Macrocycles, derivatives of nitrogen-containing heterocycles 3*Synthesis of di(imidazo[1, 5-a]quinoxalma)-2(1, 3)- benzadithiacycloalkaphanes

Article abstract of DOI:10.1007/s11172-009-0201-5

A three-step method for the construction of di(imidazo[1, 5-a]quinoxalina)-2(1, 3)-benza-dithiacycloalkaphanes has been developed, which includes introduction of a haloalkyl group of various length and nature into 1, 3-bis(4(5H)-oxo-3-phenylimidazo[1, 5-a

Full text of DOI:10.1007/s11172-009-0201-5

Russian Chemical Bulletin, International Edition, Vol. 58, No. 7, pp. 1493—1503, July, 2009
1493
Macrocycles, derivatives of nitrogenꢀcontaining heterocycles
3.* Synthesis of di(imidazo[1,5ꢀa]quinoxalina)ꢀ2(1,3)ꢀbenzadithiacycloalkaphanes
V. A. Mamedov,a A. A. Kalinin,a I. Kh. Rizvanov,a I. Bauer,b and V. D. Habicherb
aA. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: mamedov@iopc.knc.ru
bDresden University of Technology, Institute of Organic Chemistry,
13 Momsenshtrasse, Dꢀ01062 Dresden, Germany
A threeꢀstep method for the construction of di(imidazo[1,5ꢀa]quinoxalina)ꢀ2(1,3)ꢀbenzaꢀ
dithiacycloalkaphanes has been developed, which includes introduction of a haloalkyl group of
various length and nature into 1,3ꢀbis(4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)ꢀ
benzene at the carbamoyl fragment, transformation of the bishaloꢀsubstituted compound thus
obtained to bisthiol, and coupling of the latter to a disulfide.
Key words: 1,3ꢀbis(4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzene, alkylation,
isothioureides, hydrolysis, mercaptanes, molecular iodine, oxidation, disulfides, quinoxalinaꢀ
cycloalkaphanes, IR, NMR, and mass spectra.
For assembling systems of molecular recognition
and efficient catalytic systems, design and development
of methods for the synthesis of macrocyclic ligands
containing fragments of nitrogen heterocycles are of
great importance.2 These structures are of interest inꢀ
cluding a possibility of preparation of monoꢀ and binucleꢀ
ar metal complexes, analogs of nongemic metalloproꢀ
teines, based on such macrocycles and related 1,3ꢀdiꢀ
hetarylbenzenes 1.3—5 There are several examples of macꢀ
rocycles synthesized specially for binuclear complexꢀ
ation.6—9 Some of them included biologically actual imidaꢀ
zole rings.
functional groups are present on the heterocyclic rings,
compounds 1 can be used for construction of various types
of heteromacrocyclic systems including those containing
a disulfide fragment, which is of significant interest for
organic and bioorganic chemistry.26
It is also known that macrocyclic compounds containꢀ
ing a disulfide fragment are under study as redoxꢀactive
systems and switches,27,28 in combination with amide
functional groups as selective complexation agents with
respect to various doublyꢀcharged metal cations,29 and are
of interest as compounds with a wide range of pharmaceuꢀ
tical activity30—32 including antitumor and inhibiting huꢀ
man immune deficiency virus.
Earlier, we have found that the reaction of 3ꢀ(αꢀ
chlorobenzyl)quinoxalinꢀ2ꢀone and 3ꢀbenzoylquinoxaꢀ
linꢀ2ꢀone (2) with benzylamine in DMSO gives imidꢀ
azo[1,5ꢀa]quinoxalinꢀ4(5H)ꢀone.33 Proliferation of this
new approach of assembling the imidazo[1,5ꢀa]quinoxaꢀ
linꢀ4(5H)ꢀone system on mꢀdi(aminomethyl)benzene
allowed us to obtain 1,3ꢀbis(4(5H)ꢀoxoꢀ3ꢀphenylimidꢀ
azo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzene (3), a valuable preꢀ
cursor for the synthesis of various functionalized macꢀ
roheterocycles including those containing a disulfide
fragment (Scheme 1). The use of a carbamoyl funcꢀ
tion in molecule 3 for the introduction of various strucꢀ
tural fragments opens wide possibilities for performing
a macrocycle closing. The presence in the imidazoꢀ
[1,5ꢀa]quinoxalinꢀ4ꢀone system of various types of nitroꢀ
gen atoms gives us a reason to consider them as promising
chelating agents.
Het stands for thienyl,10,11 pyrazolyl,12 imidazolyl,12,13 thiazolꢀ
yl,13,14 1,3,4ꢀoxadiazolyl,15 1,3,4ꢀthiadiazolyl,13 1,2,4ꢀtriazolꢀ
yl,16—18 benzoxazolyl,19,20 indolyl21, benzimidazolyl,22—24 1,2,4ꢀ
triazolo[3,2ꢀa]isoindolyl,25 1,2,4ꢀtriazolo[3,2ꢀc]quinazoline18 (1 are
10,10´ꢀarylenebis(7Hꢀbenzo[de]ꢀ1,2,4ꢀtriazollo[5,1ꢀa]isoquinolinꢀ
7ꢀones25).
The presence in metaꢀpositions of the benzene ring of
two heterocyclic fragments rigidly oriented with respect to
each other makes 1,3ꢀdihetarylbenzenes 1 very interesting
as both the bidentate chelating agents and the macrocycle
precursors. When appropriate and easily transformable
* For Part 2, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1450—1459, July, 2009.
1066ꢀ5285/09/5807ꢀ1493 © 2009 Springer Science+Business Media, Inc.

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Mamedov et al.
Scheme 1
Scheme 2
Results and Discussion
In the 1H NMR spectra of compounds 5 and 6, in
addition to the signals for the aromatic protons, there are
signals for the haloalkyl fragment: two triplet signals for
the CH2Cl and NCH2 groups and a multiplet signal for
the third CH2 group (see Experiment). In this case, the
signals for the CH2Cl and OCH2 groups of the newly inꢀ
troduced fragment in the Oꢀalkylated isomer 6 are disꢀ
placed, respectively, upfield and downfield approximately
by 0.3—0.4 ppm as compared to the signals for the CH2Cl
and NCH2 groups in compound 5.
The second way is a twoꢀstep reaction, which is based
on the alkylation of 1,3ꢀdiphenylimidazo[1,5ꢀa]quinꢀ
oxalinꢀ4(5H)ꢀone (4) with haloalcohols with subsequent
reaction of the hydroxyalkyl derivative of compound 7
with thionyl chloride. The reaction of imidazo[1,5ꢀa]ꢀ
quinoxalinꢀ4(5H)ꢀone 4 with 6ꢀbromohexanꢀ1ꢀol in the
presence of КOH in DMSO for 30 h at 40 °C gives two
products (Scheme 3). The first, minor product, precipiꢀ
tates from the solution in analytically pure form. In its
1H NMR spectrum, there are two triplet signals with relaꢀ
tive intensities 1 : 1 in the region 4.0—4.5 ppm, one of
which, resonating more highꢀfield, is broadened like the
triplet signal for the NCH2 group in compound 5, the
other is not broadened like the signal for the OCH2 group
in compound 6, which confirms the presence of the Nꢀ and
Oꢀalkylation fragments in the compound formed. In the
region 6.5—7.0 ppm, there are two signals with δ 6.81 and
6.92 ppm having, respectively, constants J = 8.3, 7.3, 1.5
and 8.6, 7.4, 1.5 Hz for the H(8) protons of various quiꢀ
noxaline systems in the proportion 1 : 1 with intensities
half as large as compared to the triplet signal in the region
4.0—4.5 ppm.
The purpose of the present work is to reveal possibiliꢀ
ties of using compound 3 as a building block for developꢀ
ment of macrocyclic systems containing various chains
with disulfide groups. To solve the problem set, we impleꢀ
mented a threeꢀstep process consisting of (1) introduction
of a haloalkyl fragment into 1,3ꢀbis(4(5H)ꢀoxoꢀ3ꢀpheꢀ
nylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzene (3), (2) transꢀ
formation of the haloalkyl fragments to mercaptoalkyl
ones, and (3) oxidation of 1,3ꢀbis{5ꢀ(3ꢀmercaptoalkylꢀ1)ꢀ
4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl}benzꢀ
ene with molecular iodine.
Introduction of a haloalkyl spacer into mꢀbis(4(5H)ꢀ
oxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzene (3).
The presence in the 1,3ꢀbis(4(5H)ꢀoxoꢀ3ꢀphenylimidꢀ
azo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzene molecule (3) of two
carbamoyl fragments, capable of being alkylated at the
nitrogen and oxygen atoms in the reactions with dihaloalꢀ
kanes, suggests formation of products of the N,N´ꢀ, O,O´ꢀ,
and N,Oꢀalkylation, as well as their oligomeric derivaꢀ
tives. Therefore, we started from the development of alkylꢀ
ation procedure and isolation of products based on the
model compound, which formally was a half of the moleꢀ
cule of compound 3, viz., 1,3ꢀdiphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ4(1H)ꢀone (4) synthesized by the reaction of
3ꢀbenzoylquinoxalinꢀ2(1H)ꢀone 1 with benzylamine proꢀ
ceeding through the oxidative imidazoannulation.33
Two ways were used to introduce a haloalkyl fragment
into compound 4. The first of them is a oneꢀstep and
includes direct alkylation of imidazo[1,5ꢀa]quinoxalinꢀ
4(1H)ꢀone 4 with dihaloalkanes in the presence of КOH
in dioxane, which yields two regioisomeric products
of Nꢀ (5) and Oꢀalkylation (6) easily separated by colꢀ
umn chromatography. The overall yield of the alkylation
products was 48%, the ratio was 47 : 1 in favor of the
Nꢀalkylation product (Scheme 2).
These data indicate formation of the product containꢀ
ing Nꢀ and Oꢀalkylated imidazo[1,5ꢀa]quinoxaline sysꢀ
tems bound with the hexamethylene chain. Position, splitꢀ
ting, and intensity of other signals do not conflict with the
structure suggested and the MALDI mass spectra, in which

Macrocycles, derivatives of Nꢀheterocycles
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1495
the molecular ion peak MH+ 757 is present, and elemenꢀ
tal analysis data definitively confirm the structure and
composition of the minor product 8.
Scheme 4
Scheme 3
a possibility of formation of unsymmetric product of the
N,Oꢀalkylation. A poor solubility of 1,3ꢀbis(4(5H)ꢀoxoꢀ
3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzene (3) even
in warm DMSO or DMF makes it difficult to involve it
into the reaction and purify desired products. Nevertheꢀ
less, we succeeded in the introduction of two haloalkyl
fragments into compound 3.
In fact, alkylation of compound 3 with various 1,nꢀ
dihaloalkanes (1ꢀbromoꢀ3ꢀchloropropane (a), 1,4ꢀdichloꢀ
robutane (b), 1,5ꢀdichloroꢀ3ꢀoxapentane (c), 1,6ꢀdibroꢀ
mohexane (d), 1,6ꢀdichlorohexane (e)) sometimes leads
to the formation of a mixture of isomers insoluble in orꢀ
ganic solvents in ~30% yield together with oligomeric
products.
Only in the case of 1ꢀbromoꢀ3ꢀchloropropane (a), exꢀ
clusive formation of the N,N´ꢀalkylation product, comꢀ
pound 11a, occurs (Scheme 5). In other cases, formation
of a difficult to isolate mixture of isomers of the N,N´ꢀ
and N,Oꢀalkylation is observed, which leads to the reducꢀ
tion in the yield of the desired product to 15—20%. The
maximum yield of Oꢀalkylated derivatives was reached in
the reaction in DMF when 1,6ꢀdichlorohexane was used
as the alkylating reactant. This reaction results in the forꢀ
mation of all three isomeric products 11e´, 11e″, and 11e´´´
in the ratio 39.2 : 60 : 0.8 (the HPLC data).
To sum up, compound 11e″, the product of the N,Oꢀ
alkylation, is the major product in the reaction of 1,3ꢀbisꢀ
(4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)ꢀ
benzene 3 with dichlorohexane. However, the use of
DMSO or dioxane as the solvent instead of DMF allowed
us to increase the yields of the desired N,N´ꢀregioisomer
to 70—80%, whereas alkylation in dioxane, unlike in
DMSO, allowed us to use dibromoalkanes (1,4ꢀdibromoꢀ
butane and 1,6ꢀdibromohexane) as the alkylating agents
i. Br(CH2)6Cl, KOH, DMSO.
As it was expected, Nꢀhydroxyhexyl derivative 7 was
the major product of this reaction, it was isolated from the
mother liquor in 40% yield and purified by column chroꢀ
matography mainly from the unreacted starting tricycle 4.
1
In the H NMR spectrum of the product, in addition to
the aromatic protons there are present five signals for the
hydroxyhexyl fragment including the triplet signal for the
hydroxy group at δ 4.38 (J = 5.2 Hz) and tripletꢀofꢀ
doublet signal for the methylene group at δ 3.40 ppm
(J = 5.9, 5.2 Hz) bonded to the hydroxy group (see Exꢀ
perimental).
The reaction of compound 7 with thionyl chloride upon
reflux in excess thionyl chloride for 8 h leads to the
substitution of the hydroxy group for the chlorine atom
and preparation of imidazo[1,5ꢀa]quinoxaline 9 with the
Nꢀchlorohexyl substituent in 79% yield. It should be notꢀ
ed that the MALDI mass spectrum of the reaction mixꢀ
ture, in addition to the peak of compound 9 with MH+
456, exhibits the peak with MH+ 876 corresponding to
the bisimidazo[1,5ꢀa]quinoxalinone monohydrate 10
(Scheme 4). However, we failed in isolation and characꢀ
terization of this compound in the individual state due to
its trace amount in the reaction mixture.
The presence of two carbamoyl groups in 1,3ꢀbisꢀ
(4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzꢀ
ene 3 should increase the probability of formation of
Oꢀalkylated compounds (observed as the side products in
the alkylation of imidazo[1,5ꢀa]quinoxalinꢀ4(1H)ꢀone 4)
in the reactions with 1,nꢀdihaloalkanes, as is increased

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Mamedov et al.
and obtain compounds with more reactive terminal broꢀ
moalkyl fragments.
tion of compounds 11 with thiourea and subsequent alkaꢀ
line hydrolysis of isothiuronium salts 12 (see Ref. 34) and
the reaction of compounds 11 with potassium thioacetate
and subsequent acid hydrolysis of thioacetates 13 (see Ref. 35)
(Schemes 6 and 7). The reaction of bishalides 11 with
thiourea was performed upon heating in dioxane. Bisisothiꢀ
uronium salts 12 precipitated from the solution in the
analytically pure form. The reaction time depended not
only on the nature of the halogen, but also on the nature of
the substituent. For instance, if dibromides 11b,d were
converted to the corresponding isothioureides in almost
quantitative yields over 20 h and dichloride 11a over 70 h,
then the reaction of dichloride 11c with thiourea even over
120 h led only to 5% yield of isothiuronium salt 12c.
The 1H NMR spectra of compounds 12 and 13 exhibit
an upfield displacement of the triplet signals for the termiꢀ
nal CH2 group from 3.5—3.7 ppm in compounds 11 to
3.2—3.4 ppm in compounds 12 and to 3.0 ppm in comꢀ
Position and splitting of the signals for the mꢀpheꢀ
nylene protons in the 1H NMR spectra of compounds 11,
independent of the haloalkyl fragment in them, always
remain virtually the same. These protons resonate in form
of three rather than four signals, which suggests symmetꢀ
ric structure of compounds under study. In addition to the
signals for other aromatic protons, in high fields there are
additional three signals in compound 11a, four in comꢀ
pounds 11b,c, six in compound 11d, which also confirms
symmetry of the structures. The presence in the IR spectra of
the absorption band for C=O in the region 1649—1655 cm–1
confirms that the N,N´ꢀ rather than O,O´ꢀalkylated prodꢀ
ucts are formed.
Scheme 5
1
pounds 13. In addition, in the H NMR spectra together
with the signals for the aromatic protons there are present
the singlet signal for the protons of the methylene groups
of the thioacetyl fragments at δ 2.3 ppm in compound 13
and broadened singlet signals for the isothioureide fragꢀ
ments in compound 12.
Alkaline hydrolysis of isothiuronium salts 12 and acid
hydrolysis of thioacetates 13 leads to bisthiols 14 (Scheme 7).
The formation of the latter is confirmed by the presence of
the peaks for the MH+ ions in the ESI mass spectra: 745
for compound 14a, 773 for compound 14b, and 805 for
X´CH2CH2YCH2X
1
compound 14c. The presence in the H NMR spectra of
X
X´
Br
Br
Cl
Br
Cl
Y
—
CH2
Solvent
DMSO
Dioxane
DMSO
Dioxane
DMF
11
a
b
c
d
the triplet signal for the SH group in the region 1.32—1.59
(t, J = 7.7—8.1 Hz) and the doublet of triplet signals
for the CH2 group bound with the SH group in the
region 2.52—2.63 (td, J = 7.5—8.1, 6.2—7.0 Hz), as well as
the presence in the IR spectra of the absorption band for
the SH group in the region 2542—2566 cm–1 confirm the
structure of compounds 14. The yields of bisthione in these
reactions is approximately the same and is about 40%.
Oxidation of 1,3ꢀbis[5ꢀ(3ꢀmercaptoalkylꢀ1)ꢀ4ꢀoxoꢀ3ꢀ
phenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzenes with molecꢀ
ular iodine. Oxidation reaction yielding mainly disulfide is
Cl
Br
Cl
Br
Cl
OCH2
(CH2)3
(CH2)3
e
Introduction of a mercapto group into N,N´ꢀalkylated
derivatives of mꢀbis(4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl)benzene (11). Transformation of the haloꢀ
alkyl substituent to mercaptoalkyl one in 1,3ꢀbis(4(5H)ꢀ
oxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl)benzene deꢀ
rivatives was accomplished by two known ways: the reacꢀ

Macrocycles, derivatives of Nꢀheterocycles
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1497
Scheme 6
Y
X
Y
X
Y
13a
13b
—
OCH2
12a
12b
Cl
Br
—
CH2
12c
12d
Cl
Br
OCH2
(CH2)3
the base. 1,3ꢀBis[5ꢀ(3ꢀmercaptoalkylꢀ1)ꢀ4ꢀoxoꢀ3ꢀpheꢀ
nylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzenes 14 are easily
oxidized with molecular iodine in chloroform at room
temperature with the formation of dithiacyclophanes 15
(Scheme 8). It was shown that the longer the substituents
with the mercapto group in 1,3ꢀbis[5ꢀ(3ꢀmercaptoalkylꢀ1)ꢀ
4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzenes
14 the higher the yields of macrocyclic disulfides, which
are 8% for 15a, 30% for 15b, and 45% for 15c.
Scheme 7
1
In the H NMR spectra, the signals for the geminal
methylene protons of the spacer of macrocycles 15 are
found separately from the corresponding protons for the
starting bismercaptanes 15, one is more downfield, another
is more upfield, the Δδ value varies in the range 1.0—1.5 ppm
for signals of the NCH2 group, which unambiguously inꢀ
dicates the nonequivalence of the protons confirming the
formation of macrocyclic systems. Transformation of bisꢀ
mercaptanes 14 to imidazoquinoxalinadithiocycloalkaꢀ
phanes 15 as well significantly changes position of the
singlet signal for the H(2) of the 1,3ꢀphenylene ring, which
is displaced upfield from 8.2 ppm in compounds 14 to
7.2 ppm in macrocycle 15a, 7.4 ppm in macrocycle 15b,
7.6 ppm in macrocycle 15c.
14
a
b
X
Cl
Br
Y
—
CH2
14
c
d
X
Cl
Br
Y
OCH2
(CH2)3
of importance in chemistry of thiols. First of all, this is
due to the fact that some compounds with the mercapto
group, for example, glutathione and cysteine play imporꢀ
tant part in living organisms. Various oxidation proceꢀ
dures have been developed36 with application of such oxidꢀ
ants as molecular oxygen in the presence of strong bases,37
salts of highꢀatomicꢀweight metals including peroxocomꢀ
plexes of molybdenum, tungsten, vanadium,38,39 chromiꢀ
1
It should be also noted that in the IR and H NMR
spectra of the oxidation products of bismercaptanes 15, no
signs of the SH group are found.
um,40—42 stannum compounds,43 FeIII 44
hydrogen perꢀ
oxide,45 halogens,46,47 disulfide dicationic salts.48
,
The formation of macrocycles 15 is additionally conꢀ
firmed by the presence of characteristic peaks of ions in
the ESI and EI mass spectra. For example, for the reacꢀ
tion products of compound 14a with I2, there are observed
peaks of ions with m/z 743 and [2M+H]+ 1485 (comꢀ
pound 15a), whereas for the reaction product of 14c with
I2, the EI mass spectrum exhibits the peak of the molecuꢀ
lar ion M+ 826 corresponding to compound 15c.
We have chosen molecular iodine successfully used in
oxidation of indolisines to biindolisines.49 The use of moꢀ
lecular iodine as the oxidant for mercaptanes, as a rule,
requires presence of a base to combine with the liberated
hydrogen iodide, which is a strong reducing agent. Howꢀ
ever, the presence in bisthiols 14 of the "pyridine" nitrogen
atom allowed us to carry out this reaction without using

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Mamedov et al.
Scheme 8
temperature and 5 h at 40 oC. The reaction mixture was cooled,
the crystals formed were filtered off, washed with PriOH and
water to obtain analytically pure compound 5. The filtrate was
poured into water, the crystals formed were filtered off, washed
with water, dried, products 5 and 6 were separated by column
chromatography (eluent: CHCl3 : EtOAc = 9 : 1) on silica
gel (Merck).
5ꢀ(3ꢀChloropropꢀ1ꢀyl)ꢀ1,3ꢀdiphenylimidazo[1,5ꢀa]quinoxaꢀ
linꢀ4ꢀone (5). The yield of compound 5 was 0.58 g (47%), white
powder, m.p. 210—212 °C. IR, ν/cm–1: 1326, 1394, 1443, 1483,
1591, 1611, 1651. 1H NMR, δ: 2.10—2.25 (m, 2 H, CH2CH2CH2);
3.83 (t, 2 H, CH2Cl, J = 6.6 Hz); 4.37 (m, 2 H, CH2N, J = 7.2 Hz);
7.00 (dd, 1 H, H(8), J = 7.9 Hz, J = 7.5 Hz); 7.20 (d, 1 H, H(9),
J = 8.6 Hz); 7.35—7.68 (m, 8 H, H(6), H(7), mꢀ, pꢀHPh); 7.73
(dd, 2 H, oꢀH, CPh(1), J = 7.6 Hz, J = 1.6 Hz); 8.15 (dd, 2 H,
oꢀH, CPh(3), J = 8.6 Hz, J = 1.7 Hz). MS MALDI TOF, m/z:
[M+H]+ 414. Found (%): C, 72.37; H, 4.97; N, 10.05; Cl, 8.51.
C25H20N3OCl. Calculated (%): C, 72.55; H, 4.87; N, 10.15;
Cl, 8.57.
4ꢀ(3ꢀChloropropꢀ1ꢀyloxy)ꢀ1,3ꢀdiphenylimidazo[1,5ꢀa]quinꢀ
oxaline (6). The yield of compound 6 was 12 mg (1%), white
powder, m.p. 139—141 °C. IR, ν/cm–1: 563, 594, 651, 686, 698,
753, 731, 773, 914, 928, 971, 1024, 1094, 1128, 1157, 1226,
1302, 1322, 1350, 1365, 1425, 1473, 1539, 1559, 1615, 2904,
2971, 3058. 1H NMR, δ: 2.15—2.25 (m, 2 H, CH2CH2CH2);
3.44 (m, 2 H, CH2Cl, J = 6.5 Hz); 4.67 (m, 2 H, CH2O, J = 6.0 Hz);
7.00—7.10 (m, 1 H, H(8)); 7.30—7.90 (m, 13 H, HPh(6), HPh(7),
HPh(9)). MS MALDI TOF, m/z: [M+H]+ 414. Found (%):
C, 72.42; H, 4.99; N, 10.22; Cl, 8.43. C25H20N3OCl. Calculatꢀ
ed (%): C, 72.55; H, 4.87; N, 10.15; Cl, 8.57.
15: n = 0 (a), 1 (b), 3 (c)
In conclusion, a threeꢀstep method was developed for
the synthesis of diimidazo[1,5ꢀa]quinoxalinaꢀ2(1,3)ꢀbenꢀ
zadithiacycloalkaphanes, which includes (1) introduction
of a haloalkyl fragment of various length and nature into
1,3ꢀbis(4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinoxalinꢀ1ꢀ
yl)benzene at the carbamoyl group, (2) transformation of
the haloalkyl fragments to the mercaptoalkyl through
isothioureide and thioacetate derivatives, and (3) oxidaꢀ
tion of 1,3ꢀbis{5ꢀmercaptoalkylꢀ4ꢀoxoꢀ3ꢀphenylimidꢀ
azo[1,5ꢀa]quinoxalinꢀ1ꢀyl}benzene with molecular iodine.
Experimental
Melting points were determined on a Boetius heating stage.
IR spectra were recorded on a Avatarꢀ360 spectrometer in КBr
pellets for compounds 5—9, 11a—c, 12a—c, 13a,b, and 14a—c
and on a Bruker Vectorꢀ22 spectrometer for compounds 11d,
12d, 14d, and 15a—c. 1H NMR spectra were recorded on a
Bruker Avanceꢀ300 Fourierꢀspectrometer (300.13 (1H)) in
CDCl3 for compounds 6, 8, 11a,b, 13a, and 14a—c, in DMSOꢀd6
for compounds 5, 7, 9, and 12a—c; on a Bruker Avanceꢀ600
spectrometer (600.00 MHz (1H)) in CDCl3 for compound 15a;
on a Bruker Avanceꢀ400 spectrometer (400.00 MHz (1H)) in
CDCl3 for compounds 14d and 15a—c and in DMSOꢀd6 for
compounds 11d and 12d. 1H NMR spectrum for compound 11c
and 13C NMR spectra for all compounds were recorded on
a Bruker DRXꢀ500 (500.13 MHz (1H) and 125.75 (13C)) in
DMSOꢀd6 for compounds 12a—c and in CDCl3 for compounds
11a—c. Residual signal of the corresponding solvent was used as
an internal standard. Mass spectra of electron ionization (EI)
were obtained on a ThermoQuest TRACE MS quadrupole mass
spectrometer with direct injection of the sample using water
cooling (DIP). MALDI mass spectra were obtained on a Bruker
Daltonic GmbH ULTRAFLEX III mass spectrometer, pꢀnitroꢀ
aniline was used as a matrix. Mass spectra obtained by electroꢀ
spray method (ESIꢀMS) were recorded on a Bruker Esquire mass
spectrometer with detector of ions.
Reaction of 1,3ꢀdiphenylimidazo[1,5ꢀa]quinoxalinꢀ4(5H)ꢀone
(4) with 6ꢀbromohexanol. A mixture of compound 4 (0.95 g,
2.8 mmol), КOH (0.24 g, 4.3 mmol), and DMSO (25 mL) was
stirred for 5 min, 6ꢀbromohexanol (0.44 mL, 3.4 mmol)l was
added, and the mixture was stirred for 30 h at 40 °C. The reacꢀ
tion mixture was cooled, the crystals formed were filtered off,
washed with PriOH and water to obtain analytically pure comꢀ
pound 8 (characteristics are given below). The filtrate was poured
into water, the crystals formed were filtered off, washed with
water, dried, and purified by column chromatography (eluent:
CHCl3 : MeOH = 100 : 1) on silica gel (60A, 0.060—0.200 mm)
to obtain compound 7.
5ꢀ(6ꢀHydroxyhexꢀ1ꢀyl)ꢀ1,3ꢀdiphenylimidazo[1,5ꢀa]quinoxaꢀ
linꢀ4ꢀone (7). The yield of compound 7 was 0.47 g (38%), white
powder, m.p. 109—112 °C. IR, ν/cm–1: 556, 591, 667, 697, 745,
768, 779, 924, 1012, 1056, 1115, 1249, 1298, 1394, 1460, 1485,
1592, 1612, 1659, 2853, 2927, 3000—3500. 1H NMR, δ: 1.35—1.45
(m, 6 H, OCH2(CH2)3); 1.55—1.65 (m, 2 H, NCH2CH2); 3.40
(td, 2 H, OCH2, J = 5.9 Hz, J = 5.2 Hz); 4.22 (t, 2 H, CH2N,
J = 7.4 Hz); 4.38 (t, 1 H, OH, J = 5.2 Hz); 7.00 (dd, 1 H, H(8),
J = 7.6 Hz, J = 7.5 Hz); 7.20 (d, 1 H, H(9), J = 8.6 Hz);
7.38—7.68 (m, 8 H, H(6), H(7), mꢀ, pꢀHPh); 7.72—7.78 (m, 2 H,
oꢀH, CPh(1)); 8.14 (dd, 2 H, oꢀH, CPh(3), J = 8.2 Hz, J = 1.3 Hz).
MS MALDI TOF, m/z: [MH]+ 438. Found (%): C, 76.79;
H, 6.30; N, 9.57. C28H27N3O2. Calculated (%): C, 76.86;
H, 6.22; N, 9.60.
The IUPAC nomenclature was used in naming of macroꢀ
cycles.50,51
Reaction of 1,3ꢀdiphenylimidazo[1,5ꢀa]quinoxalinꢀ4(5H)ꢀone
(4) with 3ꢀbromochloropropane. A mixture of compound 4 (1.0 g,
3 mmol), КOH (0.26 g, 4.6 mmol), and DMSO (15 mL) was
stirred for 5 min, then 1ꢀbromoꢀ3ꢀchloropropane (0.35 mL,
3.5 mmol) was added, the mixture was stirred for 25 h at room
1ꢀ(1,3ꢀDiphenylimidazo[1,5ꢀa]quinoxalinꢀ4ꢀyloxy)ꢀ6ꢀ(4ꢀ
oxoꢀ1,3ꢀdiphenylimidazo[1,5ꢀa]quinoxalinꢀ5ꢀyl)hexane (8).
The yield of compound 8 was 50 mg (2.3%), white powder,
m.p. 138—140 °C. IR, ν/cm–1: 558, 594, 669, 693, 744, 770,
917, 1026, 1116, 1228, 1300, 1322, 1392, 1463, 1486, 1540,

Macrocycles, derivatives of Nꢀheterocycles
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1499
1612, 1653, 2854, 2929, 3052. 1H NMR, δ: 1.20—1.35
(m, 4 H, O(CH2)2CH2CH2(CH2)2N); 1.60—1.80 (m, 4 H,
OCH2CH2(CH2)2CH2CH2N); 4.09 (t, 2 H, CH2N, J = 7.7 Hz);
4.44 (t, 2 H, OCH2, J = 6.2 Hz); 6.81 (ddd, 1 H, H(8), quinoxaꢀ
line, J = 8.6 Hz, J = 7.4 Hz, J = 1.5 Hz); 6.92 (ddd, 1 H, H(8),
quinoxaline, J = 8.3 Hz, J = 7.3 Hz, J = 1.5 Hz); 7.13—7.62
(m, 18 H, H(5)—H(7), quinoxaline, mꢀ, pꢀHPh); 7.77 (dd, 2 H,
oꢀH, CPh(1), J = 7.5 Hz, J = 1.3 Hz); 8.14 (dd, 2 H, oꢀH,
CPh(3), J = 8.4 Hz, J = 1.4 Hz). MS MALDIꢀTOF, m/z: [MH]+
757. Found (%): C, 79.37; H, 5.37; N, 11.02. C50H40N6O2.
Calculated (%): C, 79.34; H, 5.33; N, 11.10.
127.49, 127.88, 128.62, 129.53, 129.81, 129.86, 130.08, 130.20,
130.86, 131.01, 131.17, 132.63, 132.93, 143.51, 149.90, 155.48.
MS MALDI TOF, m/z: [MH]+: 749. Found (%): C, 70.37;
H, 4.67; N, 11.28; Cl, 9.54. C44H34N6Cl2O2. Calculated (%):
C, 70.49; H, 4.57; N, 11.21, Cl, 9.46.
1,3ꢀBis[5ꢀ(4ꢀbromobutꢀ1ꢀyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzene (11b). The yield of compound 11b was
0.62 g (17%), white powder, m.p. 244—246 °C. IR, ν/cm–1: 606,
667, 692, 745, 756, 783, 803, 920, 967, 988, 1126, 1234, 1250,
1300, 1360, 1396, 1445, 1486, 1609, 1649, 2856, 2926, 3027,
1
3061. H NMR, δ: 1.90—2.07 (m, 8 H, CH2(CH2)2CH2); 3.48
5ꢀ(6ꢀChlorohexꢀ1ꢀyl)ꢀ1,3ꢀdiphenylimidazo[1,5ꢀa]quinoxalinꢀ
4ꢀone (9). A solution of compound 7 (0.73 g, 1.7 mmol) in SOCl2
(5 mL) was refluxed for 8 h, the solvent was evaporated, the
residue was treated with aqueous NaHCO3, the crystals formed
were filtered off, washed with water, dried, and purified by colꢀ
umn chromatography (eluent: CHCl3 : EtOAc = 9 : 1). The yield
of compound 9 was 0.60 g (79%), white powder, m.p. 137—139 °C.
IR, ν/cm–1: 555, 585, 646, 668, 691, 744, 780, 881, 969, 1027,
1072, 1121, 1180, 1252, 1299, 1392, 1462, 1484, 1590,
1610, 1648, 2851, 2925, 2951, 3055. 1H NMR, δ: 1.40—1.60
(m, 4 H, Cl(CH2)2CH2CH2(CH2)2N); 1.65—1.85 (m, 4 H,
ClCH2CH2(CH2)2CH2CH2N); 3.65 (t, 2 H, ClCH2, J = 6.4 Hz);
4.23 (t, 2 H, CH2N, J = 7.4 Hz); 7.00 (dd, 1 H, H(8), J = 7.9 Hz,
J = 7.5 Hz); 7.20 (d, 1 H, H(9), J = 7.9 Hz); 7.38—7.68 (m, 8 H,
H(6), H(7), mꢀ, pꢀHPh); 7.72—7.78 (m, 2 H, oꢀH, CPh(1));
8.14 (d, 2 H, oꢀH, CPh(3), J = 6.9 Hz). MS MALDI TOF,
m/z: [MH]+ 456. Found (%): C, 73.70; H, 5.71; N, 9.30;
Cl, 7.71. C28H26N3OCl. Calculated (%): C, 73.75; H, 5.75;
N, 9.22; Cl, 7.78.
Reaction of 1,3ꢀbis(4(5H)ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]quinꢀ
oxalinꢀ1ꢀyl)benzene (3) with dihaloalkanes. A. Reaction of comꢀ
pound 3 with dichloroalkanes. A mixture of compound 3 (3.0 g,
5.03 mmol), КOH (0.85 g, 15.2 mmol), and DMSO (150 mL)
was heated to 100 °C, stirred for 15 min, and cooled to 50 °C,
followed by addition of the corresponding dichloroalkane
(12.0 mmol). The reaction mixture was stirred for 72 h at 50 °C,
poured into water, the crystals formed were filtered off, washed
with water, dried, and purified by column chromatography on
silica gel (eluent CH2Cl2).
B. Reaction of compound 3 with dibromoalkanes. A mixture of
compound 3 (2.5 g, 4.2 mmol), КOH (0.70 g, 12.5 mmol), 1,nꢀ
dibromoalkane (12 mmol), and dioxane (200 mL) was stirred for
48 h at 100 °C, cooled, the crystals were filtered off and washed
with CH2Cl2 (3×80 mL). Dioxane and CH2Cl2 were evaporated
in vacuo of a waterꢀjet pump. The residual tarꢀlike mass was
dried in vacuo at 50 °C for 6 h, then purified by column chromaꢀ
tography (eluent CH2Cl2) on silica gel (60A, 0.060—0.200 mm).
1,3ꢀBis[5ꢀ(3ꢀchloropropꢀ1ꢀyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzene (11a). The yield of compound 11a was
1.13 g (30%), white powder, m.p. 279—281 °C. IR, ν/cm–1: 571,
648, 668, 692, 745, 754, 763, 781, 966, 1129, 1175, 1250, 1276,
1299, 1374, 1396, 1443, 1484, 1592, 1609, 1655. 1H NMR,
δ: 2.20—2.35 (m, 4 H, CH2CH2CH2); 3.72 (t, 4 H, CH2Cl,
J = 6.1 Hz); 4.41 (t, 4 H, CH2N, J = 7.6 Hz); 6.99 (ddd, 2 H,
H(8), quinoxaline, J = 8.4 Hz, J = 7.7 Hz, J = 1.3 Hz); 7.30—7.50
(m, 10 H, H(7), H(9), quinoxaline, mꢀ, pꢀHPh); 7.54 (dd, 2 H,
H(6), quinoxaline, J = 8.4 Hz, J = 1.0 Hz); 7.75 (dd, 1 H, H(5),
J = 7.7 Hz, J = 7.6 Hz); 7.93 (dd, 2 H, H(4), H(6), J = 7.7 Hz,
J = 1.7 Hz); 8.10—8.15 (m, 5 H, H(2), oꢀHPh). 13C NMR, δ:
29.93, 39.72, 42.64, 115.56, 118.11, 118.46, 122.49, 122.67,
(t, 4 H, CH2Br, J = 6.2 Hz); 4.30 (t, 4 H, CH2N, J = 7.1 Hz);
6.98 (ddd, 2 H, H(8), quinoxaline, J = 8.4 Hz, J = 6.1 Hz,
J = 2.4 Hz); 7.25—7.50 (m, 10 H, H(7), H(9), quinoxaline, mꢀ,
pꢀHPh); 7.53 (d, 2 H, H(6), quinoxaline, J = 7.9 Hz); 7.75 (dd,
1 H, H(5), J = 7.9 Hz, J = 7.6 Hz); 7.94 (dd, 2 H, H(4), H(6),
J = 7.6 Hz, J = 1.7 Hz); 8.00—8.10 (m, 5 H, H(2), oꢀHPh).
13C NMR, δ: 25.85, 29.85, 33.09, 40.66, 115.71, 118.15, 118.45,
122.38, 122.71, 127.36, 128.58, 129.81, 129.89, 130.17, 130.86,
131.16, 132.71, 132.96, 143.43, 145.86, 155.38. MS ESI, m/z:
[MH]+: 865.2, 867.2, 869.2, [2M+H] 1729.2, 1731.4, 1732.3,
1735.3, 1736.3. Found (%): C, 63.67; H, 4.37; N, 9.60; Br, 18.39.
C46H38N6Br2O2. Calculated (%): C, 63.75; H, 4.42; N, 9.70,
Br, 18.44.
1,3ꢀBis[5ꢀ(5ꢀchloroꢀ3ꢀoxapentꢀ1ꢀyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidaꢀ
zo[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene (11c). The yield of compound
11c was 0.73 g (18%), white powder, m.p. 195—197 °C. IR,
ν/cm–1: 464, 695, 750, 921, 968, 1006, 1057, 1123, 1259, 1301,
1
1334, 1398, 1484, 1593, 1611, 1655. H NMR, δ: 3.57 (t, 4 H,
CH2Cl, J = 5.4 Hz); 3.73 (t, 4 H, OCH2CH2Cl, J = 5.4 Hz);
3.90 (t, 4 H, OCH2CH2N, J = 5.4 Hz); 4.46 (t, 4 H, CH2N,
J = 5.4 Hz); 6.97 (dd, 2 H, H(8), quinoxaline, J = 8.3 Hz,
J = 8.0 Hz); 7.33 (dd, 2 H, H(7), quinoxaline, J = 5.9 Hz,
J = 7.6 Hz); 7.35 (dd, 2 H, pꢀHPh, J = 6.9 Hz, J = 6.9 Hz); 7.46
(dd, 4 H, mꢀHPh, J = 7.6 Hz, J = 7.3 Hz); 7.51 (d, 2 H, H(9),
quinoxaline, J = 8.2 Hz); 7.58 (d, 2 H, H(6), quinoxaline,
J = 8.2 Hz); 7.74 (dd, 1 H, H(5), J = 7.9 Hz, J = 7.6 Hz); 7.93
(d, 2 H, H(4), H(6), J = 7.6 Hz); 8.13 (s, 1 H, H(2)); 8.14 (d, 4 H,
oꢀHPh, J = 7.3 Hz). 13C NMR, δ: 41.99, 42.81, 68.51, 71.16,
116.80, 118.09, 118.18, 122.45, 122.48, 127.13, 127.83, 128.54,
129.74, 129.82, 130.82, 131.10, 132.65, 132.88, 143.46, 145.82,
155.65. MS MALDI TOF, m/z: [MH]+: 809. Found (%):
C, 68.07; H 4.70; N, 10.50; Cl, 8.90. C46H38N6Cl2O4. Calculatꢀ
ed (%): C, 68.23; H, 4.73; N, 10.38, Cl, 8.76.
1,3ꢀBis[5ꢀ(6ꢀbromohexyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzene (11d). The yield of compound 11d was
0.58 g (15%), white powder, m.p. 180—182 °C. IR, ν/cm–1: 696,
728, 748, 782, 804, 845, 881, 920, 968, 1073, 1121, 1178, 1260,
1301, 1396, 1483, 1593, 1610, 1657. 1H NMR, δ: 1.38—1.50
(m, 8 H, Br(CH2)2CH2); 1.65—1.75 (m, 4 H, BrCH2CH2);
1.75—1.85 (m, 4 H, NCH2CH2); 3.53 (t, 4 H, CH2Br, J = 6.7 Hz);
4.22 (t, 4 H, CH2N, J = 7.1 Hz); 7.07 (ddd, 2 H, H(8), quinoxaꢀ
line, J = 7.9 Hz, J = 7.6 Hz); 7.37—7.50 (m, 10 H, H(7), H(9),
quinoxaline, mꢀ, pꢀHPh); 7.58 (d, 2 H, H(6), quinoxaline,
J = 8.6 Hz); 7.88 (dd, 1 H, H(5), J = 7.6 Hz, J = 7.6 Hz); 8.02
(d, 2 H, H(4), H(6), J = 8.0 Hz); 8.10 (s, 1 H, H(2)); 8.15 (dd, 4 H,
oꢀHPh, J = 7.3 Hz). Found (%): C, 65.07; H, 5.17; N, 9.20;
Br, 17.20. C50H46N6Br2O2. Calculated (%): C, 65.08; H, 5.02;
N, 9.11, Br, 17.32.
1,3ꢀBis[5ꢀ(3ꢀisothioureidoalkyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazoꢀ
[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene hydrohalides 12. A solution of

1500
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
Mamedov et al.
compound 11 (0.5 mmol) and thiourea (1.2 mmol) in dioxane
(50 mL) was stirred for 20—120 h (20 h for 11b,d, 70 h for 11a,
120 h for 11c) at 100 °C. The crystals formed were filtered off,
washed with dioxane, and dried.
1,3ꢀBis[5ꢀ(6ꢀisothioureidohexyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazoꢀ
[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene hydrobromide (12d). The yield
of compound 12d was 0.46 g (86%), white powder, m.p.
241—243 °C. IR, ν/cm–1: 696, 727, 758, 920, 968, 1070, 1126,
1178, 1255, 1301, 1335, 1397, 1551, 1611, 1649, 2700—3500.
1H NMR, δ: 1.46 (br.s, 8 H, (CH2)2(CH2)2(CH2)2); 1.60—1.80
(m, 4 H, CH2CH2(CH2)2CH2CH2); 3.16 (t, 4 H, CH2S, J = 7.1 Hz);
4.23 (t, 4 H, CH2N, J = 6.8 Hz); 7.10 (dd, 2 H, H(8), quinoxaꢀ
line, J = 8.2 Hz, J = 7.6 Hz); 7.35—7.52 (m, 10 H, H(7), H(9),
quinoxaline, mꢀ, pꢀHPh); 7.60 (d, 2 H, H(6), quinoxaline,
J = 8.6 Hz); 7.89 (dd, 1 H, H(5), J = 7.9 Hz, J = 7.60 Hz); 8.03
(dd, 2 H, H(4), H(6), J = 7.9 Hz, J = 1.6 Hz); 8.11 (s, 1 H,
H(2)); 8.15 (dd, 4 H, oꢀHPh, J = 8.0 Hz, J = 1.0 Hz); 8.96
(br.s, 8 H, SC(NH)NH2•HBr). Found (%): C, 57.88; H, 5.21;
N, 13.14; S, 5.88; Br, 14.82. C52H56N10O2S2Br2. Calculated (%):
C, 57.99; H, 5.24; N, 13.01; S, 5.95; Br, 14.84.
1,3ꢀBis[5ꢀ(3ꢀacetylthioalkyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzenes 13. A mixture of compound 11 (30 mmol)
and KSC(O)Me (96 mmol) in dioxane (30 mL) was stirred for
40 h at 100 °C. Dioxane was partially evaporated in vacuo of
a waterꢀjet pump, CH2Cl2 (30 mL) was added to the residue, the
mixture was washed with water (3×10 mL). The solvent was
evaporated. Compound 13 thus obtained was used in further
reactions without purification.
1,3ꢀBis[5ꢀ(3ꢀisothioureidopropyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazoꢀ
[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene hydrochloride (12a). The yield
of compound 12a was 0.4 g (90%), white powder, m.p. 244—245 °C.
IR, ν/cm–1: 669, 693, 746, 783, 804, 1129, 1175, 1260,
1392, 1442, 1483, 1592, 1611, 1646, 2600—3500. 1H NMR, δ:
1.95—2.41 (m, 4 H, CH2CH2CH2); 3.35 (t, 4 H, CH2S, J =
= 7.29 Hz); 4.36 (br.s, 4 H, CH2N); 7.09 (dd, 2 H, H(8), quinꢀ
oxaline, J = 7.9 Hz, J = 7.8 Hz); 7.30—7.50 (m, 10 H, H(7),
H(9), quinoxaline, mꢀ, pꢀHPh); 7.70 (d, 2 H, H(6), quinoxaline,
J = 8.6 Hz); 7.78 (dd, 1 H, H(5), J = 7.7 Hz, J = 7.3 Hz); 8.01
(d, 2 H, H(4), H(6), J = 8.0 Hz, J = 1.3 Hz); 8.06 (s, 1 H, H(2));
8.14 (dd, 4 H, oꢀHPh, J = 7.5 Hz, J = 1.5 Hz); 9.30 (br.s, 8 H,
SC(NH)NH2•HCl). 13C{1H} NMR, δ: 27.03, 27.41, 116.46,
117.69, 118.00, 122.29, 127.35, 127.61, 128.18, 129.63, 129.82,
130.55, 131.10, 132.70, 132.81, 143.08, 143.73, 154.86, 169.77.
MS ESI, m/z: [M – 2 HCl + H]+ 829, [M – 2 HCl + Na]+ 851.
Found (%): C, 61.01; H, 4.80; N, 15.34; S, 7.15; Cl, 7.71.
C46H44N10O2S2Cl2. Calculated (%): C, 61.12; H, 4.91; N, 15.50;
S, 7.09; Cl, 7.84.
1,3ꢀBis[5ꢀ(4ꢀisothioureidobutyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazoꢀ
[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene hydrobromide (12b). The yield
of compound 12b was 0.34 g (66%), white powder, m.p.
260—262 °C. IR, ν/cm–1: 678, 693, 701, 746, 757, 784, 803,
1127, 1260, 1301, 1322, 1399, 1443, 1484, 1591, 1611, 1639,
2700—3500. 1H NMR, δ: 1.77 (br.s, 8 H, CH2(CH2)2CH2); 3.23
(br.s, 4 H, CH2S); 4.26 (br.s, 4 H, CH2N); 7.10 (dd, 2 H, H(8),
quinoxaline, J = 8.0 Hz, J = 7.9 Hz); 7.30—7.50 (m, 10 H, H(7),
H(9), quinoxaline, mꢀ, pꢀHPh); 7.63 (d, 2 H, H(6), quinoxaline,
J = 8.6 Hz); 7.88 (dd, 1 H, H(5), J = 7.7 Hz, J = 7.2 Hz);
8.03 (dd, 2 H, H(4), H(6), J = 7.4 Hz, J = 1.5 Hz); 8.11 (s, 1 H,
H(2)); 8.14 (dd, 4 H, oꢀHPh, J = 8.1 Hz, J = 1.5 Hz); 9.00
(br.s, 8 H, SC(NH)NH2•HCl). 13C{1H} NMR, δ: 25.78, 26.03,
29.83, 116.61, 117.78, 118.01, 122.34, 127.47, 127.73, 128.30,
129.73, 129.88, 130.12, 130.71, 131.24, 132.80, 132.92, 143.22,
143.79, 154.79, 169.79. MS ESI, m/z: [M – 2 HBr + H]+ 857.4.
Found (%): C, 56.38; H, 4.70; N, 13.64; S, 6.35; Cl, 15.72.
C48H48N10O2S2Br2. Calculated (%): C, 56.47; H, 4.74; N, 13.72;
S, 6.28; Br, 15.65.
1,3ꢀBis[5ꢀ(3ꢀacetylthiopropyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzene (13a). The yield of compound 13a was
0.21 g (85%), yellow powder, m.p. 202—204 °C. IR, ν/cm–1
:
629, 692, 698, 746, 754, 782, 965, 1048, 1116, 1246, 1299,
1334, 1356, 1396, 1442, 1483, 1591, 1608, 1654, 1686. 1H NMR,
δ: 2.00—2.15 (m, 4 H, CH2CH2CH2); 2.34 (s, 6 H, CH3);
3.01 (t, 4 H, CH2S, J = 7.2 Hz); 4.29 (t, 4 H, CH2N, J = 7.6 Hz);
6.78 (ddd, 2 H, H(8), quinoxaline, J = 8.3 Hz, J = 6.3 Hz,
J = 1.9 Hz); 7.25—7.50 (m, 10 H, H(7), H(9), quinoxaline,
mꢀ, pꢀHPh); 7.53 (d, 2 H, H(6), quinoxaline, J = 8.1 Hz);
7.74 (dd, 1 H, H(5), J = 7.9 Hz, J = 7.6 Hz); 7.93 (dd, 2 H,
H(4), H(6), J = 7.6 Hz, J = 1.68 Hz); 8.10—8.15 (m, 5 H, H(2),
oꢀHPh).
1,3ꢀBis[5ꢀ(5ꢀacetylthioꢀ3ꢀoxapentyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidꢀ
azo[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene (13b). The yield of compound
13b was 0.19 g (78%), yellow powder, m.p. 88—90 °C. IR,
ν/cm–1: 623, 747, 781, 966, 1099, 1254, 1297, 1361, 1386, 1442,
1
1484, 1590, 1610, 1653, 1687. H NMR, δ: 2.02 (s, 6 H, CH3);
1,3ꢀBis[5ꢀ(5ꢀisothioureidoꢀ3ꢀoxapentyl)ꢀ4ꢀoxoꢀ3ꢀphenylꢀ
imidazo[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene hydrochloride (12c). The
yield of compound 12c was 24 mg (5%), white powder, m.p.
203—205 (decomp.) °C. IR, ν/cm–1: 669, 690, 747, 814, 966,
1055, 1110, 1178, 1300, 1396, 1444, 1484, 1499, 1609, 1648,
2660—3500. 1H NMR, δ: 3.36 (t, 4 H, CH2S, J = 5.6 Hz); 3.73
(t, 4 H, OCH2CH2S, J = 5.6 Hz); 3.81 (t, 4 H, OCH2CH2N,
J = 5.9 Hz); 4.44 (t, 4 H, CH2N, J = 5.9 Hz); 7.11 (ddd, 2 H,
H(8), quinoxaline, J = 8.3 Hz, J = 8.0 Hz); 7.35—7.50 (m, 10 H,
H(7), H(9), quinoxaline, mꢀ, pꢀHPh); 7.67 (d, 2 H, H(6), quinꢀ
oxaline, J = 8.7 Hz); 7.89 (dd, 1 H, H(5), J = 7.7 Hz, J = 7.3 Hz);
8.03 (dd, 2 H, H(4), H(6), J = 7.6 Hz, J = 1.5 Hz); 8.11 (s, 1 H,
H(2)); 8.15 (dd, 4 H, oꢀHPh, J = 8.3 Hz, J = 1.5 Hz); 9.12 (br.s,
8 H, SC(NH)NH2•HCl). 13C{1H} NMR, δ: 30.62, 67.38, 68.48,
116.95, 117.66, 117.98, 122.21, 122.45, 127.42, 127.74, 128.33,
129.72, 130.27, 131.26, 132.75, 132.86, 143.29, 143.98, 154.95,
170.19. MS ESI, m/z: [M–2HCl+H]+ 889.2. Found (%): C,
59.68; H, 5.20; N, 14.64; S, 6.55; Cl, 7.32. C48H48N10O4S2Cl2.
Calculated (%): C, 59.81; H, 5.02; N, 14.53; S, 6.65; Cl, 7.36.
3.03 (t, 4 H, CH2S, J = 6.2 Hz); 3.60 (t, 4 H, OCH2CH2S,
J = 6.2 Hz); 3.86 (t, 4 H, OCH2CH2N, J = 5.9 Hz); 4.43 (t, 4 H,
CH2N, J = 5.9 Hz); 6.97 (ddd, 2 H, H(8), quinoxaline, J = 7.9 Hz,
J = 7.4 Hz, J = 0.8 Hz); 7.30—7.52 (m, 10 H, H(7), H(9),
quinoxaline, mꢀ, pꢀHPh); 7.56 (dd, 2 H, H(6), quinoxaline,
J = 8.2 Hz, J = 0.6 Hz); 7.74 (dd, 1 H, H(5), J = 8.0 Hz, J = 7.5 Hz);
7.93 (dd, 2 H, H(4), H(6), J = 7.7 Hz, J = 1.5 Hz); 8.10—8.15
(m, 5 H, H(2), oꢀHPh).
1,3ꢀBis[5ꢀ(3ꢀmercaptoalkyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzenes 14. A. A mixture of compound 12
(0.62 mmol), КOH (1.5 mmol), and water (50 mL) was stirred
for 3 h at 100 °C and cooled. Crystals were filtered off, washed
with water, dried, and purified by column chromatography on
silica gel (eluent CH2Cl2 : MeOH = 500 : 1).
B. A solution of compound 13 (0.14 mmol) in THF (10 mL)
and conc. HCl (0.5 mL) was stirred for 20 h at 55 °C,
cooled, neutralized with aqueous КOH, extracted with CH2Cl2
(3×10 mL), and washed with water. The solvent was evaporated
in vacuo of a waterꢀjet pump, the residue was purified by column

Macrocycles, derivatives of Nꢀheterocycles
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1501
chromatography (eluent: CH2Cl2 : MeOH = 500 : 1) on silica
gel (60A, 0.060—0.200 mm).
J = 7.7 Hz, J = 7.7 Hz); 7.94 (dd, 2 H, H(4), H(6), J = 7.7 Hz,
J = 1.8 Hz); 8.11—8.18 (m, 5 H, H(2), oꢀHPh). Found (%):
C, 72.34; H, 5.80; N, 10.10; S, 7.65. C50H48N6O2S2. Calculatꢀ
ed (%): C, 72.43; H, 5.84; N, 10.14; S, 7.73.
1,3ꢀBis[5ꢀ(3ꢀmercaptopropyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzene (14a). The yield of compound 14a was
0.18 g (40%) (procedure A), 50 mg (48%) (procedure B), white
powder, m.p. 263—265 °C. IR, ν/cm–1: 604, 668, 693, 711, 747,
763, 783, 804, 921, 966, 1128, 1175, 1260, 1299, 1396, 1442,
1483, 1592, 1609, 1649, 2542. 1H NMR, δ: 1.59 (t, 2 H, SH,
J = 8.1 Hz); 2.00—2.15 (m, 4 H, CH2CH2CH2); 2.62 (dt, 4 H,
CH2S, J = 8.1 Hz, J = 6.9 Hz); 4.37 (t, 4 H, CH2N, J = 7.5 Hz);
6.98 (ddd, 2 H, H(8), quinoxaline, J = 8.4 Hz, J = 7.5 Hz,
J = 1.4 Hz); 7.32—7.49 (m, 10 H, H(7), H(9), quinoxaline, mꢀ,
pꢀHPh); 7.54 (dd, 2 H, H(6), quinoxaline, J = 8.3 Hz, J = 1.1 Hz);
7.75 (dd, 1 H, H(5), J = 7.9 Hz, J = 7.6 Hz); 7.93 (dd, 2 H, H(4),
H(6), J = 7.7 Hz, J = 1.7 Hz); 8.10—8.15 (m, 5 H, H(2), oꢀHPh).
MS ESI, m/z: [MH]+ 745.2. Found (%): C, 70.88; H, 4.71;
N, 11.30; S, 8.65. C44H36N6O2S2. Calculated (%): C, 70.94;
H, 4.87; N, 11.28; S, 8.61.
1,3ꢀBis[5ꢀ(4ꢀmercaptobutꢀ1ꢀyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazoꢀ
[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene (14b). Procedure A yielded 0.19 g
(39%) of compound 14b as white powder, m.p. 245—247 °C. IR,
ν/cm–1: 603, 668, 692, 745, 755, 782, 803, 967, 990, 1129, 1176,
1259, 1300, 1359, 1396, 1443, 1484, 1591, 1609, 1649, 2561,
2849, 2919, 3065. 1H NMR, δ: 1.38 (t, 2 H, SH, J = 7.9 Hz);
1.72—1.97 (m, 8 H, CH2(CH2)2CH2); 2.61 (dt, 4 H, CH2S,
J = 7.8 Hz, J = 6.9 Hz); 4.26 (t, 4 H, CH2N, J = 7.5 Hz); 6.98
(ddd, 2 H, H(8), quinoxaline, J = 8.5 Hz, J = 6.6 Hz, J = 2.2
Hz); 7.25—7.50 (m, 10 H, H(7), H(9), quinoxaline, mꢀ, pꢀHPh);
7.55 (dd, 2 H, H(6), quinoxaline, J = 8.6 Hz, J = 1.0 Hz); 7.68
(dd, 1 H, H(5), J = 8.0 Hz, J = 7.5 Hz); 7.86 (dd, 2 H, H(4),
H(6), J = 7.6 Hz, J = 1.7 Hz); 8.00—8.10 (m, 5 H, H(2), oꢀHPh).
MS ESI, m/z: [MH]+ 773.3, [M+Na]+ 795.3, [M+K]+ 811.3.
Found (%): C, 71.71; H, 5.11; N, 10.70; S, 8.35. C46H40N6O2S2.
Calculated (%): C, 71.48; H, 5.22; N, 10.87; S, 8.30.
13,33ꢀDiphenylꢀ1,3(1,5)ꢀdiimidazo[1,5ꢀa]quinoxalinaꢀ2(1,3)ꢀ
benzadithiacycloalkaphaneꢀ14,34ꢀdiones 15. A solution of bisꢀ
mercaptane 14 (0.12 mmol) and a solution of iodine (15 mg,
0.06 mmol) in dichloromethane (50 mL) were added over 1 h
from two dropping funnels into a flask with dichloromethane
(100 mL) with stirring, the mixture was stirred for 4 h, followed
by addition of 5% aq. sodium thiosulfate (50 mL) and 5% aq.
NaHCO3 (50 mL). The reaction mixture was stirred, the organic
layer was separated, washed with water, dried with sodium sulꢀ
fate, and filtered. The solvent was evaporated and the residue
was purified by column chromatography (eluent CH2Cl2 : EtOH
= 300 : 1) on silica gel (60A, 0.060—0.200 mm).
13,33ꢀDiphenylꢀ1,3(1,5)ꢀdiimidazo[1,5ꢀa]quinoxalinaꢀ2(1,3)ꢀ
benzaꢀ7,8ꢀdithiacycloundecaphaneꢀ14,34ꢀdione (15a). The yield
of compound 15a was 7 mg (8%), white powder, m.p. 312—314
°C. 1H NMR, δ: 2.20—2.45 (m, 8 H, SCH2CH2); 3.78 (ddd, 2 H
(1 H, NCH2), J = 15.0 Hz, J = 4.1 Hz, J = 3.5 Hz); 5.21 (ddd,
2 H (1 H, NCH2), J = 15.0 Hz, J = 10.8 Hz, J = 3.7 Hz); 6.93
(dd, 2 H, H(8), quinoxaline, J = 7.9 Hz, J = 7.4 Hz, J = 1.0 Hz);
7.07 (d, 2 H, H(9), quinoxaline, J = 8.0 Hz); 7.20 (s, 1 H,
Hbenz(2)); 7.26—7.30 (m, 4 H, H(6), H(7), quinoxaline); 7.43
(dd, 2 H, pꢀHPh, J = 7.6 Hz, J = 7.3 Hz); 7.50 (dd, 2 H, mꢀHPh
,
J = 7.6 Hz, J = 7.3 Hz); 8.00 (dd, 1 H, Hbenz(5), J = 7.9 Hz,
J = 7.6 Hz); 8.19 (d, 4 H, oꢀHPh, J = 7.3 Hz); 8.34 (d, 2 H,
Hbenz(4), Hbenz(6), J = 7.6 Hz). MS ESI, m/z: [MH]+ 743.6,
[2M+H]+ 1485.4. MS EI, m/z (Irel): 744(17), 743(38), 742(69)
M+, 711(23), 710(45), 709(28), 678(18), 677(41), 676(27),
650(15), 649(11), 637(13), 636(11), 635(13), 623 (19), 622(13),
621(15), 596(19), 436(21), 403(15), 389(11), 377(10), 376(22),
375(23), 363(13), 362(14), 361(10), 335(20), 324(12), 318(13),
292(10), 291(23), 252(16), 235(28), 233(29), 219(78), 218(26),
206(23), 205(88), 170(16), 128(14), 118(10), 104(44), 103(15),
90(49), 89(100), 76(18), 72(42). No peaks for masses of fragment
ions with relative intensities less than 10% are given.
13,33ꢀDiphenylꢀ1,3(1,5)ꢀdiimidazo[1,5ꢀa]quinoxalinaꢀ2(1,3)ꢀ
benzaꢀ8,9ꢀdithiacyclotridecaphaneꢀ14,34ꢀdione (15b). The yield
of compound 15b was 28 mg (30%), white powder, m.p.
302—304 °C (DMSO). IR, ν/cm–1: 694, 750, 993, 1051, 1074,
1122, 1172, 1239, 1296, 1335, 1395, 1444, 1485, 1600, 1657,
2854, 2926. 1H NMR, δ: 1.35—1.48 (m, 2 H); 1.50—1.75 (m, 4 H);
1.85—2.00 (m, 2 H); 2.45—2.53 (m, 2 H (1 H, SCH2); 2.35—2.44
(m, 2 H (1 H, SCH2); 3.70 (ddd, 2 H (1 H, NCH2), J = 14.4 Hz,
J = 4.4 Hz, J = 4.4 Hz); 5.17 (ddd, 2 H (1 H, NCH2), J = 14.4 Hz,
J = 10.4 Hz, J = 4.0 Hz); 7.02 (dd, 2 H, H(8), quinoxaline,
J = 8.6 Hz, J = 5.1 Hz, J = 3.3 Hz); 7.23 (d, 2 H, H(9), quinoxaꢀ
line, J = 8.04 Hz); 7.31—7.35 (m, 4 H, H(6), H(7), quinoxaꢀ
line); 7.39 (s, 1 H, Hbenz(2)); 7.44 (dd, 2 H, pꢀHPh, J = 7.3 Hz,
J = 7.3 Hz); 7.51 (dd, 2 H, mꢀHPh, J = 7.7 Hz, J = 7.0 Hz); 8.03
(dd, 1 H, Hbenz(5), J = 7.7 Hz, J = 7.7 Hz); 8.20 (dd, 4 H,
oꢀHPh, J = 7.7 Hz, J = 1.3 Hz); 8.27 (dd, 2 H, Hbenz(4), Hbenz(6),
J = 7.9 Hz, J = 1.3 Hz). MS EI, m/z (Irel): 771(4) 770(7) M+,
202(28), 198(16), 188(17), 184(17), 174(16), 170(34), 156(22),
146(30), 132(27), 131(39), 118(33), 117(63), 104(39), 103(24),
91(64), 90(51), 89(79), 86(100), 78(39). No peaks for masses of
fragment ions with relative intensities less than 10% are given.
Found (%): C, 71.64; H, 4.80; N, 10.81; S, 8.25. C46H38N6O2S2.
Calculated (%): C, 71.66; H, 4.97; N, 10.90; S, 8.32.
1,3ꢀBis[5ꢀ(5ꢀmercaptoꢀ3ꢀoxapentyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidꢀ
azo[1,5ꢀa]quinoxalinꢀ1ꢀyl]benzene (14c). Procedure B yielded
55 mg (49%) of compound 14c as white powder, m.p. 103—105 °C.
IR, ν/cm–1: 667, 692, 745, 781, 863, 967, 1054, 1100, 1178,
1254, 1297, 1362, 1385, 1442, 1484, 1590, 1609, 1652, 2566,
2855, 2922. 1H NMR, δ: 1.45 (t, 2 H, SH, J = 8.1 Hz); 2.63 (dt, 4 H,
CH2S, J = 8.1 Hz, J = 6.2 Hz); 3.67 (t, 4 H, OCH2CH2S, J =
= 6.2 Hz); 3.86 (t, 4 H, OCH2CH2N, J = 5.7 Hz); 4.46 (t, 4 H,
CH2N, J = 5.7 Hz); 6.98 (dd, 2 H, H(8), quinoxaline, J = 7.9 Hz,
J = 7.4 Hz); 7.32—7.58 (m, 10 H, H(7), H(9), quinoxaline, mꢀ,
pꢀHPh); 7.59 (d, 2 H, H(6), quinoxaline, J = 8.5 Hz); 7.75 (dd, 1 H,
H(5), J = 7.9 Hz, J = 7.4 Hz); 7.93 (dd, 2 H, H(4), H(6), J = 7.7 Hz,
J = 0.9 Hz); 8.10—8.17 (m, 5 H, H(2), oꢀHPh). MS ESI, m/z:
[MH]+ 805.3. Found (%): C, 68.78; H, 5.99; N, 10.33; S, 7.87.
C46H40N6O4S2. Calculated (%): C, 68.64; H, 5.01; N, 10.44; S, 7.97.
1,3ꢀBis[5ꢀ(6ꢀmercaptohexyl)ꢀ4ꢀoxoꢀ3ꢀphenylimidazo[1,5ꢀa]ꢀ
quinoxalinꢀ1ꢀyl]benzene (14d). Procedure A yielded 0.16 g (32%)
of compound 14d as white powder, m.p. 108—110 °C. IR, ν/cm–1
:
667, 693, 712, 749, 1073, 1122, 1174, 1246, 1296, 1385, 1441,
1484, 1609, 1656, 2852, 2924. 1H NMR, δ: 1.32 (t, 2 H, SH,
J = 7.7 Hz); 1.45—1.50 (m, 8 H, (CH2)2(CH2)2(CH2)2);
1.60—1.68 (m, 4 H, SCH2CH2CH2(CH2)3); 1.75—1.83 (m, 4 H,
NCH2CH2CH2(CH2)3); 2.52 (dt, 4 H, CH2S, J = 7.7 Hz,
J = 7.0 Hz); 4.23 (t, 4 H, CH2N, J = 7.9 Hz); 6.98 (ddd, 2 H,
H(8), quinoxaline, J = 8.1 Hz, J = 7.1 Hz, J = 1.1 Hz); 7.27—7.49
(m, 10 H, H(7), H(9), quinoxaline, mꢀ, pꢀHPh); 7.55 (dd, 2 H,
H(6), quinoxaline, J = 8.4 Hz, J = 1.1 Hz); 7.76 (dd, 1 H, H(5),

1502
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
Mamedov et al.
13,33ꢀDiphenylꢀ1,3(1,5)ꢀdiimidazo[1,5ꢀa]quinoxalinaꢀ2(1,3)ꢀ
benzaꢀ10,11ꢀdithiacycloheptadecaphaneꢀ14,34ꢀdione (15c). The
yield of compound 15c was 45 mg (45%), white powder, m.p.
287—289 °C. IR, ν/cm–1: 753, 782, 996, 1035, 1076, 1097, 1123,
1167, 1244, 1298, 1337, 1360, 1403, 1442, 1464, 1486, 1551,
1607, 1665, 2853, 2925. 1H NMR, δ: 1.20—1.40 (m, 8 H); 1.40—1.60
(m, 4 H); 1.60—1.80 (m, 4 H); 2.40—2.60 (m, 4 H); 3.45—3.65
(m, 2 H (1 H, NCH2); 4.95—5.15 (m, 2 H (1 H, NCH2);
6.80—7.00 (m, 2 H, H(8), quinoxaline); 7.26—7.30 (m, 4 H,
H(7), H(9), quinoxaline); 7.32 (d, 2 H, H(6), quinoxaline,
J = 7.7 Hz); 7.40 (dd, 2 H, pꢀHPh, J = 7.3 Hz, J = 7.0 Hz); 7.47
(dd, 2 H, mꢀHPh, J = 7.7 Hz, J = 7.00 Hz); 7.64 (s, 1 H, Hbenz(2));
7.94 (dd, 1 H, Hbenz(5), J = 8.1 Hz, J = 7.7 Hz); 8.11 (d, 4 H,
oꢀHPh, J = 7.3 Hz); 8.15 (d, 2 H, Hbenz(4), Hbenz(6), J = 7.7 Hz).
MS EI, m/z (Irel): 827(3) 826(5) M+, 794(12), 793(19), 362(19),
230(30), 216(25), 202(78), 188(43), 170(13), 132(14), 130(43),
104(37), 103(35), 90(35), 89(54), 86(22), 78(15), 77(100), 76(28),
65(27), 64(26), 63(25). No peaks for masses of fragment ions
with relative intensities less than 10% are given. Found (%):
C, 72.65; H, 5.55; N, 10.11; S, 7.66. C50H46N6O2S2. Calculatꢀ
ed (%): C, 72.61; H, 5.61; N, 10.16; S, 7.75.
16. V. V. Korshak, A. L. Rusanov, E. L. Baranov, Ts. G. Ireꢀ
mashvili, T. I. Bezhuashvili, Dokl. Akad. Nauk CCCР, 1971,
196, 1357 [Dokl. Chem. (Engl. Transl.), 1971].
17. V. V. Korshak, A. L. Rusanov, T. G. Iremashvili, L. Kh.
Plieva, T. V. Lekae, Die Makromolekulare Chemie, 1973,
176, 1233.
18. V. V. Korshak, A. L. Rusanov, Ts. G. Iremashvili, I. V.
Zhuravleva, S. S. Gittis, E. L. Vulakh, V. M. Ivanova, Khim.
Geterotsikl. Soedin., 1973, 1574 [Chem. Heterocycl. Comp.
(Engl. Transl.), 1973].
19. V. V. Korshak, A. L. Rusanov, D. S. Tugushi, Z. Sh.
Dzhaparidze, G. G. Andronikashvili, I. M. Gverdtsiteli,
Khim. Geterotsikl. Soedin., 1979, 1620 [Chem. Heterocycl.
Comp. (Engl. Transl.), 1979].
20. J. Preston, W. DeWinter, W. L. Hoffebert, Jr., J. Heteroꢀ
cyclic. Chem., 1968, 5, 269.
21. V. V. Rozhkov, A. M. Kuvshinov, V. I. Gulevskaya, I. I.
Chervin, S. A. Shevelev, Synthesis, 1999, 12, 2065.
22. K. Sung, S.ꢀH. Wu, P.ꢀI. Chen, Tetrahedron, 2002, 58, 5599.
23. T. A. Fairley, R. R. Tidwell, I. Donkor, N. A. Naiman, K. A.
Ohemeng, R. J. Lombardy, J. A. Bentley, M. Cory, J. Med.
Chem., 1993, 36, 1746.
24. V. V. Korshak, A. L. Rusanov, D. S. Tugushi, G. M. Cherkaꢀ
sova, Macromolecules, 1973, 5, 807.
25. V. V. Korshak, A. L. Rusanov, S. N. Leont´ev, T. K. Dzhashꢀ
iashvili, Khim. Geterotsikl. Soedin., 1974, 1569 [Chem. Heteroꢀ
cycl. Compd. (Engl. Transl.), 1974].
26. B. Dietrich, P. Viout, J.ꢀM. Lehn, Macrocyclic Chemistry,
Aspects of Organic and Inorganic Supramolecular Chemistry
(Engl. Transl.), VCH, Weinheim—New York—Basel—Camꢀ
bridge, 1993, 37—94.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ00613ꢀa)
and the International Bureu of the Federal Ministry
of Education and Reserch (Germany) (Grant BMBF,
RUS 04/011).
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Received July 31, 2008;
in revised form April 21, 2009