Study of the reaction of trinitromethane with oxiranes

Full text of DOI:10.1134/S0012500808040010

ISSN 0012-5008, Doklady Chemistry, 2008, Vol. 419, Part 2, pp. 83–86. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © Yu.A. Volkova, O.A. Ivanova, E.B. Averina, E.M. Budynina, T.S. Kuznetsova, N.S. Zefirov, 2008, published in Doklady Akademii Nauk, 2008, Vol. 419,
No. 4, pp. 500–503.
CHEMISTRY
Study of the Reaction of Trinitromethane with Oxiranes
Yu. A. Volkova, O. A. Ivanova, E. B. Averina, E. M. Budynina,
T. S. Kuznetsova, and Academician N. S. Zefirov
Received September 19, 2007
DOI: 10.1134/S0012500808040010
The reaction of olefins with polynitromethanes is a diverse heterocycles, and as a possible approach to the
known method for the preparation of 3,3-dinitroisox- synthesis of trinitroalkanols.
azolidines [1, 2]. Previously, we studied reactions of
tetranitromethane and halotrinitromethanes with unsat-
urated compounds containing small rings [3–8]. It was
shown that the reactions of polynitromethanes with
strained alkenes and acetylenes give a range of N- and
O-containing heterocycles (dinitroisoxazolidines,
nitroisoxazolines, dinitropiperidones, dinitroaziri-
dines), tetranitropropanes, and gem-dinitrocyclopro-
panes [3–9].
The trinitromethyl anion is known to show ambident
properties, functioning as either an O- or a C-nucleo-
phile depending on the substrate nature [1, 4, 7]. We
suggested two possible pathways for its reaction with
epoxides (Scheme 1), namely, pathway Ä including
C-alkylation of the oxonium cation I to give 3,3,3-tri-
nitropropanols II (two-component reaction) and path-
way B including O-alkylation of the oxonium cation I
with generation of an unstable nitronic ester III, which
No data on reactions of oxiranes with polyni- can either decompose to α-hydroxy ketone IV or
tromethanes have been reported so far, although these undergo [3+2]-cycloaddition in the presence of an ole-
reactions can be considered as a new method for gener- fin to give 3,3-dinitroisoxazolidines V (three-compo-
ation of alkyl nitronates, which are precursors of nent reaction).
ꢀ
H
C(NO2)3
O
C C
HC(NO2)3
C-alkylation
O
C
OH
C⊕C
C
(O2N)3C
pathway A
I
II
ꢀ
pathway B
O-alkylation
C(NO2)3
⊕
C(NO2)2
NO2
O2N
ꢀ
N
O
C
O
O
HO
C
OH
–[HON=C(NO2)2]
[3+2]-cycloaddition
N
C C
O
O
OH
IV
III
V
Scheme 1.
The ratio of C- to O-alkylation of cation I with the tromethane and aimed at the search for the ways of
trinitromethyl anion depends on the positive charge implementation of C-alkylation of oxonium cation I to
delocalization properties of substituents in the sub- give type II adducts (Scheme 1, pathway A).
strate.
As the model reaction, we studied the reaction of
This study is devoted to the previously unknown
two-component reaction of oxiranes with trini-
styrene oxide (VIa) with trinitromethane at room tem-
perature in nonpolar and polar solvents (Scheme 2).
One could expect that the presence of the phenyl group
in the styrene oxide would facilitate C-alkylation of the
oxonium cation I with trinitromethane.
Moscow State University, Vorob’evy gory,
Moscow, 119992 Russia
83

84
VOLKOVA et al.
OH
O
O
C(NO2)3
OH
20°C
+ HC(NO2)3
+
VIa
VIIa
Scheme 2.
VIIIa
The reaction of styrene oxide (VIa) with trini- zyl carbocation. These results are in line with pub-
tromethane in benzene was found to follow two path- lished data concerning the effect of steric factors on
ways, namely, C-alkylation to give γ-trinitropropanol
VIIa (yield 40%) and O-alkylation to give α-keto alco-
hol VIIIa (yield 55%). The latter results from decom-
position of unstable nitronic ester III formed from trin-
itromethane and styrene oxide according to pathway B.
The 13ë NMR spectrum of the trinitro derivative
VIIa exhibits signals at δ 38.0 and 74.7 ppm corre-
sponding to the methylene carbon atom of the
CH2C(NO2)3 fragment and methine carbon atom of the
CHOH group, respectively, which attests unambigu-
ously to the formation of the proposed regioisomer.
Thus, in this case, the attack by the shielded C-center
on the trinitromethyl anion involves only the terminal,
spatially more accessible carbon atom of oxirane (VIa).
the regioselectivity of nucleophilic oxirane ring open-
ing [11, 12].
When the reaction of styrene oxide VIa with trini-
tromethane is carried out in dioxane, products VIIa and
VIIIa are formed in 50 and 20% yields, respectively;
i.e., C-alkylation becomes the predominant reaction
pathway. The reaction of styrene oxide VIa with trini-
tromethane in petroleum ether proceeds exclusively as
C-alkylation but trinitropropanol VIIa is formed in a
low yield (27%) due to partial polymerization of the
starting oxide. Note for comparison that the reaction of
an aqueous solution of the potassium salt of trini-
tromethane with styrene oxide VIa does not give any
identifiable products.
The 1H and 13C NMR spectra of keto alcohol VIIIa
correspond to published data [10]. It is obvious that the
attack by the O-center of the nucleophile is directed at
the benzyl position of oxirane and involves the interme- formation of C-alkylation products using oxide VIa
diate formation of thermodynamically more stable ben- (Scheme 3) as an example.
The reaction of trinitromethane with oxiranes VIb–
VId was carried out under conditions optimized for the
O
R2
HO
R1
R2
O
1,4-dioxane, 20°C
+
+ HC(NO )
2 3
R1
R2
R1
OH
C(NO2)3
VIa–VId
VIIa–VIId
VIIIa–VIIIc
Scheme 3.
The results are summarized in the table.
under the reaction conditions under the action of trini-
tromethane.
According to NMR data for the reaction mixture,
the reaction of p-bromostyrene oxide VIb gives trinitro
alcohol VIIb as the major product, which was formed
in 65% yield according to NMR data. However, after
chromatographic purification, the yield of alcohol VIIb
did not exceed 20% due to its low stability against silica
gel.
1,1-Diphenylethylene oxide proved to be inert with
respect to trinitromethane under the selected condi-
tions; this may be due to steric hindrance to the reaction
of the trinitromethyl anion with the oxonium cation. An
attempt to involve ethylene oxide in the reaction with
trinitromethane was also unsuccessful because the
reaction under these conditions gave only polymeriza-
tion products.
In the reaction of cycloheptene oxide VIc with tri-
nitromethane, C- and O-alkylation products VIIc and
VIIIc, respectively, were isolated in approximately
equal amounts.
Thus, we found that reactions of trinitromethane
with oxiranes containing both aryl and alkyl substitu-
ents proceed in most cases as competitive C- and O-
The reaction of propylene oxide VId with trini- alkylation to give γ-trinitropropanols VII and α-keto
tromethane was carried out in a sealed tube using a alcohols VIII, respectively. Trinitro alcohols proved to
fourfold excess of oxirane VId with respect to trini- be rather labile compounds that decompose during stor-
tromethane. The reaction affords trinitro alcohol VIId age or during chromatography on silica gel. Neverthe-
in a low yield and 1,2-propanediol IX in 40% yield. less, these compounds should be classified as rather
Note that propylene oxide is substantially polymerized readily accessible and promising intermediates, for
DOKLADY CHEMISTRY Vol. 419 Part 2 2008

STUDY OF THE REACTION OF TRINITROMETHANE WITH OXIRANES
85
Reaction conditions and product yields for the reaction of oxiranes VIa–VId with trinitromethane
Chromatographic yield, %
Time,
days
Oxirane
R1
Ph
R2
Products
VII
VIII
VIa
VIb
VIc
VId
H
H
VIIa, VIIIa
VIIb, VIIIb
VIIc, VIIIc
VIId, VIIId
1
7
2
2
50
20
20
14
20
30
23
–
p-BrPh
–(CH2)5–
Me
H
example, for nitration and preparation of trinitronitra-
toalkanes, new high-energy compounds.
1-(4-Bromophenyl)-3,3,3-trinitro-1-propanol VIIb.
Yield 140 mg (20%); yellow liquid; Rf 0.84 (petroleum
2
ether–EtOAc, 4 : 1). 1H NMR (CDCl3, δ, ppm) : 2.98
2
3
2
(dd, J = 13.7, J = 9.8 Hz, 1 H, CH2), 3.06 (dd, J =
EXPERIMENTAL
13.7, 3J = 1.7 Hz, 1 H, CH2), 5.09 (dd, 3J = 1.7, 9.8 Hz,
1H and 13C NMR spectra were recorded on a Bruker
AM-400 spectrometer (400 and 100 MHz, respec-
tively). Chloroform signals (δç 7.28 and δë 77.1 ppm)
were used as the internal standard. Mass spectra were
recorded on an MC Finnigan MAT ITD-700 instru-
ment at an ionization energy of 70 eV. Positive ion
MALDI TOF mass spectra were run on a Bruker Dal-
tonics Ultraflex instrument (1,8,9-trihydroxyan-
thracene was used as the matrix).
1 H, CH), 7.08–7.18 (m, 4 H, Ph). 13C NMR (CDCl3, δ,
ppm): 37.5 (CH2), 74.2 (CH), 123.1 [C(NO2)3], 131.3
(2 × CH, Ph), 131.6 (C, Ph), 132.0 (2 × CH, Ph), 132.7
(C, Ph).
1-(4-Bromophenyl)-2-hydroxyethanone VIIIb
[13]. Yield 90 mg (20%); pale yellow liquid; Rf 0.35
1
(petroleum ether–EtOAc, 4 : 1). H NMR (CDCl3, δ,
2
ppm): 1.87 (br.s, 1 H, OH), 3.05 (d, J = 2.0 Hz, 1 H,
2
CH2), 3.67 (d, J = 2.0 Hz, 1 H, CH2), 7.49–7.52 (m,
The reactions were monitored and the compound
purity was checked by TLC (Silufol UV-254). Prepara-
tive column chromatography was performed using
Acros silica gel (60–200 mesh).
4 H, Ph). 13C NMR (CDCl3, δ, ppm): 65.3 (CH2), 129.1
(2 × CH, Ph), 131.4 (C, Ph), 132.4 (2 × CH, Ph), 132.9
(C, Ph), 201.3 (CO).
2-(Trinitromethyl)cycloheptanol VIIc. Yield
110 mg (20%); yellow liquid; Rf 0.75 (petroleum ether–
General procedure. Trinitromethane (4 mmol) was
added to a solution of oxirane (2 mmol) in 1,4-dioxane
(5 ml) at room temperature. The reaction mixture was
stirred at 20°ë for 1–7 days (table). Then the solvent
was evaporated under reduced pressure. The products
were isolated by column chromatography on silica gel
(elution with petroleum ether–EtOAc, 4 : 1).
1
EtOAc, 4 : 1). H NMR (CDCl3, δ, ppm)3: 1.51–1.88
(m, 10 H, CH2), 3.80–3.85 (m, 1 H, CHC(NO2)3), 4.91–
4.97 (m, 1 H, CHOH). 13C NMR (CDCl3, δ, ppm):
22.4, 26.6, 28.9, 32.9, 33.7 (CH2), 40.6 [CH(NO2)3],
3
70.9 (CHOH), 128.2 [C(NO2)3].
3,3,3-Trinitro-1-phenyl-1-propanol VIIa. Yield
270 mg (50%); yellow liquid; Rf 0.63 (petroleum ether–
2-Hydroxyheptanone VIIIc [10]. Yield 60 mg
(23%); yellow liquid; Rf 0.58 (petroleum ether–EtOAc,
EtOAc, 4 : 1). 1ç NMR (CDCl3, δ, ppm): 3.06 (dd, 2J =
13.9, 3J = 9.9 Hz, 1 H, CH2), 3.17 (dd, 2J = 13.9, 3J =
2.0 Hz, 1 H, CH2), 3.45 (br.s, 1 H, OH), 5.14 (dd, 3J =
2.0, 9.9 Hz, 1 H, CH), 7.28–7.92 (m, 5 H, Ph). 13ë
4 : 1). 1H NMR (CDCl3, δ, ppm)3: 1.51–1.88 (m, 10 H,
3
13
CH2), 4.31 (dd, J = 3.4, 9.6 Hz, 1 H, CH). C NMR
(CDCl3, δ, ppm): 22.4, 24.9, 28.7, 33.7, 40.1 (CH2),
77.4 (CH), 203.7 (CO).
1
NMR (CDCl3, δ, ppm) : 38.0 (CH2), 74.7 (CH), 128.8,
4,4,4-Trinitro-2-butanol VIIId [14]. Yield 60 mg
(14%); yellow liquid; Rf 0.45 (petroleum ether–EtOAc,
129.1 (×2), 129.5 (×2) (CH, Ph), 134.8 (C). MS: m/z =
271 [å]+.
4 : 1). 1H NMR (CDCl3, δ, ppm)3: 1.31 (d, 3J = 5.3 Hz,
3 H, CH3), 3.64 (dd, 2J = 12.8, 3J = 6.7 Hz, 1 H, CH2),
3.73 (dd, 2J = 12.8, 3J = 3.3 Hz, 1 H, CH2), 4.06–4.12
(m, 1 H, CH). 13C NMR (CDCl3, δ, ppm): 18.9 (CH3),
41.8 (CH2), 81.5 (CH), 128.1 [C(NO2)3]. MALDI TOF
MS: m/z = 209 [M]+.
2-Hydroxy-1-phenylethanone VIIIa [10]. Yield
50 mg (20%); pale yellow liquid; Rf 0.38 (petroleum
1
ether–EtOAc, 4 : 1). H NMR (CDCl3, δ, ppm): 3.45
(br.s, 1 H, OH), 4.88 (s, 2 H, CH2), 7.28–7.92 (m, 5 H,
Ph). 13ë NMR (CDCl3, δ, ppm): 65.3 (CH2), 127.8
(×2), 127.9 (CH, Ph), 129.0 (2 × CH, Ph), 134.8 (C,
Ph), 198.6 (CO).
2
No signal for the hydroxyl group proton was observed in the
1
H NMR spectrum of compound VIIb.
1
13
3
No signal for the C(NO ) group was observed in the C NMR
No signals for the hydroxyl group protons were observed in the
2 3
1
spectrum of VIIa.
H NMR spectra of VIIc, VIIIc, VIIId, or IX.
DOKLADY CHEMISTRY Vol. 419 Part 2 2008

86
VOLKOVA et al.
6. Averina, E.B., Budynina, E.M., Ivanova, O.A.,
ACKNOWLEDGMENTS
Grishin, Yu.K., Gerdov, S.M., Kuznetsova, T.S., and
Zefirov, N.S., Zh. Org. Khim., 2004, vol. 40, no. 2,
pp. 186–198.
This work was supported by the Division of Chem-
istry and Materials Science of the Russian Academy of
Sciences (program no. 1.5), the Russian Foundation for
Basic Research (project no. 07–03–00685a), and the
Council for Grants of the President of the Russian Fed-
eration for Support of Leading Scientific Schools (grant
no. NSh–2552.2006.3).
7. Budinina, E.M., Averina, E.B., Ivanova, O.A., Kuzne-
tsova, T.S., and Zefirov, N.S., Tetrahedron Lett., 2005,
vol. 46, pp. 657–659.
8. Budinina, E.M., Ivanova, O.A., Averina, E.B.,
Grishin, Yu.K., Kuznetsova, T.S., and Zefirov, N.S., Syn-
thesis, no. 2, 2005, pp. 286–290.
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DOKLADY CHEMISTRY Vol. 419 Part 2 2008