Chromophoric Macrocycles from the Oxidation of Bis(aminofurazanylic) Ethers of 1,2-Diols

Article abstract of DOI:10.1002/hc.10226

A series of chromophoric azofurazan-containing macrocycles 6a-c and 7a-d were synthesized from bis(aminofurazanylic) ethers of 1,2-diols 4a-d by dibromoisocyanurate oxidation. The macrocycle closure is a result of N=N bond formation. An ion-binding ability of these compounds was tested. The macrocycles were characterized by NMR, MS, IR, and UV spectroscopy. The X-ray crystal structures of the macrocycles 6a, 7c, and linear counterpart 12 are reported.

Full text of DOI:10.1002/hc.10226

Heteroatom Chemistry
Volume 15, Number 2, 2004
Chromophoric Macrocycles from the
Oxidation of Bis(aminofurazanylic)
Ethers of 1,2-Diols
Aleksei B. Sheremetev,1 Elena V. Shatunova,1 Boris B. Averkiev,2
Dmitrii E. Dmitriev,1 Viktor A. Petukhov,1 and Mikhail Yu. Antipin2
1N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47, Leninsky Prosp.,
119991 Moscow, Russia
2A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28
Vavilov Street B-334, 119991 Moscow, Russia
Received 24 September 2003
cryptand synthesis involves reaction of appropri-
ABSTRACT: A series of chromophoric azofurazan-
ately functionalized dicarboxylic acid chlorides with
containing macrocycles 6a–c and 7a–d were synthe-
diamines, following reduction of the amide. Both
sized from bis(aminofurazanylic) ethers of 1,2-diols
these routes were utilized in the synthesis of chro-
4a–d by dibromoisocyanurate oxidation. The macro-
mophoric ligands possessing azobenzene bridge [1–
cycle closure is a result of N N bond formation. An
6]. Diazotization of bis(aminophenyl) ether of gly-
ion-binding ability of these compounds was tested. The
cols followed by azo coupling with a suitable sub-
macrocycles were characterized by NMR, MS, IR, and
strate is another route to analogous ligands [7–11].
UV spectroscopy. The X-ray crystal structures of the
Azobenzene crown ethers have been also synthe-
macrocycles 6a, 7c, and linear counterpart 12 are re-
sized by reductive macrocyclization of correspond-
ꢀ
C
ported. 2004 Wiley Periodicals, Inc. Heteroatom Chem
ing bis(nitrophenoxy) oxa alkanes [12,13]. These
macrocycles change their binding ability for am-
monium salts and metal cations in response to
15:131–145, 2004; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.10226
photoirradiation. This is a result of the cavity vol-
ume changing of the macrocycle by the photoin-
duced E–Z isomerism of the azobenzene subunit.
Chromophoric ligands are also interesting analyti-
cal reagents for colorimetry and metal-ion indication
[14–18].
However, realization of these approaches is of-
ten difficult and total yields are poor. Furthermore,
high-dilution technique is necessary, in most cases to
perform such reactions, to obtain reasonable yields
because of a tendency to form linear oligomers. It
should be noted that analogous macrocycles where
the benzene ring is replaced by any heteroaromatic
ring are unknown. At the same time the presence of
additional heteroatoms in the subunit can evidently
INTRODUCTION
The classical synthetic route to crown ethers in-
volves cyclizations between appropriate polyethy-
lene glycol dichloride or ditosylate and a com-
pound incorporating two-hydroxy units. Common
Correspondence to: Aleksei B. Sheremetev; e-mail: sab@cacr.ioc.
ac.ru.
Contract grant sponsor: International Science Foundation.
Contract grant numbers: MM9000 and MM9300.
Contract grant sponsor: Russian Foundation for Basic
Research.
Contract grant numbers: 98-03-33024a and 00-15-97359.
2004 Wiley Periodicals, Inc.
c
ꢀ
131

132 Sheremetev et al.
induce some corrections into their ability to com-
plexation [19].
The goal of our work was to replace a part of
this structure, namely the benzene ring, by a hete-
rocyclic subunit. To this end we designed a series of
furazan derivatives. In our earlier communication
we disclosed results on synthesis of zero-hydrogen
furazan macrocycles with oxy and azo bridges via
ether bond formation [20]. It has been shown that
some of azofurazan macrocycles are useful as ingre-
dients to explosives and rocket propellants [21,22]. A
series of macrocycles incorporating few azofurazan
subunits was found to be effective inhibitors of sol-
uble guanylate cyclase [23].
In 1991 we developed and exploited over the past
time an alternative synthetic methodology to chro-
mophoric macrocycles, which involves the prior syn-
thesis of linear bis(aminofurazanylic) ether followed
by final oxidative cyclization via N N bond forma-
tion [24–27]. Following our report, Makhova et al.
[28] and Batog et al. [29–33] reported the synthesis
of a series of macrocycles incorporating only furazan
rings and azo bridges.
Reagents and conditions: i, 0.5 mol of 1,2-diol, K2CO3,
75–80◦C
This is the first detailed paper describing a pro-
jected strategy.
SCHEME 1
RESULTS AND DISCUSSION
were also chosen to modify physical properties of
the products (e.g., solubility, reactivity, partition co-
efficient). A series of diamines 4 containing modi-
fied bridging units was prepared in a straightforward
manner following the above procedure.
We prepared several bis(aminofurazanylic) ethers
of 1,2-glycols 4 as outlined in Scheme 1. Start-
ing from glyoxal 1 or a suitable glyoxal equivalent,
3,4-diaminofurazan 2 was prepared in a one-pot
synthesis following literature procedures [21]. Hy-
drogen peroxide oxidation of 2 afforded 3-amino-
4-nitrofurazan 3, as we have previously described
[34].
Reaction of the di-sodium salt of glycol with
3 gave a mixture of 1,2-bis(3-aminofurazan-4-oxy)
ethane 4a and 2-(3-aminofurazan-4-oxy) ethanol 5a
from which 4a was isolated in 17% yield. However,
more successful preparation of 4a was achieved uti-
lizing K2CO3 in DMSO in the reaction of 3 with gly-
col at 75–80◦C. Thus, when 2 equiv of 3 was allowed
to react with 1 equiv of glycol, the diamine 4a was
the major product. The extent of the reaction was
followed by a combination of TLC and electrospray
mass spectrometry (ESMS). The reaction was com-
pleted after 6 h, and no further significant change in
distribution was seen, even after 3 days. Compound
4a was isolated as an amorphous off-white powder
in good yield.
The steric factors play an important role in the
reaction. The main product (84%) in this reaction
was the diamine 4a at R = Rꢁ = H. The presence
of the methyl group in starting glycol (R = H, Rꢁ =
CH3) resulted in diamine 4b with 68% yield. The 2,3-
butanediol produced diamine 4c (R = Rꢁ = CH3) in
45% yield. The highest sterically overcrowded diol,
such as 1,2-cyclohexanediol, in the reaction with 3
gave corresponding diamine 4d with only 30% yield.
For all products 4a–d, the presence of the amino
group was confirmed from the ν(NH2) doublet at
ca. 3450 and ca. 3350 cm−1 in the infrared spectra.
1
The H and 13C NMR spectra of the diamines and
amino alcohols were all consistent with the struc-
tures shown in Scheme 1. For each compound, two
quaternary furazan ring carbons were discernible at
ca. δ 149 for C O and ca. δ 158 for C N in the 13C
spectra, similar to those reported for the analogous
furazan derivatives [35].
We were interested in studying the effect of the
steric factors of the bridging unit at invariable length
(four-atom linker between furazan rings). An assort-
ment of different 1,2-dioles was examined. These
The macrocyclization is a key step of the study
and results in the formation of N N bond. This
step is based on the oxidative condensation of two
amino groups. Various methods for the oxidative

Chromophoric Macrocycles from the Oxidation of Bis(aminofurazanylic) Ethers of 1,2-Diols 133
cyclization of diamines 4a–d to the corresponding
macrocycles were examined.
isomers were also separated by chromatography on
silica gel. It should be noted that any individual iso-
mer readily isomerized at storage giving a mixture
of three isomers that was clearly seen from TLC.
The isomers 7aꢀ, 7aꢀꢀ, and 7aꢀꢀꢀ showed the same
molecular ion in MS and elemental composition at
microanalysis but different melting points and TLC
spots; also no structural difference were observed by
1H and 13C NMR [40].
For azofurazan moiety four cis and four trans
conformers [41] (at R1 = R2) are possible with re-
spect to the N N bond. All these eight possible con-
formers may be classified by indicating a relative
There are several methods available for the ox-
idation of aminofurazans to azofurazans. The com-
mon reagent systems consisting of KMnO4, NaOCl,
or NaOBr in acidic or basic conditions gave usu-
ally linear azofurazans in excellent yields [36]. In
our case, however, these classical procedures were
unsuccessful; the colorless starting material 4a pro-
duced red-orange insoluble material, which was
probably either a mixture of linear azo polymer
and inorganic residue or a coordination compound
of oligomeric azofurazans [37]. The last hypothesis
provoked us to utilize an oxidizer that did not con-
tain inorganic cation. The preferred reagent was di-
bromoisocyanurate (DBI). DBI was first introduced
by Semenov et al. in the synthesis of linear azo com-
pounds [38].
orientation (cis and trans) of the N C and N
N
bonds (with respect to single C N bonds) and these
bonds in the system N C N N C N [42]. In our
work we used notations from Klyne and Prelog [43]
(see Fig. 1).
We found that a mixture of 10-membered macro-
cycles 6a and dimeric 20-membered macrocycle 7a
can be easily prepared by the reaction of 4a with DBI
(Scheme 2). It turned out that stirring of a suspen-
sion of the reagents in CH2Cl2 at ambient temper-
ature gave desired macrocycles in moderate yields
by simple filtration of the reaction mixture (separa-
tion of cyanuric acid and a polymer) and evapora-
tion of the solvent. Monitoring of the cyclization by
ESMS showed initial formation of some open chain
dimer, which then disappeared to give cyclic dimer.
The course of reaction was followed by the disap-
pearance of the IR bands due to ν(NH2) and was also
evident from the red-brown coloring of the initially
white suspension. The 10-membered cycle 6a was
obtained in 23% yield [39] by silica gel flash chro-
matography. The 20-membered macrocycle was iso-
lated as a mixture of three isomers in a ratio of 5:7:1
(7aꢀ:7aꢀꢀ:7aꢀꢀꢀ) and in a combined 38% yield. These
A similar notation to define the conformation
of azofurazans of interest was used [44], when the
conformation of C N bond with respect to azo
group is indicated and then (in brackets) two let-
ters D(cis) and P(trans) are noted, which charac-
terize a relative orientation of the N N and C
N
bonds. For example, trans(P,D) means ap–ap–sp. The
Klyne and Prelog nomenclature allows one to de-
scribe the molecular conformation more definitely
because the torsion angle between bonds may devi-
ate significantly from 0◦ or 180◦, and in such a case
notations ac and sc may be used instead of ap and sp,
respectively. Usage of notations by Klyne and Prelog
is more convenient because symbols ac and sc may
be used at strong distortion of the azofurazan frag-
ment in the N C C N part.
However, only trans-azofurazans were isolated
and characterized by X-ray analysis at present
[27,30,32,33,42,44,45]. Most probably, in the solid
state these conformers are most stable; that is for
solutions, mutual conformational changes are pos-
sible, which makes identification of the conformers
more difficult.
The observed abundance of possible isomers
(conformers) for macrocycles 7 is a result of the
presence of two azofurazan moieties, which al-
lows an existence of one more type of the isomer
differing by mutual orientation of these fragments in
the molecule (Fig. 2). Because of a quite short alkyl
spacer that links the heterocycles, a mutual intercon-
vertion of such isomers should be prohibited.
When 4b was used as precursor for the reaction,
a small amount of intramolecular cyclization prod-
uct 6b (9%) was obtained along with the mixture of
dimeric product 7b (49%) and a polymer. In this case
it was possible to expect a formation of a large num-
ber of isomeric macrocycles 7b. Indeed, in addition
SCHEME 2

134 Sheremetev et al.
FIGURE 1 Possible conformers for the azofurazan frame.
to conformational isomers, which were found for 7a,
two positional isomers 7ba and 7bb are also possible
(Fig. 3). However, column chromatography resulted
in only three fractions for the dimeric product with
an approximate ratio of 5:2:1. All these fractions con-
tained two positional isomers 7ba and 7bb in com-
parable quantities as determined by the NMR spec-
tra. This means that conformational isomerism of
the macrocycles produces more effect on their prop-
erties than positional changes of the methyl group.
Oxidation of diamine 4c in analogous manner af-
forded only 0.5% yield of intramolecular cyclization
product 6c. A mixture of four isomeric 20-membered
macrocycles, 7cꢀ, 7cꢀꢀ, 7cꢀꢀꢀ, and 7cꢀv, was obtained in
51% yield.
In the case of compound 4d, corresponding
macrocycle 6d was not formed. In the reaction only a
mixture of the dimers 7dꢀ, 7dꢀꢀ, and 7dꢀꢀꢀ (68% yield)
was obtained.
An alternate route to similar macrocycles based
on nucleophilic displacement of nitro groups in 4,4ꢁ-
dinitroazofurazan 8 [46] by glycolate was investi-
gated (Scheme 4). A variety of reaction conditions
similar to those employed previously by us [35] have
been examined. However, the reaction failed to give
6a or 7a.
Macrocycles 6 and 7 are yellow to red amor-
phous powders or crystals and were found to be
stable when kept at room temperature for a long
time. They are highly stable to acids and heat. In
FIGURE 2 Possible orientation of the azofurazan moieties
in the molecule 7a.
FIGURE 3 Positional isomers 7ba and 7bb.

Chromophoric Macrocycles from the Oxidation of Bis(aminofurazanylic) Ethers of 1,2-Diols 135
TABLE 1 13C NMR Data for Macrocycles 6 and 7
Furazan
C O
C N
R
Solvent
6a
160.9
161.6
162.9
163.2
160.3
160.5
155.8
156.3
157.7
158.1
155.8
156.0
72.9 (CH2)
72.4
73.8
CDCl3
DMSO-d6
Acetone-d6
CD3OD
SCHEME 3
74.4
6b
6c
82.0 (CH2)
79.2 (CH)
21.3 (CH3)
81.3 (CH)
19.7 (CH3)
70.7 (CH2)
78 (CH)
75 (CH2)
14 (CH3)
85.0 (CH)
15.9 (CH3)
87.6 (CH)
CDCl3
2 months 30–50% of the compounds were hy-
drolyzed in glim by 5% aqueous KOH. Macrocycles
6 and 7 are soluble in common organic solvents;
10-membered cycles 6 display better solubility than
the corresponding 20-membered cycles 7, and more
substituted macrocycles exhibit higher solubility. All
macrocycles are not soluble in water.
160.7
156.2
CDCl3
DMSO-d6
DMSO-d6,
CDCl3
7a
7b
158.1
158.0
159.0
155.1
155.0
156.0
7c
7d
157.8
157.7
155.0
155.0
CDCl3
23.3; 29.9 (CH2)
NMR Spectroscopy of Macrocycles
We next needed to establish the structure of the
macrocycles. Here, the literature on 13C NMR of fu-
razans was very helpful [35,47].
MS Analysis
It should be noted that most favorable exis-
tence of compounds 6 in the ap–ap–sp conformation
proved by X-ray data (see below) must result (at low
conformational flexibility) in the absence of the cy-
cle symmetry relative to the plane normal to the azo-
bond. In the 13C NMR spectra of such compounds,
four signals of the furazan carbon atoms must be
observed. However, the spectra involved only two
signals. Moreover, low-temperature 13C data for the
compound 6a had demonstrated that until −70◦C its
symmetry was held in a solution. This allows one
to make a suggestion about relatively small rigidity
of the azofurazan moiety in a solution. Presence of
some relatively stable forms of 20-membered cycles
7a–d may result from the combination of different
isomeric types.
The 10-membered cycles 6a–c and 20-membered
cycles 7a–d could be distinguished by their 13C NMR
spectra. The peak attributable to the carbon of the
furazan ring bonded to the oxygen atom was at δ
160.3–163.2 for 6a–c, whereas the same peak was
shifted upfield to 157.7–159.0 for 7a–d (Table 1).
The peaks attributable to the carbons of the fu-
razan ring bonded to the azo moiety for both cycles
6a–c and 7a–d were observed in common region at
ca. δ 155.5.
The mass spectrum of all macrocycles by electron
impact ionization at 70 eV showed the expected
molecular ion peak together with the characteris-
tic fragmentation. The fragmentation was additional
support for this series of structure [35]. For example,
MS of 6a confirmed the sequence by the fragment
ion peaks shown in Fig. 4. The product ion peaks
at m/z 194 (M+ − 30) confirmed the presence of fu-
razan unit [49]. The presence of the azo linkage in
the product ion peaks at m/z 166 (M+ − 30 − 28) was
confirmed.
Similar fragmentation was also observed for 6b
and 6c. Dimeric macrocycles showed more com-
plicated mass spectra. The spectra for all com-
pounds also showed the molecular ion and peaks
corresponding to the loss of NO and N2, giving
rise to signals with m/z values for (M+ − NO)
and (M+ − NO − N2). For example, MS data for
7aꢀ showed ion peaks at m/z 448 (M+), 390, 363,
We had used 13C NMR to examine the distinction
of the individual isomeric macrocycles 7. The peaks
attributable to similar carbon atoms differed in 0.5–
2 ppm. It may be noted that the deviations were com-
parable to those from solvent effects. Assignment of
peaks to different conformers is impossible [48].
FIGURE 4 MS fragmentation ways for macrocycles 6a, m/z
224 (M+).

136 Sheremetev et al.
and 166, the same as for 7aꢀꢀ or 7aꢀꢀꢀ, and corre-
sponded to a molecular formula of C12H8N12O8. Frag-
mentation of isomers 7b, 7c, and 7d characterized
the similar picture. The product ion peaks useful
for structure assignment are listed in Experimental
section.
Ion-Binding Ability
We were also interested in determining the possibil-
ity to utilize the macrocycles 6 and 7 as complexing
agents. Reactions of 7a with nitrate (NO3−), perchlo-
rate (ClO4−), dinitramide (N3O4−) [50], and nitro-
formate (CN3O6−) salts (Na+, K+, NH4+, NH3OH+,
N2H5+, and N2H6+2) were attempted by adding 7a
(dissolved in the reaction solvent) to 1–15 ml of a so-
lution containing 20–100 mg of a salt in methanol,
acetonitrile, acetone, or nitromethane. Mole ratios
of 7a to salt varied from 3:1 to 1:1. However, the so-
lution gave no color changes or a precipitate separa-
tion. No detectable changes of the UV spectrum were
observed.
Alkali metal picrate extraction studies were per-
formed using a CH2Cl2/H2O extraction system for
10-membered cycle 6a (where a sandwich-type inter-
action is possible) and 20-membered macrocycle 7a
(where host–guest complex formation is possible).
These compounds display no extraction of the salt
from aqueous solution.
UV–Vis Absorption Spectroscopy
Worthy of comment from the spectroscopic data we
have collected on the basic macrocycles described
above are the UV–vis spectra. The observed trends
are listed in Table 2 along with the data for sim-
ple furazans 9–12 for comparison. The main results
are as following: (i) As expected, the presence of two
disconnected azofurazan subunits in macrocycles 7
increases the λmax by about twice as compared to
macrocycles 6. (ii) For all macrocycles, the furazan
ring has absorption bands with a constant λmax of
208–220 nm and 242–252 nm (ꢀ → ꢀ∗ transition)
[49], azo group displayed maximum absorption in
the 420–440 nm region (n → ꢀ transition). (iii) In
contrast to linear compound 12, these bands for
higher macrocycle 7 are less clear; for macrocycle
6, the band at λmax of about 440 nm was apparent
in the UV–vis spectrum as a broad low-energy tail.
Probably, this effect is manifested by the conforma-
tion of azofurazan moiety.
In contrast, coordination of PdCl2 to the macro-
cycle 7a results in the formation of an intense metal-
to-ligand transition in the visible spectrum (λmax ca.
450 and 680). During the addition of PdCl2, the re-
action proceeded through a series of notable color
changes to afford the final precipitate. The complex
[(C12H8N12O8)·2PdCl2] was isolated as an amorphous
khaki powder.
The following factors may be responsible for this
result: (i) The electron-withdrawing azofurazan unit
absorbs the lone electron pairs of the oxygen atoms
in the bridging unit, denuding them of donor prop-
erties. (ii) The combination of large and rigid azofu-
razan unit with small flexible ethylene glycol unit is
unfavorable for coordination geometry of the donor
centers. (iii) The alkali metal salts used are weak
partners as acceptors to the macrocycles 6 and 7.
(iv) Preliminary studies on the transition metal salt,
namely PdCl2, indicate powerful interaction with the
azofurazan macrocycles.
Crystal Structure of 6a, 7c, and 12
Single crystals for X-ray diffraction analysis were
grown for macrocycles 6a, 7c, and related linear azo-
furazan 12. General view of molecules 6a, 7c, and
12 and atom numbering scheme are presented in
Figs. 5–7. Important bond lengths and crystal data
are listed in Tables 3 and 4. Molecules 7c and 12 in
crystal occupy the centers of symmetry. In the crys-
tal of 6a (diffraction data at 110 K) there are two
independent molecules having very similar geome-
try, and a phase transition has been observed at ca.
It should be noted that all of our at-
tempts to establish E,Z-isomerism for macrocy-
cles 6 and 7, as well as for linear compound
11 and 12 by UV–vis spectroscopic analysis failed.
For example, refluxing a sample of macrocycle 7a in
methanol, ethyl acetate, and nitromethane or irra-
diation with a medium-pressure Hg lamp (360 nm)
gave no changes in the UV spectrum.

Chromophoric Macrocycles from the Oxidation of Bis(aminofurazanylic) Ethers of 1,2-Diols 137
TABLE 2 UV-Vis Data of Macrocycles and Related Furazans
λmax (nm)
ε
λmax (nm)
ε
λmax (nm)
ε
λmax (nm)
ε
6a
450
445
445
445
445
450
450
450
445
445
447
455
54
62
63
310
310
310
300
300
302
302
302
314
306
310
312
6300
3500
4220
215
220
220
208
212
208
215
215
215
215
206
216
210
216
205
213
215
8550
5250
6800
6b
245
250
250
252
247
252
249
250
250
248
252
4900
6400
9300
6c
7aꢁ
7aꢁꢁ
7bꢁ
7bꢁꢁ
7bꢁꢁꢁ
7cꢁ
7cꢁꢁ
7c
280
342
343
282
308
223
394
265
216
260
248
140
214
11200
11700
11500
14300
15300
13000
14700
14600
13000
12300
14600
14700
17400
14800
14250
18900
22000
14500
23100
21800
11100
9400
13500
14400
13600
14400
10700
14200
14000
10500
7cꢁꢁꢁ
7cꢁꢁV
7dꢁꢁ
7d
450
445
445
445
312
306
310
306
12700
12400
6600
250
252
242
251
12600
14900
9700
7dꢁꢁꢁ
9
7300
8450
2700
10
257
270
247
5700
10300
6550
11
438
445
80
187
204
212
7250
9050
12
302
8600
295 K to the orthorhombic modification 6a∗ where
the molecule is disordered in the crystal.
position in molecules 6a and 7c is related to steric
effects.
The 10-membered cycle 6a has the sc–ap confor-
mation. The small value of the macrocycle cavity of
the cycle 6a results in the molecule strain that might
increase bond and torsion angles. The azofurazan
moiety in 6a is strongly deformed: torsion angles
N(6) C(7) N(8) N(9) and N(8) N(9) C(10) N(11)
are equal to 32◦ and 167◦ (data at 110 K). Similar
torsion angles in less strained 20-membered cycle
7c, having sp–ap configuration, are equal to 23◦ and
171◦, respectively. It is clear that larger distortion
of the torsion angle N C N N at the cis-position
to the double bond in comparison to the trans-
Unfortunately, because of crystal disorder of the
alkoxy bridge in the structure 7c we cannot discuss
molecular geometry in details.
When passing from strained macrocycle 6a
to its linear unstrained counterpart 12 (having a
ap–ap configuration), bond lengths at the oxygen
FIGURE 5 General view of one independent molecule of 6a.
FIGURE 6 General view of molecule 7c.

138 Sheremetev et al.
Geometry of the furazan ring in all the three
structures is similar. Bond lengths N O are in the
˚
interval 1.357–1.406 A that corresponds to the single
N O bond. So, lone pairs of the oxygen atoms do
not participate in formation the ꢀ-system of the fu-
razan ring or its contribution is small; the electronic
conjugation is realized mostly in the N C C
N
system. It has been noted earlier that in the fu-
razan ring the length of the N O bond proxi-
mate to an electron-donating substituent is longer
than that proximate to an electron-withdrawing sub-
stituent [51,52]. In molecules 6a, 7c, and 12 the
difference in corresponding N O bonds is equal
˚
0.007–0.034 A.
As may be expected, the bond length C N be-
tween the furazan ring and azo group (see, Table 3)
FIGURE 7 General view of molecule 12.
˚
is intermediate between the single bond (1.47 A) and
˚
the double (1.29 A) [53] one, which might be related
atoms bonded to furazan ring are shortening by
˚
to conjugation between these fragments. On increas-
ing the torsion angle N N C N, the bond length
0.01 A. The strength of the macrocycle 6a is
evidence in distortion of the azo-group; torsion
angle C(7) N(8) N(9) C(10) is equal to 171◦. For
molecules 7c and 12 these angles are equal to 178◦
and 180◦, respectively.
˚
N C increases from 1.404 A in 12 (torsion angle
◦
˚
179 ) to 1.419 A for N(7) N(8) in 7c (torsion angle
23◦).
◦
˚
TABLE 3 Important Bond Lengths (A) and Bond Angles ( ) in Molecules 6a, 7c, and 12
Compounds
Bond
6a(I)a
6a(II)b
7c
12
C(1) O(2)
O(2) C(3)
C(3) N(4)
C(3) C(7)
N(4) O(5)
O(5) N(6)
N(6) C(7)
C(7) N(8)
1.464(3)
1.338(3)
1.305(3)
1.431(3)
1.406(3)
1.376(2)
1.305(3)
1.390(3)
1.257(3)
1.413(3)
1.304(3)
1.444(3)
1.372(3)
1.397(3)
1.304(3)
1.332(3)
1.462(3)
119.4(2)
105.8(2)
118.6(2)
120.8(2)
113.7(2)
108.9(2)
−171.0(2)
143.6(2)
1.467(3)
1.328(3)
1.308(3)
1.434(3)
1.404(3)
1.383(3)
1.306(3)
1.391(3)
1.262(3)
1.411(3)
1.304(3)
1.446(3)
1.372(3)
1.398(3)
1.302(3)
1.342(3)
1.460(3)
118.6(2)
106.0(2)
118.4(2)
120.1(2)
112.5(2)
109.0(2)
−167.9(2)
146.4(2)
1.480(6)
1.309(6)
1.298(6)
1.433(6)
1.391(6)
1.385(5)
1.274(6)
1.419(5)
1.254(5)
1.407(6)
1.309(6)
1.399(7)
1.357(6)
1.379(6)
1.319(6)
1.322(6)
1.473(7)
110.4(3)
112.5(3)
1.451(3)
1.319(3)
1.292(3)
1.426(3)
1.394(3)
1.360(3)
1.305(3)
1.404(3)
N(8) N(9)
N(9) C(10)
1.244(4)b
–
–
–
–
–
–
–
–
C(10) N(11)
C(10) C(14)
N(11) O(12)
O(12) N(13)
N(13) C(14)
C(14) O(15)
O(15) C(16)
C(7) N(8) N(9)
N(8) N(9) C(10)
C(1) O(2) C(3)
C(14) O(15) C(16)
C(16) C(1) O(2)
C(1) C(16) O(15)
C(7) N(8) N(9) C(10)
O(2) C(1) C(16) O(15)
112.3(2)
–
c
–
–
–
–
115.3(2)
c
–
–
–
180
–
c
c
177.6(3)
c
–
a(I) refers to the first independent molecule and (II) refers to the second independent molecule of low-temperature modification of 6a.
bN(8) N(8A) bond.
cThis part of molecule 7c is disordered.

Chromophoric Macrocycles from the Oxidation of Bis(aminofurazanylic) Ethers of 1,2-Diols 139
TABLE 4 Crystal Data for Compounds 6a, 7c, and 12
6a
C6H4N6O4
6aa
7c
12
Empirical formula
Molecular weight
T (K)
C6H4N6O4
224.14
C16H16N12O8
504.38
C6H6N6O4
226.15
110
224.14
110
300
293
Crystal system
Space group
Monoclinic
P21/c
Orthorhombic
Pbca
Monoclinic
P21/c
Triclinic
P1bar
˚
a (A)
20.528(7)
11.794(4)
20.745(9)
11.597(5)
11.009(4)
15.52(1)
4.246(4)
7.190(6)
˚
b (A)
˚
c (A)
7.187(2)
90
92.18(1)
90
1739(1)
8
0.142
7.454(3)
90
6.656(2)
90
103.52(2)
90
1105.7(9)
2
0.125
7.830(7)
85.55(1)
78.57(2)
79.50(2)
230.2(3)
1
α(◦)
β(◦)
γ(◦)
90
90
1793(2)
8
0.142
3
˚
V (A )
Z
µ(Mo-Kα) (mm−1
)
0.139
1.632
Dx (g cm−3
)
1.713
1.660
1.515
Scan method
ω
ω
θ/2θ
ω
46
2θ
(◦)
60
0.35 × 0.20 × 0.15
11407
50
0.35 × 0.20 × 0.15
8015
54
0.20 × 0.15 × 0.05
2602
max
Crystal size (mm)
Reflections measured
Unique reflections
Rint
0.15 × 0.10 × 0.05
965
647
0.040
547
74
4973
0.025
3390
321
0.055
1.05
0.165
1583
0.034
1094
143
0.050
1.084
0.1495
2393
0.061
1002
159
0.080
0.96
0.255
Reflections with I ≥ 2σ(I )
Refined variables
R(F 2 ≥ 2σ(F 2))
Goodness-of-fit
0.048
1.08
0.129
wR(F 2), all data
aFor high-temperature modification of compound 6a.
Crystal packing of the compounds 6a, 7c, and
12 is different. The planar molecules of the linear
azofurazan 12 form layers parallel to (111) plane
(Fig. 8). The shortest interplanar distances between
molecular layers does not exceed significantly the
Van-der-Waals distances [54], so we may conclude
that there is no specific intermolecular interactions
in the crystal. Molecules of the 20-membered macro-
cycle 7c form parquet-like motif parallel to (100)
plane (Fig. 9). Furazan rings of the neighboring
¯
FIGURE 8 The crystal packing diagram for compound 12
(projection on the (011) plane).
FIGURE 9 The crystal packing diagram for compound 7c
(projection on the (101) plane).

140 Sheremetev et al.
compound 6a with changing crystal symmetry from
monoclinic (P21/c, Z = 8) to the orthorhombic one
(Pbca, Z = 8) at ca. 295 K. Crystal structure anal-
ysis at different temperatures has revealed that on
increasing the temperature from 110 K (where azo
groups are ordered), a graduate increasing of their
disorder by two positions is observed in both inde-
pendent molecules.
At 295 K both orientations of the azo group
became equivalent and each molecule attains C2-
symmetry (Fig. 12). The crystal symmetry change
also from monoclinic (P21/c) to orthorhombic one
(Pbca) as a result of the appearance new crystal 21-
axis, which related two independent (in the mono-
clinic modification) molecules. Details of the phase
transition in the macrocycle 6a will be described
elsewhere.
FIGURE 10 The crystal packing diagram for compound 6a
(projection on the (100) plane).
molecules are parallel, which may be related to their
stacking interaction in the crystal.
Crystal packing of the 10-membered macrocy-
cle 6a (Fig. 10) is close to that in the compound
7c; however, the “parquet” motif is formed by the
two molecules forming a centrosymmetric dimer.
Shortest intermolecular distances in these dimers
(O(15)· · ·O(15ꢁ) for one independent molecule and
O(2)· · ·O(2ꢁ) for the second one) are equal to 2855
CONCLUSION
A number of novel crown ether analogs, 10-
and 20-membered macrocycles incorporating
azofurazan subunit, have been synthesized. We
have demonstrated that oxidative cyclization
of bis(aminofurazanylic) ethers of 1,2-diols by
dibromoisocyanurate provided a new and versa-
tile approach to the synthesis of chromophoric
macrocycles. Their structures were studied by
X-ray crystallography, MNR, MS, and UV analysis.
Nevertheless, these methods do not allow one to
get clear understanding of the nature of observed
isomerism.
˚
and 2918 A, respectively.
A multitemperature X-ray diffraction analysis of
the crystal structure 6a was performed in the wide
temperature interval 110–335 K. The full data set
were measured at 110, 240, 270, and 300 K, and in
addition, unit cell parameters were measured (from
one single crystal sample) at 14 points between 110
and 335 K.
Our current efforts are focused on the fur-
ther applications of this methodology to the forma-
tion of related macrocycles. For a further study of
These data are presented in Fig. 11, and they indi-
cate a continuous and reversible phase transition in
˚
˚
FIGURE 11 Temperature dependence of some crystall parameters in macrocycle 6a. +: a (A); : angle ꢁ; : b (A).
•

Chromophoric Macrocycles from the Oxidation of Bis(aminofurazanylic) Ethers of 1,2-Diols 141
1,2-Di(3-aminofurazan-4-oxy) ethane (4a) was
obtained as a white solid (1.91 g, 84%). mp 206–
207◦C. 1H NMR ([D6]DMSO): δ = 4.64m (CH2),
6.15bs (NH2). 13C NMR ([D6]DMSO): δ = 69.9 (CH2),
148.7 (C N), 152.7 (C O). MS (EI), m/z: 228 [M+],
198 [M+ − NO]. IR: 3467, 3348, 2960, 1647, 1585,
1320, 1065, 1010, 910 cm−1. C6H8N6O4 (228.17):
Calcd C 31.58, H 3.53, N 36.83; Found C 31.96, H
3.88, N 36.51.
Byproduct 3-amino-4-(2-hydroxyethoxy)furazan
1
(5a) was obtained as an oil (0.44 g, 15%). H NMR
(CD3OD): δ = 3.91m (CH2OH), 4.38m (CH2O), 5.6bs
FIGURE 12 General view of disordered macrocycle 6a.
(NH2). 13C NMR (CD3OD): δ = 60.6 (CH2OH), 74.3
(CH2O), 149.8 (C N), 158.8 (C O). MS (EI), m/z:
145 [M+]. IR: 3390, 3345, 3220, 2950, 1645, 1575,
1455, 1320, 1250, 1080, 1030, 1007, 910, 850 cm−1.
C4H7N3O3 (145.12): Calcd C 33.11, H 4.86, N 28.96;
Found C 33.86, H 5.34, N 28.28.
structure–properties relations within this series, we
are investigating structural requirements of the
bridge linking the azofurazan subunits.
1,2-Di(3-aminofurazan-4-oxy) propane (4b) was
obtained as a white solid (1.65 g, 68%). mp 188–
189◦C. 1H NMR ([D6]acetone): δ = 1.46d (CH3), 5.09t
(CH), 4.45–4.6m (CH2), 6.07s, 6.13s (NH2). 13C NMR
([D6]acetone): δ = 17.8 (CH3), 73.3 (CH2), 77.2 (CH),
148.9, 149.3 (C N), 157.1, 157.9 (C O). MS (EI),
m/z: 242 [M+]. IR: 3480, 3450, 3340, 3290, 3005,
2947, 1654, 1580, 1480, 1340, 1090, 1020, 855 cm−1.
C7H10N6O4 (242.19): Calcd C 34.71, H 4.16, N 34.70;
Found C 35.02, H 4.32, N 34.60.
EXPERIMENTAL
Melting points were uncorrected. Infrared spec-
tra were determined in KBr pellets on a Perkin-
Elmer Model 577 spectrometer. Mass-spectra were
recorded on a Varian MAT-311A instrument. UV
spectra were taken in MeOH on a Beckman
DU-7 spectrophotometer. 1H NMR spectra were
recorded at 300 MHz and 13C NMR spectra at
75 MHz on a Bruker AM-300 instrument. Chem-
ical shifts were measured relative to internal ref-
erence TMS (13C and 1H). All separations were
carried out under flash chromatography condition
on silica gel. Analytical thin layer chromatography
(TLC) was conducted on precoated silica gel plates
( Silufol F254).
Byproduct
3-amino-4-(2-hydroxypropoxy-1)-
furazan (5b) was obtained as an oil (0.8 g, 25%).
1H NMR ([D6]acetone): δ = 1.21d (CH3), 4.1–4.2m
(CH2), 4.22–4.26m (CH), 4.4bs (OH), 5.50bs (NH2).
13C NMR ([D6]acetone): δ = 19.4 (CH3), 65.8 (CH),
77.7 (CH2), 149.6 (C N), 158.8 (C O). MS (EI), m/z:
159 [M+]. IR: 3420, 3340, 2975, 1645, 1590, 1375,
1240, 1085, 1005, 970 cm−1. C5H9N3O3 (159.14):
Calcd C 37.74, H 5.70, N 26.40; Found C 37.98, H
6.00, N 26.12.
2,3-Di(3-aminofurazan-4-oxy) butane (4c): 1.15
General Procedure for Reaction of
3-Amino-4-nitrofurazan (3) with 1,2-Dioles
1
g (45%). mp 189–191◦C. H NMR ([D6]DMSO): δ =
1.42d (CH3), 4.9m (CH), 6.03s (NH2). 13C NMR
([D6]DMSO): δ = 14.7 (CH3), 79.9 (CH), 149.4 (C N),
157.2 (C O). MS (EI), m/z: 256 [M+]. IR: 3460, 3345,
3280, 2992, 1644, 1572, 1320, 1095, 1050, cm−1.
C8H12N6O4 (256.22): Calcd C 37.50, H 4.72, N 32.80;
Found C 37.61, H 4.88, N 32.75.
To solution of 3 (2.6 g, 20 mmol) and 1,2-diole
(10 mmol) in DMCO (20 ml) was added K2CO3 (1.8 g,
13 mmol). The resulting suspension was stirred 6–
10 h at 75–80◦C. TLC indicated complete reaction.
The reaction was cooled. After addition of water
(100 ml), the resulting solid was collected by fil-
tration. The residue was dissolved in acetonitrile
and precipitated by water. Recrystallization from
propanol-2 gave white fine crystals of 4. The filtrate
was extracted with ethyl acetate (3 × 30 ml). The
combined extracts were concentrated by distilling off
solvent. The residue was a mixture of compounds 4
and 5. The products were separated by crystalliza-
tion from propanol-2.
Byproduct
3-amino-4-(2-hydroxybutoxy-3)-
furazan (5c) was obtained as an oil (1.07 g, 31%).
1H NMR ([D6]acetone): δ = 1.18d (CH3CHOH),
1.35d (CH3CHO), 3.39m (CHOH), 4.54m (CHO),
5.51bs (NH2). 13C NMR ([D6]acetone): δ = 15.3
(CH3CHOH), 19.8 (CH3CHO), 69.7 (CHOH), 84.0
(CHO), 150.0 (C N), 152.8 (C O). MS (EI), m/z: 173
[M+]. IR: 3475, 3380, 3345, 3206, 2990, 1644, 1580,
1570, 1316, 1205, 1108, 1035, 1008, 980, 830 cm−1.

142 Sheremetev et al.
1580, 1496, 1450, 1356, 1310, 1282, 1260, 1056, 910
cm−1. C12H8N12O8 (448.27): Calcd C 32.15, H 1.80, N
37.50; Found C 32.24, H 1.85, N 37.48.
C6H11N3O3 (173.17): Calcd C 41.62, H 6.40, N 24.27;
Found C 41.93, H 6.58, N 23.96.
1,2-Di(3-aminofurazan-4-oxy) cyclohexane (4d):
0.85 g (30%). mp 182–183◦C. 1H NMR ([D6]DMSO):
δ = 1.3–1.7bm (CH2), 1.75, 2.3bm (CH2CH), 4.75bm
(CH), 6.02bs (NH2). 13C NMR ([D6]DMSO): δ = 22.0
(CH2), 27.9 (CH2CH), 91.3 (CH), 149.0 (C N), 156.7
(C O). MS (EI), m/z: 282 [M+]. IR: 3455, 3335, 2970,
1650, 1585, 1340, 1315, 1270, 1100, 1010, 960 cm−1.
C10H14N6O4 (282.26): Calcd C 42.55, H 5.00, N 29.77;
Found C 42.66, H 5.08, N 29.71.
Oxidative Cyclization of 4b
Following the general procedure and starting
from diamine 4b (1.21 g, 5 mmol), a mixture of
compounds 6b and 7b was obtained. Chromatogra-
phy (same as above) gave the following.
The first fraction, orange oil 6b (0.11 g, 9%). MS
(EI), m/z: 238 [M+], 180 [M+ − NO − N2], 169, 150,
113, 97, 83. IR: 2958, 2922, 1580, 1488, 1448, 1416,
1388, 1290, 1226, 1052, 1040, 982 cm−1. C7H6N6O4
(238.16): Calcd C 35.30, H 2.54, N 35.29; Found C
35.35, H 2.59, N 35.31.
Byproduct
3-amino-4-(2-hydroxycyclohexa-
noxy-1)furazan (5d) was obtained as white solid
(2.03 g, 51%). mp 101–102◦C. 1H NMR (CD3OD):
δ = 1.0–1.5, 1.7, 2.0, 2.3bm (CH2), 3.67m (CHOH),
4.80m (CHO), 4.7 (NH2 + OH + H2O). 13C NMR
(CD3OD): δ = 23.7, 23.8, 29.2, 33.0 (CH2), 79.0
(CHOH), 86.8 (CHO), 149.5 (C N), 157.6 (C O).
MS (EI), m/z: 199 [M+]. IR: 3490, 3460, 3345, 2955,
1690, 1650, 1565, 1525, 1375, 1205, 1110, 1050, 830
cm−1. C8H13N3O3 (199.21): Calcd C 48.23, H 6.58, N
21.09; Found C 48.78, H 6.79, N 20.87.
The second fraction, isomer 7bꢀ (0.36 g, 30.6%).
mp 253–255◦C. MS (EI), m/z: 476 [M+], 418 [M+
−
NO − N2], 391, 292, 279, 219, 180. IR: 3000, 1565,
1490, 1450, 1355, 1280, 1250, 1115, 1045, 982, 928
cm−1. C14H12N12O8 (476.32): Calcd C 35.30, H 2.54, N
35.29; Found C 35.33, H 2.57, N 35.25.
The third fraction, isomer 7bꢀꢀ (0.14 g, 12.2%).
mp 195–197◦C. MS (EI), m/z: 476 [M+], 418 [M+
−
Oxidative Cyclization of 4a
NO − N2], 219, 205, 192. IR: 2988, 2935, 1568, 1488,
1448, 1412, 1384, 1356, 1346, 1328, 1292, 1252, 1164,
1040, 1016, 984, 926, 884 cm−1. C14H12N12O8 (476.32):
Calcd C 35.30, H 2.54, N 35.29; Found C 35.38, H
2.57, N 35.24.
General Procedure for Construction of Macrocycles. A
suspension of diamine 4a (1.14 g, 5 mmol) and DBI
(5.74 g, 20 mmol) in CH2Cl2 (20 ml) was stirred vig-
orously for 0.5 h. The precipitate (cyanuric acid) was
collected by filtration. The filtrate was evaporated in
vacuo, a crude mixture of compounds 6a and 7a was
obtained. The products were separated by silica gel
flash chromatography using CH2Cl2/hexane (4:1) as
eluent.
The fourth fraction, isomer 7bꢀꢀꢀ (0.06 g, 6.1%).
mp 149–150◦C. MS (EI), m/z: 476 [M+], 418
[M+ − NO − N2]. C14H12N12O8 (476.32): Calcd C
35.30, H 2.54, N 35.29; Found C 35.34, H 2.56,
N 35.26.
The first fraction, compound 6a (0.26 g, 23%)
was obtained as orange crystals. mp 118–120◦C
(chloroform). MS (EI), m/z: 224 [M+], 194 [M+
−
Oxidative Cyclization of 4c
NO], 178, 155, 126, 112. IR: 2924, 1580, 1532, 1488,
1456, 1416, 1392, 1284, 1228, 1048, 1032, 972 cm−1.
C6H4N6O4 (224.14): Calcd C 32.15, H 1.80, N 37.50;
Found C 32.21, H 1.94, N 37.44.
Following the general procedure and starting from
diamine 4c (1.28 g, 5 mmol), a mixture of com-
pounds 6c and 7c was obtained. Chromatography
(same as above) gave the following:
The first fraction, macrocycle 6c (0.006 g, 0.5%).
mp 118–120◦C Calcd for C8H8N6O4 (252.19): MS m/z
252 [M+], 237 [M+ − CH3], 223, 219, 210, 205, 194,
183, 167, 164, 154, 152, 140. IR: 2992, 2958, 2924,
1570, 1532, 1454, 1412, 1392, 1290, 1255, 1228, 1050,
1040, 982, 924 cm−1.
The second fraction, isomer 7aꢀ (0.16 g, 14.6%).
mp 219–220◦C. MS (EI), m/z: 448 [M+], 390 [M+
−
NO − N2], 363, 278, 225, 166. IR: 2960, 1580, 1496,
1440, 1356, 1284, 1260, 1028, 896 cm−1. C12H8N12O8
(448.27): Calcd C 32.15, H 1.80, N 37.50; Found C
32.19, H 1.88, N 37.34.
The third fraction, isomer 7aꢀꢀ (0.23 g, 20.5%).
mp 263–265◦C. MS (EI), m/z: 448 [M+]. IR: 2960,
2928, 1580, 1496, 1452, 1436, 1356, 1300, 1280, 1256,
1236, 1060, 1024, 912, 892, 880, 868, 852 cm−1.
C12H8N12O8(448.27): Calcd C 32.15, H 1.80, N 37.50;
Found C 32.22, H 1.83, N 37.41.
The second fraction, isomer 7cꢀ (0.14 g, 11%).
mp 259–260◦C. MS (EI), m/z: 504 [M+], 445, 365,
305, 256, 253, 234, 222, 219, 199, 194, 164, 152,
139. IR: 3000, 2930, 1570, 1495, 1450, 1350, 1250,
1045, 1020, 935 cm−1. C16H16N12O8 (504.38): Calcd
C 38.10, H 3.20, N 33.32; Found C 38.15, H 3.25,
N 33.34.
The fourth fraction, isomer 7aꢀꢀꢀ (0.03 g, 2.9%).
mp 185–186◦C. MS (EI), m/z: 448 [M+]. IR: 2960,

Chromophoric Macrocycles from the Oxidation of Bis(aminofurazanylic) Ethers of 1,2-Diols 143
The third fraction, isomer 7ꢀꢀ (0.1 g, 8%). mp 263–
and H atoms in isotropic one, except for disordered
groups, which were refined in isotropic approxima-
tion. Atomic coordinates, thermal parameters, and
bond lengths and angles for compounds 6a, 7c, and
12 have been deposited at the Cambridge Crystallo-
graphic Data Centre as supplementary publication
numbers 222151–222154.
265◦C. MS (EI), m/z: 504 [M+], 474 [M+ − NO], 444
[M+ − NO − 2CH3], 419, 401, 392, 386, 372, 365, 306,
256, 253, 234, 222, 219, 199, 194, 183. C16H16N12O8
(504.38): Calcd C 38.10, H 3.20, N 33.32; Found C
38.18, H 3.24, N 33.25.
The fourth fraction, isomer 7cꢀꢀꢀ (0.33g, 26%). mp
249–250◦C. MS (EI), m/z: 504 [M+]. IR: 2990, 2958,
1570, 1488, 1450, 1356, 1348, 1330, 1292, 1254, 1165,
1038, 1016, 985, 930 cm−1. C16H16N12O8 (504.38):
Calcd C 38.10, H 3.20, N 33.32; Found C 38.11, H
3.25, N 33.30.
REFERENCES
[1] Shiga, M.; Takagi, M.; Ueno, K. Chem Lett 1980,
1021–1022.
[2] Shinkai, S.; Nakaji, T.; Nishida, Y.; Ogawa, T.;
Manabe, O. J Am Chem Soc 1980, 102, 5860–
5862.
[3] Shinkai, S.; Honda, Y.; Kusano, Y.; Manabe, O. J
Chem Soc, Chem Commun 1982, 848–850.
[4] Shinkai, S.; Honda, Y.; Minami, T.; Ueda, K.; Manabe,
O.; Tashiro, M. Bull Chem Soc Jpn 1983, 56, 1700–
1704.
The fifth fraction, isomer 7cꢀv (0.07g, 6%). mp
240–242◦C. MS (EI), m/z: 504 [M+]. C16H16N12O8
(504.38): Calcd C 38.10, H 3.20, N 33.32; Found C
38.14, H 3.26, N 33.34.
Oxidative Cyclization of 4d
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Similarly, starting from diamine 4d (1.41 g, 5 mmol),
a mixture of isomeric macrocycles 7b was obtained.
Chromatography (same as above) gave the following:
The first fraction, isomer 7dꢀ (0.24 g, 17%).
mp 258–260◦C. MS (EI), m/z: 556 [M+], 526 [M+
− NO], 498 [M+ − NO − N2], 456, 241, 217, 185.
IR: 2950, 2870, 1585, 1495, 1280, 1045, 1000 cm−1.
C20H20N12O8 (556.45): Calcd C 43.17, H 3.62, N 30.21;
Found C 43.20, H 3.66, N 30.15.
The second fraction, isomer 7dꢀꢀ (0.43 g, 31%).
mp 92–95◦C. MS (EI), m/z: 556 [M+], 498, 391, 359,
292, 279, 241. IR: 2940, 2868, 1584, 1504, 1448,
1352, 1280, 1140, 1036, 928, 896 cm−1. C20H20N12O8
(556.45): Calcd C 43.17, H 3.62, N 30.21; Found C
43.18, H 3.65, N 30.19.
The third fraction, isomer 7dꢀꢀꢀ (0.28 g, 20%).
mp 224–225◦C. MS (EI), m/z: 498 [M+ − NO − N2],
279, 241. IR: 2928, 1580, 1496, 1448, 1364, 1344,
1292, 1272, 1152, 1108, 1040, 1020, 932, 892 cm−1.
C20H20N12O8 (556.45): Calcd C 43.17, H 3.62, N 30.21;
Found C 43.19, H 3.69, N 30.17.
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X-Ray Crystallography
Single-crystal X-ray diffraction experiments were
carried out with an Enraf-Nonius CAD-4 diffrac-
tometer (7c) and a SMART 1000 CCD area detector
mounted on a 3-circle diffractometer (12 and 6a),
using graphite monochromated Mo-Kꢂ radiation (λ
˚
= 0.71073 A). Crystal data and experimental details
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[39] Our initial communication [25] described the re-
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[40] In contrast, E and Z-isomers of azobenzene crowns
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[41] In an earlier paper [42], the term “trans/cis position”
refers to the position of furazan rings relative one to
the other, the term “configuration” to Z, E geometry
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[48] It seems that in this case we have encountered a spe-
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are broadened what makes detailed research impossi-
ble (for an example, see Sheremetev, A. B., Mantseva,
E. V., Dmitriev, D. D., Izv AN, Ser Khim 2001, (12),
2366–2367; Russ Chem Bull (Engl. Transl.) 2001, 50,
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drastically thereby hampering low-temperature ex-
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