From 3-chloromethyl-1,2,4-triazine 4-oxides to various substituted pyridines and 1,2,4-triazines

Article abstract of DOI:10.1007/s11172-006-0095-4

An efficient strategy for the synthesis of new pyridine and 1,2,4-triazine derivatives starting from available 6-aryl-3-chloromethyl-1,2,4-triazine 4-oxides was proposed. The deoxygenative nucleophilic hydrogen substitution in the triazine-oxide ring, nuc

Full text of DOI:10.1007/s11172-006-0095-4

Russian Chemical Bulletin, International Edition, Vol. 54, No. 9, pp. 2187—2196, September, 2005
2187
From 3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxides to various substituted
pyridines and 1,2,4ꢀtriazines*
V. N. Kozhevnikov,a,b D. N. Kozhevnikov,a,bꢀ O. V. Shabunina,a N. N. Kataeva,a S. A. Yushchuk,a
V. L. Rusinov,a,b and O. N. Chupakhina,b
aUral State Technical University (UPI),
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 0458. Eꢀmail: dnk@htf.ustu.ru
bI. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
22 ul. S. Kovalevskoi, 620219 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 1189. Eꢀmail: chupakhin@ios.uran.ru
An efficient strategy for the synthesis of new pyridine and 1,2,4ꢀtriazine derivatives starting
from available 6ꢀarylꢀ3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxides was proposed. The deoxygenative
nucleophilic hydrogen substitution in the triazineꢀoxide ring, nucleophilic substitution of the
chlorine atom in the side chain, and transformations of the 1,2,4ꢀtriazine ring into the pyridine
ring via the inverseꢀelectronꢀdemand Diels—Alder reactions, being used in different orders, are
a rather flexible tool for the functionalization of the titled heterocycles. The cyanide anion,
indoles, thiophenols, amines, and triphenylphosphine were used as nucleophiles. The direct
introduction of indole residues into the 1,2,4ꢀtriazine ring followed by the substitution of the
chlorine atom by a residue of the primary or secondary aliphatic amine was found to be the
most convenient method for the library synthesis.
Key words: pyridine, indole, 1,2,4ꢀtriazine, nucleophilic substitution, inverseꢀelectronꢀ
demand Diels—Alder reaction, Wittig reaction.
Pyridine derivatives are undoubtedly among the most
abundant heterocyclic compounds with useful properties.1
It is mentioned2 that "The wide ranging biological activity
associated with many pyridine derivatives, both naturally
occurring and synthetic, ensures that the synthesis of this
important ring systems remains a topic of current interꢀ
est." Moreover, the pyridine derivatives are interesting as
ligands for the preparation of transition metal complexes
with valuable photophysical3,4 or magnetic properties5,6
and find use as chemosensors7 or catalysts.8
In this work, we propose a strategy for the synthesis of
new pyridine derivatives, including the preparation of
1,2,4ꢀtriazines, their functionalization mainly due to nuꢀ
cleophilic hydrogen substitution (SNH), and the transforꢀ
mation into the pyridine derivatives via the inverseꢀelecꢀ
tronꢀdemand Diels—Alder reaction. This sequence of reꢀ
actions makes it possible to obtain new compounds under
the conditions of library liquidꢀphase synthesis. It should
be noted that the 1,2,4ꢀtriazines used can be of indepenꢀ
dent interest. For instance, the 1,2,4ꢀtriazine derivatives
are used as analytical reagents9,10 or selective extractꢀ
ing agents for actinides during spent nuclear fuel proꢀ
cessing.11,12
The proposed strategy for the synthesis of funcꢀ
tionalized pyridines and 1,2,4ꢀtriazines includes the four
main stages (Scheme 1). The first stage is the preparation
of the starting 6ꢀarylꢀ3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxꢀ
ides 1 from different aryl methyl ketones using an earlier
described approach.13
The nucleophilic attack in 1,2,4ꢀtriazine 4ꢀoxides 1
can be directed on either the chloromethyl group or the
carbon atom in position 5 of the heterocycle. Thus, it can
be expected that the substitution of a chlorine atom is the
next stage for further modification (see Scheme 1, routes a:
variation of the Nu´ residues). The third stage, viz., the
introduction of Cꢀnucleophile residues into the heteroꢀ
cycle by hydrogen atom substitution (see Scheme 1,
routes b: variation of the Nu residues), is the reaction
typical of 1,2,4ꢀtriazine 4ꢀoxides.14—16 The last stage inꢀ
cludes the transformation of functionalized 1,2,4ꢀtriazines
to the corresponding pyridines (where the substituents
introduced in the previous steps were retained) due to
the inverseꢀelectronꢀdemand Diels—Alder reaction (see
Scheme 1, routes c).17—19 As a whole, a possibility of
consecutive employment of these reactions in different
combinations using different nucleophiles and dienophiles
can be assumed.
Route b—c—a (Scheme 1). One of the most interesting
substituents, which can be introduced into the 1,2,4ꢀtriꢀ
* Dedicated to Academician N. S. Zefirov on the occasion of his
70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2122—2131, September, 2005.
1066ꢀ5285/05/5409ꢀ2187 © 2005 Springer Science+Business Media, Inc.

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Kozhevnikov et al.
Scheme 1
Ar = Ph (1a), pꢀTol (1b), 4ꢀClC6H4 (1c), 4ꢀMeOC6H4 (1d), naphthꢀ2ꢀyl (1e)
Scheme 2
azine cycle according to the proposed approach (reacꢀ
tion b, Scheme 1), is a cyano group. Its transformations
produce heterocycles bearing different functional substituꢀ
ents (from the carboxyl or carboxamide group to the pyriꢀ
dine20 or oxazoline21 fragments). In addition, due to proꢀ
nounced donorꢀacceptor properties of the cyano group,
its presence in the 1,2,4ꢀtriazine cycle considerably faciliꢀ
tates the inverseꢀelectronꢀdemand Diels—Alder reacꢀ
tions.22
An attempt to directly cyanate triazine oxides 1 under
the earlier proposed conditions (acetone cyanohydrin in
the presence of triethylamine23) resulted, unfortunately,
in the resinification of the reaction mixture. However,
6ꢀarylꢀ3ꢀchloromethylꢀ5ꢀcyanoꢀ1,2,4ꢀtriazines 2 are acꢀ
tually formed: according to the TLC data, triazine oxꢀ
ides 1 are completely converted into cyanotriazines 2
within 7—10 min, after which the product is rapidly resiniꢀ
fied. We decided to exclude the isolation of cyanotriazines
2 from the reaction mixture but to perform immediately
the subsequent reaction: cycloaddition. In fact, the
gas (N2) begins to evolve upon the addition of 1ꢀmorphoꢀ
linocyclopentene 5—10 min after the onset of cyanation,
indicating the Diels—Alder reaction followed by retroꢀ
decomposition.
The final transformation of the 1,2,4ꢀtriazine ring into
the pyridine cycle is achieved by the elimination of a
morpholine molecule due to the heating of the intermediꢀ
ate cycloadduct in acetic acid without its additional puriꢀ
fication. As a result, a series of 5ꢀarylꢀ2ꢀchloromethylꢀ6ꢀ
cyanoꢀ3,4ꢀcyclopentenopyridines 3 in 45—50% yields are
formed (Scheme 2).
Ar = Ph (1a, 3a, 4a—c), pꢀTol (1b, 3b, 4d—g),
naphthylꢀ2 (1c, 3c, 4h)
NRR´ = pyrrolidino (4a), 2ꢀmethylpiperidino (4b),
3ꢀmethylpiperidino group (4c), 4ꢀ(2ꢀhydroxyethyl)ꢀ
piperazinꢀ1ꢀyl (4d), (1ꢀhydroxyꢀ2ꢀmethylꢀ2ꢀyl)ꢀ
amino (4e), dimethylamino group (4f), 4ꢀmethylꢀ
piperazinꢀ1ꢀyl (4g), morpholino group (4h)
Reagents and conditions: i. Acetone cyanohydrin, NEt3, CH2Cl2,
40 °C, 10 min; ii. 1ꢀMorpholinocyclopentene, 20 °C, 1 h;
iii. AcOH, 117 °C, 10 min; iv. HNRR´, 80 °C, 2 h.
we synthesized a library of 36 aminomethylpyridines 4 by
the action of excess aliphatic amines on chloromethylꢀ
pyridines 3a—c. The reaction is very convenient from the
preparative point of view, because aminomethylpyridines 4
are readily isolated from the reaction mixture (dilution
with water and filtrationꢀoff of residues) and need no
additional purification. Here we present the characterisꢀ
The resulting chloromethylpyridines 3 are convenient
building blocks for the synthesis of other pyridine derivaꢀ
tives by the nucleophilic substitution of halogen, for inꢀ
stance, by amine residues. In the framework of this work,

Substituted pyridines and 1,2,4ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2189
Scheme 3
tics of eight synthesized compounds 4a—h of the whole
series (see Scheme 2 and Experimental).
As a whole, the proposed approach is convenient for
the synthesis of new pyridine derivatives with a possibility
to vary in a rather wide range the Ar substituents (starting
from substituted acetophenones), the annelated cycloalkyl
fragment (using different enamines in the inverseꢀelecꢀ
tronꢀdemand Diels—Alder reactions), and the NRR´
group.
Route a—b—c (Scheme 1). Resinification in the cyanaꢀ
tion reaction can be avoided if the chlorine atom can be
replaced by a less labile group. The arylthiol group was
chosen as such a group in this work. For instance, the
reactions of 3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxides 1 with
different thiophenols under basic conditions afford 6ꢀarylꢀ
3ꢀarylthiomethylꢀ1,2,4ꢀtriazine 4ꢀoxides 5. Under the acꢀ
tion of acetone cyanohydrin in the presence of triethylꢀ
amine, the latter are transformed into the corresponding
5ꢀcyano derivatives 6, which are convenient building
blocks for new heterocyclic compounds (Scheme 3). They
rather easily undergo the Diels—Alder reactions to form
functionalized pyridines. For instance, the reflux of
5ꢀcyanoꢀ1,2,4ꢀtriazines 6 with excess 2,5ꢀnorbornadiene
in toluene affords 3ꢀarylꢀ6ꢀarylthiomethylꢀ2ꢀcyanoꢀ
pyridines 7 (see Scheme 3), which can hardly be prepared
via any other route. In addition, the cyano group in
5ꢀcyanoꢀ1,2,4ꢀtriazines 6 acts as a good leaving group in
nucleophilic substitution reactions. The action of excess
aliphatic amines on compounds 6 produces the correꢀ
sponding 5ꢀaminoꢀ6ꢀarylꢀ2ꢀarylthiomethylꢀ1,2,4ꢀtriꢀ
azines 8 in high yields (see Scheme 3).
5, 6: Ar = Ph (a), pꢀTol (b), 4ꢀClC6H4 (c), 4ꢀMeOC6H4 (d);
5: R1 = pꢀTol (a—d), 5e: Ar = Ph, R1 = 3ꢀMeOC6H4,
5f: Ar = Ph, R1 = 4ꢀClC6H4
8: Ar = Ph (a), 4ꢀClC6H4 (b, c), R2N is pyrrolidino (a, b),
morpholino group (c)
Routes b—a and a—b (Scheme 1). The presence of the
Nꢀoxide group in the 1,2,4ꢀtriazine cycle enables one to
introduce residues of other nucleophiles, which differ from
Reagents and conditions: i. R1SH, ethanol, NEt3, 50 °C, 1 h;
ii. acetone cyanohydrin, NEt3, CH2Cl2, 20 °C, 30 min;
iii. 2,5ꢀnorbornadiene, toluene, 110 °C, 4 h; iv. HNR´R″,
80 °C, 1 h.
H
the nitrile group, into the heterocycle via the SN reacꢀ
tions.14 We have chosen indoles as nucleophiles that are
of independent interest for synthetic chemists. The proꢀ
posed approach using these nucleophiles can be considꢀ
ered as a method for preparing functional derivatives of
this pharmacophoric fragment. For example, the reꢀ
actions of 1,2,4ꢀtriazine 4ꢀoxides 1 with indole and
1ꢀmethylindole in the presence of benzoyl chloride afford
the corresponding 6ꢀarylꢀ3ꢀchloromethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ
1,2,4ꢀtriazines 9 in 50—65% yields. The subsequent
substitution of the chlorine atom by thiophenol residues
occurs under the aboveꢀdescribed conditions to form
6ꢀarylꢀ3ꢀarylthiomethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ1,2,4ꢀtriazines 10
(Scheme 4).
the triazine ring with the formation of a σHꢀadduct, beꢀ
cause the acylating agent that is necessary for aromatizaꢀ
tion (benzoyl chloride) is consumed to the acylation of
the sulfur atom. The reaction with a twofold excess of
benzoyl chloride or the interaction of adduct 11 with
1 equivalent of benzoyl chloride affords an aromatic prodꢀ
uct of hydrogen substitution: benzoyl(indolyltriazinylꢀ
methyl)(tolyl)sulfonium chloride 12 (see Scheme 4).
The addition of indole with simultaneous Sꢀacylation
produces adduct 11 with two asymmetric centers: the carꢀ
bon atom in position 5 of the triazine ring and the sulfur
atom. The double set of signals in the 1Н NMR spectra of
compound 11 with the almost equal integral intensities
indicates that a mixture of diastereomers 11 in a ratio of
~1 : 1 is formed. For instance, the signal of the proton in
position 5 of the triazine ring is presented by two singlets
An attempt to change the reaction sequence does not
produce the expected product 10. The reaction of triazine
oxide 5a with indole in the presence of an equimolar
amount of benzoyl chloride affords benzoylꢀ[4ꢀhydroxyꢀ
5ꢀ(indolꢀ3ꢀyl)ꢀ4,5ꢀdihydroꢀ1,2,4ꢀtriazinꢀ3ꢀylmethyl](pꢀ
tolyl)sulfonium chloride 11 (see Scheme 4). The reaction
ceases at the step of nucleophile addition to position 5 of

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Kozhevnikov et al.
Scheme 4
coupling constants between the protons of the CH=CH
fragment (J = 16.1—16.7 Hz) in the H NMR spectra of
1
compounds 14, only the Eꢀisomers are formed. The reacꢀ
tion of indolyltriazine 9a with triphenylphosphine folꢀ
lowed by the treatment with anisaldehyde affords the
Wittig reaction product 16 (see Scheme 5) (intermediate
phosphonium salt 15 was not isolated from the reaction
mixture).
It is found that the chlorine atom in 5ꢀindolylꢀ1,2,4ꢀ
triazines 9 is rather easily substituted by residues of priꢀ
mary and secondary aliphatic amines. For example, the
reactions of triazines 9a,d with chiral amines, viz.,
(–)ꢀcytisine and Lꢀalaninol, in a DMF solution in
the presence of triethylamine afford the corresponding
3ꢀaminomethylꢀ6ꢀarylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ1,2,4ꢀtriazine
17a—c in 60—71% yields (Scheme 6).
Many of the reactions described here are convenient
from the preparative point of view and occur in good
yields. We distinguished three reactions, namely, the forꢀ
mation of 3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxides 1, the
introduction of indole residues into the triazine ring, and
the substitution of the chlorine atom by the amino group,
which can be used under the conditions of library liquidꢀ
phase synthesis. In this case, the products can be varied
by an independent change in three components: isoꢀ
nitrosoacetophenone hydrazones 18 (replacement of Ar),
indoles, and amines. All reactions proceed rather
smoothly, which makes it possible to exclude the stages of
purification of intermediate compounds 1 and 9 and simꢀ
plifies the isolation of final aminomethyltriazines 17. The
solvents were chosen in such a way that evaporation steps
were excluded, and only filtration of precipitates remained
(intermediates 1 and 9 are crystallized from the reaction
mixture, whereas the latter are crystallized as hydrochloꢀ
rides). To form a precipitate of aminomethyltriazines 17,
it is enough to dilute the reaction mixture with water.
Thus, of four hydrazones 18 and two indoles, eight
chloromethyltriazines 9a—h were synthesized. They were
introduced into the reaction with twelve aliphatic amines.
As a result, a library of ninetyꢀsix 3ꢀaminomethylꢀ1,2,4ꢀ
triazines 17 was obtained. Products 17 were obtained withꢀ
out purification as individual compounds (according to
Ar = Ph (9a, e), pꢀTol (9b, f), 4ꢀClC6H4 (9c, g),
4ꢀMeOC6H4 (9d, h); R2 = H (9a—d), Me (9e—h);
R
1 = pꢀTol (10a), 3ꢀMeOC6H4 (10b), 4ꢀClC6H4 (10c)
Reagents and conditions: i. Indole or 1ꢀmethylindole, PhCOCl
(1 equiv.), THF, 20 °C, 15 h; ii. R1SH, ethanol, NEt3, 50 °C,
1 h; iii. PhCOCl (1 equiv.), THF, 20 °C, 15 h.
at δ 6.41 and 6.47. It should be mentioned that the
nonequivalent protons of the Sꢀmethylene fragment are
presented by the singleꢀproton singlets (Jgem = 0 Hz) in
both adduct 11 and aromatic hydrogenꢀsubstitution prodꢀ
uct 12.
1
the data of Н NMR spectroscopy) in 45—90% yields in
the last step (for all compounds 17 of the library). In this
article, we present a representative set of five thus obꢀ
tained compounds 17a—e (see Scheme 6).
1,2,4ꢀTriazine 4ꢀoxide 1a acts as an alkylating agent
in the reactions of triphenylphosphine to form (4ꢀoxidoꢀ
6ꢀphenylꢀ1,2,4ꢀtriazinꢀ3ꢀyl)methyltriphenylphosphoꢀ
nium chloride (13), which is easily isolated from the reacꢀ
tion mixture. The resulting phosphonium salt 13 underꢀ
goes the Wittig reaction with benzaldehydes in the presꢀ
ence of triethylamine under mild conditions to form the
corresponding 3ꢀstyrylꢀ1,2,4ꢀtriazine 4ꢀoxides 14a—e
(Scheme 5). As follows from the values of the spinꢀspin
The structures of new compounds were determined
from the data of elemental analysis, mass spectrometry,
and NMR spectroscopy. The following signals were used
1
as characteristic chemical shifts in the Н NMR spectra
of the synthesized products. For all compounds, these are
the signals of the protons of the methylene group bonded
to the heteroatom: δ 4.8—5.0 for CH2Cl (compounds 3
and 9), δ 3.5—4.1 for CH2N (compounds 4 and 17),
δ 4.2—4.6 for CH2S (compounds 5—8, 10), δ 6.5—7.2 for

Substituted pyridines and 1,2,4ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2191
Scheme 5
R = 4ꢀNO2 (14a), 3ꢀNO2 (14b), 4ꢀBr (14c), 4ꢀMeO (14d), 4ꢀNMe2 (14e)
Reagents and conditions: i. Ph3P, MeCN, NEt3, 80 °C, 1 h; ii. Indole, PhCOCl, THF, 20 °C, 15 h; iii. 4ꢀMeOC6H4CHO, NEt3,
EtOH, 20 °C, 15 h.
Scheme 6
with the asymmetric center (benzoylated sulfur atom;
asymmetric carbon atoms of the residues of cytisine,
alaninol, and 2ꢀmethylpiperidine). For 5ꢀindolylꢀ1,2,4ꢀ
triazines 9, 10, 12, 16, 17, and 19, the characteristic sigꢀ
nal of the proton in position 4 of the indol fragment
exhibits a considerable downfield shift (δ 8.4—8.5) comꢀ
pared to the signals of other indole protons (δ 6.8—7.5)
due to the anisotropic influence of the aromatic substituꢀ
ent in position 6 of the triazine ring.15
Naturally, the spectra of the products contain signals
of protons of the introduced substituents in their usual
region. For 1,2,4ꢀtriazine 4ꢀoxides 5, 13, and 14, the
signal of the proton in position 5 of the triazine ring at
δ 9.2—9.3 is characteristic. The transformation of the
1,2,4ꢀtriazine ring into the pyridine cycle is accompanied
1
by the appearance in the Н NMR spectra of highꢀfield
signals of the —CН2—CН2—CН2— fragments (pyridines 3
and 4) or two lowꢀfield doublets of the protons of the
central pyridine cycle (compounds 7).
However, it should be noted that the proposed synꢀ
thetic strategy has several restrictions. For instance, the
chlorine atom in compounds 9 is not substituted in the
reaction with ammonia, whereas substitution by an alcoꢀ
hol residue occurs under drastic conditions: only a proꢀ
longed reflux of chloromethyltriazine 9а in butanol with
sodium methoxide provides 3ꢀhydroxymethylꢀ1,2,4ꢀtriꢀ
azine 19 (see Scheme 6). Attempts to carry out at first the
substitution reactions of the chlorine atom in 1,2,4ꢀtriꢀ
azine 4ꢀoxides 1 by the amine residue and then the substiꢀ
tution of a hydrogen atom by any Cꢀnucleophile were
unsuccessful, because the 1,2,4ꢀtriazine ring decomposed
in the first step under the action of amines. Indolyltriazines
9, 10, and 16 were not either transformed into the correꢀ
Ar = Ph (17a,c,d 18a), pꢀTol (17e, 18b), 4ꢀClC6H4 (18c),
4ꢀMeОC6H4 (17b, 18d);
NRR´ is cytisino (17a,b), (1ꢀhydroxypropylꢀ2)amino (17c),
isopropylamino group (17d), 4ꢀ(2ꢀhydroxyethyl)ꢀ
piperazinꢀ1ꢀyl (17e); R2 = H (17a—e)
Reagents and conditions: i. HNRR´; ii. MeONa, BuOH, 118 °C.
CH2S+Bz (compounds 11 and 12), and δ 5.85 for CH2P
(compound 13). In the spectra of products 4b, 11, 12, and
17a—c, the signals of the protons of the methylene group
undergo diastereotopic splitting due to their neighboring

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Kozhevnikov et al.
and immersed into a water bath. Each of the three vessels was
loaded with the corresponding amine (0.5 mL), DMF (1 mL),
and one of chloromethylpyridines 3a—c (100 mg). The mixture
was heated for 2 h in a water bath at 70 °C and diluted with water
(8—13 mL). A precipitate that formed in some time was filtered
off and washed with water.
sponding indolylpyridines because, most likely, the introꢀ
duction of the electronꢀreleasing indole fragment deꢀ
creases sharply the reactivity of 1,2,4ꢀtriazines in the inꢀ
verseꢀelectronꢀdemand Diels—Alder reactions.
It should be mentioned in conclusion that the accessiꢀ
bility of 3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxides, their easy
chemical modification using the nucleophilic substituꢀ
tion of hydrogen and halogen in different combinations
and with different nucleophiles, and the use of other transꢀ
formations (Wittig reactions, inverseꢀelectronꢀdemand
Diels—Alder reactions) allow one to obtain various pyriꢀ
dine and 1,2,4ꢀtriazine derivatives. These circumstances
are important for the library liquidꢀphase synthesis.
6ꢀCyanoꢀ5ꢀphenylꢀ2ꢀpyrrolidinomethylꢀ3,4ꢀcyclopentenoꢀ
pyridine (4a). The yield was 88 mg (78%), m.p. 66—68 °C
(EtOH). Found (%): C, 79.17; H, 6.98; N, 13.85. C20H21N3.
1
Calculated (%): C, 79.17; H, 6.98; N, 13.85. Н NMR, δ: 1.87
(m, 4 H); 2.12 (m, 2 H, J = 7.6 Hz); 2.86 (m, 6 H); 3.11 (t, 2 H,
J = 7.6 Hz); 3.71 (s, 2 H, CH2N); 7.45 (m, 2 H); 7.55 (m, 3 H).
6ꢀCyanoꢀ2ꢀ(2ꢀmethylpiperidino)methylꢀ5ꢀphenylꢀ3,4ꢀcycloꢀ
pentenopyridine (4b). The yield was 78 mg (64%), m.p.
136—138 °C. Found (%): C, 79.61; H, 7.74; N, 12.90. C25H25N3.
1
Calculated (%): C, 79.72; H, 7.60; N, 12.68. Н NMR, δ: 1.12
Experimental
(d, 3 H); 1.25 (m, 2 H); 1.28, 1.45 (both m, 1 H each); 1.60 (m,
2 H); 2.07 (m, 3 H); 2.37 (m, 1 H); 2.61 (m, 2 H); 2.78 (dd, 1 H,
J = 14.2 Hz, J = 7.6 Hz); 2.86 (dd, 1 H, J = 17.0 Hz, J =
7.6 Hz); 3.11 (dt, 1 H, J = 17.0 Hz, J = 7.6 Hz); 3.18 (dt, 1 H,
J = 14.2 Hz, J = 7.2 Hz); 3.29, 4.09 (both d, 1 H each, CH2N,
J = 13.1 Hz); 7.52 (m, 5 H).
NMR spectra were recorded on a Bruker WMꢀ250 specꢀ
trometer (250 MHz) using a DMSOꢀd6—CCl4 (1 : 1) mixture as
the solvent and Me4Si as the internal standard. Mass spectra
were obtained on a Varian MATꢀ311A instrument (electron
ionization). The starting hydroxyiminoacetophenone hydrazoꢀ
nes 18 24 and 3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxides 1 13 were
synthesized according to known procedures.
Synthesis of 2ꢀchloromethylꢀ6ꢀcyanoꢀ3,4ꢀcyclopentenoꢀ
pyridines 3 (general procedure). The corresponding 3ꢀchloroꢀ
methylꢀ1,2,4ꢀtriazine 4ꢀoxide 1 (20 mmol) was dissolved in
CH2Cl2 (20 mL), acetone cyanohydrin (2.0 mL, 22.2 mmol)
and triethylamine (3.1 mL, 22.2 mmol) were added, and the
resulting mixture was refluxed for 10 min. Morpholinocycloꢀ
pentene (3.5 mL, 22.2 mmol) was poured to the mixture, the
resulting mixture was refluxed for 10 min, and toluene (10 mL)
was added. The reaction mixture was concentrated under reꢀ
duced pressure to a volume of 10 mL. A precipitate that formed
was filtered off, dried in air, and dissolved with boiling in acetic
acid (13 mL). The obtained solution was cooled and diluted
with water. A precipitate that formed was filtered off and recrysꢀ
tallized from ethanol.
2ꢀChloromethylꢀ6ꢀcyanoꢀ5ꢀphenylꢀ3,4ꢀcyclopentenopyridine
(3a). The yield was 2.41 g (44%), m.p. 109—110 °C. Found (%):
C, 71.60; H, 4.92; N, 10.28. C16H13ClN2. Calculated (%):
C, 71.51; H, 4.88; N, 10.42. 1Н NMR, δ: 2.13 (m, 2 H, J =
7.5 Hz); 2.90, 3.17 (both t, 2 H each, J = 7.5 Hz); 4.78 (s, 2 H,
CH2Cl); 7.46 (m, 2 H); 7.53 (m, 3 H).
2ꢀChloromethylꢀ6ꢀcyanoꢀ5ꢀ(pꢀtolyl)ꢀ3,4ꢀcyclopentenopyriꢀ
dine (3b). The yield was 2.94 g (52%), m.p. 123—124 °C.
Found (%): C, 72.20; H, 5.27; N, 10.05. C17H15ClN2. Calcuꢀ
lated (%): C, 72.21; H, 5.35; N, 9.91. 1Н NMR, δ: 2.14 (m, 2 H,
J = 7.5 Hz); 2.43 (s, 3 H); 2.90, 3.16 (both t, 2 H each, J =
7.5 Hz); 4.75 (s, 2 H, CH2Cl); 7.32 (s, 4 H, Tol).
6ꢀCyanoꢀ2ꢀ(3ꢀmethylpiperidino)methylꢀ5ꢀphenylꢀ3,4ꢀcycloꢀ
pentenopyridine (4c). The yield was 87 mg (71%), m.p. 97—99 °C.
Found (%): C, 79.81; H, 7.78; N, 12.84. C25H25N3. Calcuꢀ
lated (%): C, 79.72; H, 7.60; N, 12.68. 1Н NMR, δ: 0.82 (d, 3 H,
J = 6.8 Hz); 0.85, 1.43 (both m, 1 H each); 1.60 (m, 3 H); 1.69
(t, 2 H, J = 7.6 Hz); 2.02 (m, 2 H, J = 7.6 Hz); 2.72 (m, 2 H);
3.15 (t, 2 H, J = 7.6 Hz); 3.58 (s, 2 H, CH2N); 7.52 (m, 5 H).
6ꢀCyanoꢀ2ꢀ[4ꢀ(2ꢀhydroxyethyl)piperazino]methylꢀ5ꢀ
(pꢀtolyl)ꢀ3,4ꢀcyclopentenopyridine (4d). The yield was 85 mg
(64%), m.p. 149—150 °C. Found (%): C, 75.08; H, 6.60;
N, 13.29. C20H21N3O. Calculated (%): C, 75.21; H, 6.63;
1
N, 13.16. Н NMR, δ: 2.07 (m, 2 H, J = 7.6 Hz); 2.37 (t, 2 H,
J = 6.1 Hz); 2.43 (s, 3 H); 2.45 (m, 8 H); 2.84, 3.13 (both t,
2 H each, J = 7.6 Hz); 3.47 (m, 2 H, J = 6.1 Hz, J = 2.4 Hz);
3.59 (s, 2 H, CH2N); 3.99 (br.t, 1 H, ОH, J = 2.4 Hz); 7.30 (s,
4 H, Tol).
6ꢀCyanoꢀ2ꢀ(1ꢀhydroxyꢀ2ꢀmethylpropꢀ2ꢀyl)aminomethylꢀ5ꢀ
(pꢀtolyl)ꢀ3,4ꢀcyclopentenopyridine (4e). The yield was 69 mg
(58%). 1Н NMR, δ: 1.04 (s, 6 H); 2.07 (m, 2 H, J = 7.6 Hz);
2.42 (s, 3 H); 2.85, 3.09 (both t, 2 H each, J = 7.6 Hz); 3.24 (d,
2 H, J = 2.0 Hz); 3.76 (s, 2 H, CH2N); 4.39 (br.s, 1 H, ОH, J =
2.0 Hz); 7.30 (s, 4 H, Tol).
6ꢀCyanoꢀ2ꢀdimethylaminomethylꢀ5ꢀ(pꢀtolyl)ꢀ3,4ꢀcycloꢀ
pentenopyridine (4f). The yield was 81 mg (79%). 1Н NMR, δ:
2.08 (m, 2 H, J = 7.6 Hz); 2.30 (s, 6 H); 2.42 (s, 3 H); 2.85, 3.12
(both t, 2 H each, J = 7.6 Hz); 3.52 (s, 2 H, CH2N); 7.30 (s,
4 H, Tol).
6ꢀCyanoꢀ2ꢀ(4ꢀmethylpiperazino)methylꢀ5ꢀ(pꢀtolyl)ꢀ3,4ꢀ
cyclopentenopyridine (4g). The yield was 104 mg (85%).
1Н NMR, δ: 2.07 (m, 2 H, J = 7.6 Hz); 2.17 (s, 3 H); 2.31 (m,
4 H); 2.42 (s, 3 H); 2.50 (m, 4 H); 2.84, 3.12 (both t, 2 H each,
J = 7.6 Hz); 3.59 (s, 2 H, CH2N); 7.31 (s, 4 H, Tol).
6ꢀCyanoꢀ2ꢀmorpholinomethylꢀ5ꢀ(2ꢀnaphthyl)ꢀ3,4ꢀcycloꢀ
pentenopyridine (4h). The yield was 102 mg (88%). 1Н NMR, δ:
2.13 (m, 2 H, J = 7.6 Hz); 2.48 (m, 4 H); 2.91, 3.18 (both t,
2 H each, J = 7.6 Hz); 3.60 (m, 4 H); 3.73 (s, 2 H, CH2N); 7.60,
7.95 (both m, 3 H each); 8.02 (d, 1 H).
2ꢀChloromethylꢀ6ꢀcyanoꢀ5ꢀ(2ꢀnaphthyl)ꢀ3,4ꢀcyclopentenoꢀ
pyridine (3c). The yield was 2.94 g (52%), m.p. 145—146 °C.
Found (%): C, 75.29; H, 4.76; N, 8.62. C20H15ClN2. Calcuꢀ
lated (%): C, 75.35; H, 4.74; N, 8.79. 1Н NMR, δ: 2.17 (m, 2 H,
J = 7.5 Hz); 2.95, 3.20 (both t, 2 H each, J = 7.5 Hz); 4.79 (s,
2 H, CH2Cl); 7.57, 7.97 (both m, 3 H each); 8.03 (d, 1 H,
J = 8.5 Hz).
Library synthesis of 3ꢀaminomethylpyridines (4) (general proꢀ
cedure). The synthesis was carried out in 18 (3×6) glass 15ꢀmL
vessels (Aldrich) equipped with screwꢀtops with a Teflon layer
Synthesis of 3ꢀarylthiomethylꢀ1,2,4ꢀtriazine 4ꢀoxides 5 (genꢀ
eral procedure). The corresponding 1,2,4ꢀtriazine 4ꢀoxide 1

Substituted pyridines and 1,2,4ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2193
(2 mmol) was dissolved in ethanol (10 mL) in the presence of
triethylamine (0.7 mL, 3 mmol) at 50 °C with stirring, the correꢀ
sponding thiophenol (2.1 mmol) was added, and the mixture
was stirred at the same temperature for 30 min. Crystals precipiꢀ
tated after cooling were filtered off and recrystallized from
ethanol.
2 H, CH2S); 7.14, 7.33 (both m, 2 H each); 7.66 (m, 3 H);
8.00 (m, 2 H).
5ꢀCyanoꢀ6ꢀ(pꢀtolyl)ꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine
(6b). The yield was 299 mg (60%), m.p. 86—88 °C. Found (%):
C, 64.31; H, 4.01; N, 16.75. C19H16N4S. Calculated (%):
C, 64.27; H, 3.90; N, 16.66. 1Н NMR, δ: 2.29, 2.46 (both s,
3 H each); 4.56 (s, 2 H, CH2S); 7.09, 7.29, 7.42, 7.90 (all m,
2 H each).
6ꢀPhenylꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine 4ꢀoxide (5a).
The yield was 460 mg (75%), m.p. 140—145 °C. Found (%):
66.05; H, 4.96; N, 13.63. C17H15N3OS. Calculated (%): C, 66.00;
6ꢀ(4ꢀChlorophenyl)ꢀ5ꢀcyanoꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriꢀ
azine (6c). The yield was 320 mg (60%), m.p. 96—98 °C.
Found (%): C, 61.31; H, 3.69; N, 15.75. C18H13ClN4S. Calcuꢀ
lated (%): C, 61.27; H, 3.71; N, 15.88. 1Н NMR, δ: 2.24 (s, 3 H);
4.58 (s, 2 H, CH2S); 7.10, 7.30, 7.64, 8.01 (all m, 2 H each).
5ꢀCyanoꢀ6ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀ
triazine (6d). The yield was 380 mg (73%), m.p. 70—72 °C.
Found (%): C, 65.51; H, 4.58; N, 16.05. C19H16N4OS. Calcuꢀ
1
H, 4.89; N, 13.58. Н NMR, δ: 2.30 (s, 3 H, Me); 4.43 (s, 2 H,
CH2S); 7.09, 7.32 (both m, 2 H); 7.52 (m, 3 H); 8.13 (m, 2 H);
9.23 (s, 1 H, H(5)). Mass spectrum, m/z (Irel (%)): 309 [M+] (3).
6ꢀ(pꢀTolyl)ꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine 4ꢀoxide (5b).
The yield was 586 mg (90%), m.p. 158—160 °C. Found (%):
66.41; H, 5.88; N, 12.90. C18H19N3OS. Calculated (%): C, 66.43;
H, 5.88; N, 12.91. 1Н NMR, δ: 2.31, 2.43 (both s, 3 H each);
4.44 (s, 2 H, CH2S); 7.12 (m, 2 H); 7.34 (m, 4 H); 8.03 (m, 2 H);
9.21 (s, 1 H, H(5)). Mass spectrum, m/z (Irel (%)): 325 [M+] (4).
6ꢀ(4ꢀChlorophenyl)ꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine
4ꢀoxide (5c). The yield was 600 mg (87%), m.p. 178—180 °C.
Found (%): 59.41; H, 4.12; N, 12.30. C17H14ClN3OS. Calcuꢀ
lated (%): C, 59.39; H, 4.10; N, 12.22. 1Н NMR, δ: 2.29 (s, 3 H);
4.43 (s, 2 H, CH2S); 7.09, 7.32, 7.53, 8.16 (all m, 2 H each);
9.29 (s, 1 H, H(5)). Mass spectrum, m/z (Irel (%)): 343 (15) and
345 (6) [M+].
1
lated (%): C, 65.50; H, 4.63; N, 16.08. Н NMR, δ: 2.29, 3.89
(both s, 3 H each); 4.55 (s, 2 H, CH2S); 7.16 (m, 4 H); 7.29,
7.99 (both m, H each).
6ꢀCyanoꢀ5ꢀphenylꢀ2ꢀ(pꢀtolyl)pyridine (7a). Cyanotriazine 6a
(1.5 mmol) and 2,5ꢀnorbornadiene (0.27 mL, 3 mmol) were
refluxed in toluene for 1—10 g. The course of the reaction was
monitored by TLC. The solvent was evaporated, and the residue
was recrystallized from ethanol. The yield was 280 mg (59%),
m.p. 70—75 °C. Found (%): C, 75.87; H, 5.12; N, 8.78.
C20H16N2S. Calculated (%): C, 75.92; H, 5.10; N, 8.85.
1Н NMR, δ: 2.30 (s, 3 H); 4.29 (s, 2 H, CH2S); 7.08, 7.24
(both m, 2 H each); 7.53 (m, 5 H); 7.69, 7.93 (both d, 1 H each,
J = 8.3 Hz).
6ꢀ(4ꢀMethoxyphenyl)ꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine
4ꢀoxide (5d). The yield was 545 mg (81%), m.p. 155—157 °C.
Found (%): C, 63.71; H, 5.08; N, 12.4.7. C18H17N3O2S. Calcuꢀ
1
lated (%): C, 63.70; H, 5.05; N, 12.38. Н NMR, δ: 2.29, 3.85
(both s, 3 H each); 4.43 (s, 2 H, CH2S); 7.08 (m, 4 H); 7.32,
8.11 (both m, 2 H each); 9.19 (s, 1 H, H(5)). Mass spectrum,
m/z (Irel (%)): 339 [M+] (20).
Synthesis of 5ꢀaminoꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazines 8
(general procedure). The corresponding 5ꢀcyanoꢀ1,2,4ꢀtriazine 6
(0.5 mmol) and amine (1 mL) were heated at 80 °C. The mixꢀ
ture was stored for 30 min and diluted with water. The resulting
precipitate was filtered off, washed with water, and recrystalꢀ
lized from acetonitrile.
6ꢀPhenylꢀ5ꢀpyrrolidinoꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine
(8a). The yield was 125 mg (68%), m.p. 125—130 °C. Found (%):
C, 69.46; H, 6.11; N, 15.55. C12H22N4S. Calculated (%):
C, 69.58; H, 6.12; N, 15.46. 1Н NMR, δ: 1.78 (m, 4 H); 2.29
(s, 3 H); 3.07 (m, 4 H); 4.16 (s, 2 H, CH2S); 7.07, 7.33 (both m,
2 H each); 7.44 (m, 5 H).
3ꢀ(3ꢀMethoxyphenyl)thiomethylꢀ6ꢀphenylꢀ1,2,4ꢀtriazine
4ꢀoxide (5e). The yield was 550 mg (85%), m.p. 135—140 °C.
Found (%): C, 62.85; H, 4.86; N, 12.80. C17H15N3O2S. Calcuꢀ
lated (%): C, 62.75; H, 4.65; N, 12.91. 1Н NMR, δ: 3.77 (s, 3 H,
ОMe); 4.52 (s, 2 H, CH2S); 6.75 (dd, 1 H, J = 8.2 Hz, J =
2.5 Hz); 7.00 (dd, 1 H, J = 8.2 Hz, J = 1.2 Hz); 7.04 (dd, 1 H,
J = 2.5 Hz, J = 1.2 Hz); 7.19 (dd, 1 H, J = 8.2 Hz, J = 8.2 Hz);
7.52 (m, 3 H); 8.14 (m, 2 H); 9.26 (s, 1 H, H(5)). Mass specꢀ
trum, m/z (Irel (%)): 325 [M+] (9).
3ꢀ(4ꢀChlorophenyl)thiomethylꢀ6ꢀphenylꢀ1,2,4ꢀtriazine 4ꢀoxꢀ
ide (5f). The yield was 570 mg (87%), m.p. 140—145 °C.
Found (%): C, 58.31; H, 3.49; N, 12.72. C16H12ClN3OS. Calꢀ
6ꢀ(4ꢀChlorophenyl)ꢀ5ꢀpyrrolidinoꢀ3ꢀ(pꢀtolyl)thiomethylꢀ
1,2,4ꢀtriazine (8b). The yield was 130 mg (70%), m.p.
115—120 °C. Found (%): C, 63.48; H, 5.30; N, 14.12.
C21H21ClN4S. Calculated (%): C, 63.54; H, 5.33; N, 14.11.
1Н NMR, δ: 1.80 (m, 4 H); 2.29 (s, 3 H); 3.10 (m, 4 H); 4.16 (s,
2 H, CH2S); 7.07, 7.33, 7.45, 7.51 (all m, 2 H each).
6ꢀ(4ꢀChlorophenyl)ꢀ5ꢀmorpholinoꢀ3ꢀ(pꢀtolyl)thiomethylꢀ
1,2,4ꢀtriazine (8c). The yield was 460 mg (75%), m.p.
120—125 °C. Found (%): C, 61.06; H, 5.11; N, 13.55.
C21H21ClN4OS. Calculated (%): C, 61.08; H, 5.13; N, 13.57.
1Н NMR, δ: 2.29 (s, 3 H); 3.29, 3.50 (both m, 4 H each); 4.20
(s, 2 H, CH2S); 7.07, 7.30, 7.49, 7.67 (all m, 2 H each).
Synthesis of chloromethylindolyltriazines 9 (general proceꢀ
dure). Benzoyl chloride (1.25 mL, 10.5 mmol) was added to
a suspension of the corresponding 1,2,4ꢀtriazine 4ꢀoxide 1
(10 mmol) and indole or 1ꢀmethylindole (10 mmol) in THF
(50 mL) at 60 °C, and the mixture was stored for 12 h at ~20 °C.
The precipitate was filtered off and recrystallized from ethanol.
3ꢀChloromethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine (9a).
The yield was 2.4 g (65%), m.p. 203—204 °C. Found (%):
1
culated (%): C, 58.27; H, 3.67; N, 12.74. Н NMR, δ: 4.52 (s,
2 H, CH2S); 7.32, 7.47 (both m, 2 H each); 7.55 (m, 3 H); 8.14
(m, 2 H); 9.26 (s, 1 H, H(5)). Mass spectrum, m/z (Irel (%)): 331
(2) and 329 (6) [M+].
Synthesis of 5ꢀcyanoꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazines 6
(general procedure). Acetone cyanohydrine (0.27 mL, 3 mmol)
and triethylamine (0.35 mL, 1.5 mmol) were added to a solution
of the corresponding 3ꢀarylthiomethylꢀ1,2,4ꢀtriazine 4ꢀoxide 5
(1.5 mmol) in CH2Cl2 (10 mL). The reaction mixture was reꢀ
fluxed for 10—15 min (the end of the reaction was monitored by
TLC) and concentrated in vacuo. The residue was stirred with a
small amount of ethyl acetate for 30 min, filtered off, and reꢀ
crystallized from propanꢀ2ꢀol.
5ꢀCyanoꢀ6ꢀphenylꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine (6a).
The yield was 315 mg (66%), m.p. 74—76 °C. Found (%):
C, 67.94; H, 4.43; N, 17.61. C18H14N4S. Calculated (%):
1
C, 67.90; H, 4.43; N, 17.60. Н NMR, δ: 2.26 (s, 3 H); 4.67 (s,

2194
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Kozhevnikov et al.
C, 60.58; H, 4.05; N, 15.43. C18H13ClN4•HCl. Calculated (%):
C, 60.69; H, 3.96; N, 15.73. 1Н NMR, δ: 5.02 (s, 2 H, CH2Cl);
6.75 (d, 1 H, H(2)indole, J = 3.0 Hz); 7.2 (m, 2 H); 7.42 (m, 1 H);
7.06 (m, 5 H); 8.57 (m, 1 H, H(4)indole); 11.82 (br.d, 1 H, NH,
J = 3.0 Hz). Mass spectrum, m/z (Irel (%)): 320 (43) and
322 (14) [M+].
Synthesis of 3ꢀarylthiomethylꢀ5ꢀindolylꢀ1,2,4ꢀtriazines 10
(general procedure). 3ꢀChloromethylꢀ5ꢀindolylꢀ1,2,4ꢀtriazine 9a
(714 mg, 2 mmol) was dissolved in ethanol (10 mL) in the
presence of triethylamine (0.7 mL, 3 mmol) with stirring and
heating, and the corresponding thiophenol (2.1 mmol) was
added. The resulting solution was stirred at room temperature
for 30 min. A precipitate that formed was filtered off and recrysꢀ
tallized from ethanol.
5ꢀ(Indolꢀ3ꢀyl)ꢀ6ꢀphenylꢀ3ꢀ(pꢀtolyl)thiomethylꢀ1,2,4ꢀtriazine
(10a). The yield was 735 mg (90%), m.p. 180—182 °C.
Found (%): C, 73.53; H, 4.89; N, 13.77. C25H20N4S. Calcuꢀ
lated (%): C, 73.50; H, 4.93; N, 13.71. 1Н NMR, δ: 2.26 (s, 3 H);
4.49 (s, 2 H, CH2S); 6.74 (s, 1 H, H(2)indole); 7.15 (m, 4 H);
7.36 (m, 3 H); 7.55 (m, 5 H); 8.33 (m, 1 H, H(4)indole); 11.57
(br.s, 1 H, NH). Mass spectrum, m/z (Irel (%)): 408 [M+] (35).
5ꢀ(Indolꢀ3ꢀyl)ꢀ3ꢀ(3ꢀmethoxyphenyl)thiomethylꢀ6ꢀphenylꢀ
1,2,4ꢀtriazine (10b). The yield was 750 mg, 88%, m.p.
180—185 °C. Found (%): C, 70.82; H, 4.59; N, 13.25.
3ꢀChloromethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀ(pꢀtolyl)ꢀ1,2,4ꢀtriazine
(9b). The yield was 2.5 g (68%), m.p. 217—218 °C. Found (%):
C, 68.23; H, 4.24; N, 16.84. C19H15ClN4. Calculated (%):
1
C, 68.16; H, 4.52; N, 16.73. Н NMR, δ: 2.47 (s, 3 H); 4.98 (s,
2 H, CH2Cl); 6.85 (d, 1 H, H(2)indole, J = 3.0 Hz); 7.19 (m, 2 H);
7.38 (m, 3 H); 7.50 (m, 2 H); 8.53 (m, 1 H, H(4)indole); 11.68
(br.d, 1 H, NH, J = 3.0 Hz). Mass spectrum, m/z (Irel (%)): 334
(41) and 336 (15) [M+].
3ꢀChloromethylꢀ6ꢀ(4ꢀchlorophenyl)ꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ1,2,4ꢀtriꢀ
azine (9c). The yield was 2.2 g (57%), m.p. 140—145 °C.
Found (%): C, 55.24; H, 3.20; N, 13.96. C18H12Cl2N4•HCl.
1
Calculated (%): C, 55.34; H, 3.36; N, 14.34. Н NMR, δ: 4.98
(s, 2 H, CH2Cl); 6.94 (d, 1 H, H(2)indole, J = 2.9 Hz); 7.18
(m, 2 H); 7.41 (m, 1 H); 7.59, 7.64 (both m, 2 H each); 8.46 (m,
1 H, H(4)indole); 11.72 (br.d, 1 H, NH, J = 2.9 Hz). Mass
spectrum, m/z (Irel (%)): 354 (37), 356 (23), and 358 (4) [M+].
3ꢀChloromethylꢀ6ꢀ(4ꢀmethoxyphenyl)ꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ1,2,4ꢀ
triazine (9d). The yield was 1.8 g (52%), m.p. 223—224 °C.
Found (%): C, 65.39; H, 4.39; N, 16.03. C19H15ClN4О. Calcuꢀ
lated (%): C, 65.05; H, 4.31; N, 15.97. 1Н NMR, δ: 3.88 (s,
3 H); 4.97 (s, 2 H, CH2Cl); 6.93 (d, 1 H, H(2)indole, J = 3.0 Hz);
7.08, 7.18 (both m, 2 H each); 7.41 (m, 1 H); 7.56 (m, 2 H); 8.50
(m, 1 H, H(4)indole); 11.70 (br.d, 1 H, NH, J = 3.0 Hz). Mass
spectrum, m/z (Irel (%)): 350 (53) and 352 (19) [M+].
C25H20N4OS. Calculated (%): C, 70.73; H, 4.75; N, 13.20.
1Н NMR, δ: 3.71 (s, 3 H); 4.56 (s, 2 H, CH2S); 6.68 (dd, 1 H,
J = 8.1 Hz, J = 2.5 Hz); 6.75 (d, 1 H, H(2)indole, J = 3.0 Hz);
7.10 (m, 5 H); 7.36 (m, 1 H); 7.56 (m, 5 H); 8.39 (m, 1 H,
H(4)indole); 11.58 (br.d, 1 H, NH, J = 3.0 Hz). Mass spectrum,
m/z (Irel (%)): 424 [M+] (30).
3ꢀ(4ꢀChlorophenyl)thiomethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀphenylꢀ
1,2,4ꢀtriazine (10c). The yield was 860 mg, 85%, m.p.
175—180 °C. Found (%): C, 67.26; H, 3.88; N, 13.15.
C
24H17ClN4S. Calculated (%): C, 67.20; H, 3.99; N, 13.06.
1Н NMR, δ: 4.56 (s, 2 H, CH2S); 6.75 (m, 1 H); 7.14 (m, 2 H);
7.35 (m, 3 H); 7.56 (m, 7 H); 8.33 (m, 1 H, H(4)indole); 11.59
(br.s, 1 H, NH). Mass spectrum, m/z (Irel (%)): 428 (21) and
430 (8) [M+].
3ꢀChloromethylꢀ5ꢀ(1ꢀmethylindolꢀ3ꢀyl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriꢀ
azine (9e). The yield was 2.1 g (56%), m.p. 175—176 °C.
Found (%): C, 61.74; H, 4.10; N, 14.89. C19H15ClN4•HCl.
Benzoyl[4ꢀhydroxyꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀphenylꢀ4,5ꢀdihydroꢀ
1,2,4ꢀtriazinꢀ3ꢀylmethyl](pꢀtolyl)sulfonium chloride (11). Benꢀ
zoyl chloride (0.098 mL, 0.84 mmol) was added to a suspension
of 6ꢀphenylꢀ3ꢀ(pꢀtolyl)thioꢀ1,2,4ꢀtriazine 4ꢀoxide (5a) (260 mg,
0.84 mmol) and indole (98 mg, 0.84 mmol) in tetrahydrofuran
(5 mL) at 60 °C, and the mixture was stored at ~20 °C for 12 h.
The precipitate was filtered off and recrystallized from ethanol.
The yield was 340 mg (72%), m.p. 193 °C (decomp.). Found (%):
C, 67.66; H, 4.86; N, 9.69. C32H27ClN4O2S. Calculated (%):
C, 67.77; H, 4.80; N, 9.88. 1Н NMR, δ: 2.14 и 2.29 (both s,
1.5 H each); 6.41 and 6.47 (both s, 0.5 H each, H(5)); 6.75 and
6.77 (both s, 0.5 H each, CH2S); 7.09 (m, 8 H); 7.18 and 7.22
(both s, 0.5 H each, CH2S); 7.45 (m, 5 H); 7.80 (m, 4 H); 8.17
(m, 2 H); 11.50 (br.s, 1 H, NH).
1
Calculated (%): C, 61.63; H, 4.36; N, 15.13. Н NMR, δ: 3.67
(s, 3 H); 4.99 (s, 2 H, CH2Cl); 6.80 (s, 1 H, H(2)indole); 7.23
(m, 2 H); 7.44 (m, 1 H); 7.65 (m, 5 H); 8.47 (m, 1 H, H(4)indole).
Mass spectrum, m/z (Irel (%)): 334 (53) and 336 (16) [M+].
3ꢀChloromethylꢀ5ꢀ(1ꢀmethylindolꢀ3ꢀyl)ꢀ6ꢀtolylꢀ1,2,4ꢀtriꢀ
azine (9f). The yield was 2.0 g (53%), m.p. 130—135 °C.
Found (%): C, 62.41; H, 4.57; N, 14.67. C20H17ClN4•HCl.
1
Calculated (%): C, 62.51; H, 4.72; N, 14.58. Н NMR, δ: 2.48,
3.69 (both s, 3 H each); 4.97 (s, 2 H, CH2Cl); 6.90 (s, 1 H,
H(2)indole); 7.22, 7.33 (both m, 2 H each); 7.43 (m, 1 H);
7.52 (m, 2 H); 8.46 (m, 1 H, H(4)indole). Mass spectrum,
m/z (Irel (%)): 348 (51) and 350 (18) [M+].
3ꢀChloromethylꢀ6ꢀ(4ꢀchlorophenyl)ꢀ5ꢀ(1ꢀmethylindolꢀ3ꢀyl)ꢀ
1,2,4ꢀtriazine (9g). The yield was 2.5 mg (62%), m.p.
142—144 °C. Found (%): C, 56.37; H, 3.65; N, 13.99.
Benzoyl[5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazinꢀ3ꢀylꢀ
methyl](pꢀtolyl)sulfonium chloride (12). Adduct 11 (280 mg,
0.5 mmol) and benzoyl chloride (0.066 mL, 0.55 mmol) in tetꢀ
rahydrofuran (15 mL) were refluxed for 1 h. The solvent was
removed under reduced pressure, and the residue was chromaꢀ
tographed (silica gel, CHCl3 as eluent). The yield was 180 mg
(66%), m.p. > 250 °C (decomp.). Found (%): C, 70.09; H, 4.51;
N, 10.02. C32H25ClN4OS. Calculated (%): C, 70.00; H, 4.59;
C
19H14Cl2N4•HCl. Calculated (%): C, 56.25; H, 3.73; N, 13.81.
1Н NMR, δ: 3.71 (s, 3 H); 5.09 (s, 2 H, CH2Cl); 7.08 (s, 1 H,
H(2)indole); 7.27 (m, 2 H); 7.54 (m, 1 H); 7.61, 7.71 (both m,
2 H each); 8.47 (m, 1 H, H(4)indole). Mass spectrum,
m/z (Irel (%)): 368 (30), 370 (18), and 372 (4) [M+].
3ꢀChloromethylꢀ6ꢀ(4ꢀmethoxyphenyl)ꢀ5ꢀ(1ꢀmethylindolꢀ3ꢀ
yl)ꢀ1,2,4ꢀtriazine (9h). The yield was 2.30 g (57%), m.p.
153—154 °C. Found (%): C, 65.78; H, 4.57; N, 15.46.
C20H17ClN4О. Calculated (%): C, 65.84; H, 4.70; N, 15.39.
1Н NMR, δ: 3.71, 3.88 (both s, 3 H each); 4.96 (s, 2 H, CH2Cl);
6.99 (s, 1 H, H(2)indole); 7.04, 7.22 (both m, 2 H each); 7.47
(m, 1 H); 7.58 (m, 2 H); 8.43 (m, 1 H, H(4)indole). Mass specꢀ
trum, m/z (Irel (%)): 364 (76) and 366 (27) [M+].
1
N, 10.20. Н NMR, δ: 2.29 (s, 3 H); 6.48 (s, 1 H, CH2S); 7.11
(m, 8 H); 7.20 (s, 1 H, CH2S); 7.48 (m, 5 H); 7.66 (m, 1 H);
7.85 (m, 3 H); 8.14 (m, 2 H); 11.50 (br.s, 1 H, NH).
(4ꢀOxidoꢀ6ꢀphenylꢀ1,2,4ꢀtriazinꢀ3ꢀylmethyl)triphenylphosꢀ
phonium chloride (13). Triphenylphosphine (920 mg, 3.5 mmol)
and 3ꢀchloromethylꢀ1,2,4ꢀtriazine 4ꢀoxide 1а (900 mg,
3.5 mmol) were dissolved in acetonitrile (10 mL), and the mixꢀ

Substituted pyridines and 1,2,4ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2195
ture was refluxed for 30 min. A precipitate that formed after
cooling was filtered off and recrystallized from DMF. The yield
was 1.27 g (75%), m.p. 175—180 °C. Found (%): C, 69.49;
H, 4.79; N, 8.68. C28H23ClN3OP. Calculated (%): C, 69.49;
H, 4.79; N, 8.68. 1Н NMR, δ: 5.85 (d, 2 H, CH2P, J = 14.0 Hz);
7.52 (m, 6 H); 7.84 (m, 15 H); 8.08 (m, 2 H); 9.33 (s, 1 H, H(5)).
Synthesis of 3ꢀstyrylꢀ1,2,4ꢀtriazine 4ꢀoxides 14 (general proꢀ
cedure). The corresponding benzaldehyde (0.75 mmol) was disꢀ
solved in ethanol (5 mL) in the presence of triethylamine
(0.18 mL, 0.75 mmol) with stirring for 20 min. Continuing
stirring, a solution of (4ꢀoxidoꢀ1,2,4ꢀtriazinꢀ3ꢀylmethyl)triꢀ
phenylphosphonium chloride 13 (390 mg, 0.75 mmol) in ethaꢀ
nol was added dropwise. The solution was stirred at ~20 °C for
30 min. A precipitate that formed was filtered off and recrystalꢀ
lized from DMF.
C26H20N4О. Calculated (%): C, 77.21; H, 4.98; N, 13.85.
1Н NMR, δ: 3.84 (s, 3 H, MeО); 6.86 (d, 1 H, H(2)indole, J =
3.05 Hz); 6.98, 7.18 (both m, 2 H each); 7.31 and 8.09 (both d,
1 H each, J = 16.3 Hz); 7.40 (m, 1 H); 7.52 (m, 3 H); 7.61, 7.69
(both m, 2 H each); 8.50 (m, 1 H, H(4)indole); 11.55 (br.d, 1 H,
NH). Mass spectrum, m/z (Irel (%)): 404 [M+] (70).
Synthesis of 3ꢀaminomethylꢀ5ꢀ(indolꢀ3ꢀyl)triazines 17a—c
(general procedure). A solution of the corresponding 5ꢀindolylꢀ
1,2,4ꢀtriazine 9 (0.5 mmol) and amine (0.7 mmol) in DMF
(5 mL) was stored for 5 h in the presence of triethylamine
(1 mmol) at room temperature, diluted with water (50 mL), and
extracted with CH2Cl2. The solvent was distilled off under reꢀ
duced pressure, and the residue was purified by column chromaꢀ
tography (silica gel, CHCl3 and then EtOH as eluents).
3ꢀCytisinomethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine
(17a). The yield was 160 mg (67%), m.p. 148—149 °C.
Found (%): C, 71.29; H, 5.88; N, 16.17. C30H28N6О2. Calcuꢀ
lated (%): C, 71.41; H, 5.59; N, 16.65. 1Н NMR, δ: 1.79
(m, 2 H); 2.42 (m, 1 H); 2.73 (m, 2 H); 3.10 (m, 3 H); 3.76
(m, 2 H); 3.84 and 4.00 (both d, 1 H each, CH2N, J = 12.3 Hz);
6.04, 6.24, 6.83 (all m, 1 H each); 7.17 (m, 3 H); 7.37 (m, 1 H);
7.57 (m, 5 H); 8.19 (m, 1 H, H(4)indole); 11.59 (br.d, 1 H, NH).
3ꢀCytisinomethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀ(4ꢀmethoxyphenyl)ꢀ1,2,4ꢀ
triazine (17b). The yield was 151 mg (60%), m.p. 148—149 °C.
Found (%): C, 73.52; H, 5.74; N, 17.68. C29H26N6О. Calcuꢀ
lated (%): C, 73.40; H, 5.52; N, 17.71. 1Н NMR, δ: 1.71
(m, 2 H); 2.49, 2.57 (both m, 1 H each); 2.71 (m, 1 H); 3.07
(m, 3 H); 3.76 (m, 2 H); 3.84 (s, 3 H, OMe); 3.86 and 3.98
(both d, 1 H each, CH2N, J = 12.0 Hz); 6.11, 6.22, 6.91 (all m,
1 H each); 7.09, 7.79 (both m, 2 H each); 7.32, 7.42 (both m,
1 H each); 7.53 (m, 2 H); 8.26 (m, 1 H, H(4)indole); 11.71
(br.d, 1 H, NH).
5ꢀ(Indolꢀ3ꢀyl)ꢀ3ꢀ(1ꢀhydroxypropꢀ2ꢀyl)aminomethylꢀ6ꢀpheꢀ
nylꢀ1,2,4ꢀtriazine (17c). The yield was 78 mg (71%), m.p.
103—104 °C. Found (%): C, 70.19; H, 5.87; N, 19.48.
C21H21N5O. Calculated (%): C, 70.18; H, 5.89; N, 19.48.
1Н NMR, δ: 1.07 (m, 3 H, Me); 2.86 (m, 1 H); 3.35 (m, 2 H);
4.11 and 4.24 (both d, 1 H each, CH2N, J = 14.8 Hz); 6.79
(d, 1 H); 7.16 (m, 2 H); 7.38 (m, 1 H); 7.57 (m, 5 H, Ph); 8.46
(m, 1 H, H(4)indole); 11.52 (br.d, 1 H, NH).
Synthesis of 3ꢀaminomethylꢀ5ꢀ(indolꢀ3ꢀyl)ꢀtriazines (17d,e)
(general procedure). The synthesis was carried out in 15ꢀmL
vessels (Aldrich) equipped with screwꢀtops with a Teflon layer
and immersed into a water bath. Each of the vessels was loaded
with the corresponding amine (0.5 mL), DMF (1 mL), and one
of the chloromethyltriazines 9a,b (100 mg) and heated on a
water bath at 70 °C for 2 h. The mixture was diluted with water
(8—13 mL), and a precipitate that formed after 1—12 h was
filtered off and washed with water.
3ꢀ(4ꢀNitrostyryl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine 4ꢀoxide (14a). The
yield was 110 mg (46%), m.p. > 300 °C. Found (%): C, 63.68;
H, 3.78; N, 17.49. C17H12N4О3. Calculated (%): C, 63.75;
H, 3.78; N, 17.49. 1Н NMR, δ: 7.58 (m, 3 H); 7.95, 8.38 (both d,
1 H each, J = 16.2 Hz); 8.07 (m, 2 H); 8.22 (m, 4 H); 9.26 (s,
1 H, H(5)). Mass spectrum, m/z (Irel (%)): 320 [M+] (50).
3ꢀ(3ꢀNitrostyryl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine 4ꢀoxide (14b). The
yield was 130 mg (53%), m.p. 238—240 °C. Found (%): C, 63.79;
H, 3.82; N, 17.48. C17H12N4О3. Calculated (%): C, 63.75;
1
H, 3.78; N, 17.49. Н NMR, δ: 7.57 (m, 3 H); 7.74 (m, 1 H);
7.89, 8.36 (both d, 1 H each, J = 16.7 Hz); 8.20 (m, 4 H); 8.57
(m, 1 H); 9.20 (s, 1 H, H(5)). Mass spectrum, m/z (Irel (%)):
320 [M+] (20).
3ꢀ(4ꢀBromostyryl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine 4ꢀoxide (14c).
The yield was 119 mg (45%), m.p. 235—237 °C. Found (%):
C, 57.46; H, 3.41; N, 12.03. C17H12BrN3О. Calculated (%):
C, 57.65; H, 3.41; N, 11.86. 1Н NMR, δ: 7.60 (m, 3 H); 7.65,
7.78 (both m, 2 H each); 7.80 and 8.26 (both d, 1 H each, J =
16.5 Hz); 8.19 (m, 2 H); 9.24 (s, 1 H, H(5)). Mass spectrum,
m/z (Irel (%)): 354 (30) and 352 (29) [M+].
3ꢀ(4ꢀMethoxystyryl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine 4ꢀoxide (14d).
The yield was 140 mg (60%), m.p. 207—209 °C. Found (%):
C, 70.91; H, 4.96; N, 13.89. C18H15N3О2. Calculated (%):
1
C, 70.81; H, 4.95; N, 13.76. Н NMR, δ: 3.82 (s, 3 H, MeО);
7.02 (m, 2 H); 7.55 (m, 3 H); 7.63 and 8.25 (both d, 1 H each,
J = 16.1 Hz); 8.17 (m, 2 H); 9.13 (s, 1 H, H(5)). Mass spectrum,
m/z (Irel (%)): 305 [M+] (50).
3ꢀ(4ꢀN,NꢀDimethylaminostyryl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine
4ꢀoxide (14e). The yield was 110 mg (45%), m.p. 210 °C.
Found (%): C, 71.71; H, 5.67; N, 17.60. C19H18N4О. Calcuꢀ
lated (%): C, 71.68; H, 5.70; N, 17.60. 1Н NMR, δ: 3.01 (s, 6 H,
2 Me); 6.77 (m, 2 H); 7.49 and 8.20 (both d, 1 H each, J =
16.0 Hz); 7.57 (m, 3 H); 7.61, 8.18 (both m, 2 H each); 9.15 (s,
1 H, H(5)). Mass spectrum, m/z (Irel (%)): 318 [M+] (50).
5ꢀ(Indolꢀ3ꢀyl)ꢀ3ꢀ(4ꢀmethoxystyryl)ꢀ6ꢀphenylꢀ1,2,4ꢀtriazine
(16). A solution of triphenylphosphine (920 mg, 3.5 mmol) and
3ꢀchloromethylꢀ1,2,4ꢀtriazine 9а (1120 mg, 3.5 mmol) in acꢀ
etonitrile (10 mL) was refluxed for 30 min, and the reaction
mixture was evaporated to dryness and dissolved in ethanol
(15 mL). The resulting solution was added dropwise with stirring
to a solution of benzaldehyde (3.5 mL, 3.5 mmol) in ethanol
(20 mL) in the presence of triethylamine (0.5 mL, 3.5 mmol),
and the mixture was stirred for 1 h and left to stand for 18 h.
A crystalline precipitate that formed was filtered off and reꢀ
crystallized from acetonitrile. The yield was 1.2 g (85%),
m.p. 214—215 °C. Found (%): C, 77.23; H, 4.96; N, 13.88.
5ꢀ(Indolꢀ3ꢀyl)ꢀ3ꢀisopropylaminomethylꢀ6ꢀphenylꢀ1,2,4ꢀtriꢀ
azine (17d). The yield was 98 mg (61%), m.p. 165 °C. Found (%):
C, 73.44; H, 6.16; N, 20.39. C21H21N5. Calculated (%): C, 73.41;
H, 6.16; N, 20.35. 1Н NMR, δ: 1.12 (m, 6 H, Me); 2.97 (m, 1 H);
4.13 (s, 2 H, CH2N); 6.78 (d, 1 H); 7.17 (m, 2 H); 7.38
(m, 1 H); 7.52 (m, 5 H, Ph); 8.43 (m, 1 H, H(4)indole); 11.53
(br.s, 1 H, NH).
3ꢀ[1ꢀ(2ꢀHydroxyethyl)piperazinomethyl]ꢀ5ꢀ(indolꢀ3ꢀyl)ꢀ6ꢀ
(pꢀtolyl)ꢀ1,2,4ꢀtriazine (17e). The yield was 90 mg (70%), m.p.
186 °C. Found (%): C, 69.96; H, 6.59; N, 19.75. C25H28N6O.
1
Calculated (%): C, 70.07; H, 6.59; N, 19.61. Н NMR, δ: 2.48
(m, 1 H); 2.70 (m, 4 H); 3.48 (m, 2 H); 3.96 (s, 2 H, CH2N);

2196
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Kozhevnikov et al.
4.00 (br.t, 1 H, OH); 6.84 (d, 1 H); 7.36 (m, 7 H); 8.52 (m, 1 H,
H(4)indole); 11.53 (br.d, 1 H, NH).
9. P. L. Croot and K. A. Hunter, Anal. Chim. Acta, 2000,
406, 289.
5ꢀ(Indolꢀ3ꢀyl)ꢀ3ꢀmethoxymethylꢀ6ꢀphenylꢀ1,2,4ꢀtriazine
(19). 1,2,4ꢀTriazine 9a (357 mg, 1 mmol) in butanol (5 mL) in
the presence of sodium methoxide (2 mmol) was refluxed for
30 min. A precipitate that formed was filtered off and recrystalꢀ
lized from butanol. The yield was 210 mg (60%). Found (%):
C, 68.90; H, 5.24; N, 16.51. C20H18N4О2. Calculated (%):
C, 69.35; H, 5.24; N, 16.17. 1Н NMR, δ: 3.50, 3.83 (both s,
3 H each, MeO); 4.81 (s, 2 H, CH2O); 6.90 (d, 1 H); 7.10, 7.12
(both m, 2 H each); 7.44, 7.56 (both m, 1 H each); 7.17 (m, 2 H);
8.53 (s, 1 H, H(4)indole); 11.75 (br.d, 1 H, NH).
10. H. Katano, H. Kuboyama, and M. Senda, J. Electroanal.
Chem., 2000, 483, 117.
11. Z. Kolarik, U. Mullich, and F. Gassner, Solv. Extr. Ion
Processes, 1999, 17, 23.
12. P. B. Iveson, C. Riviere, M. Nierlich, P. Thuery,
M. Ephritikhine, D. Guillaneux, and C. Madic, J. Chem.
Soc., Chem. Commun., 2001, 1512.
13. D. N. Kozhevnikov, N. N. Kataeva, V. L. Rusinov, and
O. N. Chupakhin, Izv. Akad. Nauk, Ser. Khim., 2004, 1243
[Russ. Chem. Bull., Int. Ed., 2004, 53, 1295 (Engl. Transl.)].
14. D. N. Kozhevnikov, V. L. Rusinov, and O. N. Chupakhin,
Adv. Heterocycl. Chem., Ed. A. R. Katritzky, 2002, 82, 261.
15. V. L. Rusinov, D. N. Kozhevnikov, I. S. Kovalev, O. N.
Chupakhin, and G. G. Aleksandrov, Zh. Org. Khim., 2000,
36, 1081 [Russ. J. Org. Chem., 2000, 36, 1050 (Engl. Transl.)].
16. D. N. Kozhevnikov, V. L. Rusinov, O. N. Chupakhin,
M. Makosza, A. Rykowski, and E. Wolinska, Eur. J. Org.
Chem., 2002, 1412.
This work was financially supported in part by the
Russian Foundation for Basic Research (Project No. 05ꢀ
03ꢀ32134), the US Civilian Research and Development
Foundation (CRDF, Grants EKꢀ005ꢀX1 and Y1ꢀ05ꢀ03),
and the Council on Grants of the President of the Rusꢀ
sian Federation (Program for State Support of Leading
Scientific Schools of the Russian Federation, Grant
NSh 1766.2003.3).
17. G. R. Pabst, K. Schmid, and J. Sauer, Tetrahedron Lett.,
1998, 39, 6691.
18. V. N. Kozhevnikov, D. N. Kozhevnikov, T. V. Nikitina,
V. L. Rusinov, O. N. Chupakhin, M. Zabel, and B. Koenig,
J. Org. Chem., 2003, 68, 2882.
19. S. P. Stanforth, B. Tarbit, and M. D. Watson, Tetrahedron
Lett., 2002, 43, 6015.
20. G. Chelucci, M. Faloni, and G. Giacomelli, Synthesis,
1990, 1121.
21. S. Gladiali, L. Pinna, G. Delogu, E. Graf, and H. Brunner,
Tetrahedron: Asymmetry, 1990, 937.
22. D. N. Kozhevnikov, V. N. Kozhevnikov, T. V. Nikitina,
V. L. Rusinov, O. N. Chupakhin, I. L. Eremenko, and G. G.
Aleksandrov, Tetrahedron Lett., 2002, 43, 4923.
23. D. N. Kozhevnikov, V. N. Kozhevnikov, I. S. Kovalev, V. L.
Rusinov, O. N. Chupakhin, and G. G. Aleksandrov, Zh. Org.
Khim, 2002, 38, 780 [Russ. J. Org. Chem., 2002, 38, 744
(Engl. Transl.)].
References
1. G. Henry, Tetrahedron, 2004, 60, 6043.
2. K. E. Bashford, M. B. Burton, S. Cameron, A. L. Cooper,
R. D. Hogg, P. D. Kane, D. A. MacManus, C. A. Matrunola,
C. J. Moody, A. A. B. Robertson, and M. Warne, Tetraꢀ
hedron Lett., 2003, 44, 1627.
3. K. Kalyanasundaram, Photosensitization and Photoꢀ
catalysis Using Inorganic and Organic Compounds,
Eds K. Kalyanasundaram and M. Grätzel, Kluwer Academic
Publishers, Dordrecht, 1993, 247.
4. E. C. Constable, A. M. W. Cargill Thompson, D. A. Tocher,
and M. A. M. Daniels, New J. Chem., 1992, 16, 855.
5. G. Zoppellaro, A. Ivanova, V. Enkelmann, A. Geies, and
M. Baumgarten, Polyhedron, 2003, 22, 2099.
6. R. Ziessel, G. Ulrich, R. C. Lawson, and L. Echegoyen,
J. Mater. Chem., 1999, 9, 1435.
24. B. B. Dey, J. Chem. Soc., 1914, 105, 1039.
7. M. H. Keefe, K. D. Benkstein, and J. T. Hupp, Coord. Chem.
Rev., 2000, 205, 201.
8. G. Chelucci and R. P. Thummel, Chem. Rev., 2002,
102, 3129.
Received July 4, 2005;
in revised form September 12, 2005