78 (s, 4 H,
C(2)H , C(6)H ); 7.38 (m, 2 H, H(5´) (C H N)); 7.71 (d, 2 H,
1
2
2
5
4
H(4´) (C H N), J = 6.9 Hz); 7.73 (s, 2 H, CH=); 8.60 (d,
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4
4´—5´
2
H, H(6´) (C H N), J = 4.6 Hz); 8.68 (br.s, 2 H,
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5
4
5´—6´
H(2´) (C H N)).
5
4
(
2E,8E,5R*,6R*,11R*,12R*)ꢀ11,12ꢀDi(3ꢀpyridyl)ꢀ2,8ꢀ
bis[(3ꢀpyridyl)methylidene]dispiro[4.0.4.2]dodecaneꢀ1,7ꢀdione
33), m.p. 212 °C. Found (%): C, 77.95; H, 5.41; N, 10.57.
C H N O. Calculated (%): C, 77.84; H, 5.38; N, 10.68. IR,
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(
2
0
21
3
–
1
1
ν/cm : 1710 (C=O), 1630 (C=C). H NMR, δ: 1.40—1.50,
2
4
7
1
2
1
.26—2.40, 2.54—2.62, and 2.75—2.84 (all m, 2 H each, CH );
.63 (s, 2 H, cyclobutane); 7.25—7.30 (m, 4 H, βꢀРу , βꢀРу );
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2
2
1
2
.52 (br.s, 2 H, CH=); 7.57 (dt, 2 H, γꢀРу , J = 8.0 Hz, J =
1
2
1
.8 Hz); 7.69 (dd, 2 H, αꢀРу , J = 4.8 Hz, J = 1.6 Hz); 8.47 (d,
1
2
2
2
H, α´ꢀРу , J = 1.6 Hz); 8.50 (dd, 2 H, αꢀРу , J = 4.4 Hz, J =
.6 Hz); 8.53 (dm,, 2 H, γꢀРу , J = 8.0 Hz); 8.86 (d, 2 H,
1
2
1
1
α´ꢀРу , J = 2.0 Hz).

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