Synthesis and structures of 4,6-disubstituted 2-(5-methyl-1,2,4-oxadiazol- 3-yl)-1,3,5-triazines

Article abstract of DOI:10.1007/s11172-006-0056-y

New 1,2,4-oxadiazolyl-1,3,5-triazines were synthesized from amidoximes derived from sym-triazine mononitriles. The structure of one of the resulting compounds was studied in detail by X-ray diffraction.

Full text of DOI:10.1007/s11172-006-0056-y

1900
Russian Chemical Bulletin, International Edition, Vol. 54, No. 8, pp. 1900—1906, August, 2005
Synthesis and structures of 4,6ꢀdisubstituted
2ꢀ(5ꢀmethylꢀ1,2,4ꢀoxadiazolꢀ3ꢀyl)ꢀ1,3,5ꢀtriazines
A. A. Chesnyuk,a S. N. Mikhaylichenko,b L. D. Konyushkin,c S. I. Firgang,c and V. N. Zaplishnyia
ꢀ
aKuban State Agricultural University,
13 ul. Kalinina, 350044 Krasnodar, Russian Federation.
Fax: +7 (861 2) 20 2935. Eꢀmail: vlad_zplv@mail.ru
bUniversity of Toronto at Scarborough,
1265 Military Trail, Toronto, M1C 1A4 Canada.
Eꢀmail: mikhay@utsc.utoronto.ca
cN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation
New 1,2,4ꢀoxadiazolylꢀ1,3,5ꢀtriazines were synthesized from amidoximes derived from
symꢀtriazine mononitriles. The structure of one of the resulting compounds was studied in
detail by Xꢀray diffraction.
Key words: amidoximes of the symꢀtriazine series, 4,6ꢀdisubstituted 2ꢀacetoxyamidinoꢀ
1,3,5ꢀtriazines, 4,6ꢀdisubstituted 2ꢀ(5ꢀmethylꢀ1,2,4ꢀoxadiazolꢀ3ꢀyl)ꢀ1,3,5ꢀtriazines, cyꢀ
clization.
Scheme 1
1,2,4ꢀOxadiazole and symꢀtriazine derivatives possess
a wide spectrum of biological activities.1—3 It was of interꢀ
est to synthesize new compounds containing both these
heterocycles.
We synthesized (Scheme 1) oxadiazolyltriazines 4 from
nitriles 1. Amidoximes 2a—i were prepared by the reacꢀ
tion of nitriles 1 with a 20% excess of hydroxylamine in an
waterꢀethanol solution.
It is known4,5 that the hydroxy group in aromatic
amidoximes smoothly reacts with carboxylic acid anꢀ
hydrides and chlorides to form the corresponding acylated
derivatives. The reactions of compounds 2a—i with acetyl
and isobutyroyl chlorides, which were used in a 5% excess
with respect to the stoichiometric amount, under mild
conditions (solutions in anhydrous benzene, 5—20 °C) in
the presence of an excess of pyridine produced acylated
derivatives 3a—m.
Refluxing of solutions of compounds 3a—m in glacial
acetic acid for 2—5 h smoothly afforded the correspondꢀ
ing substituted 1,2,4ꢀoxadiazolylꢀ1,3,5ꢀtriazines 4a—m in
good yields.
The crystal structure of one of the resulting oxaꢀ
diazolylꢀ1,3,5ꢀtriazines, viz., compound 4d containing the
amino and diethylamino groups at positions 4 and 6 of the
triazine ring, was established by Xꢀray diffraction study of
a single crystal grown from ethanol. A projection of the
crystal structure of compound 4d is shown in Fig. 1. The
interatomic distances and bond angles are given in Tables 1
and 2, respectively.
Compound
R1
R2
1a, 2a, 3a,b, 4a,b
1b, 2b, 3c, 4c
1c, 2c, 3d,e, 4d,e
1d, 2d, 3f,g, 4f,g
1e, 2e, 3h,i, 4h,i
1f, 2f, 3j, 4j
1g, 2g, 3k, 4k
1h, 2h, 3l, 4l
1i, 2i, 3m, 4m
morpholino
NMe2
NH2
EtNPh
NH2
OMe
OMe
OEt
piperidino
morpholino
NMe2
NEt2
EtNPh
NPh2
morpholino
pyrrolidino
NPh2
piperidino
3a,c,d,f,h,j—m, 4a,c,d,f,h,j—m: R3 = Me;
3b,e,g,i, 4b,e,g,i: R3 = Pri
Molecule 4d is virtually planar (see Fig. 1). The bond
angles at the nitrogen atoms in the symꢀtriazine fragment
(see Table 2) vary from 112.9(2)° (N(1)) to 121.6(2)°
(N(4a)) and differ substantially from the bond angles at
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1845—1850, August, 2005.
1066ꢀ5285/05/5408ꢀ1900 © 2005 Springer Science+Business Media, Inc.

2ꢀ(5ꢀMethylꢀ1,2,4ꢀoxadiazolꢀ3ꢀyl)ꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 8, August, 2005
1901
C(9)
C(7)
C(8)
O(1a)
N(7a)
H(51a)
N(5a)
N(4)
N(1a)
C(5a)
C(4a)
C(10)
C(3)
C(6a)
N(2)
C(2a)
N(2a)
H(52a)
H(52)
N(3)
C(1)
C(1a)
N(3a)
N(6)
N(6a)
C(2)
C(5)
O(1)
C(6)
C(3a)
C(4)
N(7)
C(8a)
C(10a)
N(5)
H(51)
N(1)
N(4a)
C(9a)
C(7a)
Fig. 1. Crystal structure of compound 4d; the centrosymmetric dimers linked to each other by H bonds are shown.
Table 1. Interatomic distances in molecule 4d
potentially biologically active connected 1,2,4ꢀoxadiꢀ
azolylꢀ1,3,5ꢀtriazines. The crystal structure of compound
4d was established by Xꢀray diffraction.
Bond
d/Å
Bond
d/Å
O(1)—C(5)
O(1)—N(7)
N(1)—C(1)
N(1)—C(2)
N(2)—C(2)
N(2)—C(3)
N(3)—C(1)
N(3)—C(3)
N(4)—C(3)
N(4)—C(9)
N(4)—C(7)
N(5)—C(2)
N(6)—C(5)
N(6)—C(4)
N(7)—C(4)
C(1)—C(4)
C(5)—C(6)
C(7)—C(8)
C(9)—C(10)
1.336(2)
1.413(2)
1.323(2)
1.365(2)
1.338(2)
1.350(2)
1.325(2)
1.362(2)
1.336(2)
1.465(3)
1.468(3)
1.326(2)
1.289(2)
1.371(2)
1.301(2)
1.479(3)
1.468(3)
1.484(4)
1.494(5)
O(1A)—C(5A)
O(1A)—N(7A)
N(1A)—C(1A)
N(1A)—C(2A)
N(2A)—C(2A)
N(2A)—C(3A)
N(3A)—C(1A)
N(3A)—C(3A)
N(4A)—C(3A)
N(4A)—C(9A)
N(4A)—C(7A)
N(5A)—C(2A)
N(6A)—C(5A)
N(6A)—C(4A)
N(7A)—C(4A)
C(1A)—C(4A)
C(5A)—C(6A)
C(7A)—C(8A)
C(9A)—C(10A)
1.335(2)
1.414(2)
1.323(2)
1.355(2)
1.341(2)
1.348(2)
1.326(2)
1.358(2)
1.339(2)
1.457(3)
1.465(3)
1.333(2)
1.292(2)
1.369(2)
1.291(2)
1.485(3)
1.488(3)
1.503(4)
1.461(6)
Experimental
The IR spectra were recorded on a Specordꢀ75 IR spectroꢀ
photometer in Nujol mulls. The 1H NMR spectra were meaꢀ
sured on a Bruker DRXꢀ500 radiospectrometer in DMSOꢀd6.
The mass spectra were obtained on a Finnigan MAT INCOS50
instrument (ionizing radiation energy was 70 eV). Elemental
analysis was carried out on a CarloꢀErba model 1106 analyzer.
The progress of the reactions was monitored and the purities of
the compounds were checked by TLC on Silufol UVꢀ250 plates
in a 1 : 1 acetone—hexane system.
Xꢀray diffraction study of 4ꢀaminoꢀ6ꢀdiethylaminoꢀ2ꢀ(5ꢀmeꢀ
thylꢀ1,2,4ꢀoxadiazolꢀ3ꢀyl)ꢀ1,3,5ꢀtriazine (4d). Crystals were
grown from an ethanolic solution. The prismatic crystals belong
to the triclinic system; the unit cell parameters: a = 10.027(2) Å,
b =10.978(2) Å, c = 12.182(2) Å, α = 80.64(3)°, β = 77.50(3)°,
γ = 76.83(3)°, Z = 4, d = 1.308 mg m–3, V = 1265.6(4) Å3, space
group P–1. Xꢀray diffraction data were collected on an autoꢀ
mated EnrafꢀNonius CAD 4 diffractometer (βꢀfiltered MоꢀKα
radiation) using the θ/2θ scanning technique. A total of
4085 reflections were measured, of which 1507 reflections were
with I > 2δ(I ). The structure of 4d was solved by direct methods
using the SHELXTL program package6 and refined anisotropiꢀ
cally (isotropically for H atoms) to R = 0.0308, Rw = 0.0743.
The starting mononitriles 1a—i were prepared according to
a procedure described earlier.7 All reagents were purified by
crystallization from an appropriate solvent or by fractional disꢀ
tillation immediately before use. The solvents were purified and
dried according to known procedures.8
the carbon atoms, which vary from 124.6(2)° (C(3)) to
128.6(2)° (C(1)). In the oxadiazole fragments, the bond
angles at the N(7) and N(7a) atoms are 103.0(2) and
103.2(2)°, respectively (see Table 2). The bond angles at
the C(4) and C(5) atoms of the oxadiazole ring have close
values (113.9(2) and 112.1(2)°, respectively). The crystal
structure of compound 4d consists of centrosymmetric
dimers linked to each other by the hydrogen bonds beꢀ
tween the N(2) and N(2a) atoms of the triazine ring and
the H(52a) and H(52) atoms of the amine groups. The
hydrogen bond lengths are 2.08(2) Å. The geometric paꢀ
rameters of molecules 4d in the dimer are identical within
the experimental error.
2ꢀHydroxyamidinoꢀ4,6ꢀdimorpholinoꢀ1,3,5ꢀtriazine (2a). An
aqueous solution (10 mL) containing hydroxylamine hydrochloꢀ
ride (4.3 mmol) and sodium hydrocarbonate (4.3 mmol) was
allowed to stand until CO2 bubbling ceased, after which 2ꢀcyanoꢀ
4,6ꢀdimorpholinoꢀ1,3,5ꢀtriazine (1a) (3.6 mmol) and ethanol
(20 mL) were successively added. The reaction mixture was
refluxed for 2 h and cooled. The solvent was evaporated to
dryness in vacuo, and the precipitate that formed was thoroughly
washed with water and dried to a constant weight. After purifiꢀ
To summarize, we synthesized new amidoximes of the
1,3,5ꢀtriazine series, performed their acylation, and carꢀ
ried out cyclization of acyloxyamidinotriazines accompaꢀ
nied by dehydration giving rise to previously unknown

1902
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 8, August, 2005
Chesnyuk et al.
Table 2. Bond angles in compound 4d
Angle
ω/deg
Angle
ω/deg
Angle
ω/deg
C(5)—O(1)—N(7)
C(1)—N(1)—C(2)
C(2)—N(2)—C(3)
C(1)—N(3)—C(3)
C(3)—N(4)—C(9)
C(3)—N(4)—C(7)
C(9)—N(4)—C(7)
C(5)—N(6)—C(4)
C(4)—N(7)—O(1)
N(1)—C(1)—N(3)
N(1)—C(1)—C(4)
N(3)—C(1)—C(4)
N(5)—C(2)—N(2)
N(5)—C(2)—N(1)
N(2)—C(2)—N(1)
N(4)—C(3)—N(2)
N(4)—C(3)—N(3)
N(2)—C(3)—N(3)
107.00(13)
112.89(15)
114.97(16)
113.50(15)
120.73(17)
121.15(17)
117.98(18)
103.95(16)
103.03(14)
128.60(17)
117.03(16)
114.35(16)
117.42(18)
117.20(17)
125.38(17)
118.00(16)
117.49(17)
124.51(16)
N(7)—C(4)—N(6)
N(7)—C(4)—C(1)
N(6)—C(4)—C(1)
N(6)—C(5)—O(1)
N(6)—C(5)—C(6)
O(1)—C(5)—C(6)
N(4)—C(7)—C(8)
N(4)—C(9)—C(10)
C(5A)—O(1A)—(7A)
C(1A)—N(1A)—(2A)
C(2A)—N(2A)—(3A)
C(1A)—N(3A)—(3A)
C(3A)—N(4A)—(9A)
113.88(17)
122.33(17)
123.71(16)
112.13(17)
130.0(2)
117.92(18)
113.4(2)
113.9(3)
106.34(15)
113.39(16)
114.85(16)
113.74(16)
121.56(19)
N(1A)—C(1A)—N(3A)
N(1A)—C(1A)—C(4A)
N(3A)—C(1A)—C(4A)
N(5A)—C(2A)—N(2A)
N(5A)—C(2A)—N(1A)
N(2A)—C(2A)—N(1A)
N(4A)—C(3A)—N(2A)
N(4A)—C(3A)—N(3A)
N(2A)—C(3A)—N(3A)
N(7A)—C(4A)—N(6A)
N(7A)—C(4A)—C(1A)
N(6A)—C(4A)—C(1A)
N(6A)—C(5A)—O(1A)
N(6A)—C(5A)—C(6A)
O(1A)—C(5A)—C(6A)
N(4A)—C(7A)—C(8A)
N(4A)—C(9A)—(10A)
127.91(18)
116.60(16)
115.45(17)
117.11(18)
117.55(18)
125.34(17)
118.68(17)
116.93(17)
124.40(16)
114.52(17)
122.68(17)
122.75(17)
112.74(18)
129.8(2)
C(3A)—N(4A)—C(7A) 120.25(18)
C(9A)—N(4A)—C(7A) 117.7(2)
C(5A)—N(6A)—C(4A) 103.16(16)
C(4A)—N(7A)—O(1A) 103.23(15)
117.5(2)
113.6(2)
112.1(3)
cation by crystallization from ethanol, amidoxime 2a was obꢀ
tained in a yield of 0.9 g (80%).
Compounds 2b—i were prepared under analogous condiꢀ
tions and crystallized from appropriate solvents.
The characteristics of compounds 2a—i are given in
Tables 3 and 4.
(5 mL) was slowly (dropwise) added with vigorous stirring to a
solution containing amidoxime 2a (3.2 mmol), anhydrous benꢀ
zene (10 mL), and pyridine (5 mL) at 5—10 °C. Then the reacꢀ
tion mixture was stirred at this temperature for 1 h and allowed
to stand at room temperature for 12 h. The solvent was removed
in vacuo, and the precipitate was repeatedly washed with water
and purified by crystallization from acetonitrile. Compound 3a
was obtained in a yield of 0.85 g (75%).
2ꢀAcetoxyamidinoꢀ4,6ꢀdimorpholinoꢀ1,3,5ꢀtriazine (3a).
A solution of acetyl chloride (3.4 mmol) in anhydrous benzene
Table 3. Characteristics of compounds 2, 3, and 4
Comꢀ
pound
M.p./°C
Yield
(%)
Found
Calculated
Molecular
formula
Molecular
ion,
(%)
m/z (Irel (%))
С
Н
N
2а
2b
2c
2d
2e
2f
268—269
80
75
67
82
90
70
85
68
90
46.70
46.59
42.83
42.65
42.70
42.65
63.80
63.64
59.98
59.80
42.64
42.51
45.50
45.37
62.39
62.27
55.23
55.06
6.05
6.19
6.86
6.71
6.87
6.71
6.00
6.14
4.88
4.71
5.67
5.55
6.07
5.92
5.33
5.18
7.66
7.59
31.57
31.70
43.65
43.53
43.40
43.53
25.85
25.98
30.69
30.52
33.20
33.06
35.20
35.28
23.87
23.99
31.94
32.11
C12H19N7O3
C8H15N7O
C8H15N7O
C20H23N7O
C16H15N7O
C9H14N6O3
C9H14N6O2
C18H18N6O2
C14H23N7O
309 (100)
225 (70)
225 (80)
377 (75)
321 (60)
254 (75)
238 (60)
350 (100)
305 (70)
>225
(decomp.)
240—241
184—185
272—273
209—210
270—271
234—235
2g
2h
2i
>220
(decomp.)
(to be continued)

2ꢀ(5ꢀMethylꢀ1,2,4ꢀoxadiazolꢀ3ꢀyl)ꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 8, August, 2005
1903
Table 3 (continued)
Comꢀ
pound
M.p./°C
Yield
(%)
Found
Calculated
Molecular
formula
Molecular
ion,
(%)
m/z (Irel (%))
С
Н
N
3a
3b
3c
3d
3e
3f
248—249
214—215
207—208
244—245
215—216
149—150
152—153
252—253
179—180
175—176
134—135
168—169
186—187
222—223
171—172
181—182
205—206
123—124
119—120
84—85
75
65
91
80
68
85
69
93
87
70
65
66
63
76
62
70
65
60
62
57
68
71
71
60
65
75
47.99
47.85
50.79
50.65
45.05
44.93
45.00
44.93
48.90
48.79
63.13
62.99
64.55
64.40
59.69
59.50
61.50
61.36
44.70
44.59
47.25
47.13
61.36
61.20
55.37
55.31
50.60
50.44
53.30
53.17
48.02
48.18
48.35
48.18
52.17
51.97
65.97
65.81
67.28
67.11
62.69
62.60
64.38
64.33
47.55
47.47
50.20
50.37
64.33
64.16
58.22
58.34
6.17
6.03
6.50
6.64
6.53
6.41
6.49
6.41
7.03
7.17
6.15
6.01
6.66
6.53
4.83
4.72
5.26
5.41
5.31
5.44
5.90
5.75
5.00
5.14
7.40
7.25
5.88
5.74
6.55
6.41
6.20
6.07
6.22
6.07
7.06
6.90
5.83
5.77
6.44
6.34
4.27
4.38
5.23
5.13
5.19
5.07
5.44
5.38
5.00
4.85
6.95
7.04
28.08
27.91
25.62
25.85
36.87
36.68
36.85
36.68
33.09
33.20
23.50
23.38
22.01
21.91
26.80
26.99
25.21
25.05
28.22
28.37
30.17
29.99
21.30
21.42
28.36
28.22
29.30
29.42
27.30
27.13
39.49
39.34
39.49
39.34
35.50
35.36
24.56
24.42
22.95
22.83
28.20
28.39
26.37
26.26
30.36
30.20
32.19
32.05
22.57
22.45
29.94
29.77
C14H21N7O4
C16H25N7O4
C10H17N7O2
C10H17N7O2
C12H21N7O2
C22H25N7O2
C24H29N7O2
C18H17N7O2
C20H21N7O2
C11H16N6O4
C11H16N6O3
C20H20N6O3
C16H25N7O2
C14H19N7O3
C16H23N7O3
C10H15N7O
C10H15N7O
C12H19N7O
C22H23N7O
C24H27N7O
C18H15N7O
C20H19N7O
C11H14N6O3
C11H14N6O2
C20H18N6O2
C16H23N7O
351 (80)
379 (50)
267 (70)
267 (50)
295 (20)
419 (40)
447 (45)
363 (25)
391 (55)
296 (40)
280 (35)
392 (40)
347 (45)
333 (80)
361 (90)
249 (70)
249 (30)
277 (70)
401 (50)
429 (60)
345 (50)
373 (60)
278 (65)
262 (80)
374 (60)
329 (80)
3g
3h
3i
3j
3k
3l
3m
4a
4b
4c
4d
4e
4f
4g
4h
4i
245—246
138—139
164—165
128—129
165—166
156—157
4j
4k
4l
4m

1904
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 8, August, 2005
Chesnyuk et al.
Table 4. Spectroscopic data for amidoximes 2
Comꢀ
poꢀ
und
IR, ν/cm–1
1H NMR, δ (J/Hz)
С=С, C=N,
conj.
NH2, OH
СОС
=N—OH
(s)
Other protons
2а
2b
2c
1500, 1550,
1655
1520, 1535,
1650
1510, 1570,
1670
3350, 3460
3320, 3440
—
—
—
9.98
9.94
3.55—3.90 (m, 16 H, NCH2, OCH2); 5.35 (s, 2 H, NH2)
3.15 (s, 12 H, NMe2); 5.33 (s, 2 H, NH2)
3310, 3380,
3450
10.00
1.05—1.12 (t, 6 H, СH2Me, J = 8.2); 3.50—3.60 (q, 4 H,
CH2Me, J = 7.1); 5.50 (s, 2 H, NH2CNOH); 6.85 (br.s,
2 H, NH2 in the triazine ring)
2d
1530, 1580,
1660
3360, 3480
—
10.12
1.00—1.15 (t, 6 H, СH2Me, J = 8.2); 3.80—4.00 (q, 4 H,
CH2Me, J = 7.5); 5.32 (s, 2 H, NH2 in the triazine ring);
7.15—7.40 (m, 10 H, H arom.)
2e
2f
1525, 1550,
1675
1520, 1560,
1650
3350, 3375,
3460
3340, 3470
—
10.05
10.20
10.13
5.30 (s, 2 H, NH2CNOH); 7.05 (br.s, 2 H, NH2);
7.20—7.40 (m, 10 H, H arom.)
3.60—3.85 (m, 8 H, NCH2, OCH2);
3.95 (s, 3 H, OMe); 5.45 (br.s, 2 H, NH2)
1.95—2.05 (m, 4 H, СH2 of pyrrolidine);
3.50—3.65 (m, 4 H, NCH2 of pyrrolidine); 3.90 (s, 3 H,
OMe); 5.35 (s, 2 H, NH2)
1.20—1.30 (t, 3 H, ОСH2Me, J = 8.1); 4.20—4.30 (q,
2 H, ОCH2Me, J= 7.2); 5.25 (s, 2 H, NH2); 7.20—7.40 (m,
10 H, H arom.)
1055, 1120
1060, 1150
2g
1585, 1655
3380, 3445
3370, 3490
3390, 3485
2h
2i
1570, 1680
1530, 1655
1080, 1130
—
10.30
9.90
1.50—1.75 (m, 12 H, СH2 of piperidyl); 3.65—3.85 (m, 8 H,
NCH2); 5.30 (s, 2 H, NH2)
Table 5. Spectroscopic characteristics of acylated amidoximes 3
Comꢀ
poꢀ
und
IR, ν/cm–1
1H NMR, δ (J/Hz)
С=С,
C=N,
conj.
NH2
C=O
СОС
NH2
Other protons
3a
3b
3c
3d
3e
1550,
1600
1540,
1590
1530,
1640
1550,
1620
1555,
1620
3340
3330
3350
1750
1740
1730
1740
1740
—
—
—
—
—
6.70
(s)
6.65
(s)
6.35
(s)
6.60
(s)
2.05 (s, 3 H, СОMe); 3.60—3.85 (m, 16 H, NCH2, OCH2)
1.00—1.15 (m, 6 H, СHMe2); 2.65—2.75 (m, 1 H, CHMe2);
3.60—3.85 (m, 16 H, NCH2, OCH2)
2.15 (s, 3 H, СОMe); 3.20 (s, 12 H, NMe2)
3380,
3470
3375,
3480
1.00—1.15 (t, 6 H, СH2Me, J = 8.3); 2.15 (s, 3 H, СОMe);
3.50—3.65 (q, 4 H, CH2Me, J = 7.0)
1.05—1.20 (m, 12 H, СHMe2, СH2Me); 2.70—2.80 (m, 1 H,
CHMe2); 3.50—3.65 (m, 4 H, CH2Me); 7.15 (br.s, 2 H, NH2
in the triazine ring)
6.55
(s)
3f
1570,
1630
1575,
1640
1530,
1590,
1660
1560,
1600,
1670
3380
3375
1720
1730
1720
—
—
—
6.50
(br.s)
6.53
(br.s)
5.85
(s)
1.00—1.20 (t, 6 H, СH2Me, J = 8.3); 2.10 (s, 3 H, СОMe);
3.75—3.95 (q, 4 H, CH2Me, J = 7.7); 7.15—7.45 (m, 10 H, H arom.)
0.95—1.25 (m, 12 H, СHMe2, СH2Me); 2.60—2.75 (m, 1 H, CHMe2);
3.80—4.00 (m, 4 H, CH2Me); 7.20—7.50 (m, 10 H, H arom.)
2.07 (s, 3 H, СОMe); 6.80 (br.s, 2 H, NH2 in the triazine
ring); 7.20—7.50 (m, 10 H, H arom.)
3g
3h
3360,
3380
3i
3370,
3400
1720
—
5.95
(s)
1.05—1.25 (m, 6 H, СHMe2); 2.60—2.80 (m, 1 H, CHMe2);
6.90 (br.s, 2 H, NH2 in the triazine ring); 7.25—7.50 (m,
10 H, H arom.)
(to be continued)

2ꢀ(5ꢀMethylꢀ1,2,4ꢀoxadiazolꢀ3ꢀyl)ꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 8, August, 2005
1905
Table 5 (continued)
Comꢀ
poꢀ
und
IR, ν/cm–1
1H NMR, δ (J/Hz)
С=С,
C=N,
conj.
NH2
C=O
СОС
NH2
Other protons
3j
1510,
1570,
1620
1580,
1640
1530,
1630
1550,
1620
3350
3375
1715
1050,
1130
6.45
(br.s)
2.20 (s, 3 H, СОMe); 3.65—3.90 (m, 8 H,
NCH2, OCH2); 3.95 (s, 3 H, OMe)
3k
3l
1725
1725
1720
1055,
1145
1050,
1120
—
6.30
(br.s)
6.47
(br.s)
6.25
(s)
1.90—2.00 (m, 4 H, СH2 of pyrrolidine); 2.15 (s, 3 H, СОMe);
3.55—3.70 (m, 4 H, NCH2 of pyrrolidine); 3.90 (s, 3 H, OMe)
1.25—1.35 (t, 3 H, СH2Me, J = 8.2); 2.20 (s, 3 H, СОMe);
4.25—4.40 (q, 2 H, CH2Me, J = 7.3); 7.15—7.55 (m, 10 H, H arom.)
1.55—1.75 (m, 12 H, СH2 of piperidine); 2.20 (s, 3 H, СОMe);
3.65—3.90 (m, 8 H, NCH2)
3380,
3500
3400
3m
Table 6. Spectroscopic characteristics of oxadiazolyltriazines 4a—m
Comꢀ
poꢀ
und
IR, ν/cm–1
1H NMR, δ (J/Hz)
Other protons
С=С,
Other
Me
(s)
C=N,
conj.
groups
4a
4b
4c
4d
4e
1560,
1600
1510,
1580
1545,
1610
1570,
1620
1530,
1600
—
—
—
2.65
—
3.65—3.90 (m, 16 H, NCH2, OCH2)
1.31—1.40 (m, 6 H, СHMe2); 2.63—2.75 (m, 1 H, CHMe2);
3.60—3.85 (m, 16 H, NCH2, OCH2)
3.20 (s, 12 H, NMe2)
2.67
2.65
—
3310
(NH2)
3300
1.07—1.15 (m, 6 H, NCH2Me); 3.50—3.62 (m, 4 H, NCH2);
7.05, 7.20 (both s, 2 H each, NH2 in the triazine ring)
1.05—1.15 (m, 6 H, NCH2Me); 1.32—1.40 (m, 6 H, СHMe2);
2.60—2.70 (m, 1 H, CHMe2); 3.50—3.65 (m, 4 H, NCH2);
7.10 (br.s, 2 H, NH2 in the triazine ring)
4f
1580,
1610
1570,
1600
1545,
1600
1550,
1640
1500,
1550
1540,
1580
1575,
1590
1560,
1620
—
—
2.65
—
1.05—1.25 (t, 6 H, СH2Me, J = 8.2); 3.80—4.00 (q, 4 H, CH2Me, J = 8.0);
7.20—7.50 (m, 10 H, H arom.)
1.05—1.25 (m, 6 H, СH2Me); 1.35—1.45 (m, 6 H, СHMe2); 2.65—2.75 (m,
1 H, CHMe2); 3.45—3.65 (m, 4 H, CH2Me); 7.20—7.50 (m, 10 H, H arom.)
7.23 (br.s, 2 H, NH2 in the triazine ring); 7.25—7.50 (m, 10 H, H arom.)
4g
4h
4i
3370 (br.s,
NH2)
3400
(NH2)
1020, 1150
(СОС)
1030, 1080
(СОС)
1070, 1120
(СОС)
—
2.61
—
1.25—1.40 (m, 6 H, СHMe2); 2.55—2.67 (m, 1 H, CHMe2); 7.10—7.40 (m,
10 H, H arom.); 7.15 (br.s, 2 H, NH2 in the triazine ring)
3.60—3.85 (m, 8 H, NCH2, OCH2); 3.90 (s, 3 H, OMe)
4j
2.60
2.70
2.60
2.65
4k
4l
1.90—2.05 (m, 4 H, СH2 of pyrrolidine); 3.55—3.75 (m, 4 H, NCH2
of pyrrolidine); 3.95 (s, 3 H, OMe)
1.20—1.30 (t, 3 H, СH2Me, J = 8.3); 4.20—4.35 (q, 2 H, CH2Me, J = 7.1);
7.20—7.45 (m, 10 H, H arom.);
4m
1.55—1.75 (m, 12 H, СH2 of piperidine); 3.70—3.90 (m, 8 H, NCH2 of piperidine)
Compounds 3c,d,f,h,j—m were synthesized analogously.
Compounds 3b,e,g,i were prepared with the use of isobutyroyl
chloride.
The spectroscopic characteristics of compounds 3a—m are
given in Table 5.
2ꢀ(5ꢀMethylꢀ1,2,4ꢀoxadiazolꢀ3ꢀyl)ꢀ4,6ꢀdimorpholinoꢀ1,3,5ꢀ
triazine (4a). A solution of compound 3a (1.4 mmol) in glacial
acetic acid (10 mL) was refluxed for 2.5 h. Then the acetic acid
was concentrated to dryness under reduced pressure. The ground
dry residue was washed on a filter with water until neutral and

1906
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 8, August, 2005
Chesnyuk et al.
then dried to a constant weight in vacuo at 56 °C. After purificaꢀ
tion by crystallization from ethanol, oxadiazolyltriazine 4a was
obtained in a yield of 0.36 g (76%).
Compounds 4b—m were synthesized analogously.
The spectroscopic characteristics of compounds 4a—m are
given in Table 6.
[Bull. Min. Sci. Nat. Acad. Sci. Republic of Kazakhstan, Div.
Chem. Sci.], 2000, No. 4, 41 (in Russian).
3. G. M. Pogosyan, V. A. Pankratov, V. N. Zaplishnyi, and
S. G. Matsoyan, Politriaziny [Polytriazines], Izdꢀvo AN
Arm. SSR, 1987, 614 pp. (in Russian).
4. Methoden der organischen Chemie, HoubenꢀWeyl, Georg
Thieme Verlag, Stuttgart, 1955, 944 p.
We thank V. E. Zavodnik (L. Ya. Karpov Institute of
Physical Chemistry, Moscow) for performing Xꢀray difꢀ
fraction analysis and interpreting the Xꢀray data.
5. L. A. Kayukova, Khim. Geterotsikl. Soedin., 2003, 253 [Chem.
Heterocycl. Compd., 2003 (Engl. Transl.)].
6. G. M. Sheldrick, Computational Crystallography, Oxford Univ.
Press, Oxford, 1982, 506 р.
7. A. A. Chesnyuk, S. N. Mikhaylichenko, V. S. Zavodnov, and
V. N. Zaplishnyi, Khim. Geterotsikl. Soedin., 2002, 197 [Chem.
Heterocycl. Compd., 2002 (Engl. Transl.)].
References
1. A. G. Tyrkov, Izv. Vuzov, Ser. Khim. i Khim. Tekh. [Proceedꢀ
ings of Universities: Chemistry and Chemical Technology], 2003,
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Received November 9, 2004;
in revised form June 15, 2005