Trinitromethylation reactions of chloro-1,3,5-triazines

Article abstract of DOI:10.1007/s11172-009-0294-x

Reactions of chloro-1,3,5-triazines with trinitromethane salts were studied. Depending on conditions, trinitromethane salts used and special additives, six types of 2,4,6-trichloro-1,3,5-triazine trinitromethylation reactions were revealed, namely, bis-trinitromethylation-nitro-nyloxylation, bis-trinitromethylation-amination, bis-trinitromethylation-hydroxylation, trinitromethylation-dialkoxylation, trinitromethylation-diaryloxylation, and trinitromethylation-alkoxylation-aryloxylation. The mechanisms of reactions are proposed.

Full text of DOI:10.1007/s11172-009-0294-x

Russian Chemical Bulletin, International Edition, Vol. 58, No. 10, pp. 2154—2163, October, 2009
2154
Trinitromethylation reactions of chloroꢀ1,3,5ꢀtriazines
A. A. Gidaspov, V. V. Bakharev, and I. K. Kukushkin
Samara State Technical University,
244 ul. Molodogvardeiskaya, 443100 Samara, Russian Federation.
Eꢀmail: knil@sstu.smr.ru
Reactions of chloroꢀ1,3,5ꢀtriazines with trinitromethane salts were studied. Depending on
conditions, trinitromethane salts used and special additives, six types of 2,4,6ꢀtrichloroꢀ1,3,5ꢀ
triazine trinitromethylation reactions were revealed, namely, bisꢀtrinitromethylation—nitroꢀ
nyloxylation, bisꢀtrinitromethylation—amination, bisꢀtrinitromethylation—hydroxylation, triꢀ
nitromethylation—dialkoxylation, trinitromethylation—diaryloxylation, and trinitromethylꢀ
ation—alkoxylation—aryloxylation. The mechanisms of reactions are proposed.
Key words: chloroꢀ1,3,5ꢀtriazines, 2,4,6ꢀtrichloroꢀ1,3,5ꢀtriazine, trinitromethane salts, triꢀ
nitromethylation, bisꢀ and monotrinitromethylꢀ1,3,5ꢀtriazines.
Polynitromethylꢀ1,3,5ꢀtriazines are of interest as enerꢀ
Institute of Organic Chemistry, Russian Academy of Sciꢀ
ences, these works were initiated in 1953, for a long period
of time being headed by S. S. Novikov. Trinitromethyl
anion is ambident, so generally, its interaction with
halogenated organic compounds (if occurs) may proceed
giving two types of products, i.e., trinitromethyl derivaꢀ
tives (Cꢀalkylation) and dinitromethanenitronic acid esꢀ
ters (Oꢀalkylation).24—27 Nitronic esters (with rare excepꢀ
tion28) are unstable and highly susceptible to decomꢀ
position.24—26
In its chemical properties, 2,4,6ꢀtrichloroꢀ1,3,5ꢀtriꢀ
azine (cyanuric chloride (CC))17 is similar to acid chloꢀ
rides. The latter interact with polynitro compound salts to
yield unstable mixed nitronic anhydrides.29,30 This is exꢀ
actly how CC reacts in acetone or acetonitrile with a range
of (NO2)3C–Ct+ trinitromethane salts (1), in which
Ct+ is cation of metal (Ct+ = K+ (1a), Na+ (1b), Ag+ (1c)),
tertiary amine (Ct+ = Me3NH+ (1d), Et3NH+ (1e)) either
quaternary ammonium (Ct+ = Me4N+ (1f), Et4N+ (1g),
MeEt3N+ (1h), Bu4N+ (1i)). After a certain time lag (typꢀ
ically 20—40 min) decomposition began as evidenced by
the sharp temperature increase, darkening of the mixture,
rapid gas evolution and the reactor content overflow deꢀ
spite cooling (ice + CaCl2). There were specific features
indicating at least one of three possible steps of chlorine
substitution in CC involving formation of nitronic ester
whose decomposition controls the process.
getic materials as well as intermediates in synthesis of
the latter1 and bioactive compounds.2,3 To date the known
synthetic methods for polynitromethylꢀ1,3,5ꢀtriazines are
based on the building of 1,3,5ꢀtriazine cycle from the moiꢀ
eties carrying polynitromethyl group (through the cycloꢀ
trimerization of polynitro acetonitriles and imido esters4—7
)
either on generation of trinitromethyl group in 1,3,5ꢀtriꢀ
azine derivatives (the nitration of methylꢀ1,3,5ꢀtriazines8
and the destructive nitration of dicarboxymethyl derivaꢀ
tives of 1,3,5ꢀtriazine6,9). To synthesize bisꢀ and monoꢀ
trinitromethylꢀ1,3,5ꢀtriazines with various substituents on
the ring, the method has been proposed that is based on
replacing trinitromethyl groups in trinitromethylꢀ1,3,5ꢀ
triazines under the action of nucleophilic reagents.10—15
As yet there are no literature data on the routes to triꢀ
nitromethylꢀ1,3,5ꢀtriazines involving nucleophilic reꢀ
placement of chlorine atoms in chloroꢀ1,3,5ꢀtriazines reꢀ
acted with trinitromethane salts. In the comprehensive
reviews on the chemistry of 1,3,5ꢀtriazines16—19 and in the
review papers on the synthesis of 1,3,5ꢀtriazine derivatives
exploiting chloroꢀ1,3,5ꢀtriazine reactions,20—23 no menꢀ
tion has been made of the chloroꢀ1,3,5ꢀtriazine reactions
with trinitromethane salts. This work attempts to generalꢀ
ize the results obtained while studying chloroꢀ1,3,5ꢀtriꢀ
azine trinitromethylation with trinitromethane salts (the
results mostly belong to 1980´s—90´s but could not be
reported earlier).
Surprisingly, CC was found to react in this manner not
with all trinitromethane salts. With the ammonium (1j) as
well as primary and secondary amine (1k—r) salts CC
interacts without decomposition affording 2ꢀaminoꢀ4,6ꢀ
bis(trinitromethyl)ꢀ1,3,5ꢀtriazines 3a—i in 45—55% yield
instead of 2,4,6ꢀtris(trinitromethyl)ꢀ1,3,5ꢀtriazine (2).
Results and Discussion
Trinitromethylation is a bimolecular nucleophilic subꢀ
stitution reaction that was studied in detail over a range of
aliphatic halogenated compounds.24—26 In N. D. Zelinsky
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2089—2098, October, 2009.
1066ꢀ5285/09/5810ꢀ2154 © 2009 Springer Science+Business Media, Inc.

Trinitromethylation of chloroꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2155
Scheme 2
Thus, the aforesaid trinitromethane salts provide bisꢀtriꢀ
nitromethylation—amination of CC (Scheme 1).
Scheme 1
4: Ct = K (a), Me4N (b)
forming trinitromethylation of CC in the presence of waꢀ
ter. Trinitromethylation of CC with salts 1a,b,j,k in the
presence of water (1—3 mol per 1 mol CC) in acetone
(acetonitrile) occurs without exploding, and the product
thus formed is unaffected by the nature of trinitromethane
salt cation (Scheme 3).
+
+
+
+
1: Ct+ = NH4 (j), MeNH3 (k), Me2NH2 (l), Et2NH2 (m),
+
+
PrNH3 (n), BnNH3 (o),
(p),
(q),
(r)
3: NR1R2 = NH2 (a), NHMe (b), NMe2 (c), NEt2 (d), NHPr (e),
NHBn (f), (g), (h), (i)
Scheme 3
Bisꢀtrinitromethylation—amination of CC is peculiar
in that the chlorine substitution in CC is mediated by the
salt cation in addition to trinitrocarbanion attack.
The results obtained prompted us to turn back to the
reaction proceeding with intense decomposition as it
seemed quite probable that nitronic ester forms in the last
step furnishing products of CC trinitromethylation on deꢀ
composition. Using rather forcing cooling conditions (acꢀ
etone + solid CO2), the reaction in acetone (run with salts
1a,f) was brought to completion (as evidenced by the
absence of CC in the mixture and lack of gas evoluꢀ
tion; meanwhile the reaction temperature varied within
5—35 °C). The following organic products have been idenꢀ
tified: 2ꢀhydroxyꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazine
salts 4 (isolated as tetramethylammonium salt 4b, yield
50—55%), cyanuric acid (10—15%), and chlorotrinitroꢀ
methane (45—50% based on CC; the yield determined by
GC/MS). Along with these, detected qualitatively were
CtCl, CtNO2, CtNO3, N2O3, CO2 (Ct = K, NMe4). In
combination, the results obtained provide the evidence for
nitronic ester formation in the last step with its decompoꢀ
sition leading to salts 4 (Scheme 2), which means the
applied conditions afford bisꢀtrinitromethylation—nitroꢀ
nyloxylation of CC.
4: Ct = K (a), Me4N (b), Na (c), NH4 (d), MeNH3 (e),
MeEt3N (f), Et4N (g)
The interaction involves bisꢀtrinitromethylation—hyꢀ
droxylation of CC with the formation of salts 4a—g in
85—95% yield (see Scheme 3). Here, isolation of salts
4a,c—e is rather difficult because of their good solubility
in water (preparation of waterꢀsoluble salts 4 will be reꢀ
ported elsewhere). Therefore salts 4a,c—e were converted
without isolation into tetraalkylammonium salts 4b,f,g that
are sparingly soluble in water.
When run with the aliphatic alcohols, trinitromethylꢀ
ation of CC yields the products with essentially different
structures. Interaction of CC with salts 1a,b,j,k in the
presence of alcohols (3—5 mol per 1 mol CC) in acetone
Obviously, synthesizing salts 4 under conditions posꢀ
ing the risk of thermal explosion is dangerous and unreaꢀ
sonable, especially when the risk can be avoided by perꢀ

2156
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
Gidaspov et al.
Scheme 6
(acetonitrile) leads to 2,4ꢀdialkoxyꢀ6ꢀtrinitromethylꢀ
1,3,5ꢀtriazines 5a—k in 40—60% yield (Scheme 4).
Scheme 4
5: R = Me (a), Et (b), Pr (c), Pri (d), Bu (e), Bn (f), CH2CH2Cl (g),
cycloꢀC6H11 (h), CH2C(NO2)2F (i), CH2C(NO2)2Cl (j),
CH2CH2C(NO2)3 (k)
It turned out possible to perform trinitromethylaꢀ
tion—dialkoxylation with both primary and secondary alꢀ
cohols strongly differing in basicity (dependent on the subꢀ
stituent electronegativity which ranged from the electronꢀ
donating ethyl group (σ* = –0.1)31 to electronꢀwithdrawꢀ
ing fluorodinitromethyl group (σ* = 4.4)24).
Interaction between CC and salts 1a,b,j,k in the presꢀ
ence of phenol either a range of substituted phenols in
acetone (acetonitrile) gave 2,4ꢀdiaryloxyꢀ6ꢀtrinitromethꢀ
ylꢀ1,3,5ꢀtriazines 6a—q in 20—65% yield (Scheme 5). In
the reaction we successfully used phenols characterized by
pKa values spanning six orders of magnitude: from pꢀcresol
(pKa = 10.26)32 to 2,4ꢀdinitrophenol (pKa = 4.11).32 Thus,
these conditions provide trinitromethylation—diaryloxyꢀ
lation of CC.33
7: R = CH2COOMe (a), Ph (b), 4ꢀClC6H4 (c)
Trinitromethylation of CC in the presence of both
alcohols and phenols furnished three types of prodꢀ
ucts:
5a,d,f,h,
2,4ꢀdialkoxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazines
2,4ꢀdiaryloxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriꢀ
azines 6f,h,m,p, and 2ꢀalkoxyꢀ4ꢀaryloxyꢀ6ꢀtrinitromethꢀ
ylꢀ1,3,5ꢀtriazines 8a—g (Tables 1 and 2). Trinitromethylꢀ
1,3,5ꢀtriazines 8a—g were formed under conditions of
trinitromethylation—alkoxylation—aryloxylation of CC
(Scheme 7).
Scheme 7
Scheme 5
8: R = 4ꢀNO2, R´ = Me (a), Pri (b), cycloꢀC6H11 (c), Bn (d);
R = 2ꢀNO2, R´ = Me (e); R = 4ꢀCOOMe, R´ = Me (f);
R = 3ꢀCOOMe, R´ = Me (g)
6: R = H (a), 2ꢀMe (b), 2ꢀCOOMe (c), 2ꢀI (d), 2ꢀCl (e),
2ꢀNO2 (f), 3ꢀMe (g), 3ꢀCOOMe (h), 3ꢀCl (i),
3ꢀNO2 (j), 4ꢀMe (k), 4ꢀBut (l), 4ꢀCOOMe (m),
4ꢀCl (n), 4ꢀBr (o), 4ꢀNO2 (p), 2,4ꢀ(NO2)2 (q)
The aboveꢀpointed reactions of trinitromethylation of
CC (except for bisꢀtrinitromethylation—nitronyloxylation
and bisꢀtrinitromethylation—hydroxylation) proceed givꢀ
ing salts 4 (isolated as 4b) in 20—25% yield and chloroꢀ
trinitromethane (yield 2—5% based on CC) as byꢀprodꢀ
ucts. Their formation is due to a minor process of bisꢀ
trinitromethylation—nitronyloxylation of CC and, most
likely, to residual moisture of reactants and solvents. Notꢀ
ably, bisꢀtrinitromethylation—hydroxylation of CC domꢀ
In the presence of thiophenols and thiols, CC interacts
with salts 1a,b,j,k with slow decomposition. No derived
arylthioꢀ or alkylthioꢀsubstituted trinitromethylꢀ1,3,5ꢀtriꢀ
azines were detected, the isolated products were excluꢀ
sively those of thiophenol and thiol oxidation, e.g., diarylꢀ
and dialkyl sulfides 7a—c (Scheme 6).

Trinitromethylation of chloroꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2157
Table 1. Yields of 2,4ꢀdialkoxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazines 5a,d,f,h, 2,4ꢀdiaryloxyꢀ6ꢀtriꢀ
nitromethylꢀ1,3,5ꢀtriazines 6f,h,m,p, and 2ꢀalkoxyꢀ4ꢀaryloxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazines
8a—g under conditions of using both alcohols and phenols for CC trinitromethylation reaction
(see Scheme 7)*
Alcohol
Phenol
Yield (%)
5
6
8
MeOH
4ꢀNO2C6H4OH
4ꢀNO2C6H4OH
4ꢀNO2C6H4OH
4ꢀNO2C6H4OH
2ꢀNO2C6H4OH
4ꢀMeOOCC6H4OH
3ꢀMeOOCC6H4OH
22 (5a)
24 (5d)
29 (5h)
27 (5f)
25 (5a)
26 (5a)
26 (5a)
16 (6p)
19 (6p)
22 (6p)
18 (6p)
07 (6f)
13 (6m)
14 (6h)
50 (8a)
37 (8b)
45 (8c)
40 (8d)
45 (8e)
45 (8f)
39 (8g)
PriOH
cycloꢀC6H11OH
BnOH
MeOH
MeOH
MeOH
* Separation of products by column chromatography.
inates over all the reactions revealed. Adding 0.85 mol of
water per 1 mol CC into any of trinitromethylation reacꢀ
tion leads selectively to salts 4 in 85—95% yield. Applying
competition reactions gave the contributions from the reꢀ
actions of trinitromethylation of CC in descending orꢀ
der: bisꢀtrinitromethylation—hydroxylation, trinitromeꢀ
Table 2. Yields, melting points, and elemental analysis data for compounds 3a—i, 4b,f,g, 5a—k, and 8a—g
Comꢀ Yield M.p.
pound (%) /°C
Found
Calculated
Molecular
formula
Comꢀ Yield M.p.
pound (%) /°C
Found
Calculated
Molecular
formula
(%)
(%)
C
H
N
C
H
N
3a
3b
3с
3d
3e
3f
52 118—120 15.17 0.59 35.65 C5H2N10O12
(decomp.) 15.23 0.51 35.53
54 101—102 17.52 1.04 34.40 C6H4N10O12
17.65 0.98 34.31
48 140—142 19.83 1.36 33.25 C7H6N10O12
(decomp.) 19.91 1.42 33.18
46 138—139 24.12 2.20 31.08 C9H10N10O12
(decomp.) 24.01 2.24 31.11
52 40—42 22.09 1.89 32.02 C8H8N10О12
22.03 1.85 32.11
47 74—75 29.67 1.73 28.98 C12H8N10О12
29.75 1.65 28.93
5d
5e
5f
54 127—128 34.54 4.12 24.35 C10H14N6О8
(decomp.) 34.68 4.05 24.28
46 40—42
56 89—90
48 59—60
38.44 4.93 22.37 C12H18N6О8
38.50 4.81 22.46
48.95 3.26 19.10 C18H14N6О8
48.87 3.17 19.00
24.69 2.12 21.81 C8H8Cl2N6О8
24.81 2.07 21.71
5g
5h
5i
58 114—115 45.00 5.24 19.61 C16H22N6О8
45.07 5.16 19.72
47 109—110 18.05 0.92 26.31 C8H4F2N10О16
17.98 0.75 26.22
3g
3h
3i
50 152—153 24.14 1.85 31.22 C9H8N10О12
(decomp.) 24.12 1.80 31.25
45 148—150 25.91 2.23 30.25 C10H10N10О12
(decomp.) 25.98 2.18 30.30
54 99—100 27.80 2.49 29.34 C11H12N10О12
27.74 2.54 29.41
95 178—179 23.16 2.42 29.82 C9H12N10О13
(decomp.) 23.08 2.56 29.91
5j
45 100—102 17.02 0.84 24.60 C8H4Cl2N10О16
16.93 0.71 24.69
5k
8a
8b
8с
8d
8e
8f
47 78—80
19.41 1.36 27.25 C10H8N12О20
19.48 1.30 27.27
50 118—121 33.20 1.80 24.60 C11H7N7O10
33.26 1.78 24.68
37 132—134 36.60 2.72 23.09 C13H7N7O10
36.72 2.61 23.06
45 123—126 41.36 3.33 21.11 C16H15N7O10
41.30 3.25 21.07
4b
4f
92 165—167 28.31 3.62 27.40 C12H18N10О13
(decomp.) 28.24 3.53 27.45
4g
5a
5b
5c
85
—
29.71 3.93 26.78 C13H20N10О13
29.78 3.84 26.71
40 94—97
43.20 2.27 20.85 C17H11N7O10
43.14 2.34 20.72
60 60—62 24.80 2.00 28.89 C6H6N6О8
24.83 2.07 28.97
44 69—70 30.13 3.23 26.33 C8H10N6О8
30.18 3.14 26.42
45 138—140 33.30 1.70 24.64 C11H7N7O10
(decomp.) 33.26 1.78 24.68
45 134—136 38.00 2.50 20.40 C13H10N6O10
38.06 2.46 20.49
47
—
34.49 4.00 24.40 C10H14N6О8
34.68 4.05 24.28
8g
39 38—39
38.12 2.52 20.38 C13H10N6O10
38.06 2.46 20.49

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Gidaspov et al.
Scheme 8
thylation—alkoxylation—aryloxylation, bisꢀtrinitromeꢀ
thylation—amination, bisꢀtrinitromethylation—nitronylꢀ
oxylation.
It is important to emphasize that the yields of triniꢀ
tromethylꢀ1,3,5ꢀtriazines are equal for reactions proceedꢀ
ing in acetone (ε = 20.56)34 and acetonitrile (ε = 35.94),34
however, their completion times differ considerably (that
in acetonitrile being ~4 times larger). Interestingly,
the same ratio was observed for a more simple bimoleꢀ
cular reaction (with the known kinetics35) between
salt 1a and methyl iodide: in acetone at 25 °C k2 =
= (2.28 0.02)•10–5 L mol–1 s–1. Using the literature
procedure,35 in acetonitrile we have obtained k2
=
= (0.62 0.02)•10–5 L mol–1 s–1. Consequently, the qualꢀ
itative Hughes—Ingold theory34 predicting that an increase
in solvent dielectric constant would decrease the reaction
rate proved equally productive for relative completion time
estimation for both SN2 (with methyl iodide) and SN2Ar
(with CC) reactions.
Trinitromethylation has been
also studied with 2ꢀsubstituted
4,6ꢀdichloroꢀ1,3,5ꢀtriazines 9a—d.
In acetone (acetonitrile) no interꢀ
action of salts 1a,b,j,k with any of
these species was evident.
This result on the one hand is
probably attributable to the relaꢀ
12: X = OH (a), OAlk (b), OC6H4R (c), NR1R2 (d)
tively low nucleophilicity of triniꢀ
tromethyl anion and, on the other, to the lower reactivity
of our chloroꢀ1,3,5ꢀtriazines as compared to CC with one
Intermediate 10 can react with various nucleophiles
present in the reaction mixture. The substitution is most
likely to occur on the chlorine in 10 since sterically Cl
(Es = –2.81)36 hinders the reaction center in 1,3,5ꢀtriazꢀ
ine ring much lesser than does trinitromethyl group
(Es = –7.4).36 The formation of nitronate 11 is quite unꢀ
derstandable considering first, the presence of ambident
trinitrocarbanion in the reaction mixture and, second, takꢀ
ing into account that the substrate 10 is itself a rather
strong electrophile carrying the chlorine atom with acꢀ
cordingly high mobility. Hence, the reaction with ambiꢀ
dent trinitrocarbanion is very likely to yield nitronic ester
11. This pathway dominates in bisꢀtrinitromethylation—nitꢀ
ronyloxylation of CC (see Scheme 2) because of the lack
of other reactants in the mixture, while bisꢀtrinitromethyꢀ
lation—nitronyloxylation of CC is dominated by other reꢀ
actions since trinitrocarbanion is the most sterically hinꢀ
dered nucleophile. The resulting ester 11 is decomposed to
give salts 4 and other products (see Scheme 2). Besides that,
nitronate 11 interacts with chlorotrinitromethylꢀ1,3,5ꢀtriꢀ
azines formed as intermediates either with CC (analogs of
chloroanhydrides), leading through several steps to formꢀ
ation of chlorine and chlorotrinitromethane. The reacꢀ
tion mechanism was suggested by analogy with a reaction
between dinitromethanenitronate with acid chlorides.30
In the case of CC bisꢀtrinitromethylation—amination
(see Scheme 1), the reaction mixture contains low amounts
chlorine (σ* = 2.89, σ0 = 0.37)31 replaced by a more
m
electronegative group like NH2 (σ* = 0.72, σ0m = –0.14),31
NMe2 (σ* = 1.1, σ0 = –0.12),31 OMe (σ* = 1.79,
m
σ0 = 0.08),31 and OPh (σ* = 2.38, σ0m(calc.) =
m
= 0.22).31
The mechanism of trinitromethylation of CC that we
propose treats all the processes involved from the same
principles. Nucleophilic attack of the trinitrocarbanion
on CC (SN2Ar) in the first step results in the introduction
of two trinitromethyl groups into triazine cycle to give
2ꢀchloroꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazine (10)
(Scheme 8). It is the only version that explains formation
of bisꢀtrinitromethyl derivatives 3 and 4. Following the
general rules of nucleophilic substitution in πꢀdeficient
heterocycles, it would be natural to anticipate the second
and the third CC chlorine atoms to be replaced with highꢀ
er rates, knowing σ* = 4.54 for C(NO2)3,24 σ* = 2.89 for
Cl,31 that is, the replacement of the first chlorine atom by
trinitrocarbanion is presumed rate determining. This was
proved experimentally: performing trinitromethylation
with less than 2 mol of trinitromethane salt per 1 mol CC
still afforded trinitromethylꢀ1,3,5ꢀtriazines 3—6, 8 but the
CC conversion was incomplete. The suggested mechaꢀ
nism is additionally supported by the aboveꢀmentioned
solvent effect on the reaction time.

Trinitromethylation of chloroꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2159
of free ammonia, primary or secondary amine formed in
the equilibrium reaction as illustrated in Scheme 9.
As compared to amino groups, alkoxy and aryloxy
groups are much less protective against substitution of the
remaining trinitromethyl groups, so in products 12b,c one
of them was replaced by alkoxy(aryloxy) group to yield
5a—k and 6a—q. The substitution in 12b,c occurs so rapꢀ
idly that these activated triazines cannot be detected in the
reaction mixture. The possible explanation is that the subꢀ
stitution of the second trinitromethyl group in 12b,c by an
alcohol (phenol) (Scheme 13) invokes trinitromethaneꢀ
catalyzed mechanism (such bifunctional acid catalysis
was described previously20—22 for the substitution of chloꢀ
rine in CC).
Scheme 9
1j—r
R1R2NH + HC(NO2)3
Their concentration is quite enough to compete sucꢀ
cessfully with bisꢀtrinitromethylation—nitronyloxylation
of CC, with nucleophilic substitution of the chlorine atom
in reactive intermediate 10 affording the amino derivaꢀ
tives 3a—i (Scheme 10; see also Scheme 1); it is, however,
insufficient to compete with other reactions of trinitromeꢀ
thylation of CC.
Scheme 13
Scheme 10
10
3a—i
Introduction of the electronꢀdonating amino group reꢀ
duces reactivity of trinitromethyl groups in 3a—i, thus
preventing substitution of the second trinitromethyl group.
At the same time, the free amine concentration decreases
in the course of the reaction due to bonding with the
formed HCl.
Bisꢀtrinitromethylation—hydroxylation of CC (see
Scheme 3) involves the substitution of chlorine atoms in
intermediate 10 under the action of water leading to hyꢀ
droxytriazine 12a, which is a strong acid (its pKa is comꢀ
parable with that of pentanitrophenol37) and as such disꢀ
sociates to yield the anion thus protecting from the substiꢀ
tution the remainder trinitromethyl groups (Scheme 11).
The mobility of the remaining trinitromethyl group in
dialkoxy(aryloxy) derivatives 5a—k and 6a—q is lowered
to a level that makes its substitution under the given reacꢀ
tion conditions (that is, in the absence of bases) impossiꢀ
ble. This is confirmed by the results of trinitromethyl group
substitution in 2,4,6ꢀtris(trinitromethyl)ꢀ1,3,5ꢀtriazine in
the reactions with alcohols.12
Scheme 11
Under trinitromethylation—alkoxylation—aryloxylaꢀ
tion of CC (see Scheme 7), trinitromethyl groups in 12b,c
can be substituted by both alcohols and phenols leading
correspondingly to three types of products, 5, 6, and 8
(Scheme 14). Their proportion depends on the nature and
ratio of alcohols and phenols.
Water being the least sterically hindered nucleophile,
bisꢀtrinitromethylation—hydroxylation of CC dominates
over other trinitromethylation reactions.
The reactions of trinitromethylation—dialkoxy(arylꢀ
oxy)lation of CC (see Schemes 4 and 5) proceed with the
consecutive replacement of the chlorine atom in intermeꢀ
diate 10 and one trinitromethyl group in compounds 12b,c
by alkoxy or aryloxy groups (Scheme 12).
Scheme 14
Scheme 12
Clearly, the proposed mechanism of trinitromethylaꢀ
tion of CC is still the subject of discussion. Some aspects
of this work were reported at the international conferencꢀ
es.38—41 The progress in the chemistry of polynitromethꢀ
ylꢀ1,3,5ꢀtriazines has been reviewed in Ref. 42.

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Gidaspov et al.
the insoluble residue was filtered off, and the filtrate was cooled
to –5—0 °C. Precipitated compound 3c—i was filtered off and
air dried.
Experimental
1
Warning: Preparation and manipulation of polynitro compounds
can potentially lead to explosions. Polynitro compounds are shockꢀ,
frictionꢀ and temperatureꢀsensitive. Proper safety precautions are
therefore essential.
The IR and H NMR spectra of 2ꢀaminoꢀ4,6ꢀbis(trinitroꢀ
methyl)ꢀ1,3,5ꢀtriazine (3a), 2ꢀmethylaminoꢀ4,6ꢀbis(trinitroꢀ
methyl)ꢀ1,3,5ꢀtriazine (3b), and 2ꢀdimethylaminoꢀ4,6ꢀbisꢀ
(trinitromethyl)ꢀ1,3,5ꢀtriazine (3c) are identical with those deꢀ
scribed in Ref. 13.
Melting points were measured with a PTP melting point
apparatus, and are uncorrected. Elemental analysis was perꢀ
formed with an Eurovector EA 3000 analyzer. 1H NMR spectra
were recorded on a Bruker AMꢀ300 spectrometer operating at
300.13 MHz. All chemical shifts are reported on a δ scale with
Me4Si as an internal reference. IR spectra were recorded on an
Avatar 360ESP spectrometer (solids were examined in KBr tabꢀ
lets, and liquids in thin films). TLC (Silufol UVꢀ254) was used to
monitor reaction evolution and assess product purity. The prodꢀ
ucts were isolated by preparative chromatography on MN Kieꢀ
selgel 60 (0.063—0.2 mm) silica (MachereyꢀNagel GmbH).
Chlorotrinitromethane was assessed by GC/MS with a Finnigan
Trace DSQ instrument.
2ꢀAminoꢀ4,6ꢀdichloroꢀ1,3,5ꢀtriazine (9a), 4,6ꢀdichloroꢀ2ꢀ
dimethylaminoꢀ1,3,5ꢀtriazine (9b), 4,6ꢀdichloroꢀ2ꢀmethoxyꢀ
1,3,5ꢀtriazine (9c), and 4,6ꢀdichloroꢀ2ꢀphenoxyꢀ1,3,5ꢀtriazine
(9d) were prepared according the previously reported proceꢀ
dures.17 2ꢀChloroꢀ2,2ꢀdinitroethanol,43 2ꢀfluoroꢀ2,2ꢀdinitroꢀ
ethanol,44 and 3,3,3ꢀtrinitropropanol45 were synthesized using
literature procedures. The synthesis, physicoꢀchemical properꢀ
2ꢀDiethylaminoꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazine (3d).
IR, ν/cm–1: 3000 (w), 2850 (w), 1640 (s), 1580 (s), 1450 (w),
1280 (s), 1215 (m), 1175 (w), 1100—1060 (m), 975 (w), 930 (w),
1
845 (m), 795 (s). H NMR (acetoneꢀd6), δ: 1.24 (t, 6 H, CH3,
J = 6.0 Hz); 3.64 (q, 4 H, NCH2, J = 6.0 Hz).
2ꢀnꢀPropylaminoꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazine (3e).
IR, ν/cm–1: 3394 (s), 2973 (w), 2941 (w), 2881 (w), 1623 (s),
1591 (s), 1525 (m), 1463 (w), 1448 (w), 1338 (w), 1288 (m), 1191
(w), 1137 (w), 1099 (w), 1006 (w), 979 (w), 860 (w), 840 (w), 819
(w), 792 (s). 1H NMR (CDCl3) δ: 1.04 (t, 3 H, CH3, J = 7.3 Hz);
1.70 (m, 2 H, CH2); 3.52 (m, 2 H, NCH2); 6.59 (br.s, 1 H, NH).
2ꢀBenzylaminoꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazine (3f).
IR, ν/cm–1: 3320 (m), 3060 (w), 2940 (w), 2872 (w), 1650 (s),
1636 (s), 1560 (s), 1525 (s), 1480 (m), 1432 (w), 1284 (s), 1200
(m), 1112 (m), 1056 (m), 976 (w), 912 (m), 840 (m), 796 (s).
1H NMR (acetoneꢀd6), δ: 4.63 (d, 2 H, CH2, J = 5.8 Hz); 7.25
(s, 5 H, C6H5); 9.95 (br.t, 1 H, NH).
2ꢀPyrrolidinylꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazine (3g). IR,
ν/cm–1: 2989 (w), 2958 (w), 2925 (w), 2887 (w), 1625 (s), 1587
(s), 1488 (m), 1457 (w), 1344 (w), 1290 (m), 1230 (w), 1201 (w),
1141 (w), 1103 (w), 1006 (w), 970 (w), 852 (w), 804 (m), 790 (m).
1H NMR (CDCl3), δ: 2.12 (m, 4 H, CH2CH2); 3.16 (m, 4 H,
CH2NCH2).
1
ties, IR spectra, and H NMR spectra of 2,4ꢀdiaryloxyꢀ6ꢀtriꢀ
nitromethylꢀ1,3,5ꢀtriazines 6a—q are described in Ref. 33.
Trinitromethane salts. Trinitromethane was prepared as deꢀ
scribed in Ref. 46. Trinitromethane salts 1a (see Ref. 43) and
1f—i (see Ref. 47) were prepared according to the previously
published methods. The solution of salt 1c was prepared as preꢀ
viously described.30 The solution of salt 1b was synthesized by
exchange reaction between 1a and sodium perchlorate in aceꢀ
tone (acetonitrile). Precipitated potassium perchlorate was filꢀ
tered off. The resulting solution of salt 1b was used as a reagent.
The solution of salt 1d was obtained by neutralizing triꢀ
nitromethane solution in acetone (acetonitrile) with the equivaꢀ
lent amount of gaseous trimethylamine to use further as a reꢀ
agent. To prepare salts 1j—l, an excess of gaseous ammonia (meꢀ
thylamine, dimethylamine) was bubbled through solution of triꢀ
nitromethane in dichloroethane. Precipitated salt 1j—l was filꢀ
tered off, washed on a filter with the cooled dichloroethane, airꢀ
dried for 1 h, and was subsequently used as a reagent. The soluꢀ
tions of salt 1m—r were obtained by neutralizing trinitromethane
solution in acetone (acetonitrile) with the equivalent amount of
the appropriate amine to use further as a reagent.
2ꢀPiperidinoꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazine (3h). IR,
ν/cm–1: 3025 (w), 2966 (w), 2941 (w), 2908 (w), 2861 (w),
1623 (s), 1583 (s), 1488 (m), 1450 (m), 1369 (w), 1336 (w), 1286 (s),
1189 (w), 1126 (w), 1099 (w), 1029 (w), 977 (m), 850 (m), 788 (s).
1H NMR (CDCl3), δ: 1.76 (m, 12 H, CH2); 3.81 (m, 8 H,
CH2NCH2).
2ꢀ(4´ꢀMethylpiperidino)ꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriꢀ
azine (3i). IR, ν/cm–1: 2964 (w), 2927 (w), 2871 (w), 1621 (s),
1587 (s), 1488 (m), 1463 (w), 1378 (w), 1334 (w), 1288 (m),
1263 (w), 1209 (w), 1186 (w), 1101 (w), 997 (w), 970 (w), 846 (w),
1
802 (w), 788 (m). H NMR (CDCl3), δ: 1.03 (d, 3 H, CH3,
J = 6.8 Hz); 1.28 (m, 2 H, CH2); 1.77 (m, 1 H, CH); 1.90
(m, 2 H, CH2); 3.09 (t, 2 H, NCH2, J = 2.4 Hz); 4.54 (d, 2 H,
NCH2, J = 2.4 Hz).
Reaction of CC with salts 1a,f (general procedure). A stirred
solution of salt 1a,f (0.04 mol) in acetone (15 mL) was treated
with CC (1.84 g, 0.01 mol) at 20—25 °C. After 20—25 min, the
reaction became violent (indicated by the color change of the
reaction mixture, rapid gas evolution, sharp temperature increase
to 35—45 °C). At this moment the reaction was cooled (aceꢀ
tone—solid CO2) to 5—10 °C, and then the cooling was reꢀ
moved. The reaction was still violent, and hence, the cooling
was applied again. This was repeated many times until after
1—1.5 h the reaction slowed down. Qualitative detection reꢀ
vealed the presence of N2O3 and CO2 in leaving gases.49 In
1—1.5 h CC was expended completely and gas evolution stopped.
The reaction mixture was additionally stirred for 30 min at
20—25 °C and filtered from precipitate. The residue on a filter
was washed with acetone (10 mL) and air dried for 2—3 h. The
resulting precipitate was washed with water (3×10 mL) on a filter,
The yields, melting points, and elemental analysis data for
compounds 3—6, 8 are given in Tables 1 and 2.
2ꢀAminoꢀ4,6ꢀbis(trinitromethyl)ꢀ1,3,5ꢀtriazines 3a—i (genꢀ
eral procedure) (for details see Ref. 48). A stirred solution of salt
1j—r (0.04 mol) in acetone (acetonitrile) (13 mL) was treated
with CC (1.84 g, 0.01 mol) at 20—25 °C. The reaction mixꢀ
ture was held at 25—32 °C until CC was completely reacted
(which took 4—5 h in acetone and 20—25 h in acetonitrile).
Then the mixture was poured with stirring into water (150 mL).
The resulting precipitate was filtered off, washed with water
(2×20 mL), and allowed to air dry. Aminoderivatives 3a,b were
thus obtained as pure compounds. To isolate derivatives 3c—i,
the product was treated with CCl4 (20 mL) at 70—75 °C,

Trinitromethylation of chloroꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2161
and then dried at 80—90 °C to constant weight to yield (0.17 g,
14%) cyanuric acid (by IR spectrometry50). The water filtrate
contained (as detected qualitatively) CtCl, CtNO2, CtNO3
(Ct = K, Me4N).49 Acetone filtrate and washing acetone were
combined and poured into water (200 mL) with stirring (when
running synthesis with salt 1a, Me4N+Cl– (1.1 g) was added to
water). Water suspension 4b was treated with CCl4 (25 mL).
Precipitate 4b that formed was filtered off, washed on a filter
with CCl4 (2×10 mL) and water (3×20 mL), and allowed to air
dry to yield salt 4b (2.48 g, 53%). CCl4 was separated from water,
dried over Na2SO4, and then chlorotrinitromethane was assessed
by GC/MS.
1226 (m), 1099 (w), 1033 (w), 991 (m), 862 (w), 800 (s). 1H NMR
(acetoneꢀd6), δ: 1.12 (t, 6 H, CH3, J = 7.6 Hz); 1.94 (m, 4 H,
CH2); 4.40 (t, 4 H, OCH2, J = 7.6 Hz).
2,4ꢀDiisopropoxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazine (5d). IR,
ν/cm–1: 2992 (w), 2936 (w), 2865 (w), 1628 (s), 1592 (s), 1532 (s),
1504 (s), 1424 (s), 1392 (w), 1376 (m), 1324 (s), 1288 (m),
1224 (w), 1184 (w), 1136 (w), 1096 (m), 984 (m), 960 (w),
844 (w), 824 (w), 800 (s). 1H NMR (acetoneꢀd6), δ: 1.36 (d, 12 H,
CH3, J = 6.8 Hz); 5.30 (m, 2 H, OCH).
2,4ꢀDi(nꢀbutoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazine (5e). IR,
ν/cm–1: 2853 (w), 1625 (s), 1581 (s), 1408 (m), 1376 (s), 1322 (s),
1
1280 (m), 1119 (w), 980 (m), 820 (w), 797 (s). H NMR (aceꢀ
Preparation of tetraalkylammonium salts of 2ꢀhydroxyꢀ4,6ꢀ
bis(trinitromethyl)ꢀ1,3,5ꢀtriazine 4b,f,g (general procedure).
A solution of salt 1a,b,j,k (0.04 mol) in acetone (acetonitrile)
(15 mL) was treated with CC (1.84 g, 0.01 mol) with stirring and
then with water (0.18 mL, 0.01 mol) at 20—25 °C. The reaction
mixture was held at 20—25 °C until CC was completely reacted
(which took 3—4 h in acetone and 20—22 h in acetonitrile).
Then the mixture was poured with stirring into water (150 mL).
In the case of salts 1f—h, salts 4b,f,g precipitated immediately.
When using salts 1a,b,j,k, the obtained solution was treated dropꢀ
wise with a solution of appropriate tetraalkylammonium chloꢀ
ride (0.011 mol) in water (15 mL) over 10—15 min. The resulting
precipitate of salts 4b,f,g was filtered off, washed with water
(3×20 mL), and allowed to air dry.
Tetramethylammonium salt of 2ꢀhydroxyꢀ4,6ꢀbis(trinitroꢀ
methyl)ꢀ1,3,5ꢀtriazine (4b). IR, ν/cm–1: 3048 (w), 2930 (w),
2870 (w), 1655 (s), 1640 (s), 1625 (s), 1590 (s), 1580 (s), 1480 (m),
1460 (s), 1420 (w), 1335 (m), 1295 (s), 1115 (w), 1080 (w),
950 (m), 910 (w), 860 (w), 840 (w), 810 (w), 800 (s), 780 (m).
1H NMR (acetoneꢀd6), δ: 3.37 (s, 12 H, CH3).
toneꢀd6), δ: 0.97 (t, 6 H, CH3, J = 7.4 Hz); 1.44, 1.74 (both m,
8 H, CH2); 4.36 (t, 4 H, OCH2, J = 7.4 Hz).
2,4ꢀDibenzyloxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazine (5f). IR,
ν/cm–1: 3020 (w), 2944 (w), 1628 (s), 1592 (s), 1512 (s), 1432 (s),
1336 (s), 1288 (m), 1216 (m), 1120 (m), 1003 (m), 968 (w),
848 (m), 800 (m), 752 (m). 1H NMR (acetoneꢀd6), δ: 5.27 (s, 4 H,
OCH2); 7.34 (s, 10 H, Ph).
2,4ꢀDi(2´ꢀchloroethoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazine (5g).
IR, ν/cm–1: 2976 (w), 2888 (w), 1630 (s), 1596 (s), 1576 (s),
1548 (s), 1508 (s), 1464 (m), 1448 (m), 1424 (s), 1392 (m),
1356 (s), 1296 (s), 1232 (s), 1136 (m), 1076 (w), 1016 (m), 984 (w),
1
920 (w), 848 (m), 824 (w), 800 (s). H NMR (acetoneꢀd6), δ:
4.01 (t, 4 H, OCH2, J = 7.2 Hz); 5.00 (t, 4 H, CH2Cl, J = 7.2 Hz).
2,4ꢀDicyclohexyloxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazine (5h).
IR, ν/cm–1: 2944 (s), 2864 (m), 1624 (s), 1600 (s), 1576 (s), 1528 (s),
1500 (s), 1448 (s), 1432 (s), 1364 (m), 1344 (m), 1328 (m),
1288 (m), 1216 (m), 1112 (m), 1032 (w), 1004 (m), 984 (m), 960 (s),
920 (m), 844 (w), 800 (s). 1H NMR (acetoneꢀd6), δ: 1.54, 1.95,
2.15 (m, 20 H, cycloꢀC6H10); 5.05 (m, 2 H, OCH).
2,4ꢀDi(2´ꢀfluoroꢀ2´,2´ꢀdinitroethoxy)ꢀ6ꢀtrinitromethylꢀ
1,3,5ꢀtriazine (5i). IR, ν/cm–1: 3035 (w), 2860 (w), 1640 (s),
1570 (s), 1545 (s), 1500 (m), 1415 (m), 1385 (m), 1350 (m),
1280 (s), 1255 (m), 1135 (m), 990 (w), 935 (w), 850 (w), 835 (w),
795 (s). 1H NMR (acetoneꢀd6), δ: 6.04 (d, 4 H, OCH2, J = 7.0 Hz).
2,4ꢀDi(2´ꢀchloroꢀ2´,2´ꢀdinitroethoxy)ꢀ6ꢀtrinitromethylꢀ
1,3,5ꢀtriazine (5j). IR, ν/cm–1: 3000 (w), 2850 (w), 1620 (s),
1605 (s), 1580 (s), 1545 (s), 1495 (m), 1445 (m), 1415 (m),
1365 (m), 1330 (w), 1295 (s), 1255 (m), 1135 (w), 990 (w), 825 (w),
800 (s), 780 (m). 1H NMR (acetoneꢀd6), δ: 5.96 (s, 4 H, OCH2).
2,4ꢀDi(3´,3´,3´ꢀtrinitropropoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriꢀ
azine (5k). IR, ν/cm–1: 3000 (w), 2880 (w), 1640 (s), 1620 (s),
1580 (s), 1545 (s), 1510 (m), 1480 (m), 1435 (m), 1375 (s),
1350 (m), 1300 (s), 1235 (m), 1125 (w), 1030 (w), 1000 (w), 910 (w),
Triethylmethylammonium salt of 2ꢀhydroxyꢀ4,6ꢀbis(trinitroꢀ
methyl)ꢀ1,3,5ꢀtriazine (4f). IR, ν/cm–1: 3045 (w), 2925 (w),
2875 (w), 1653 (s), 1640 (s), 1625 (s), 1583 (s), 1482 (m), 1462 (s),
1418 (w), 1337 (m), 1295 (s), 1114 (w), 1078 (w), 980 (w),
1
947 (w), 920 (w), 862 (w), 842 (w), 798 (s), 782 (s). H NMR
(acetoneꢀd6), δ: 1.42 (t, 9 H, CH3, J = 6.4 Hz); 3.20 (s, 3 H,
CH3); 3.56 (q, 6 H, NCH2, J = 6.4 Hz).
Tetraethylammonium salt of 2ꢀhydroxyꢀ4,6ꢀbis(trinitromeꢀ
thyl)ꢀ1,3,5ꢀtriazine (4g). IR, ν/cm–1: 3032 (w), 2931 (w),
2883 (w), 1656 (s), 1637 (s), 1580 (s), 1491 (m), 1460 (s), 1418 (w),
1342 (m), 1303 (s), 1110 (w), 1081 (w), 980 (w), 945 (w),
922 (w), 859 (w), 840 (w), 800 (s), 781 (m). 1H NMR (acetoneꢀd6),
δ: 1.43 (t, 12 H, CH3, J = 6.0 Hz); 3.57 (q, 8 H, NCH2, J = 6.0 Hz).
Preparation of 2,4ꢀdialkoxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazines
5a—k (general procedure). A solution of salt 1a,b,f—h,j,k (0.04 mol)
in acetone (acetonitrile) (15 mL) was treated with CC (1.84 g,
0.01 mol) with stirring and then with alcohol (0.03—0.05 mol) at
20—25 °C. The reaction mixture was held at 20—25 °C until CC
was completely reacted (which took 6—24 h in acetone and
1—4 days in acetonitrile). Then the mixture was poured with
stirring into water (150 mL) and held at stirring until the product
crystallized. The resulting precipitate was filtered off, washed
with water (4×30 mL) on a filter and allowed to air dry.
1
860 (w), 835 (m), 810 (s), 780 (m). H NMR (acetoneꢀd6), δ:
4.07 (t, OCH2, J = 7.0 Hz); 5.10 (t, CH2C(NO2)3, J = 7.0 Hz).
Interaction of salts 1a,b,j,k with CC in the presence of thiols
and thiophenols (general procedure). A solution of salt 1a,b,j,k
(0.04 mol) in acetone (15 mL) was treated with CC (1.84 g,
0.01 mol) with stirring at 20—25 °C followed by the appropriate
thiol or thiophenol (0.03—0.05 mol). The reaction mixture was
held at 20—25 °C until CC was completely reacted (which took
6—24 h in acetone). On incubation the mixture changed color to
reddishꢀbrown. Then the mixture was poured with stirring into
water (150 mL) and kept stirred until the product crystallized.
The resulting precipitate was filtered off, washed with water
(2×30 mL), and allowed to air dry. In the case of a liquid product
(when running the reaction with thioglycolic acid methyl ester),
it was extracted with dichloroethane (20 mL), washed with waꢀ
ter, dried over sodium sulfate, and then the solvent was removed
1
The IR and H NMR spectra of 2,4ꢀdimethoxyꢀ6ꢀtrinitroꢀ
methylꢀ1,3,5ꢀtriazine (5a), and 2,4ꢀdiethoxyꢀ6ꢀtrinitromethylꢀ
1,3,5ꢀtriazine (5b) are identical with those described in Ref. 13.
2,4ꢀDi(nꢀpropoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriazine (5c). IR,
ν/cm–1: 2971 (w), 2942 (w), 2883 (w), 1629 (s), 1596 (s), 1540
(m), 1515 (s), 1475 (m), 1430 (s), 1357 (s), 1301 (m), 1290 (m),

2162
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
Gidaspov et al.
by rotary evaporator. The isolated products were identified as
bis(methoxycarbonylmethylene)disulfide (7a) (see Ref. 51),
diphenyldisulfide (7b) (see Ref. 52), and 4,4´ꢀdichlorodipheꢀ
nyldisulfide (7c) (see Ref. 53).
1172 (m), 1124 (m), 1028 (m), 1002 (m), 864 (w), 844 (m),
828 (w), 796 (s), 770 (m). H NMR (CDCl3), δ: 3.87 (s, 3 H,
COOCH3); 3.99 (s, 3 H, OCH3); 7.19, 8.10 (both d, 4 H, pꢀC6H4,
J = 7.2 Hz).
1
Synthesis of 2ꢀalkoxyꢀ4ꢀaryloxyꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriꢀ
azines 8a—g (general procedure). A solution of salt 1a,b,j,k
(0.04 mol) in acetone (acetonitrile) (15 mL) was treated with CC
(1.84 g, 0.01 mol) with stirring at 20—25 °C followed by an
aliphatic alcohol (0.01—0.025 mol) and phenol (0.01—0.025 mol).
The reaction mixture was held at 20—25 °C until CC was comꢀ
pletely reacted (which took 6—24 h in acetone and 1—4 days in
acetonitrile). Then the mixture was poured with stirring into
water (150 mL). The resulting product was extracted into
dichloroethane (30 mL) and dried over sodium sulfate. The prodꢀ
ucts were separated by column chromatography eluting with
dichloroethane. Dialkoxy derivatives 5a,d,f,h elute first followed
by alkoxyaryloxy derivatives 8a—g, and diaryloxy derivatives
6f,h,m,p come off last. The yields are given in Table 1.
2ꢀMethoxyꢀ4ꢀ(3´ꢀmethoxycarbonylphenoxy)ꢀ6ꢀtrinitromethꢀ
ylꢀ1,3,5ꢀtriazine (8g). IR, ν/cm–1: 3016 (w), 2964 (w), 2924 (w),
2890 (w), 1726 (s), 1644 (s), 1634 (s), 1616 (s), 1606 (s), 1596 (s),
1570 (s), 1552 (s), 1530 (s), 1520 (s), 1510 (s), 1492 (m), 1462 (m),
1450 (s), 1432 (m), 1392 (s), 1382 (m), 1372 (w), 1340 (m),
1316 (m), 1302 (w), 1284 (m), 1274 (s), 1260 (w), 1230 (m),
1210 (w), 1170 (m), 1118 (m), 1092 (s), 1082 (w), 1008 (w),
968 (w), 902 (m), 864 (w), 826 (w), 800 (s), 760 (m), 716 (m).
1H NMR (CDCl3), δ: 3.87 (s, 3 H, COOCH3); 3.99 (s, 3 H, OCH3);
7.42, 7.69, 7.96 (all m, 4 H, mꢀC6H4).
References
2ꢀMethoxyꢀ4ꢀ(4´ꢀnitrophenoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriꢀ
azine (8a). IR, ν/cm–1: 3120 (w), 3088 (w), 2976 (w), 2880 (w),
1640 (s), 1600 (s), 1580 (s), 1550 (s), 1520 (s), 1494 (s), 1464 (w),
1426 (s), 1388 (s), 1378 (s), 1356 (s), 1346 (s), 1296 (s), 1222 (s),
1172 (m), 1140 (w), 1116 (w), 1100 (m), 1024 (m), 1000 (s), 968 (w),
858 (s), 836 (w), 816 (w), 798 (s), 752 (w). 1H NMR (CDCl3), δ:
4.03 (s, 3 H, OCH3); 7.32, 8.30 (both d, 4 H, pꢀC6H4, J = 8.0 Hz).
2ꢀIsopropoxyꢀ4ꢀ(4´ꢀnitrophenoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀ
triazine (8b). IR, ν/cm–1: 3124 (w), 3100 (w), 3004 (w), 3000 (w),
1636 (s), 1620 (s), 1600 (s), 1580 (s), 1542 (s), 1530 (s), 1496 (s),
1472 (w), 1404 (s), 1350 (s), 1330 (m), 1294 (m), 1268 (m),
1212 (s), 1172 (m), 1108 (m), 1096 (m), 1020 (m), 996 (m),
936 (m), 868 (m), 856 (m), 830 (m), 798 (s), 750 (w). 1H NMR
(CDCl3), δ: 1.32 (d, 6 H, CH3, J = 6.6 Hz); 5.17 (m, 1 H, CH);
7.29, 8.32 (both d, 4 H, pꢀC6H4, J = 8.0 Hz).
2ꢀCyclohexyloxyꢀ4ꢀ(4´ꢀnitrophenoxy)ꢀ6ꢀtrinitromethylꢀ
1,3,5ꢀtriazine (8c). IR, ν/cm–1: 3128 (w), 3100 (w), 2948 (m),
2872 (w), 1640 (s), 1620 (s), 1606 (s), 1588 (s), 1530 (s), 1496 (s),
1408 (s), 1372 (m), 1350 (s), 1316 (m), 1268 (s), 1212 (m),
1172 (w), 1100 (m), 1016 (m), 998 (w), 932 (w), 892 (w), 856 (m),
832 (m), 796 (s), 752 (w). 1H NMR (CDCl3), δ: 1.61, 1.89, 2.15
(m, 10 H, cycloꢀC6H10); 4.90 (m, 1 H, CH); 7.30, 8.34 (both d,
4 H, pꢀC6H4, J = 8.0 Hz).
1. A. V. Shastin, T. I. Godovikova, B. L. Korsunskii, Usp. Khim.,
2003, 72, 311 [Russ. Chem. Rev. (Engl. Transl.), 2003,
72, 279].
2. A. A. Gidaspov, V. V. Bakharev, E. V. Kachanovskaya, E. A.
Kosareva, M. V. Galkina, E. V. Ekimova, N. G. Yakunina,
Yu. N. Bulychev, Khim.ꢀFarm. Zhurn., 2004, 38, No. 8, 9
[Pharm. Chem. J. (Engl. Transl.), 2004, 38, No. 8, 411].
3. Yu. N. Bulychev, V. V. Bakharev, A. A. Gidaspov, Proc. 3rd
Int. Conference "Chemistry and Biological Activity of Nitrogenꢀ
containing Heterocycles" (Chernogolovka, Russia, June 20—23,
2006), Moscow, 2006, 2, 58.
4. G. A. Shvekhgeimer, G. A. Mikheichev, Khim. Geterotsikl.
Soedin., 1971, 698 [Chem. Heterocycl. Compd. (Engl. Transl.),
1971, 7, 656].
5. A. V. Fokin, Yu. N. Studnev, L. D. Kuznetsova, Izv. Akad.
Nauk, Ser. Khim., 1996, 2056 [Russ. Chem. Bull. (Engl.
Transl.), 1996, 45, 1952].
6. A. V. Shastin, T. I. Godovikova, S. P. Golova, L. I. Khmel´ꢀ
nitskii, B. L. Korsunskii, Khim. Geterotsikl. Soedin., 1997,
1254 [Chem. Heterocycl. Compd. (Engl. Transl.), 1997,
33, 1095].
7. W. M. Koppes, M. C. G. Adolph, J. Org. Chem., 1981, 46,
406.
2ꢀBenzyloxyꢀ4ꢀ(4´ꢀnitrophenoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriꢀ
azine (8d). IR, ν/cm–1: 3124 (w), 3084 (w), 2976 (w), 2932 (w),
2882 (w), 1636 (s), 1620 (s), 1592 (s), 1584 (s), 1542 (s), 1532 (s),
1492 (s), 1464 (m), 1428 (m), 1400 (s), 1360 (s), 1348 (s),
1296 (m), 1264 (m), 1242 (s), 1208 (m), 1176 (w), 1140 (w),
1120 (w), 1100 (w), 1088 (w), 1020 (w), 998 (w), 952 (m), 854 (s),
828 (w), 796 (s), 760 (m), 698 (m). H NMR (CDCl3), δ: 5.38
(s, 2 H, CH2); 7.32, 8.30 (both d, 4 H, pꢀC6H4, J = 8.0 Hz); 7.30
(s, 5 H, C6H5).
8. A. J. Bellamy, N. L. Latypov, P. Goede, J. Chem. Res. S,
2003, 529.
9. A. V. Shastin, T. I. Godovikova, S. P. Golova, V. S. Kuz´min,
L. I. Khmel´nitskii, B. L. Korsunskii, Mendeleev Commun.,
1995, 17.
10. A. A. Gidaspov, Proc. Int. ScientificꢀTechnical and Methodꢀ
ological Conf. "The Problems of Special Technical Chemistry
Today" (Kazan´, Russia, December 6—8, 2006), Kazan´, 2006,
100.
1
2ꢀMethoxyꢀ4ꢀ(2´ꢀnitrophenoxy)ꢀ6ꢀtrinitromethylꢀ1,3,5ꢀtriꢀ
azine (8e). IR, ν/cm–1: 3172 (w), 2972 (w), 2876 (w), 1634 (s),
1620 (s), 1614 (s), 1596 (s), 1560 (s), 1540 (s), 1524 (s), 1488 (m),
1464 (m), 1430 (s), 1400 (s), 1390 (s), 1380 (s), 1350 (s), 1312 (m),
1294 (m), 1276 (m), 1240 (w), 1220 (s), 1170 (w), 1106 (m),
1088 (m), 1000 (s), 798 (s), 780 (m). 1H NMR (CDCl3), δ: 4.02
(s, 3 H, OCH3); 7.25, 7.50, 8.05 (all m, 4 H, oꢀC6H4).
2ꢀMethoxyꢀ4ꢀ(4´ꢀmethoxycarbonylphenoxy)ꢀ6ꢀtrinitromethꢀ
ylꢀ1,3,5ꢀtriazine (8f). IR, ν/cm–1: 3012 (w), 2964 (w), 2888 (w),
1722 (s), 1640 (s), 1600 (s), 1584 (s), 1574 (s), 1550 (s), 1520 (s),
1508 (s), 1434 (m), 1424 (s), 1384 (s), 1370 (s), 1296 (s), 1212 (s),
11. V. V. Bakharev, A. A. Gidaspov, Izv. Samarskogo nauchn.
tsentra RAN. Spetsvypusk «Khimiya i khim. tekhnologiya» [Bulꢀ
letin of Samara Scientific Center of Russian Academy of Sciꢀ
ences. Special Issue "Chemistry and Chemical Technology"],
2004, 190 (in Russian).
12. A. V. Shastin, T. I. Godovikova, S. P. Golova, L. I. Khmel´ꢀ
nitskii, B. L. Korsunskii, Khim. Geterotsikl. Soedin., 1995,
674 [Chem. Heterocycl. Compd. (Engl. Transl.), 1995, 31, 596].
13. A. V. Shastin, T. I. Godovikova, S. P. Golova, M. V. Povoꢀ
rin, D. E. Dmitriev, M. O. Dekaprilevich, Yu. A. Strelenko,
Yu. T. Struchkov, L. I. Khmel´nitskii, B. L. Korsunskii, Khim.

Trinitromethylation of chloroꢀ1,3,5ꢀtriazines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2163
Geterotsikl. Soedin., 1995, 679 [Chem. Heterocycl. Compd.
(Engl. Transl.), 1995, 31, 601].
14. A. V. Shastin, T. I. Godovikova, B. L. Korsunskii, Khim.
Geterotsikl. Soedin., 2003, 400 [Chem. Heterocycl. Compd.
(Engl. Transl.), 2003, 39, 354].
33. V. V. Bakharev, A. A. Gidaspov, E. V. Kachanovskaya,
Zh. Organ. Khim., 2007, 43, 455 [Russ. J. Org. Chem.
(Engl. Transl.), 2007, 43, 454].
34. C. Reichardt, Solvents and Solvents Effects in Organic Chemꢀ
istry, VCH, Weinheim, 1988.
15. A. V. Shastin, T. I. Godovikova, B. L. Korsunskii, Proc. 1st
Int. Conference "Chemistry and Biological Activity of Nitrogenꢀ
Containing Heterocycles and Alkaloids" (Moscow, Russia, Ocꢀ
tober 9—12, 2001), Moscow, 2001, 2, 336.
35. S. A. Shevelev, V. I. Erashko, A. A. Fainzil´berg, V. I. Sloꢀ
vetskii, Izv. Akad. Nauk SSSR, Ser. Khim., 1971, 720 [Bull.
Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1971,
20, 645].
16. E. M. Smolin, L. Rappoport, in The Chemistry of Heterocyꢀ
clic Compounds, Ed. A. Weisberger, Wiley, New York,
1959, 13.
17. G. M. Pogosyan, V. A. Pankratov, V. A. Zaplishnyi, S. G.
Matsoyan, Politriaziny [Polytriazines], Izdꢀvo AN Arm. SSR,
Erevan, 1987, 615 pp. (in Russian).
18. J. M. E. Quirke, in Comprehensive Heterocyclic Chemistry,
Eds A. R. Katrizky, C. W. Rees, Pergamon Press, Oxford,
1984, Vol. 3, Pt. 2B.
19. D. Bartolomew, in Comprehensive Heterocyclic Chemistry II,
Eds A. R. Katrizky, C. W. Rees, Pergamon Press, Oxford,
1996, Vol. 6, Pt. 6.12.
20. K. Matsui, J. Synth. Org. Chem. Jpn, 1959, 17, 528.
21. V. I. Mur, Usp. Khim., 1964, 33, 182 [Russ. Chem. Rev. (Engl.
Transl.), 1964, 33, 92].
22. K. Matsui, J. Synth. Org. Chem. Jpn, 1972, 30, 19.
23. G. Blotny, Tetrahedron, 2006, 62, 9507.
24. S. S. Novikov, G. A. Shvekhgeimer, V. V. Sevost´yanova,
V. A. Shlyapochnikov, Khimiya alifaticheskih i alitsikliꢀ
cheskikh nitrosoedinenii [The Chemistry of Aliphatic and Aliꢀ
cyclic Nitro Compounds], Khimiya, Moscow, 1974, 416 pp.
(in Russian).
36. L. A. Kruglyakova, D. Sc. (Chem.) Thesis, Siberian State
Technical University, Krasnoyarsk, 2008, 266 pp. (in Russian).
37. V. L. Rusinov, O. N. Chupakhin, Nitroaziny [Nitrazines],
Nauka, Novosibirsk, 1991, 350 pp. (in Russian).
38. A. A. Gidaspov, Proc. 3rd Int. Conference "Chemistry and
Biological Activity of Nitrogenꢀcontaining Heterocycles" (Cherꢀ
nogolovka, Russia, June 20—23, 2006), Moscow, 2006, 1, 253.
39. A. A. Gidaspov, Proc. 3rd Int. Conference "Chemistry and
Biological Activity of Nitrogenꢀcontaining Heterocycles" (Cherꢀ
nogolovka, Russia, June 20—23, 2006), Moscow, 2006, 2, 86.
40. A. A. Gidaspov, 10th Int. Seminar "New Trends in Research
of Energetic Materials" (Pardubice, Czech Republic, April 25—27,
2007), Pardubice, 2007, 602.
41. A. A. Gidaspov, 10th Int. Seminar "New Trends in Research
of Energetic Materials" (Pardubice, Czech Republic, April 25—27,
2007), Pardubice, 2007, 600.
42. V. V. Bakharev, D. Sc. (Chem.) Thesis, Samara State Techꢀ
nical University, Samara, 2008, 310 pp. (in Russian).
43. F. Borgardt, A. Seeler, P. Noble, J. Org. Chem., 1966,
31, 2806.
44. M. Kamlet, H. G. Adolph, J. Chem. Org. Chem., 1968,
33, 3073.
25. The Chemistry of Nitro and Nitroso Groups, Ed. H. Feuer,
Wiley, New York, 1969.
45. W. M. Koppes, M. E. Sitzmann, H. G. Adolph, J. Chem.
Eng. Data, 1986, 31, 119.
26. S. A. Shevelev, V. I. Erashko, A. A. Fainzil´berg, Izv. Akad.
Nauk SSSR, Ser. Khim., 1976, 2725 [Bull. Acad. Sci. USSR,
Div. Chem. Sci. (Engl. Transl.), 1976, 25, 2535].
27. V. A. Tartakovskii, I. E. Chlenov, S. S. Smagin, Izv. Akad.
Nauk SSSR, Ser. Khim., 1964, 583 [Bull. Acad. Sci. USSR,
Div. Chem. Sci. (Engl. Transl.), 1964, 13, 549].
28. O. A. Luk´yanov, I. A. Sevost´yanova, V. P. Gorelik, Izv.
Akad. Nauk, Ser. Khim., 1992, 1798 [Bull. Russ. Acad. Sci.,
Div. Chem. Sci. (Engl. Transl.), 1992, 41, 1395].
29. B. G. Sankov, V. I. Erashko, S. A. Shevelev, Izv. Akad. Nauk
SSSR, Ser. Khim., 1973, 819 [Bull. Acad. Sci. USSR, Div.
Chem. Sci. (Engl. Transl.), 1973, 22, 796].
30. S. A. Shevelev, V. I. Erashko, B. G. Sankov, A. A. Fainzil´ꢀ
berg, Izv. Akad. Nauk SSSR, Ser. Khim., 1968, 382 [Bull.
Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1968,
17, 368].
31. V. A. Pal´m, Osnovy kolichestvennoi teorii organicheskikh
reaktsii [Quantitative Theory of Organic Reactions], Khimiya,
Leningrad, 1977, 359 pp. (in Russian).
46. N. D. Boldyrev, V. D. Nikolaev, Laboratornyi Praktikum po
Khimii Nitroalkanov [Laboratory Course on Chemistry of
Nitroalkanes], Izdꢀvo LTI im. Lensoveta, Leningrad, 1985,
88 pp. (in Russian).
47. K. V. Titova, E. I. Kolmakova, V. Ya. Rosolovskii, Izv. Akad
Nauk SSSR, Ser. Khim., 1977, 1965 [Bull. Acad. Sci. USSR,
Div. Chem. Sci. (Engl. Transl.), 1977, 26, 1822].
48. RF Pat. 2330026; Buyll. Izobret. [Invention Bull.], 2008, No.
21, 867 (in Russian).
49. Spravochnik Khimika [Chemist´s Handbook], Ed. B. P. Niꢀ
kol´skii, Khimiya, Leningrad, 1967, 4, 919 pp. (in Russian).
50. W. M. Padgett, W. F. Hamner, J. Am. Chem. Soc., 1958,
80, 803.
51. R. J. Stoodley, N. S. Watson, J. Chem. Soc., Perkin Trans. 1,
1974, 252.
52. Y. Tanaka, Chem. Pharm. Bull., 1970, 18, 824.
53. Ping Zhong, MengꢀPing Guo, Synth. Commun., 2001,
31, 1825.
32. A. Albert, E. P. Sergeant, Ionization Constants of Acids and
Bases, Wiley, Inc., New York, 1962.
Received March 10, 2009;
in revised form July 21, 2009