New 1,2,4-triazine-containing podands: Synthesis and properties

Article abstract of DOI:10.1007/s11172-005-0118-6

A method of one-step C-C coupling of 1,5-bis(2,6-dimethylphenoxy)-3- oxapentane (1a) and 1,8-bis(2,6-dimethylphenoxy)-3,6-dioxaoctane (1b) with 3-methylthio- (2) and 3-amino-1,2,4-triazine (3) and 3-aryl-1,2,4-triazin-5-one (6-8) has been described. The reaction of compounds 1a,b with compounds 2 and 3 in the presence of trifluoroacetic acid results in the addition of the dimethylphenoxy group to the unsubstituted C(5) carbon atom of the triazine ring. The reactions of triazinones 6-8 with compounds 1a,b in a mixture of trifluoroacetic acid and organic anhydrides are accompanied by the acylation of the nitrogen atom adjacent to the reaction center and affords bis[(3-R-1-acyl-5-oxo-1,4,5,6-tetrahydro-1,2,4-triazin-6-yl)-2, 6-dimethylphenoxy]-3-oxapentane or -3,6-dioxaoctane. The obtained adducts can smoothly be oxidized under mild conditions to form more stable products of nucleophilic hydrogen substitution in the triazine ring. The extraction and transport of Ca²⁺ and Mg²⁺ cations through an organic membrane by the compounds synthesized are discussed.

Full text of DOI:10.1007/s11172-005-0118-6

2308
Russian Chemical Bulletin, International Edition, Vol. 53, No. 10, pp. 2308—2313, October, 2004
✾
New 1,2,4ꢀtriazineꢀcontaining podands: synthesis and properties
O. N. Chupakhin,ꢀ G. L. Rusinov, N. A. Itsikson, D. G. Beresnev, O. V. Fedorova, and I. G. Ovchinnikova
I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
22/20 ul. S. Kovalevskoi, 620219 Ekaterinburg, Russian Federation.
Fax: +7 (343 2) 74 1189. Еꢀmail: chupakhin@ios.uran.ru
A method of oneꢀstep C—C coupling of 1,5ꢀbis(2,6ꢀdimethylphenoxy)ꢀ3ꢀoxapentane (1a)
and 1,8ꢀbis(2,6ꢀdimethylphenoxy)ꢀ3,6ꢀdioxaoctane (1b) with 3ꢀmethylthioꢀ (2) and 3ꢀaminoꢀ
1,2,4ꢀtriazine (3) and 3ꢀarylꢀ1,2,4ꢀtriazinꢀ5ꢀone (6—8) has been described. The reaction of
compounds 1a,b with compounds 2 and 3 in the presence of trifluoroacetic acid results in the
addition of the dimethylphenoxy group to the unsubstituted C(5) carbon atom of the triazine
ring. The reactions of triazinones 6—8 with compounds 1a,b in a mixture of trifluoroacetic acid
and organic anhydrides are accompanied by the acylation of the nitrogen atom adjacent to the
reaction center and affords bis[(3ꢀRꢀ1ꢀacylꢀ5ꢀoxoꢀ1,4,5,6ꢀtetrahydroꢀ1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀ
dimethylphenoxy]ꢀ3ꢀoxapentane or ꢀ3,6ꢀdioxaoctane. The obtained adducts can smoothly be
oxidized under mild conditions to form more stable products of nucleophilic hydrogen substiꢀ
tution in the triazine ring. The extraction and transport of Ca2+ and Mg2+ cations through an
organic membrane by the compounds synthesized are discussed.
Key words: 1,2,4ꢀtriazines, 2,6ꢀdimethylphenylꢀcontaining podands, ANꢀreaction,
H
SN methodology, receptor ability.
A combination of heterocyclic moieties with a flexible
for the synthesis of podands 1a,b containing a nucleoꢀ
philic aromatic moiety.
spacer is of great interest in modern organic chemistry.
These compounds can be used as sensors for cations and
small organic molecules. Moreover, it is known that
heterocycleꢀcontaining receptors with donor groups are
widely used for molecular recognition.1—4 In this work,
the synthesis of new podands based on diꢀ and triethylene
glycol fragments and containing terminal 1,2,4ꢀtriazine
moieties by the direct С—С coupling of hetarenes with
podands is discussed. As a rule, Friedel—Crafts reactions,5
crossꢀcoupling,6 and nucleophilic substitution of good
leaving groups (SNipsoAr)7 are used to create a С—С bond
in (hetero)arenes. Recently, to construct a carbon—carꢀ
bon bond in πꢀdeficient aromatic or heteroaromatic comꢀ
pounds, a methodology of nucleophilic aromatic substiꢀ
tution of hydrogen (SNHAr)8 has been used successfully.
This method is also appropriate for the direct coupling of
1,2,4ꢀtriazines with πꢀexcessive carbonꢀ and heterocyclic
compounds. For example, the reactions of derivatives of
aromatic amines, phenols, and heterocycles with 1,2,4ꢀtriꢀ
azines afford products of nucleophilic addition to the
unsubstituted carbon atom of the azine ring.9—11 Using
the elaborated method, we have succeeded in synthesizꢀ
ing 1,2,4ꢀtriazineꢀcontaining podands.
It should be mentioned that podands 1a,b possess an
insufficient nucleophilicity to interact with 1,2,4ꢀtriazines.
To enhance the electrophilicity of the triazine system, we
used a general method based on the protonation of nitroꢀ
gen atoms. The resulting NHꢀtriazinium salts are more
reactive than the starting 1,2,4ꢀtriazines and react readily
with podand 1. For instance, the reaction of 3ꢀsubstituted
1,2,4ꢀtriazines 2 and 3 with 1a in the presence of triꢀ
fluoroacetic acid affords a product of nucleophilic addiꢀ
tion to a more electrophilic C(5) atom of the triazine ring
(Scheme 1).
The structures of products 4 and 5 were established by
NMR spectroscopy (Table 1). The 1H NMR spectrum of
Table 1. Data of 1H NMR spectra of compounds 4 and 5
Comꢀ
pound
δ (J/Hz)
С(5)—Н С(6)—Н
(d, 1 H) (d, 1 H)
R
Fragment
of podand
4
5
4.44
6.54
2.37
6.93 (s, 2 H, Ar);
(J = 1.8) (J = 1.8) (s, 3 H, 2.97 (m, 4 H,
SMe) CH2—CH2—O);
2.27 (s, 6 H, Me)
Synthesis of 1,2,4ꢀtriazineꢀcontaining podands
4.49
6.65
—
6.92 (s, 2 H, Ar);
3.60—3.86 (m, 4 H,
CH2—CH2—O);
2.24 (s, 6 H, Me)
(J = 2.4) (J = 2.4)
We applied a well known method for alkylation of
2,6ꢀdimethylphenol with Chlorex or polyether ditosylates
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2210—2215, October, 2004.
1066ꢀ5285/04/5310ꢀ2308 © 2004 Springer Science+Business Media, Inc.

Reactions of 1,2,4ꢀtriazinеs with polyethers
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
2309
Scheme 1
Scheme 2
R = SMe (2, 4), NH2 (3, 5)
R1 = Ph (6, 9, 11), 4ꢀTol (7, 12), SEt (8, 10, 13)
R
2 = Me (9, 10), CF3 (11—13)
the products contains a characteristic signal of a proton at
the C(5) atom of the triazine ring at 4.50—4.80 ppm as
doublets with the constant JC(5)H,C(6)H = 1.8 Hz.11 The
signals of aromatic protons of the 2,6ꢀdimethylphenol
fragment are present as a singlet at 6.90—7.00 ppm, indiꢀ
cating the exhaustive heterylation of podand 1a.
Thus, the introduction of a heterocycle into a polyether
substrate is a oneꢀstep reaction of nucleophilic addition
to the unsubstituted atom of the triazine ring. This method
differs substantially from those published previously for
syntheses of podands of this type, which represented a
ring closure of openꢀchain structures and nucleophilic
substitution of good leaving groups in a heterocycle.12—14
As should be expected, 1,2,4ꢀtriazinꢀ5ꢀones exhibited
a lower reactivity in the reactions with podands than
1,2,4ꢀtriazines 2 and 3, and no products of the reaction of
triazines 6—8 with compound 1а in the presence of
trifluoroacetic acid were found in a detector of the NMR
spectrometer.
n = 1 (a), 2 (b)
dized C(6) carbon atom is observed as a singlet at
5.90 ppm. The absence of signals from the terminal pheꢀ
nol groups indicates the 1 : 2 stoichiometry of the reacꢀ
tion. The N(4)—H tautomers are usually characterized15
by the chemical shifts of NH protons at 11.50—11.74 ppm
(Table 2).
Using compounds 9—13, we studied the ability of the
triazine ring to undergo aromatization and showed that
6ꢀsubstituted tetrahydrotriazinꢀ5ꢀones are readily oxidized
to the corresponding 1,2,4ꢀtriazinꢀ5ꢀ(2Н )ꢀones. When a
methanolic solution of compound 11b is refluxed in the
presence of diethylenetriamine, both the triazine ring is
deacylated and tetrahydroꢀsubstituted derivative 14 sponꢀ
taneously oxidizes to form podand 15b. Tetrahydroꢀsubꢀ
stituted derivatives can be isolated only when the reacꢀ
tion occurs in an inert atmosphere. For instance, refluxꢀ
ing a methanolic solution of 11а in the presence of
diethylenetriamine under argon affords compound 14a,
which was isolated by flash chromatography in 26% yield
(Scheme 3).
The 1H NMR spectrum of 14a contains the characterꢀ
istic signals of the C(6)—H and N(1)—H protons in
1,4,5,6ꢀtetrahydroꢀ1,2,4ꢀtriazinꢀ5ꢀone which are present
as doublets with the constant J = 1.2 Hz at 4.43 and
7.75 ppm, respectively. The shift of the signal of the NH
proton in compound 15b toward 13.80 ppm indicates, in
our opinion, the formation of the N(2)H tautomer, being
the most stable16 for 1,2,4ꢀtriazinꢀ5ꢀones.
Thus, 1,2,4ꢀtriazineꢀcontaining podands were syntheꢀ
sized for the first time using the methodology of nucleoꢀ
philic addition and nucleophilic hydrogen substitution in
azines.
Similarly to the reaction with phenols and benzoꢀ
annelated crown ethers,9,10 more reactive 2ꢀacylꢀ1,2,4ꢀ
triazinꢀ5ꢀones, obtained in situ when triazinones 6—8 are
dissolved in a mixture of trifluoroacetic acid and organic
anhydrides, react with podands 1a,b under mild condiꢀ
tions to produce stable adducts 9—13 in high yields
(Scheme 2). In our opinion, the process is similar to the
mechanism of the reaction of triazinones 6—8 with
benzoannelated crown ethers9 and includes nucleophilic
addition of NH salts to the unsubstituted carbon atom of
2ꢀacylꢀ1,2,4ꢀtriazinꢀ5ꢀones followed by acylotropic rearꢀ
rangement to form a more stable N(1)ꢀacylꢀsubstituted
isomer of compounds 9—13.
1
In the H NMR spectrum of the compounds syntheꢀ
sized, the characteristic signal of a proton at the sp3ꢀhybriꢀ

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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Chupakhin et al.
1
Table 2. Data of the H NMR spectra of compounds 9—13
Comꢀ
pound
δ (J/Hz)
n
NH
(1 H)
R2
(3 H)
R1
C(6)—H
(s, 1 H)
Podand
9a
1
11.55
br.s
2.37
2.38 (s)
—
7.88—7.90 (m, 2 H);
7.46—7.56 (m, 3 H)
5.94
5.91
5.82
5.81
5.81
6.86 (s, 2 H, Ar);
3.71—3.74, 3.83—3.85 (both m, 4 H);
2.19 (s, 6 H, Me)
6.82 (s, 2 H, Ar); 3.61 (br.s),
3.67—3.80, 3.81—3.83 (both m, 6 H);
2.21 (s, 6 H, Me)
6.91 (s, 2 H, Ar); 3.77—3.83
(m, 4 H, CH2—CH2—O);
2.16 (s, 6 H, Me)
9b
2
1
2
1
11.84
br.s
7.85—7.91 (m, 2 H);
7.40—7.49 (m, 3 H)
12a
11b
11a
11.78
br.s
7.78, 7.33
(both d, 2 H each, J = 8);
2.36 (s, 3 H)
8.10—8.25 (m, 2 H);
7.91 (m, 3 H)
11.79
br.s
—
6.88 (br.s, 2 H, Ar);
3.60—3.84 (m, 8 H, CH2—CH2—O);
2.13 (br.s, 6 H, Me)
11.81
s
—
7.89—7.91 (m, 2 H);
7.44—7.54 (m, 3 H)
6.87 (s, 2 H, Ar);
3.76 (t, 2 H, CH2, J = 4.4);
3.87 (t, 2 H, CH2OAr, J = 4.4);
2.21 (s, 6 H, Me)
10a
13a
1
1
11.50
br.s
2.24 (s)
—
3.09 (q, 2 H, J = 7.2);
1.31 (t, 3 H, J = 7.2)
5.86
5.68
6.83 (s, 2 H, Ar);
3.76 (t, 2 H, CH2, J = 3.8);
3.88 (t, 2 H, CH2OAr, J = 3.8);
2.19 (s, 6 H, Me)
11.70
br.s
3.00 (q, 2 H);
1.32 (t, 3 H)
6.82 (s, 2 H, Ar);
3.75 (t, 2 H, CH2, J = 4.4);
3.87 (t, 2 H, CH2OAr, J = 4.4);
2.20 (s, 6 H, Me)
Table 3. Extraction constants (Kex) of Mg2+ and Ca2+ cations by
triazineꢀcontaining podands and the stoichiometry of the comꢀ
plexes
Liquid extraction of Ca2+ and Mg2+ picrates
The liquid extraction of Ca2+ and Mg2+ picrates from
an aqueous phase to dichloromethane at 25 °C was studꢀ
ied to compare the complexation ability of triazineꢀconꢀ
taining podands with 1a,b. The distribution constant of
picrate between the aqueous and organic phases (D) is a
quantitative characteristic of the extraction ability of molꢀ
ecules 9, 11, and 13 (Table 3). Since a complex with the
same composition is formed due to the reaction, a stoꢀ
ichiometric coefficient m and an extraction constant Kex
depend linearly on D (Fig. 1) and can be calculated by the
known equation17
Comꢀ
pound
R1 R2
n
Mg2+
Kex
Ca2+
M : L
Kex
/mol–1
M : L
/mol–1
9a
9b
11a
11b
13a
Ph Me
Ph Me
Ph CF3
Ph CF3
SEt CF3
1
2
1
2
1
185
0
0
372
132
1 : 1
—
—
1 : 2
1 : 1
213
0
0
274
326
1 : 2
—
—
1 : 1
1 : 2
It is established that the stoichiometry of a complex
depends on the polyether chain length. For instance, when
compounds 11а and 13а bind Mg2+ cations, a 1 : 1 comꢀ
plex is formed. However, two ligand molecules are inꢀ
volved in the formation of a complex with a more bulky
Ca2+ cation. An increase in the polyether chain length
(for example, in compound 11b) results in binding of the
Ca2+ cation with one "host" molecule. It is of interest that
two podand molecules are involved in the formation of
complex 11b with the Mg2+ cation.
logD = log Kex + mlog[L],
(1)
L is ligand.
To determine D, a decrease in the absorbance of the
aqueous phase was measured by spectrophotometry.
It is found that podands 1a,b do not extract Ca2+ and
Mg2+ picrates from the aqueous to organic phases. The
introduction of triazine moieties induces receptor propꢀ
erties toward the metal cations. The extraction conꢀ
stants (Kex) of the Ca2+ and Mg2+ cations by the triazineꢀ
containing podands are presented in Table 3.
The extraction constant depends on both the length of
a polyether chain and the nature of substituent R2. Comꢀ

Reactions of 1,2,4ꢀtriazinеs with polyethers
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
2311
Scheme 3
logD
a
3
–1.2
1
–1.6
2
–2.0
–3.6
–3.4
–3.2
log[L]
logD
–0.8
–1.2
–1.6
–2.0
b
2
3
1
–4.0
–3.6
–3.2 log[L]
Fig. 1. Dependences of the logarithms of the distribution conꢀ
stants between the aqueous and organic phases (D) on the logaꢀ
rithm of the ligand concentration for the formation of a complex
with Mg2+ (a) and Ca2+ (b) cations of compounds 9a (1), 11b (2),
and 13a (3).
pounds with n = 1 bind Ca2+ cations better than Mg2+
cations. The study of the extraction ability of triazineꢀ
containing podands with n = 2 shows a higher Kex value
for binding Mg2+ cations. The substituent effect can be
considered by a comparison of the receptor properties of
compounds 9 and 11. In the case of R2 = CF3, extracꢀ
tion is carried out only by podands with a long polyether
chain (compound 11b). The inverse dependence is obꢀ
served for R2 = Me. It is found that more flexible and
longer podand 9b does not extract Са2+ and Mg2+ catꢀ
ions. The highest difference in extraction ability for the
Ca2+ and Mg2+ cations is observed for compound 13a
(see Table 3).
selectivity, are presented in Table 4. These data show that
an increase in the length of the polyether moiety deꢀ
Table 4. Membranotropic properties of the triazineꢀcontaining
podands
Comꢀ
pound
n
v*•10–7
/mol h–1
CaII
MgII
1a
9а
9b
11а
11b
13а
1
1
2
1
2
1
15.9
27.7
0.0
1.9
0.0
42.9
23.0
6.8
5.5
5.8
Transport of Ca2+ and Mg2+ cations
through a liquid organic membrane
The synthesized compounds are highly lipophilic and,
hence, can be used as carriers through a liquid membrane.
The transfer rate of Ca2+ and Mg2+ cations, as well as
28.6
28.6
* v is the transfer rate through the liquid membrane.

2312
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Chupakhin et al.
C, 73.92; H, 8.43. C22H30O4. Calculated (%): C, 73.74; H, 8.38.
1H NMR (DMSOꢀd6), δ: 6.98—7.00 (m, 4 H, Ar); 6.87—6.90
(m, 2 H, Ar); 3.57—3.86 (m, 12 H, ArOCH2CH2); 2.22—2.24
(m, 12 H, Me).
Synthesis of 1,5ꢀbis[2,6ꢀdimethylꢀ4ꢀ(3ꢀRꢀ1,2,4ꢀtriazineꢀ5ꢀ
yl)phenoxy]ꢀ3ꢀoxapentanes (4, 5) (general procedure). 3ꢀRꢀ1,2,4ꢀ
Triazine (1.04 mmol) and podand (0.52 mmol) were dissolved in
a mixture (4.5 mL) of dichloromethane and trifluoroacetic acid
(2 : 1). The reaction mixture was refluxed with a reflux conꢀ
denser for 20 h, and then the solvent was evaporated in vacuo.
An oily residue was washed with water and neutralized with an
aqueous solution of NaHCO3 to pH 8. The precipitate that
formed was filtered off.
1,5ꢀBis[2,6ꢀdimethylꢀ4ꢀ(3ꢀmethylthioꢀ1,2,4ꢀtriazinꢀ5ꢀ
yl)phenoxy]ꢀ3ꢀoxapentane (4). The yield was 40%, m.p.
96—98 °C. Found (%): C, 59.00; H, 6.47; N, 14.54.
C28H36N6O3S2. Calculated (%): C, 59.13; H, 6.38; N,14.78.
1,5ꢀBis[4ꢀ(3ꢀaminoꢀ1,2,4ꢀtriazinꢀ5ꢀyl)ꢀ2,6ꢀdimethylphenꢀ
oxy]ꢀ3ꢀoxapentane (5). The yield was 62%, m.p. 110—112 °C.
Found (%): C, 62.02; H, 6.98; N, 21.89. C26H34N8O3. Calcuꢀ
lated (%): C, 61.64; H, 6.76; N, 22.12.
Synthesis of 1,5ꢀbis[4ꢀ(3ꢀRꢀ1ꢀacylꢀ5ꢀoxoꢀ1,4,5,6ꢀtetraꢀ
hydroꢀ1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3ꢀoxapentanes
and 1,8ꢀbis[4ꢀ(3ꢀRꢀ1ꢀacylꢀ5ꢀoxoꢀ1,4,5,6ꢀtetrahydroꢀ1,2,4ꢀ
triazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3,6ꢀdioxaoctanes (9—13a,b)
(general procedure). 3ꢀRꢀ1,2,4ꢀTriazinꢀ5(2H )ꢀone (1.16 mmol)
and podand (0.58 mmol) were dissolved in a mixture (2 mL) of
trifluoroacetic acid and organic anhydride (1 : 1). The reaction
mixture was stirred for 24 h at room temperature, and the solꢀ
vent was removed in vacuo. The product was purified by flash
chromatography.
creases the membranotropic ability. For instance, comꢀ
pounds 9b and 11b with longer polyether chains (n = 2)
do not transfer Ca2+ cations. Compound 1a is the most
efficient carrier of Mg2+ cations. However, this podand
cannot be used as a selective cation carrier. The introducꢀ
tion of triazine substituents decreases the transfer rate but
increases the selectivity with respect to a certain type of
cations. For instance, compound 11b can be used for
selective transport of Mg2+ cations through an organic
membrane.
Experimental
The reaction course and purity of the synthesized products
were monitored by TLC on Sorbfil PTSKhꢀUF plates using a
methanol—methylene dichloride (1 : 20) mixture as eluent.
1Н NMR spectra were recorded on a Bruker DRX 400 specꢀ
trometer in DMSOꢀd6 or CDCl3 using Me4Si as internal stanꢀ
dard. Elemental analysis was carried out on a Carlo Erba EA 1108
automated analyzer. Preparative flash chromatography was perꢀ
formed on Kieselgel Woelm DC silica gel using a methylene
dichloride—methanol (20 : 1) mixture as eluent.
The membranotropic studies were carried out according to a
procedure described previously.18 Cations of Ca2+ and Mg2+
were transferred through a liquid organic membrane using a
10–4 M solution of triazineꢀcontaining podand in dichloroꢀ
methane at 20 0.5 °C for 6 h with magnetic stirring at a velocity
of 100 rotation min–1
.
Metal picrates were synthesized in situ by the dissolution of
metal chlorides in picric acid. Extraction was carried out at
1,5ꢀBis[4ꢀ(1ꢀacetylꢀ5ꢀoxoꢀ3ꢀphenylꢀ1,4,5,6ꢀtetrahydroꢀ
1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3ꢀoxapentane (9а).
The yield was 70%, m.p. 198—200 °C. Found (%): C, 67.93;
H, 6.25; N, 10.89. C42H44N6O7. Calculated (%): C, 67.73;
H, 5.95; N, 11.28.
1,8ꢀBis[4ꢀ(1ꢀacetylꢀ5ꢀoxoꢀ3ꢀphenylꢀ1,4,5,6ꢀtetrahydroꢀ
1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3,6ꢀdioxaoctane (9b).
The yield was 47%, m.p. 87—88 °C. Found (%): C, 67.00;
H, 5.99; N, 10.73. C44H48N6O8. Calculated (%): C, 66.99;
H, 6.13; N, 10.65.
concentrations of a "host" molecule of 1.0•10–4, 2.5•10–4
,
5.0•10–4, and 10•10–4 mol L–1. A 10–4 M aqueous solution of
picrate (2 mL) and a solution (2 mL) of podand in CH2Cl2
were mixed in a cell, and the mixture was stored in a thermoꢀ
stat for 30 min at 20 °C. After this, the mixture was shaken
for 2 min. Measurements were performed in three parallel
experiments. The extraction ability was determined spectrophoꢀ
tometrically by a decrease in the absorbance of the aqueous
phase.
1,5ꢀBis(2,6ꢀdimethylphenoxy)ꢀ3ꢀoxapentane (1a). Sodium
hydroxide (4.0 g, 0.1 mol) was added to a stirred solution of
2,6ꢀdimethylphenol (12.2 g, 0.1 mol) in DMF (150 mL). The
reaction mixture was stirred in an inert atmosphere until NaOH
dissolved completely. Then β,β´ꢀdichlorodiethyl ether (7.15 g,
0.05 mol) dissolved in DMF (20 mL) was added dropwise to the
reaction mixture for 30 min. The reaction mixture was heated to
110—115 °C and stirred for 20 h at this temperature. The preꢀ
cipitate that formed was filtered off and washed with water. The
product was purified by column chromatography using CH2Cl2
as eluent. The yield was 60%, m.p. 31—32 °C. Found (%):
C, 76.19; H, 8.45. C20H26O3. Calculated (%): C, 76.43; H, 8.28.
1H NMR (DMSOꢀd6), δ: 6.99 (m, 4 H, Ar); 6.89 (dd, 2 H, Ar,
J = 6.9 Hz, J´ = 8.0 Hz); 3.88—3.90 (m, 4 H, ArOCH2CH2);
3.75—3.90 (m, 4 H, ArOCH2CH2); 2.24 (s, 12 H, Me).
1,8ꢀBis(2,6ꢀdimethylphenoxy)ꢀ3,6ꢀdioxaoctane (1b) was synꢀ
thesized similarly to 1a from 2,6ꢀdimethylphenol (12.2 g,
0.1 mol) and triethylene glycol ditosylate (24.25 g, 0.05 mol).
The product was isolated by column chromatography on Al2O3
using chloroform as eluent. The yield was 76%, oil. Found (%):
1,5ꢀBis[4ꢀ(1ꢀacetylꢀ5ꢀoxoꢀ3ꢀethylthioꢀ1,4,5,6ꢀtetrahydroꢀ
1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3ꢀoxapentane (10а).
The yield was 43%, m.p. 178—180 °C. Found (%): C, 57.45;
H, 5.89; N, 11.73. C34H44N6O7S2. Calculated (%): C, 57.28;
H, 6.22; N, 11.79.
1,5ꢀBis[4ꢀ(5ꢀoxoꢀ3ꢀphenylꢀ1ꢀtrifluoroacetylꢀ1,4,5,6ꢀtetraꢀ
hydroꢀ1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3ꢀoxapentane
(11а). The yield was 63%, m.p. 223—226 °C. Found (%):
C, 58.86; H, 4.14; N, 9.92. C42H38F6N6O7. Calculated (%):
C, 59.15; H, 4.49; N, 9.85.
1,5ꢀBis{4ꢀ[5ꢀoxoꢀ3ꢀ(4ꢀtolyl)ꢀ1ꢀtrifluoroacetylꢀ1,4,5,6ꢀ
tetrahydroꢀ1,2,4ꢀtriazinꢀ5ꢀonꢀ6ꢀyl]ꢀ2,6ꢀdimethylphenoxy}ꢀ3ꢀ
oxapentane (12а). The yield was 52%. Found (%): C, 59.78;
H, 4.56; N, 9.83. C44H42F6N6O7. Calculated (%): C, 60.00;
H, 4.81; N, 9.54.
1,5ꢀBis[4ꢀ(3ꢀethylthioꢀ5ꢀoxoꢀ1ꢀtrifluoroacetylꢀ1,4,5,6ꢀ
tetrahydroꢀ1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3ꢀoxaꢀ
pentane (13а). The yield was 75%, m.p. 85—86 °C. Found (%):
C, 50.01; H, 4.29; N, 9.89. C34H38F6N6O7S2. Calculated (%):
C, 49.75; H, 4.67; N, 10.24.

Reactions of 1,2,4ꢀtriazinеs with polyethers
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
2313
1,5ꢀBis[4ꢀ(5ꢀoxoꢀ3ꢀphenylꢀ1,4,5,6ꢀtetrahydroꢀ1,2,4ꢀtriꢀ
azinꢀ6ꢀyl)ꢀ2,6ꢀdimethylphenoxy]ꢀ3ꢀoxapentane (14a). Comꢀ
pound 11a (30 mg, 0.045 mmol) was dissolved in methanol
(2 mL), and diethylenetriamine (12.9 mg, 1.36 mmol) was added
to the resulting solution. The reaction mixture was refluxed with
a reflux condenser in an inert atmosphere for 5 h. The solvent
was removed in vacuo. The product was purified by flash chroꢀ
matography. The yield was 26%. Found (%): C, 69.07; H, 6.10;
N, 12.72. C38H40N6O5. Calculated (%): C, 68.98; H, 6.24;
N, 12.57. 1H NMR (DMSOꢀd6), δ: 10.77 (br. s, 1 H, NH); 7.75
(d, 1 H, N(1)—H, J = 1.2 Hz); 7.72—7.74 (m, 2 H, Ph);
7.34—7.37 (m, 3 H, Ph); 6.98 (s, 2 H, Ar); 4.43 (d, 1 H, C(6)—H,
J = 1.2 Hz); 3.89, 3.79 (both t, 2 H each, CH2, J = 5.2 Hz); 2.25
(s, 6 H, Me).
1,8ꢀBis[4ꢀ(5ꢀoxoꢀ3ꢀphenylꢀ1,2,4ꢀtriazinꢀ6ꢀyl)ꢀ2,6ꢀdimethylꢀ
phenoxy]ꢀ3,6ꢀdioxaoctane (15b). Compound 9b (30 mg,
0.033 mmol) was dissolved in methanol (2 mL), and diethyleneꢀ
triamine (7.58 mg, 0.86 mmol) was added to the resulting soluꢀ
tion. The reaction mixture was refluxed with a reflux condenser
in an inert atmosphere for 3 h. The solvent was purified by
flash chromatography. The yield was 65%, m.p. 176—178 °C.
Found (%): C, 68.87; H, 6.11; N, 11.98. C40H40N6O6. Calcuꢀ
lated (%): C, 68.56; H, 5.75; N, 11.99. 1H NMR (DMSOꢀd6), δ:
13.8 (br.s, 1 H, NH); 8.48 (m, 2 H, Ph); 7.55 (m, 3 H, Ph); 8.13
(s, 2 H, Ar); 3.60—3.79 (m, 4 H, ArOCH2CH2); 3.54 (br.s, 2 H,
ArOCH2CH2), 2.24 (s, 6 H, Me).
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This work was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ
32332), the International Scientific Technical Center
(Grant 708), and the Russian Academy of Sciences (Proꢀ
gram "Chemistry and Physics of Supramolecular Systems
and Atomic Clusters").
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Received July 23, 2004;
in revised form September 3, 2004