Synthesis of 2,4-diaryloxy-6-trinitromethyl-1,3,5-triazines

Article abstract of DOI:10.1134/S1070428007030232

Reactions of 2,4,6-trichloro-1,3,5-triazine with trinitromethane salts in the presence of phenol and substituted phenols gave previously unknown 2,4-diaryloxy-6-trinitromethyl-1,3,5-triazines. Their yields strongly depend on the nature and position of sub

Full text of DOI:10.1134/S1070428007030232

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 3, pp. 454–457. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © V.V. Bakharev, A.A. Gidaspov, E.V. Kachanovskaya, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 3,
pp. 455–458.
Synthesis of 2,4-Diaryloxy-6-trinitromethyl-1,3,5-triazines
V. V. Bakharev, A. A. Gidaspov, and E. V. Kachanovskaya
Samara State Technical University, ul. Molodogvardeiskaya 244, Samara, 443100 Russia
e-mail: knil@sstu.smr.ru
Received May 4, 2006
Abstract—Reactions of 2,4,6-trichloro-1,3,5-triazine with trinitromethane salts in the presence of phenol and
substituted phenols gave previously unknown 2,4-diaryloxy-6-trinitromethyl-1,3,5-triazines. Their yields
strongly depend on the nature and position of substituent in the benzene ring of phenol.
DOI: 10.1134/S1070428007030232
During the last 10–15 years, the chemistry of
trinitromethyl derivatives of 1,3,5-triazine has been
extensively studied [1]. Several procedures have been
proposed for the synthesis of trinitromethyl-1,3,5-tri-
azines having various substituents; these procedures
are based on destructive nitration of 1,3,5-triazine
derivatives [2, 3] and nucleophilic replacement of al-
ready existing trinitromethyl groups [4–6]. Up to now,
the only method for the synthesis of aryloxytrinitro-
methyl-1,3,5-triazines was nucleophilic substitution of
the trinitromethyl group in 2-amino(alkoxy)-4,6-bis-
(trinitromethyl)-1,3,5-triazines by the action of phenol
and substituted phenols [6]. 2,4-Diaryloxy-6-trinitro-
methyl-1,3,5-triazines were not reported previously. In
the present communication we describe a new proce-
dure for the preparation of 2,4-diaryloxy-6-trinitro-
methyl-1,3,5-triazines, which allows simultaneous
introduction of trinitromethyl and aryloxy groups into
the 1,3,5-triazine ring.
a series of substituted phenols in acetone at 0–30°C we
obtained 2,4-diaryloxy-6-trinitromethyl-1,3,5-triazines
I–XVII (Scheme 1). The yield of products I–XVII
does not depend on the nature of cation in the tri-
nitromethane salt but is completely determined by the
substituent in the initial phenol: electron-withdrawing
substituents (NO2, COOCH3, Hlg) in the benzene ring
of phenol ensure higher yields as compared with un-
substituted phenol and phenols having electron-donor
substituents (e.g., methyl group). The position of
substituent with respect to the hydroxy group is also
important: the yield of 2,4-diaryloxy-6-trinitromethyl-
1,3,5-triazines increases in the series ortho-substituted
phenols ≈ unsubstituted phenol < meta-substituted
phenols < para-substituted phenols.
The reaction begins with nucleophilic replacement
of one chlorine atom in the 2,4,6-trichloro-1,3,5-
triazine molecule by trinitromethyl group. By special
experiments we showed that neither 2,4-dichloro-6-
phenoxy-1,3,5-triazine (XVIII) nor 2-chloro-4,6-di-
phenoxy-1,3,5-triazine (XIX) reacted with potassium
By treatment of 2,4,6-trichloro-1,3,5-triazine with
trinitromethane salts in the presence of phenol and
Scheme 1.
R
Cl
N
OH
O
N
M+ C(NO2)3–
+
N
N
N
N
+
R
O2N
O2N
Cl
Cl
O
R
NO2
I–XVII
I, R = H; II, R = o-Me; III, R = o-MeOCO; IV, R = o-I; V, R = o-Cl; VI, R = o-O2N; VII, R = m-Me; VIII, R = m-MeOCO; IX, R =
m-Cl; X, R = m-O2N; XI, R = p-Me; XII, R = p-t-Bu; XIII, R = p-Cl; XIV, R = p-Br; XV, R = p-MeOCO; XVI, R = p-O2N,
XVII, R = 2,4-(O2N)2; M = K, Na, Li, NH4, Me2NH2, Et3NH, Me4N, Et3MeN.
454

SYNTHESIS OF 2,4-DIARYLOXY-6-TRINITROMETHYL-1,3,5-TRIAZINES
455
trinitromethanide with formation of compound I under
the conditions ensuring formation of compounds I–
XVII. Presumably, introduction of the first trinitro-
methyl group into the 1,3,5-triazine ring is the rate-
determining stage of the entire process leading to
2,4-diaryloxy-6-trinitromethyl-1,3,5-triazines. The sub-
sequent steps are considerably faster; after complete
consumption of 2,4,6-trichloro-1,3,5-triazine, increase
of the reaction time did not result in increased yield of
compounds I–XVII.
mixture was stirred at 19–22°C until 2,4,6-trichloro-
1,3,5-triazine disappeared (19–30 h) according to the
TLC data (Silufol UV-254 plates). The mixture was fil-
tered, the filtrate was partially evaporated, the residue
was poured under stirring into 100 ml of water, and the
precipitate was filtered off, washed with propan-2-ol
and water, and dried in air. Compound VII was
isolated by extraction into dichloroethane. The extract
was washed with water and dried over sodium sulfate,
the solvent was distilled off, and the residue was dried
under reduced pressure.
However, some experimental data are difficult to
rationalize in terms of nucleophilic replacement of
chlorine in 2,4,6-trichloro-1,3,5-triazine by the action
of trinitromethanide ion and phenols. First, GLC anal-
ysis of the reaction mixtures revealed the presence of
small amounts of chlorotrinitromethane (2–4 mol %
with respect to 2,4,6-trichloro-1,3,5-triazine). Second,
we failed to obtain the corresponding 2,4-diaryloxy-6-
trinitromethyl-1,3,5-triazines from a number of phe-
nols having strong electron-donor groups (R = o-HO,
m-HO, p-HO, o-MeO, m-MeO, p-MeO, p-AcNH). The
reaction was accompanied by fast (at 15–30°C) or
slow (at –10 to –15°C) decomposition with gas evolu-
tion and formation of cyanuric acid, inorganic salts,
and unidentified phenol oxidation products.
2,4-Diphenoxy-6-trinitromethyl-1,3,5-triazine
(I). Yield 32%, mp 82–83°C. IR spectrum, ν, cm–1:
3066, 2876, 1628, 1598, 1574, 1538, 1488, 1466, 1386,
1326, 1288, 1234, 1192, 1164, 1114, 1072, 1022, 1004,
1
988, 914, 844, 830, 798, 764. H NMR spectrum,
δ, ppm: 6.70–7.84 m (10H, Harom). Found, %: C 46.35;
H 2.50; N 20.28. C16H10N6O8. Calculated, %: C 46.39;
H 2.43; N 20.29.
2,4-Bis(2-methylphenoxy)-6-trinitromethyl-
1,3,5-triazine (II). Yield 20%, mp 84–86°C. IR spec-
trum, ν, cm–1: 3028, 2936, 1644, 1600, 1580, 1540,
1496, 1480, 1402, 1334, 1294, 1252, 1184, 1126, 1112,
996, 912, 834, 804, 792, 750, 720. 1H NMR spectrum,
δ, ppm: 2.06 s (6H, CH3), 6.99–7.25 m (8H, Harom).
Found, %: C 48.87; H 3.19; N 19.00. C18H14N6O8. Cal-
culated, %: C 48.82; H 3.24; N 19.04.
However, nucleophilic replacement of the trinitro-
methyl group in 2-amino-4,6-bis(trinitromethyl)-1,3,5-
triazines readily occurs by the action of the same
phenols and gives the corresponding 2-amino-4-aryl-
oxy-6-trinitromethyl-1,3,5-triazines in high yields [6].
These data suggest that the reaction of 2,4,6-trichloro-
1,3,5-triazine with trinitromethane salts in the presence
of various phenols involves formation of radical inter-
mediates.
Dimethyl 2,2'-[6-trinitromethyl-1,3,5-triazine-
2,4-diyldioxy]dibenzoate (III). Yield 25%, mp 134–
136°C (decomp.). IR spectrum, ν, cm–1: 3032, 1726,
1638, 1630, 1598, 1578, 1550, 1472, 1464, 1456, 1392,
1304, 1280, 1214, 1138, 1096, 1076, 1014, 813, 796,
1
764. H NMR spectrum, δ, ppm: 3.72 s (6H, OCH3),
7.30–8.00 m (8H, Harom). Found, %: C 45.34; H 2.58;
N 15.76. C20H14N6O12. Calculated, %: C 45.29; H 2.66;
N 15.85.
EXPERIMENTAL
The IR spectra were measured in KBr (except for
2,4-Bis(2-iodophenoxy)-6-trinitromethyl-1,3,5-
triazine (IV). Yield 24%, mp 119–121°C (decomp.).
IR spectrum, ν, cm–1: 3040, 1632, 1604, 1596, 1570,
1556, 1546, 1516, 1464, 1444, 1386, 1338, 1292, 1270,
1242, 1212, 1126, 1096, 1050, 1032, 998, 912, 840,
compound VII which was examined as thin film) on
1
an Avatar spectrophotometer. The H NMR spectra
were recorded on a Bruker AM-300 spectrometer at
300 MHz using tetramethylsilane as internal reference.
1
826, 794, 758. H NMR spectrum, δ, ppm: 6.98–
Compounds XVIII and XIX were synthesized by
7.91 m (8H, Harom). Found, %: C 28.77; H 1.26;
N 12.63. C16H8I2N6O8. Calculated, %: C 28.85;
H 1.21; N 12.62.
the procedure described in [7].
2,4-Diaryloxy-6-trinitromethyl-1,3,5-triazines I–
XVII (general procedure). Potassium trinitromethan-
ide, 5.67–9.45 g (0.03–0.05 mol), and the correspond-
ing phenol, 0.025–0.04 mol, were added under stirring
to a solution of 1.84 g (0.01 mol) of 2,4,6-trichloro-
1,3,5-triazine in 13 ml of acetone at 19–22°C. The
2,4-Bis(2-chlorophenoxy)-6-trinitromethyl-1,3,5-
triazine (V). Yield 23%, mp 64–66°C. IR spectrum, ν,
cm–1: 2916, 1634, 1600, 1572, 1556, 1512, 1484, 1464,
1394, 1332, 1296, 1220, 1210, 1108, 1066, 1000, 914,
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BAKHAREV et al.
456
(decomp.). IR spectrum, ν, cm–1: 3030, 2980, 1638,
1
868, 842, 794, 760, 726. H NMR spectrum, δ, ppm:
7.18–7.39 m (8H, Harom). Found, %: C 39.72; H 1.69;
N 17.44. C16H8Cl2N6O8. Calculated, %: C 39.77;
H 1.67; N 17.39.
1600, 1584, 1542, 1514, 1472, 1396, 1292, 1228, 1200,
1
1176, 1118, 1102, 1028, 996, 914, 844, 792. H NMR
spectrum, δ, ppm: 2.27 s (6H, CH3), 7.13 s (8H, Harom).
Found, %: C 48.84; H 3.27; N 19.10. C18H14N6O8. Cal-
culated, %: C 48.82; H 3.24; N 19.04.
2,4-Bis(2-nitrophenoxy)-6-trinitromethyl-1,3,5-
triazine (VI). Yield 34%, mp 170–172°C (decomp.).
IR spectrum, ν, cm–1: 3116, 2872, 1638, 1600, 1566,
1534, 1458, 1396, 1362, 1352, 1330, 1296, 1276, 1208,
1172, 1154, 1112, 1090, 1004, 960, 916, 884, 868, 858,
2,4-Bis(4-tert-butylphenoxy)-6-trinitromethyl-
1,3,5-triazine (XII). Yield 50%, mp 165–167°C
(decomp.). IR spectrum, ν, cm–1: 3062, 2962, 2904,
2870, 1628, 1596, 1574, 1540, 1508, 1466, 1388, 1326,
1288, 1270, 1204, 1174, 1112, 1086, 1014, 988, 918,
1
836, 798, 780, 750, 708. H NMR spectrum, δ, ppm:
7.48–8.19 m (8H, Harom). Found, %: C 38.04; H 1.70;
N 22.21. C16H8N8O12. Calculated, %: C 38.11; H 1.60;
N 22.22.
1
840, 798. H NMR spectrum, δ, ppm: 1.26 s (18H,
CH3), 7.13 d and 7.30 d (8H, Harom, J = 6.9 Hz). Found,
%: C 54.82; H 5.02; N 15.90. C24H26N6O8. Calculated,
%: C 54.75; H 4.98; N 15.96.
2,4-Bis(3-methylphenoxy)-6-trinitromethyl-
1,3,5-triazine (VII). Yield 40%, viscous liquid. IR
spectrum, ν, cm–1: 2932, 1640, 1632, 1606, 1580,
1544, 1530, 1494, 1474, 1396, 1350, 1338, 1294, 1248,
2,4-Bis(4-chlorophenoxy)-6-trinitromethyl-1,3,5-
triazine (XIII). Yield 56%, mp 105–107°C. IR spec-
trum, ν, cm–1: 3056, 2976, 2960, 2908, 2872, 1614,
1608, 1578, 1550, 1514, 1466, 1396, 1344, 1316, 1276,
1210, 1184, 1120, 1096, 1024, 998, 980, 968, 900,
860, 824, 812, 782. 1H NMR spectrum, δ, ppm: 7.25 d
and 7.43 d (8H, Harom, J = 7.5 Hz). Found, %: C 39.73;
H 1.66; N 17.42. C16H8Cl2N6O8. Calculated, %:
C 39.77; H 1.67; N 17.39.
1
1234, 1162, 1012, 996, 944, 828, 796. H NMR spec-
trum, δ, ppm: 2.25 s (6H, CH3), 6.95–7.12 m (8H,
Harom). Found, %: C 48.77; H 3.26; N 19.07.
C18H14N6O8. Calculated, %: C 48.82; H 3.24; N 19.04.
Dimethyl 3,3'-[6-trinitromethyl-1,3,5-triazine-
2,4-diyldioxy]dibenzoate (VIII). Yield 54%, mp 114–
116°C. IR spectrum, ν, cm–1: 3078, 3000, 2954, 1726,
1628, 1596, 1572, 1544, 1462, 1446, 1384, 1288, 1270,
1184, 1108, 1076, 988, 928, 906, 868, 832, 798, 760.
1H NMR spectrum, δ, ppm: 3.84 s (6H, OCH3), 7.44–
7.86 m (8H, Harom). Found, %: C 45.31; H 2.71;
N 15.83. C20H14N6O12. Calculated, %: C 45.29; H 2.66;
N 15.85.
2,4-Bis(4-bromophenoxy)-6-trinitromethyl-1,3,5-
triazine (XIV). Yield 60%, mp 126–128°C. IR spec-
trum, ν, cm–1: 3072, 1640, 1608, 1592, 1580, 1538,
1490, 1412, 1388, 1296, 1266, 1196, 1176, 1076, 1022,
1000, 940, 908, 832, 808, 792, 728. 1H NMR spectrum,
δ, ppm: 7.18 d and 7.57 d (8H, Harom, J = 7.9 Hz).
Found, %: C 33.65; H 1.40; N 14.63. C16H8Br2N6O8.
Calculated, %: C 33.59; H 1.41; N 14.69.
2,4-Bis(3-chlorophenoxy)-6-trinitromethyl-1,3,5-
triazine (IX). Yield 52%, mp 78–80°C. IR spectrum,
ν, cm–1: 3110, 3080, 2880, 1634, 1628, 1602, 1590,
1580, 1570, 1550, 1542, 1520, 1510, 1482, 1468, 1440,
1388, 1354, 1336, 1296, 1274, 1242, 1208, 1168, 1108,
1080, 1012, 996, 930, 854, 828, 796, 780, 728. 1H NMR
spectrum, δ, ppm: 7.20–7.42 m (8H, Harom). Found, %:
C 39.81; H 1.63; N 17.42. C16H8Cl2N6O8. Calculated,
%: C 39.77; H 1.67; N 17.39.
Dimethyl 4,4'-[6-trinitromethyl-1,3,5-triazine-
2,4-diyldioxy]dibenzoate (XV). Yield 58%, mp 158–
159°C (decomp.). IR spectrum, ν, cm–1: 3064, 2964,
1726, 1632, 1602, 1580, 1554, 1510, 1460, 1444, 1388,
1290, 1238, 1216, 1200, 1168, 1124, 1024, 1000, 956,
1
912, 864, 848, 828, 812, 794, 768, 720, 696. H NMR
spectrum, δ, ppm: 3.83 s (6H, OCH3), 7.34 d and
8.00 d (8H, Harom, J = 8.2 Hz). Found, %: C 45.25;
H 2.69; N 15.89. C20H14N6O12. Calculated, %: C 45.29;
H 2.66; N 15.85.
2,4-Bis(3-nitrophenoxy)-6-trinitromethyl-1,3,5-
triazine (X). Yield 59%, mp 160–162°C (decomp.). IR
spectrum, ν, cm–1: 3140, 3125, 1640, 1606, 1580,
1565, 1542, 1464, 1390, 1358, 1284, 1245, 1216, 1115,
1086, 1000, 946, 834, 796, 740. 1H NMR spectrum, δ,
ppm: 7.71–8.12 m (8H, Harom). Found, %: C 38.14;
H 1.62; N 22.31. C16H8N8O12. Calculated, %: C 38.11;
H 1.60; N 22.22.
2,4-Bis(4-nitrophenoxy)-6-trinitromethyl-1,3,5-
triazine (XVI). Yield 65%, mp 169–170°C (decomp.).
IR spectrum, ν, cm–1: 3118, 3088, 1612, 1540, 1488,
1338, 1288, 1254, 1238, 1210, 1200, 1164, 1108, 1014,
990, 954, 914, 860, 842, 818, 798. 1H NMR spectrum,
δ, ppm: 7.52 d and 8.30 d (8H, Harom, J = 8.6 Hz).
Found, %: C 38.08; H 1.56; N 22.15. C16H8N8O12. Cal-
culated, %: C 38.11; H 1.60; N 22.22.
2,4-Bis(4-methylphenoxy)-6-trinitromethyl-
1,3,5-triazine (XI). Yield 49%, mp 124–126°C
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SYNTHESIS OF 2,4-DIARYLOXY-6-TRINITROMETHYL-1,3,5-TRIAZINES
457
2,4-Bis(2,4-dinitrophenoxy)-6-trinitromethyl-
REFERENCES
1,3,5-triazine (XVII). Yield 27%, mp 102–105°C. IR
spectrum, ν, cm–1: 3128, 3100, 2892, 1636, 1604,
1576, 1546, 1488, 1454, 1386, 1354, 1292, 1256, 1228,
1132, 1094, 1072, 1000, 920, 904, 852, 832, 792, 744,
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1
724, 712. H NMR spectrum, δ, ppm: 7.92 d and
8.70 d (4H, Harom, J = 8.7 Hz), 8.90 s (2H, Harom).
Found, %: C 32.37; H 1.06; N 23.49. C16H6N10O16.
Calculated, %: C 32.34; H 1.02; N 23.57.
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Reactions of 2,4-dichloro-6-phenoxy-1,3,5-tri-
azine (XVIII) and 2-chloro-4,6-diphenoxy-1,3,5-tri-
azine (XIX) with potassium trinitromethanide. Tri-
nitromethane potassium salt, 7.56 g (0.04 mol), was
added to a solution of 0.01 mol of compound XVIII or
XIX in 13 ml of acetone under stirring at 19–22°C.
The mixture was stirred for 48 h at 19–22°C, the
precipitate was filtered off and washed with acetone on
a filter, the filtrate was partially evaporated, the residue
was poured into 100 ml of water, and the precipitate
was filtered off and washed with water. No compound
I was detected by TLC among the products.
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