Synthesis and Comparative Analysis of Molecular and Supramolecular Structures of 4,8-Disubstituted 1,5-Dichloro-2,6-dioxotricyclo[5.1.0.0 3,5]octanes

Article abstract of DOI:10.1007/s00706-003-0028-y

A series of 4,8-disubstituted 1,5-dichloro-2,6-dioxotricyclo-[5.1.0.0 ^3,5]octanes, synthesized by various methods, were studied by X-ray single crystal diffraction. The conformation (syn/anti) of the molecules does not depend on the method of preparation and nature of substituents. All the compounds crystallize in centrosymmetric space groups with half of the molecules in the asymmetric part of the unit cell. The main influence which the substituents render is on the packing of molecules in crystals and on the types of intermolecular interactions and supramolecular structures.

Full text of DOI:10.1007/s00706-003-0028-y

Monatshefte f€ur Chemie 134, 1229–1240 (2003)
DOI 10.1007/s00706-003-0028-y
Synthesis and Comparative Analysis
of Molecular and Supramolecular
Structures of 4,8-Disubstituted
1,5-Dichloro-2,6-dioxotricyclo[5.1.0.03,5]octanes
Aidar T. Gubaidullin1;ꢀ, Vakhid A. Mamedov1, Igor A. Litvinov1,
Huan Ye2, and Sadao Tsuboi2;ꢀ
1
A.E.Arbuzov Institute of Organic and Physical Chemistry, 420088, Kazan,
Russian Federation
2
Department of Environmental Chemistry and Materials, Okayama University,
Tsushima, Okayama 700, Japan
Received November 7, 2002; accepted (revised) December 16, 2002
Published online June 23, 2003 # Springer-Verlag 2003
Summary. A series of 4,8-disubstituted 1,5-dichloro-2,6-dioxotricyclo-[5.1.0.03,5]octanes, synthesized
by various methods, were studied by X-ray single crystal diffraction. The conformation (syn=anti) of
the molecules does not depend on the method of preparation and nature of substituents. All the
compounds crystallize in centrosymmetric space groups with half of the molecules in the asymmetric
part of the unit cell. The main influence which the substituents render is on the packing of molecules in
crystals and on the types of intermolecular interactions and supramolecular structures.
Keywords. Michael addition; Darzens condensation; Homo-p-quinones; Supramolecular chemistry;
X-Ray structure determination.
Introduction
The full structural analysis of symmetrically substituted tricyclo-[5.1.0.03,5]octane-
2,6-diones (bis-homo-p-quinones), carried out by the two known and principally
different methods, has been made by means of NMR-studies. The methods of synthe-
sis of the title compounds include debrominative as well as dehydrobrominative
cyclopropane formations of 2,4,6,8-tetrabromocyclooctane-1,5-diones (method I)
[1] and double addition of one-carbon units to p-quinone derivatives (method II),
which has been achieved: a) by the action of diazomethane or diazoethane [2] on
duroquinone followed by nitrogen elimination, b) by the action of dimethylsulfox-
onium methylide (Corey-Chaykovsky reagent [3]) on p-quinonemonoacetal [4, 5],
ꢀ
Corresponding authors. E-mail: aidar@iopc.knc.ru, stsuboi@cc.okayama-u.ac.jp

1230
A. T. Gubaidullin et al.
and c) by the addition of dihalocarbenes to duroquinone [6]. In these investigations it
has been shown that depending on the synthetic method the configuration of bis-
homo-p-quinones is syn (method I minor, II a, b) or anti (method II major, II c).
Results and Discussion
Synthesis of Homoquinones
The formation of bis-homo-p-quinones (3–8) as by-products with 8–12% yields has
been observed by us in the reactions of ethyl 2,2-dichloroacetoacetate (1) [7] and
3,3-dichloropentane-2,4-dione (2) [8] with aldehydes under the conditions of the
Darzens condensation along with main Darzens products; chloroepoxides 9 and=or
chloroketones 10 in the first case and products 11 of insertion of aldehydes to the ꢀ
C–C bond in the second case (Scheme 1).
The mechanism of the formation of bis-homo-p-quinones (Scheme 2), which
includes intramolecular double Michael addition of the Knoevenagel product A
with the intermediate formation of 3,3,7,7-tetrachlorocyclooctane-2,6-dion-1,5-
dianione (B), allowed to develop a new convenient method to obtain these attrac-
tive compounds. It consists of the cycloaddition of dichloroacetylalkenes 13, which
was achieved by Friedel-Crafts alkylation of an appropriate hydrocarbon with the
vinylogue of dichloroacetylchloride 12 [9] obtained by addition of dichloroace-
tylchloride to acetylene under the conditions of the Kondakov reaction [10]
(Scheme 3).
A second method provides 13 by the reaction of ꢁ, ꢂ-unsaturated esters with
lithiodihalomethanes [11] (Scheme 4).
The structure of bis-homo-p-quinones obtained by these two latter methods is
established not only by spectroscopic (IR, NMR) data [12], but also by X-Ray
investigations for representatives of these compounds, for example, those received
from the reactions of ethyl 2,2-dichloroacetoacetate with propionic aldehyde [7]
Scheme 1

4,8-Disubstituted 1,5-Dichloro-2,6-dioxotricyclo[5.1.0.03,5]octanes
1231
Scheme 2
Scheme 3
Scheme 4
and 3,3-dichloropentan-2,4-dione with benzaldehyde [8a], which have shown
formation of the anti-configured diastereomers.
Because the methods for the preparation of bis-homo-p-quinones involve
different intermediates one might assume the formation of various isomeric bis-
homo-p-quinones. Therefore we have compared the X-Ray data of six bis-homo-p-
quinones obtained by various methods. The Cambridge crystallographic database
[13] contains no data of further compounds of this class.
Crystal Structure
First, it should be noted that in the X-ray investigation we used crystals of the
compounds prepared by different synthetic methods. Thus, 3, 4, 5, and 7 were
obtained via synthesis Schemes 1 and 4 and 6 and 8 via Schemes 1, 3, and 4.
Judged by cell parameters, the crystals obtained via these methods appeared to be
identical.
The X-Ray single crystal diffraction study of 3–6 revealed that bis-homo-p-
quinones exist in a symmetric chair conformation (Fig. 1). The conformation of the

1232
A. T. Gubaidullin et al.
Fig. 1. PLUTO drawing of bis-homo-p-quinones 3–6 and the atom labelling scheme
central six-membered ring is planar. The dihedral angle between the plane of
this ring and the cyclopropane ring is in the range of 74–78ꢁ. The substituents
at the C(4) and C(40) atoms occupy equatorial positions. The distances C(2)–Cl(1)
˚
are close to standard C–Cl distances in Cl-substituted cyclopropanes (1.755 A)
[14], that is the hybridisation of the C(2) atom is close to sp3. It should be noted
that all investigated compounds including 7 and 8 crystallize in centro-
symmetric space groups with half of the molecules in the asymmetric part of the
unit cells.
Molecules of all compounds are located in the centres of symmetry and have
their own symmetry ꢂ 1. Selected geometric parameters of 3–6 and the data of the
earlier published structures 7 and 8 are presented in Table 1. Because of the low
accuracy of the geometrical parameters in the reference compound 8, a more
detailed comparison with these data was impossible. For the correct analysis a
new, more accurate X-ray single-crystal experiment with 8 was performed, and
in Table 2 the data of this experiment are presented.
As shown in Table 1, the type of substituents practically does not affect both
carbocycle conformations and angles in molecules. Thus, no systematic changes of
the geometric parameters from molecules with small substituents to more
bulky ones were observed. All compounds crystallize without inclusion of solvent
molecules. The conformation of the tricycle appears to be very stable, so even
the presence of bulky substituents does not change its geometric parameters
essentially.

4,8-Disubstituted 1,5-Dichloro-2,6-dioxotricyclo[5.1.0.03,5]octanes
1233
Table 1. Selected geometrical parameters of the compounds 3–8
3
4
5
6
7
8
Dihedral angle=ꢁ
˚
d(C1-O1)=A
˚
d(C2-Cl1)=A
˚
d(C3-H3)=A
˚
d(C1-C2)=A
˚
d(C2-C3)=A
˚
d(C3-C4)=A
˚
d(C2-C4)=A
76.7(2)
74.8(3)
75.9(3)
78.0(6)
1.190(9)
1.756(7)
0.971(8)
1.51(1)
1.47(1)
1.50(1)
1.48(1)
0.977(8)
1.50(1)
76.1(1)
77.6(2)
1.203(2)
1.749(2)
0.89(2)
1.201(6)
1.751(3)
0.95(3)
1.237(4)
1.759(4)
0.96(4)
1.202(1)
1.753(1)
1.14(2rt)
1.477(2)
1.527(2)
1.533(2)
1.507(2)
1.08(1)
1.213(1)
1.744(2)
0.95(2)
1.496(2)
1.523(2)
1.522(2)
1.520(2)
1.10(2)
1.489(5)
1.495(6)
1.478(6)
1.494(4)
0.91(3)
1.459(5)
1.523(5)
1.517(4)
1.519(5)
0.92(4)
1.492(2)
1.510(2)
1.517(2)
1.528(2)
0.95(2)
˚
d(C4-H4)=A
˚
d(C4-C5)=A
1.518(2)
1.514(5)
1.503(6)
1.506(1)
1.491(2)
ff(C1-C2-C3)=ꢁ
ff(C2-C3-C4)=ꢁ
ff(C3-C2-C4)=ꢁ
ff(C3-C4-C2)=ꢁ
121.9(1)
59.90(9)
60.04(9)
60.1(1)
120.9(3)
60.3(2)
59.3(3)
60.4(3)
121.7(3)
60.0(2)
59.8(2)
60.2(2)
122.3(6)
59.6(5)
61.3(5)
59.2(5)
121.7(2)
59.0(1)
60.7(1)
60.3(1)
121.8(1)
60.66(9)
59.89(9)
59.44(9)
Hydrogen Bonding
The analysis of data gives evidence, that the main influence which the substituents
render is the type of molecular packing in crystals and the type of intermolecular
interactions. In Fig. 2 the fragments of the hydrogen bonding system (a) and
packing of molecules in crystals (b) of compounds 3–6 are shown, and in Fig. 3
similar data of 7 and 8, for which such analysis was not carried out earlier, are
presented. It is necessary to remark, that in these compounds there are no classic
hydrogen bonds. However, the presence of a significant number of weaker inter-
actions (C–Hꢃ ꢃ ꢃO, C–Hꢃ ꢃ ꢃCl) renders an essential influence on the packing of
molecules. Taking into account that all of the investigated molecules are centro-
symmetric, a rather ramified system of hydrogen bonding should be observed.
Different types of intermolecular contacts appear in the crystals. The molecules
of 3 form an infinite two-dimensional network in the 0xy plane via the bifurcate
0
˚
˚
hydrogen bonds of O(1) atoms with protons H(4 ) (x, y ꢂ 1, z) (Oꢃ ꢃ ꢃH 2.64(1) A,
ꢁ
00
ff(Oꢃ ꢃ ꢃH–C) 149.6(4) ) and (H3 ) ( ꢂ 1 þ x, ꢂ 1 þ y, z) (Oꢃ ꢃ ꢃH 2.62(2) A,
ff(Oꢃ ꢃ ꢃH–C) 123.8(5)ꢁ) (Fig. 2. 3(a)). Among other short contacts the interaction
000
ꢁ
˚
Cl(1)ꢃ ꢃ ꢃH(4 ) (1 þ x, y, z) (Clꢃ ꢃ ꢃH 2.91(1) A, ff(Clꢃ ꢃ ꢃH–C) 113.8(4) ) was found.
The mutual packing of molecules in the crystal is such that a bilayered structure is
formed in the crystal (Fig. 2. 3(b)). The layers containing chlorine atoms alternate
with layers containing tricycles parallel to crystallographic plane 0xy. Such a local-
ization of chlorine atoms in the crystal can be considered as the pseudochanel and
indicates the existence of a selected direction and probably an anisotropy of the
crystalline properties.
In 7, as investigated earlier [7], the participation of O(1) in two short contacts with
protons H(30), H(40) of the nearest molecule (x, ꢂ 1=2 þ y, 3=2 ꢂ z) is observed. The
ꢁ
˚
parameters of interactions are identical: (Oꢃ ꢃ ꢃH 2.58(3) A, ff(Oꢃ ꢃ ꢃH–C) 117.6(3) ).
As each molecule of 7 takes part in two similar contacts as an acceptor and in
four contacts as a donor, an infinite two-dimensional network of hydrogen-bonded

1234
A. T. Gubaidullin et al.
Table 2. Crystallographic data for compounds 3–6
Crystal data
3
4
5
6
Chemical formula
Chemical formula weight
Cell setting
C10H10Cl2O2
233.10
C16H22Cl2O2
317.26
C16H22Cl2O2
317.26
Triclinic
P-1
C22H18Cl2O2
385.29
Monoclinic
P21=a
Triclinic
P-1
Monoclinic
P21=n
Space group
˚
a=A
˚
b=A
5.604(3)
6.1169(8)
7.840(3)
92.97(2)
91.55(4)
109.32(3)
253(2)
5.460(4)
11.408(5)
13.387(9)
90.00
5.712(4)
6.038(2)
13.935(6)
86.37(3)
78.52(2)
68.97(2)
439(1)
1
9.337(9)
8.875(8)
11.123(7)
90.00
˚
c=A
ꢁ=ꢁ
ꢂ=ꢁ
ꢃ=ꢁ
92.12(6)
90.00
91.27(7)
90.00
3
˚
V=A
833(1)
921(1)
2
Z
1
2
Dx=mg mꢂ 3
Crystal form
Crystal size=mm
Crystal colour
F(000)
1.53
1.26
1.20
1.39
Prismatic
Prismatic
Plate
Plate
0.05 Â 0.2 Â 0.2 0.08 Â 0.2 Â 0.3 0.05 Â 0.1 Â 0.2 0.03 Â 0.3 Â 0.3
Colorless
120
Colorless
336
Colorless
168
Colorless
400
Temperature=K
Scan mode
294
294
294
294
!=2ꢄ
!=2ꢄ
49.80
None
35.53
1749
1169
5.3
!=2ꢄ
74.14
Empirical
33.68
1001
700
!=2ꢄ
26.31
None
3.64
ꢁ
Recording range ꢄmax
=
74.24
Empirical
56.49
1131
Absorption correction
ꢅ=cmꢂ 1
No. of recorded reflections
5039
730
No. of independent reflections with F2 ꢄ 3ꢀ(F2) 850
R=%
wR=%
5.0
5.0
5.2
6.1
6.0
6.2
4.8
S
2.8
1.9
2.4
1.2
H-refinement
Isotropically
84
Isotropically
135
Not refined
103
Not refined
118
No. of refined parameters
molecules in the plane 0yz is formed (Fig. 3. 7). A mutual disposition of molecules
in the unit cell and longer substituents, than in 3, prevent the localization of the
chlorine atoms in one layer. However, they do not eliminate formations of layered
superstructures.
In 4 with n-butyl substituents in a zigzag conformation, the interaction of O(1)
with the methyne proton H(710) of the molecules, related by the symmetry opera-
˚
tion (x ꢂ 1=2, 1=2 ꢂ y, 1=2 þ z) is observed (Oꢃ ꢃ ꢃH 2.59(5) A, ff(Oꢃ ꢃ ꢃH–C)
176(3)ꢁ) (Fig. 2. 4(a)) form a three-dimensional system of hydrogen bonds due
to this crystallographic special position of the molecule in the crystal.
In i-butyl-substituted compound 5 the formation of sloping stacks of molecules
is also observed and the molecules of neighboring stacks take part in inter-
0
˚
˚
molecular interactions via O(1)ꢃ ꢃ ꢃH(3 ) (x ꢂ 1, 1 þ y, z) (Oꢃ ꢃ ꢃH 2.49(3) A,
ꢁ
00
ff(Oꢃ ꢃ ꢃH–C) 122.1(5) ) and Cl(1)ꢃ ꢃ ꢃH(52 ) (x, 1 þ y, z) (Clꢃ ꢃ ꢃH 2.67(3) A,
ff(Clꢃ ꢃ ꢃH–C) 116.8(3)ꢁ) contacts (Fig. 2. 5(a)). Thus an infinite two-dimensional

4,8-Disubstituted 1,5-Dichloro-2,6-dioxotricyclo[5.1.0.03,5]octanes
1235
Fig. 2. The fragments of the 3–6 compounds’ unit cells showing intermolecular hydrogen bonding
(a) and the crystal packing (b)

1236
A. T. Gubaidullin et al.
Fig. 3. The fragments of the unit cells showing intermolecular hydrogen bonding in 7 (view along
0x, only H atoms participating in hydrogen bonds are shown) and crystals packing in 8 (view along
0y, hydrogen atoms not shown)
network of hydrogen-bonded molecules in the plane 0xy is formed. Layers
containing i-butyl groups alternate with those consisting of cyclic fragments of
molecules.
For the bis-homo-p-quinones with aromatic substituents 6 and 8 ꢆ–ꢆ and ꢆ–H
interactions in the crystal are observed. Among other short contacts in 6 the inter-
action C–Hꢃ ꢃ ꢃCl between the chlorine atom Cl(1) and the phenyl proton H(100)
ꢁ
˚
(1=2 ꢂ x, ꢂ 1=2 þ y, ꢂ z) (Clꢃ ꢃ ꢃH 2.75(6) A, ff(Clꢃ ꢃ ꢃH–C) 139.2(2) ) (Fig. 2. 6(a))
should be noted. This leads also to an infinite two-dimensional network of hydro-
gen-bonded molecules. No participation of H(3) and H(4) in hydrogen bonding is
observed. The oxygen atom O(1) takes part in contacts with phenyl and methyl
protons. For 8 an interaction between O(1) and the phenyl proton H(70) (x ꢂ 1, y, z)
only was observed. This interaction leads to an infinite layer of molecules.
Crystal Packing
Despite the different types of hydrogen bonding the crystal packing of the majority
of the investigated compounds can be presented as bilayered structures. It should
be noted that for the choice of molecular fragments as a supramolecular unit of the
structure we were guided by principles, included in Lehn’s supramolecular concept,
namely ‘‘. . . Supramolecular chemistry may be defined as ‘‘chemistry beyond the
molecule,’’ bearing on the organized entities of higher complexity that result from
the association of two or more chemical species held together by intermolecular
forces’’ [15]. Thus, layers in bilayered structures represent the complete element of
hydrogen bonding of molecules in the crystal. Depending on whether the atoms
participating in hydrogen bonding are inside these layers or on a surface, we can
speak about hydrophilic or hydrophobic shells in between them.

4,8-Disubstituted 1,5-Dichloro-2,6-dioxotricyclo[5.1.0.03,5]octanes
1237
The formation of bilayered structures with a hydrophobic part is characteristic
for compounds with methyl and ethyl substituents. However, in 3 involvement of
the oxygen atom in a bifurcate hydrogen bonding leads to the formation of layers,
in which the bis-homo-p-quinone molecules have their six-membered cycles per-
pendicular to the plane of layers (supramolecular blocks). Therefore, methyl
groups can be localized more precisely in layers. In the ethyl-substituted compound
the six-membered cycles are practically parallel to the layers. As a result the ethyl
groups are inclined towards the layer direction (Fig. 3. 7). In bis-homo-p-quinone 3
the localization of areas with chlorine atoms representing layers along the unit cell
diagonal can be observed (Fig. 2. 3(b)).
The extension of the substituents (in the case of the bis-homo-p-quinone 4 with
butyl groups) leads to formation of a three-dimensional supramolecular system
instead of layered structures. Nevertheless, as a result of supramolecular isomor-
phism the fragments of a bilayered structure can be observed. Interestingly enough,
the disposition of the alkyl-substituents with respect to bilayers appears to be even
more ‘‘slanting’’ (Fig. 2. 4(b)).
Crystal packing of the i-butyl substituted compound 5 appears to be similar to
the one of methyl-substituted bis-homo-p-quinone. The molecules of 5 are packed
into similar stacks, bound to each other by hydrogen bonds. Thus, the structure can
be designated as supramolecularely bilayered, in which molecules are located
again perpendicularly to the layer direction. Butyl groups rather precisely appear
between these layers (Fig. 2. 5(b)).
In the compounds with aromatic substituents the packing of molecules and the
supramolecular structure is also bilayered with a sloping orientation of the hydro-
gen-bonded cyclic fragments with respect to the layer, probably closer to their
perpendicular disposition (Fig. 2. 6(b) and Fig. 3. 8). The mutual disposition of
the aromatic fragments is favorable for ꢆ–ꢆ and ꢆ–H interactions between electron-
ic systems of cycles. However, no formation of layers from chlorine atoms in other
structures is observed.
Conclusions
Despite of various modes of synthesis, for each of the compounds the same crystals
are obtained. All compounds crystallize in centrosymmetric space groups without
involvement of solvate molecules in a unit cell. The conformations of all bis-homo-
p-quinone molecules are identical, geometric parameters also vary unessentially.
In spite of the absence of classical hydrogen bonds the system of intermolecular
interactions existing in the crystals leads to the formation of various supramole-
cular structures. For all compounds excluding the bis-homo-p-quinone with butyl
groups the formation of layered supramolecular structures due to weak intermole-
cular interactions is characteristic, though the character of mutual disposition of
molecules in layers and their hydrogen bonding differs significantly. On exterior
surfaces of the layers there are enough hydrophobic fragments, alkyl and aromatic
substituents or for some compounds areas containing chlorine, leading to the for-
mation of pseudo channels in the crystals. The extension of alkyl substituents leads
apparently to steric obstacles for their mutual packing.

1238
A. T. Gubaidullin et al.
Experimental
Melting points were determined with a Kofler hot plate apparatus and are uncorrected. Infrared spectra
were obtained on a Infra-Red Spectrophotometer Model ‘‘UR-20’’ (KBr). The NMR spectra were
1
measured with a Bruker MSL-400 spectrometer at 400.13 MHz for H and 100.6MHz for 13C using
TMS as internal standard. Microanalyses were performed with a elemental analyzer (CHN-3-analisator,
USSR). Their results agreed favourably with the calculated values.
General Methods
The general methods for the preparation of 1,5-dichloro-4,8-disubstituted[5.1.0.03,5]octane-2,6-diones
based on the reaction of ethyl 2,2-dichloroacetoacetate (1) and 3,3-dichloropentane-2,4-dione (2) with
aldehydes and the reaction of ꢁ,ꢂ-unsaturated esters with lithiodihalomethanes have been already
reported [7, 8, 11]. The preparation and characterization will be described only for 3 and 6 which
are hitherto unpublished. We also demonstrate a new effective method for the preparation of the title
compounds taking as an example the synthesis of 8.
1,5-Dichloro-4,8-dimethyltricyclo[5.1.0.03,5]octane-2,6-dione (3, C10H10Cl2O2)
To a solution of 12.4 cm3 of 1.61M n-BuLi (20 mmol) in n-hexane in 50cm3 of THF was added slowly
2.13g of CH2Cl2 (25 mmol) at ꢂ 95 ꢁC. The mixture was stirred for 30min at this temperature. Then
3.24g of ethyl crotonate (28 mmol) were added. The solution was stirred for 10 min and then 10 cm3 of
H2O were added. The cooling bath was removed and after the mixture was warmed up to room
temperature, 10% HCl was added to acidify the solution. The solvent was removed in vacuo and
1
the solid was washed with ether to obtain 0.944 g (41%) of 3 as a white solid, mp 228 ꢁC (dec.); H
NMR (200 MHz, CDCl3): ꢇ ¼ 1.46 (d, J ¼ 6.0Hz, 6H), 2.00 (dq, J ¼ 6.0, 6.3 Hz, 2H), 2.21 (d,
J ¼ 6.3 Hz, 2H) ppm; 13C NMR (50 MHz, CDCl3): ꢇ ¼ 13.4, 27.7, 40.6, 50.4, 192.8 ppm; IR (KBr):
ꢈꢀ¼ 3385, 3018, 2950, 2910, 2825, 1685, 1565 cmꢂ 1
.
1,5-Dichloro-4,8-di(p-tolyl)tricyclo[5.1.0.03,5]octane-2,6-dione (6, C22H18Cl2O2)
In the same manner as for 3, using ethyl (E)-4-methylcinnamate 6 was prepared in 42% yield. Mp
192 ꢁC (dec.); 1H NMR (200MHz, CDCl3): ꢇ ¼ 2.37 (s, 6H), 3.05 (d, J ¼ 6.8 Hz, 2H), 3.28 (d,
J ¼ 6.9 Hz, 2H), 7.15–7.26 (m, 8H) ppm; 13C NMR (50 MHz, CDCl3): ꢇ ¼ 21.19, 36.05, 38.51,
50.41, 127.01, 129.10, 129.42, 138.82, 191.62 ppm; IR (KBr): ꢈꢀ¼ 3400, 3052, 1709, 1515, 1445,
1243, 1098, 812, 517 cmꢂ 1
.
1,1,4-Trichlorobut-3-en-2-on (Dichloromethyl-ꢂ-chlorovinylketone, 12)
To a mixture of 20g of freshly distilled dichloroacetylchloride (12.5 mmol) in 100 cm3 of CCl4 under
vigorous stirring and cooling with ice was added 30 g of AlCl3 (22.5mmol) during 1 h in small portions.
After addition of the first portion of AlCl3 at first a weak and then more intensive current of dry
acetylene was passed through the solution. After 6 h of acetylene passage the reaction mixture was
quenched with crushed ice for 10 min. After separation of the organic layer, the aqueous layer was
extracted with 2 Â 50 cm3 of CHCl3 and 2 Â 50 cm3 of ether and then the organic extracts were com-
bined. After evaporation the crude product was purified by distillation in vacuo (72–73ꢁC=1333Pa)
1
affording 17.5 g (78%) of 12 as a colorless oil. H-NMR (250 MHz, CDCl3:CCl4 (1:1)): ꢇ ¼ 5.83 (s,
1H), 6.93 (d, J ¼ 14.5Hz, 1H), 7.43 (d, J ¼ 14.5Hz, 1H) ppm.

4,8-Disubstituted 1,5-Dichloro-2,6-dioxotricyclo[5.1.0.03,5]octanes
1239
1,1-Dichloro-4-phenylbut-3-en-2-on (Dichloromethyl-ꢂ-phenylvinylketone, 13)
Through a solution of 11g of 12 (63.44mmol) in 50 cm3 of benzene, cooled with ice, a fierce current of
moist HCl gas was passed during 10min. Then 9.49 g of AlCl3 (63.74mmol) were added in small
portions with intensive mixing and an still intensive current of HCl was passed through. After addition
of all AlCl3 cooling was stopped and the reaction mixture was stirred passing HCl through the solution
for further 8 h. A dark-red complex precipitated. After 40min at room temperature the reaction mixture
was treated with ice and conc. HCl and extracted with 3 Â 100 cm3 of ether. The organic extracts were
combined and washed with 2 Â 200 cm3 of H2O, dried (CaCl2), and evaporated. The resulting residue
was purified by distillation in vacuo (124–126 ꢁC=133 Pa) affording 11g (81%) of 13 as a colorless
1
oil. H-NMR (250 MHz, CDCl3:CCl4 (1:1)): ꢇ ¼ 5.94 (s, 1H), 7.26 (d, J ¼ 16.5Hz, 1H), 7.89 (d,
J ¼ 16.5Hz, 1H) (compare with Ref. [1]); IR (KBr): ꢈꢀ¼ 1695 (CH¼CH), 1710 (C¼O) cmꢂ 1
.
Reaction of 13 with MeONa
To a solution of 4.3 g of 13 (20 mmol) in 50 cm3 of dry ether at ꢂ 80ꢁC small portions of 1.1 g MeONa
(20 mmol) were added under Ar. At the same temperature stirring was continued for 4 h. Then the
reaction mixture was allowed to warm to room temperature and stirring was continued overnight. The
precipitated product was filtered off, washed with H2O, and dried. Recrystallization from DMSO gave
2.6 g of an analytically pure (compare Ref. [2]) sample of 8 (73%).
X-Ray Structure Determination
The X-Ray diffraction data for crystals of 3–6 were collected on a CAD4 Enraf-Nonius automatic
˚
diffractometer using graphite monochromated Cu Kꢁ (1.54184 A) radiation for 3–5 and Mo Kꢁ
˚
(0.71073 A) radiation for 6. The details of crystal data, data collection, and refinement are given in
Table 2. The stability of crystals and of experimental conditions were checked every 2 h using three
control reflections, while the orientation was monitored every 200 reflections by centering two stan-
dards. No significant decay was observed. Corrections for Lorentz and polarization effects were
applied. The structures were solved by direct methods and difference Fourier syntheses using the
SIR program [16] and MolEN package [17]. All non-hydrogen atoms were refined anisotropically, H-
atoms were located in ꢁF maps. All figures were drawn using the program PLATON [18].
Crystallographic data (excluding structure factors) for the structures 3–6 in this paper have been
deposited with the Cambridge Crystallographic Data Centre as supplementary publication numbers
CCDC 181762–181765. Copies of the data can be obtained, free of charge, on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: þ 44(0) 1223-336033 or e-mail: deposit@ccdc.
cam.ac.uk).
Acknowledgements
The authors thank the Russian Fund for Basic Research (Grants No. 02-03-32280, 03-03-32865) and
the Japan Society for the Promotion of Science (Grant No. RC 39626110) for financial support.
References
[1] Heller J, Yogev A, Dreiding AS (1972) Helv Chem Acta 55: 1003
[2] (a) Howell WC, Ktenas M, MacDonald JM (1964) Tetrahedron Lett 1719; (b) Gordon M, Howell
WC, Jackson CH, Stothers JB (1971) Canad J Chem 49: 143; (c) Eistert B, Fink H, Riedinger J,
€
Hahn H-G, Durr H (1969) Chem Ber 102: 3111
[3] Corey EJ, Chaykovsky M (1965) J Am Chem Soc 87: 1353

1240 A. T. Gubaidullin et al.: 4,8-Disubstituted 1,5-Dichloro-2,6-dioxotricyclo[5.1.0.03,5]octanes
[4] Buchanan GL, Raphael RA, Taylor R (1973) J Chem Soc, Perkin Trans I 373
[5] Heller J, Dreiding AS, O’Connor BR, Simmons HE, Buchanan GL, Raphael RA, Taylor R (1973)
Helv Chem Acta 56: 272
[6] Chapleo ChB, Dahl ChE, Dreiding AS, Griber R, Niggli A (1974) Helv Chem Acta 57: 1876
[7] Tsuboi S, Frutani H, Takeda A, Kawazoe K, Tato S (1987) Bull Chem Soc Japan 60: 2475
[8] (a) Mamedov VA, Berdnikov EA, Litvinov IA, Kuz’mina JG, Sibgatullina FG, Ismaev IE (1995)
Doklady RAN 341: 641; (b) Mamedov VA, Berdnikov EA, Ismaev IE, Litvinov IA (1995) Izv
Akad Nauk, Ser Khim 785; (c) Mamedov VA, Berdnikov EA, Litvinov IA, Kuz’mina JG (1995)
Izv Akad Nauk, Ser Khim 1294; (d) Mamedov VA, Berdnikov EA, Levin YaA (1996) XI
International Conference on Organic Synthesis. Abstracts of papers, Amsterdam, p 104
[9] Mamedov VA (2000) Senior Thesis, Kazan State University, p 399
[10] Nesmeyanov AN, Kochetkov NK (1950) Izv Akad Nauk SSSR, Ser Khim 350
[11] (a) Tsuboi S, Kunito K, Kageyama M, Sakai T, Utaka M (1994) Tetrahedron Lett 35: 8829; (b)
Tsuboi S, Ye X, Kunito K, Ono T (2001) Tetrahedron 57: 3035
[12] Berdnikov EA, Mamedov VA, Enikeev KM, Levin YaA (1998) Zhur Org Khim 1: 1337
[13] Cambridge Structural Database System (2000) Release Ver 5, 20 October
[14] Allen FH, Kennard O, Watson DG, Brammer L, Orpen G, Taylor R (1987) J Chem Soc, Perkin
Trans II 12: S1–S19
[15] Lehn J-M (1988) Angew Chem, Int Ed Engl 27: 89
[16] Altomare A, Cascarano G, Giacovazzo C, Viterbo D (1991) Acta Crystallogr A 47: 744
[17] Straver L, Schierbeek AJ (1994) MolEN Structure Determination System Nonius BV V.1–2
[18] Spek AL (2000) PLATONA Multipurpose Crystallographic Tool Utrecht University Utrecht The
Netherlands