Six Peroxide Groups in One Molecule - Synthesis of Nine-Membered Bicyclic Silyl Peroxides

Article abstract of DOI:10.1002/ejoc.201402895

Comounds containing two nine-membered peroxide rings bridged by an ethane, ethene, or ethyne group were synthesized by the reactions of 1,2-bis[dichloro(alkyl)silyl]ethanes, (E)-1,2-bis[dichloro(methyl)silyl]ethene, or 1,2-bis[dichloro(methyl)silyl]ethyne

Full text of DOI:10.1002/ejoc.201402895

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
FULL PAPER
DOI: 10.1002/ejoc.201402895
Six Peroxide Groups in One Molecule – Synthesis of Nine-Membered Bicyclic
Silyl Peroxides
[
a,b]
[a]
[a]
Ashot V. Arzumanyan,
Alexander O. Terent’ev,* Roman A. Novikov,
[
c]
[d,e]
[f]
Valentin G. Lakhtin, Vladimir V. Chernyshev,
Andrew N. Fitch, and
Gennady I. Nikishin[
a]
Keywords: Silanes / Peroxides / Energetic materials / Cyclization
Compounds containing two nine-membered peroxide rings
bridged by an ethane, ethene, or ethyne group were synthe-
sized by the reactions of 1,2-bis[dichloro(alkyl)silyl]ethanes,
gioselective. The possible 12-membered bicyclic peroxide
products are not produced. Unexpectedly, the peroxides are
extremely explosive. The reactions of 1,2-bis[dichloro(alkyl)-
silyl]ethanes with 1,1-dihydroperoxy-tert-butylcyclohexane
give only bicyclic peroxides containing two six-membered
rings also through the replacement of two geminal chlorine
atoms at the silicon atom by the hydroperoxide groups of one
dihydroperoxide molecule.
(
(
E)-1,2-bis[dichloro(methyl)silyl]ethene, or 1,2-bis[dichloro-
methyl)silyl]ethyne with 1,1Ј-dihydroperoxydicycloalkyl
peroxides. Each ring is formed by the replacement of two
geminal chlorine atoms at the silicon atom with the hydroper-
oxide groups of one peroxide molecule. The cyclization is re-
Introduction
Most of the known organic peroxides contain COO–
groups, whereas peroxides with SiOO– groups are much less
common. The chemistry of organosilicon peroxides is less
developed compared to that of organic peroxides mainly
because of their lower hydrolytic stability and the limited
number of methods for the selective synthesis of these com-
pounds. There are several routes to peroxides with the Si–
O–O group. These methods are based on the Mukaiyama–
Organic peroxides have been widely used for more than
half a century in industry and scientific research as oxi-
dants, initiators for radical polymerization and crosslinking,
and synthetic intermediates.[ Peroxides containing the C–
O–O group are traditionally considered as possible explos-
ives. For instance, hexamethylene triperoxide diamine, acet-
one di- and triperoxides, and peroxides of other ketones are
of particular interest.[ In the past three decades, organic
peroxides have attracted interest as pharmaceutically active
1]
[6]
Isayama peroxidation of unsaturated compounds and the
2]
reactions of chlorosilanes with hydroperoxides in the pres-
[7]
ence of bases, compounds containing the Si–H bond with
[3]
compounds, for example, with antimalarial or antihelmin-
[8]
[9]
ozone, singlet oxygen with silyl enolates, and hydroper-
[
4]
thic properties. In the last decade, these compounds have
[10]
oxides with N,O-bis(trimethylsilyl)acetamide.
been tested for antitumor activity.[
5]
Compounds containing the Si–O–O group have specific
fields of application and properties. They also can be used
in the same areas as organic peroxides and have some prop-
erties similar to the latter. The specificity of organosilicon
peroxides is associated with the fact that the silicon atom is
highly prone to oxidation, which is usually accompanied by
Si–C bond cleavage. For example, silyl peroxides undergo
[
a] N.D. Zelinsky Institute of Organic Chemistry,
Russian Academy of Sciences,
4
7 Leninsky prosp., 119991 Moscow, Russian Federation
E-mail: alterex@yandex.ru
http://peroxide.ucoz.org/
[
[
[
[
[
b] Institute of Chemistry, Saint Petersburg State University,
Universitetsky Pr. 26, 198504 Stary Petergof,
Russian Federation
[
11]
thermal transformations,
peroxides. Organosilicon peroxides are used for peroxid-
which is not typical of alkyl
c] State Scientific Research Institute of Chemistry and Technology
of Organoelement Compounds,
3
8 Shosse Entuziastov, 111123 Moscow, Russian Federation
[12]
[13]
ation,
of arenes,
1,2-dioxanes,
initiation of polymerization,
hydroxylation
d] Department of Chemistry, M.V. Lomonosov Moscow State
University,
[
14]
[15]
and for the synthesis of 1,2-dioxolanes,
[
15e,16]
[17]
[15e]
1
–3 Leninskie Gory, 119991 Moscow, Russian Federation
1,2,4-trioxanes,
1,2-dioxepanes,
e] A.N. Frumkin Institute of Physical Chemistry and
Electrochemistry, Russian Academy of Sciences,
,2,4,5-tetraoxepanes,[18] and 1,2,4,5-tetraoxanes.[19] Organo
1
3
1 Leninsky prosp., 119071 Moscow, Russian Federation
silicon peroxides are produced as intermediates in the Flem-
f] European Synchrotron Radiation Facility,
[20]
[21]
ing
and Tamao–Kumada
oxidations. The physico-
B. P. 220, 38043 Grenoble Cedex, France
chemical properties of Si–O–O peroxides have received con-
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402895.
[
22]
siderable attention from researchers.
The main data on
1
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
A. O. Terent’ev et al.
FULL PAPER
organosilicon peroxides have been discussed in several re- 4a–4c. The reactions were performed in diethyl ether at 20–
[
23]
views.
25 °C in the presence of imidazole as a base at a chlorodisil-
The chemistry of cyclic silyl peroxides, in particular, the ane/dihydroperoxide/imidazole molar ratio of 1:2.4:5. Un-
synthesis of these compounds, has received little study. The der these conditions, the probable 12-membered rings are
following cyclic structures containing the O–O–Si–O–O not formed (Table 1).
fragment have been reported: 3,3,6,6,9,9-hexamethyl-
The synthesized peroxides were characterized by NMR
[24]
1
,2,4,5,7,8-hexaoxa-3,6,9-trisilonane,
1,2,4,5,7,8-hexa- spectroscopy and high-resolution mass spectrometry. The
[
25]
oxa-3-silonanes, macrocycles containing the SiOOC moi- determination of their structures appeared to be a complex
ety,[ and some other related structures.
26]
[27,22f,22g]
The small problem. The formation of either nine- or twelve-membered
body of data on peroxide macrocycles is largely because rings could be proposed on the basis of the NMR spectro-
these compounds are synthesized from two bifunctional scopic and mass spectrometric data. The selective formation
reagents, which easily form linear products (oligomers and of the nine-membered rings was ultimately confirmed by an
polymers) when they react with each other. Hence, it is not X-ray diffraction study of 5a (Figure 1).
always possible to use this approach for the synthesis of
cyclic peroxides with a specific composition.
In the present study, we successfully synthesized perox-
ides consisting of two Si-containing rings with three perox-
ide groups in each ring and, as a result, the products con-
tain six peroxide groups per molecule.
In the crystal structure of 5a, the molecules are centro-
symmetric with an inversion center located at the midpoint
of the ethylene group that bridges the two Si atoms. All
bond lengths and bond angles have standard values and
are in good agreement with those observed in the crystal
[25]
structures of two related 1,2,4,5,7,8-hexaoxa-3-silonanes.
Each Si atom has a distorted tetrahedral environment
formed by two O atoms [Si–O 1.674(9) and 1.691(10) Å]
and two C atoms [Si–C 1.875(14) and 1.897(15) Å]. Two
independent cyclopentane rings adopt an envelope confor-
mation with the C-5 and C-10 atoms as flaps. The crystal
Results and Discussion
Synthesis of Nine-Membered Bicyclic Silyl Peroxides
The reactions of the tetrachlorodisilanes 1a, 1b, 2, and 3 packing is typical of branched hydrocarbons with hydro-
with the dihydroperoxyperoxides 4a–4c under mild condi- phobic space-filling contacts.
tions resulted in the formation of two nine-membered Si-
containing peroxide rings bridged by an ethane, ethene, or explosive compounds sensitive to friction, impact, and heat.
ethyne group (Scheme 1). We failed to determine their melting points; the heating of
A surprising fact was the instability of 5a–5c, which are
The chlorine atoms in the disilanes 1a, 1b, 2, and 3 are these compounds led to their extensive decomposition with
selectively replaced by peroxide groups to form the bicyclic destruction of equipment, which made it very difficult to
silyl peroxides 5a–5c, 6, 7, and 8 rather than the possible perform elemental analysis. Nine-membered monocyclic
1
2-membered ring products 5Ј. The yields of the peroxides peroxides containing three peroxide groups synthesized in
[
25]
vary from 52 to 95% and increase with increasing size of our previous work
were stable compounds. The ratio of
the cycloalkyl moiety in the starting dihydroperoxyperoxide the C, H, O, and Si atoms in the stable monocyclic perox-
Scheme 1. Synthesis of nine-membered bicyclic silyl peroxides 5a–5c, 6, 7, and 8.
2
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
Synthesis of Nine-Membered Bicyclic Silyl Peroxides
Table 1. Synthesis of nine-membered bicyclic silyl peroxides 5a–5c, ides[25] is the same as that in the bicyclic peroxides 5a–5c.
6, 7, and 8 (structures; yields).
Therefore, the explosive properties of 5a–5c are attributed
to the presence of six peroxide groups in one molecule and
the consequential higher probability of cleavage of one
O–O bond to initiate the intramolecular decomposition of
5a–5c.
Synthesis of Six-Membered Bicyclic Silyl Peroxides from
,2-Bis[dichloro(alkyl)silyl]ethanes and 1,1-
1
Bis(hydroperoxy)-4-tert-butylcyclohexane
In the next stage of our work, we investigated the reac-
tion of the 1,2-bis(alkyldichlorosilyl)ethanes 1a and 1b with
1,1-bis(hydroperoxy)-4-tert-butylcyclohexane (9, Scheme 2).
[
a] A solution of tetrachlorodisilane 1 (0.150 g, 0.586 mmol) in
Et O (1.5 mL) was added to a mixture of 1,1Ј-dihydroperoxydi-
cycloalkyl peroxide 4a–4c (0.329–0.408 g, 1.406 mmol) and imid-
azole (0.199 g, 2.930 mmol) in Et O (9 mL) at 20–25 °C for 3–
min, and then the reaction mixture was stirred for 3 h. Com-
pounds 5a–5c and 8 were isolated by crystallization. [b] A solution
of tetrachlorodisilane (0.150 g, 0.586 mmol), (0.149 g,
.586 mmol), or 3 (0.148 g, 0.586 mmol) in Et O (1.5 mL) was
added to a mixture of 1,1Ј-dihydroperoxydicycloalkyl peroxide
2
2
4
1
2
0
2
4
a–4c (0.329–0.408 g, 1.406 mmol) and imidazole (0.199 g,
2
.930 mmol) in Et O (9 mL) at 20–25 °C for 3–4 min, and then the
2
reaction mixture was stirred for 3 h. Compounds 5c and 6–8 were
isolated by silica gel filtration.
Scheme 2. Synthesis of the six-membered bicyclic silyl peroxides
1
3
1
0a and 10b and parts of the C NMR spectra with the resonances
of the OOCOO fragments.
In this case, the formation of nine-membered cyclic silyl
peroxides 10Јa and 10Јb as more-stable compounds would
be expected by analogy with the data on the formation of
cyclic structures according to Scheme 1.
However, the reaction produced exclusively the six-mem-
bered cyclic silyl peroxides 10a and 10b rather than the
Figure 1. The molecular structure of 5a showing the atomic num-
bering scheme and 50% probability displacement ellipsoids. The
unlabeled atoms are related to the labeled atoms by the symmetry
operation (1 – x, 1 – y, 1 – z). Hydrogen atoms are omitted for
clarity.
[
25,26]
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
A. O. Terent’ev et al.
FULL PAPER
nine-membered peroxides, that is, two geminal chlorine isolated, used in reactions, and stored at 0–10 °C without
atoms at the silicon atom are replaced by two geminal clear signs of decomposition over several months. After fur-
hydroperoxide groups of diperoxide 9 (Scheme 2).
ther investigations in the field of explosives, the synthesized
Unlike the nine-membered peroxides 5a–5c, the six-mem- Si–O–O peroxides could find use as such compounds along
bered bicyclic peroxides 10a and 10b are unstable. They with nitro compounds, alkyl peroxides, and azides, for ex-
were not isolated in the individual state, because these com- ample.
pounds did not withstand purification on alumina and dif-
ferent types of silica gel. The NMR monitoring of the reac-
tion presented in Scheme 2 showed that the reaction af-
forded six-membered bicyclic peroxides as the only prod-
ucts, but these compounds completely decomposed in the
reaction mixtures within 24 h.
Experimental Section
Caution: When working with peroxides, precautions, such as the use
of shields, fume hoods, and the avoidance of transition metal salts,
heating, and shaking, should be taken whenever possible.
The formation of the six-membered bicyclic peroxides
0a and 10b rather than the possible nine-membered bi- The H and 13C NMR spectra were recorded with 400 (400.1 and
1
1
1
00.6 MHz, respectively) and 300 MHz (300.1 and 75.5 MHz,
respectively) spectrometers with samples in CDCl . The assign-
ments of H and C NMR signals were made with the aid of 2D
cyclic peroxides 10Јa and 10Јb was confirmed by the NMR
spectroscopic monitoring of the reactions of 9 with 1,2-
bis(dimethylchlorosilyl)ethane (1a) and 2-dichloroethylsilyl-
3
1
13
2
9
COSY, HSQC, and HMBC spectra when necessary. The Si NMR
1-methyldichlorosilylethane (1b) in the presence of pyridine
spectra were recorded with a 300 MHz spectrometer (59.6 MHz;
in CDCl (Scheme 2). For the reaction of the diperoxide 9
3
1
3
00.1 MHz for H) with samples in CDCl
3
by using the insensitive
1
3
with tetrachlorodisilane 1a, the
Scheme 2) shows one signal of the OOCOO group at δ =
11.45 ppm, which is indicative of the formation of two made with the aid of 2D HMBC spectra when necessary. As some
C NMR spectrum
nuclei enhanced by polarization transfer (INEPT) sequence and
Me Si as the standard. The assignments of Si NMR signals were
4
(
1
29
2
9
identical rings, that is, of the equally probable peroxides 10a chemical shifts in the Si NMR spectra could not be directly de-
or 10Јa. The key data in support of the formation of the tected, they were taken from the corresponding two-dimensional
spectra. The reactions in CDCl
tubes. The diffusion coefficients were measured by 2D H DOSY
NMR spectroscopy with samples in CDCl with a 300 MHz spec-
trometer (300.1 MHz for H). The BPP-LED pulse sequence was
used with Δ = 100 ms and T = 5 ms. The DOSY spectra were
processed by monoexponential fitting and the SCORE algorithm
by using the Bruker TopSpin and DOSY Toolbox software. Di-
benzo-18-crown-6 was used as an internal and external calibrant
3
solutions were monitored in NMR
six-membered bicyclic peroxides 10a and10b were obtained
by NMR spectroscopic monitoring of the reaction of 9 with
1
1
3
3
1b. Thus, the C NMR spectrum shows two signals at δ =
1
111.41 and 111.47 ppm (Scheme 2), which belong to two
e
nonequivalent OOCOO groups of six-membered rings 10b
and by no means correspond to two identical OOCOO
groups of bicyclic peroxide 10Јb.
The structure of the six-membered bicyclic peroxide 10b for the molecular weights in a molar ratio of ca. 1:1 to the com-
was ultimately established by H, C, and Si NMR spec- pounds under study in the DOSY spectra.
1
13
29
troscopy through the 2D correlation techniques COSY,
heteronuclear single quantum coherence (HSQC), and
HMBC and by diffusion-ordered spectroscopy (DOSY).
MeCN (HPLC grade) for ESI-HRMS experiments was purchased
from Merck and used as supplied. All samples for ESI-HRMS ex-
periments were prepared in 1.5 mL Eppendorf tubes. All plastic
The DOSY NMR spectroscopic data provided an estimate disposables (Eppendorf tubes and tips) used in sample preparation
of the molecular weight of this compound and, conse- were washed with MeCN before use. High-resolution mass spectra
quently, the number of residual dihydroperoxide and disil- were recorded with a Bruker maXis instrument equipped with an
electrospray ionization (ESI) ion source.[ All measurements were
28]
ane moieties in the molecule.
performed in positive (+MS) ion mode (interface capillary voltage:
4500 V) with a scan range m/z = 50–3000. External calibration of
the mass spectrometer was performed with Electrospray Calibrant
Solution (Fluka). A direct syringe injection was used for all of the
analyzed solutions in MeCN (flow rate: 3 μL/min). Nitrogen was
used as the nebulizer gas (0.4 bar) and dry gas (4.0 L/min); the
interface temperature was set at 180 °C. All of the spectra were
Conclusions
Compounds containing two nine-membered silyl perox-
ide rings bridged by an ethane, ethene, or ethyne group were
synthesized by the reaction of 1,2-bis[dichloro(alkyl)silyl]- processed by using the Bruker DataAnalysis 4.0 software package.
ethanes, (E)-1,2-bis[dichloro(methyl)silyl]ethene, or 1,2-bis-
The TLC analysis was performed with standard silica gel
chromatography plates. The melting points were determined with
a Kofler hot-stage apparatus. Chromatography was performed with
[
dichloro(methyl)silyl]ethyne with 1,1Ј-dihydroperoxyperox-
ides and were then isolated in the individual state. Only bi-
cyclic peroxides containing two six-membered rings were
2
silica gel (63–200 mesh). Dichloromethane, Et O, petroleum ether
detected in the reactions of 1,2-bis[dichloro(alkyl)silyl]eth- (PE; 40/70), MeCN, tetrahydrofuran (THF), ethyl acetate, and
anes with 1,1-bis(hydroperoxy)-tert-butylcyclohexane. In imidazole were purchased from Acros. Silica fume (particle size
both cases, the ring is formed by the replacement of the 0.007 mm, S5130) was purchased from Sigma. 1,1Ј-Dihydroper-
oxyperoxides 4a–4c and 1,1-bis(hydroperoxy)-4-tert-butylcyclohex-
geminal chlorine atoms at the silicon atom by two hydro-
peroxide groups of one peroxide molecule. The nine-mem-
ane (9) were prepared as described previously.[
29]
bered bicyclic peroxides containing six peroxide groups in CCDC-1012863 contains the supplementary crystallographic data
one molecule are extremely explosive. However, they can be for this paper. These data can be obtained free of charge from The
4
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
Synthesis of Nine-Membered Bicyclic Silyl Peroxides
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ 32.64, 32.89, 104.98, 114.27 ppm. 29Si NMR (59.6 MHz, CDCl
):
[M +
3
data_request/cif.
δ = –28.31 ppm. HRMS (ESI): calcd. for C32
Na] 709.3046; found 709.3068.
H54NaO12Si
2
+
General Procedure for the Synthesis of 5a–c and 8: A solution of
silane 1a (0.150 g, 0.586 mmol) in Et
2
O (1.5 mL) was added with 19-Ethyl-19-[2-(19-methyl-8,9,17,18,20,21-hexaoxa-19-siladispiro-
vigorous stirring to a mixture of 1,1Ј-dihydroperoxydicycloalkyl
peroxide 4a–4c (0.329–0.408 g, 1.406 mmol) and imidazole
[6.2.6.5]heneicos-19-yl)ethyl]-8,9,17,18,20,21-hexaoxa-19-siladi-
spiro[6.2.6.5]heneicosane (8): White crystals, explosive on heating
1
(
0.199 g, 2.930 mmol) in Et
The reaction mixture was stirred for 3 h. Then, petroleum ether
40 mL) was added. The mixture was successively washed with a
% NaOH solution (2ϫ 10 mL) and water (2ϫ 10 mL). The or-
ganic phase was separated and dried with MgSO . The solvent was
evaporated by using a water-jet vacuum pump. The products
a–5c and 8 were isolated by crystallization from MeOH (Table 1,
note [a]).
Synthesis of 3,3Ј-Ethane-(or ethene or ethyne)-1,2-diylbis- lar ratio of 2.2:5 were dissolved in CDCl
,2,4,5,7,8,3-hexaoxasilonanones 5c and 6–8: A solution of silane 1
tube filled with argon. Then, bis(dimethylchlorosilyl)ethane (1a;
0.150 g, 0.586 mmol), 2 (0.149 g, 0.586 mmol), or 3 (0.148 g,
.586 mmol) in Et
O (1.5 mL) was added with vigorous stirring NMR spectra were recorded by using the 2D correlation techniques
to a mixture of 4c (0.408 g, 1.406 mmol) and imidazole (0.199 g, COSY, HSQC, and HMBC.
.930 mmol) in Et O (9 mL) at 20–25 °C over 3–4 min. The reac-
2
O (9 mL) at 20–25 °C over 3–4 min.
above 135 °C. R
f
= 0.6 (TLC, hexane/ethyl acetate, 10:1). H NMR
(300 MHz, CDCl
3
): δ = 0.26 (s, 3 H), 0.70–2.23 (m, 57 H) ppm.
3C NMR (75.5 MHz, CDCl
): δ = –7.34, 1.34, 2.25, 2.66, 6.49,
22.76, 22.91, 29.79, 29.93, 32.99 113.60 ppm.
(59.6 MHz, CDCl ): δ = 4.91, 6.57 ppm. HRMS (ESI): calcd. for
60NaO12Si
[M + Na]+ 727.3516; found 727.3521.
Compound 10a: 1,1-Bis(hydroperoxy)-4-tert-butylcyclohexane (9;
.040 g, 0.1961 mmol) and pyridine (0.035 g, 0.446 mmol) in a mo-
(0.6 mL) in an NMR
1
(
5
3
2
9
Si NMR
4
3
C
33
H
2
5
0
3
1
(
1
13
29
0.023 g, 0.0891 mmol) was added. After 1 h, H, C, and Si
0
2
2
2
Compound 10b: 1,1-Bis(hydroperoxy)-4-tert-butylcyclohexane (9;
.040 g, 0.1961 mmol) and pyridine (0.035 g, 0.446 mmol) in a mo-
lar ratio of 2.2:5 were dissolved in CDCl (0.6 mL) in an NMR
tion mixture was stirred for 3 h, petroleum ether (40 mL) was
added, and the reaction mixture was filtered through a short layer
0
3
(2 cm) of silica gel (5–40 μm). The solvent was evaporated by using
tube filled with argon. Then, 2-dichloroethylsilyl-1-methyldi-
a water-jet vacuum pump (Table 1, note [b]).
chlorosilylethane (1b; 0.024 g, 0.0891 mmol) was added. After 1 h,
1
13
29
H, C, and Si NMR spectra were recorded by using the 2D
1
5,15Ј-Ethane-1,2-diylbis(15-methyl-6,7,13,14,16,17-hexaoxa-15-sil-
adispiro[4.2.4.5]heptadecane) (5a): White crystals; explosive on
heating above 152 °C. R
correlation techniques COSY, HSQC, and HMBC.
1
f
= 0.57 (TLC, hexane/ethyl acetate, 10:1). 2D H DOSY of Peroxide 10a: 1,1-Bis(hydroperoxy)-4-tert-butyl-
1
H NMR (400.1 MHz, CDCl
3
): δ = 0.29 (s, 6 H), 0.75–2.35 (m, 36 cyclohexane (9; 0.040 g, 0.1961 mmol) and pyridine (0.035 g,
): δ = –7.30, 2.69, 2.79, 0.446 mmol) in a molar ratio of 2.2:5 were dissolved in CDCl3
H) ppm. 13C NMR (100.6 MHz, CDCl
3
2
9
24.57, 24.64, 24.92, 33.20, 33.29, 33.41, 33.57, 120.23 ppm. Si
(0.6 mL) in an NMR tube filled with argon, and then bis(di-
methylchlorosilyl)ethane (1a; 0.023 g, 0.0891 mmol) was added. Af-
ter 1 h, dibenzo-18-crown-6 (0.0250 g, 0.0694 mmol) was added as
the standard. Silica fume (1 wt.-%) was added to the NMR tube,
3
NMR (59.6 MHz, CDCl ): δ = 7.52 ppm. HRMS (ESI): calcd. for
+
C
24
H
42NaO12Si
7,17Ј-Ethane-1,2-diylbis(17-methyl-7,8,15,16,18,19-hexaoxa-17-sil-
adispiro[5.2.5.5]nonadecane) (5b): White crystals, m.p. 132–135 °C
with explosive decomposition. R = 0.58 (TLC, hexane/ethyl acet-
ate, 10:1). H NMR (400.1 MHz, CDCl ): δ = 0.29 (s, 6 H), 0.75–
.35 (m, 44 H) ppm. 13C NMR (100.6 MHz, CDCl
.81, 22.56, 22.80, 25.64, 29.92, 30.26, 30.76, 108.74 ppm. Si
): δ = 7.05 ppm. HRMS (ESI): calcd. for
2
[M + Na] 601.2107; found 601.2107.
1
1
the tube was shaken, and the 2D H DOSY NMR spectrum was
recorded.
f
1
1
3
2D H DOSY of Peroxide 10b: 1,1-Bis(hydroperoxy)-4-tert-butyl-
2
2
3
): δ = –7.22, cyclohexane (9; 0.040 g, 0.1961 mmol) and pyridine (0.035 g,
2
9
0.446 mmol) in a molar ratio of 2.2:5 were dissolved in CDCl3
(0.6 mL) in an NMR tube filled with argon, and then 2-dichloro-
ethylsilyl-1-methyldichlorosilylethane (1b; 0.024 g, 0.0891 mmol)
was added. After 1 h, dibenzo-18-crown-6 (0.0250 g, 0.0694 mmol)
was added as the standard. Silica fume (1 wt.-%) was added to the
NMR (59.6 MHz, CDCl
50NaO12Si [M + Na] 657.2733; found 657.2739.
3
+
C
28
H
2
1
9,19Ј-Ethane-1,2-diylbis(19-methyl-8,9,17,18,20,21-hexaoxa-19-sil-
adispiro[6.2.6.5]heneicosane) (5c): White crystals; M.p. 134–137 °C;
explosive on heating above 163 °C. R = 0.6 (TLC, hexane/ethyl
acetate, 10:1). H NMR (400.1 MHz, CDCl ): δ = 0.27 (s, 6 H),
.75–2.21 (m, 52 H) ppm. 13C NMR (100.6 MHz, CDCl
): δ =
7.21, 2.83, 23.01, 30.00, 30.07, 32.62, 32.86, 33.00, 113.73 ppm.
1
NMR tube, the tube was shaken, and the 2D H DOSY NMR
f
1
spectrum was recorded.
3
0
–
3
Supporting Information (see footnote on the first page of this arti-
1
13
cle): H and C NMR spectra, 2D and 3D NMR spectra, mass
spectra, and details of X-ray crystallography data.
29
3
Si NMR (59.6 MHz, CDCl ): δ = 6.58 ppm. HRMS (ESI): calcd.
+
for C32
9,19Ј-Ethene-1,2-diylbis(19-methyl-8,9,17,18,20,21-hexaoxa-19-sil-
adispiro[6.2.6.5]heneicosane) (6): White crystals, explosive on heat-
ing above 110–120 °C. R = 0.6 (TLC, hexane/ethyl acetate, 10:1).
H NMR (300 MHz, CDCl ): δ = 0.37 (s, 6 H), 0.75–2.3 (m, 48
H), 6.85 (s, 2 H) ppm. 13C NMR (75.5 MHz, CDCl
): δ = –7.34,
2.90, 29.88, 29.97, 32.49, 32.64, 32.89, 32.99, 113.93, 146.44 ppm.
2
H58NaO12Si [M + Na] 713.3359; found 713.3354.
1
Acknowledgments
f
This work was supported by the Russian Science Foundation (grant
number 14-23-00150). The authors are grateful to the European
Synchrotron Radiation Facility (ESRF) for providing access to the
ID31 beamline (experiment number CH-3696; X-ray diffraction
study of 5a). High-resolution mass spectra were recorded in the
Department of Structural Studies of Zelinsky Institute of Organic
Chemistry. The authors thankfully acknowledge Levon L. Khem-
chyan for implementation of HRMS experiments.
1
3
3
2
29
Si NMR (59.6 MHz, CDCl
3
): δ = –10.12 ppm. HRMS (ESI):
+
calcd. for C32 56NaO12Si [M + Na] 711.3203; found 711.3198.
H
2
19,19Ј-Ethyne-1,2-diylbis(19-methyl-8,9,17,18,20,21-hexaoxa-19-sil-
adispiro[6.2.6.5]heneicosane) (7): White crystals, explosive on heat-
1
f
ing above 120 °C. R = 0.6 (TLC, hexane/ethyl acetate, 10:1). H
NMR (300 MHz, CDCl
3
): δ = 0.38 (s, 6 H), 0.75–2.25 (m, 48 H)
[1] a) A. Baeyer, V. Villiger, Ber. Dtsch. Chem. Ges. 1899, 32, 3625–
3633; b) H. D. Dakin, Am. Chem. J. 1909, 42, 477–498; c) M.
ppm. 13C NMR (75.5 MHz, CDCl
): δ = –4.88, 22.79, 22.88, 29.07,
3
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
A. O. Terent’ev et al.
FULL PAPER
Alamgir, P. S. R. Mitchell, P. K. Bowyer, N. Kumar, D. S.
Black, Tetrahedron 2008, 64, 7136–7142; d) K. Elbs, J. Prakt.
Chem. 1893, 48, 179; e) E. J. Behrman, Beilstein J. Org. Chem.
Chaturvedi, A. Goswami, P. P. Saikia, N. C. Barua, P. G. Rao,
Chem. Soc. Rev. 2010, 39, 435–454; c) N. Terzi c´ , D. Opsenica,
ˇ
D. Mili c´ , B. Tinant, K. S. Smith, W. K. Milhous, B. A. Solaja,
ˇ
ˇ
2006, 2, No. 22; f) R. Criegee, Ber. Dtsch. Chem. Ges. 1944, 77,
J. Med. Chem. 2007, 50, 5118–5127; d) Z. Zi zˇ ak, Z. Jurani c´ ,
ˇ
7
22–726; g) Yu. N. Ogibin, A. O. Terent’ev, A. V. Kutkin, G. I.
D. Opsenica, B. A. Solaja, Invest. New Drugs 2009, 27, 432–
Nikishin, Tetrahedron Lett. 2002, 43, 1321–1324; h) P. A. Kra-
sutsky, I. V. Kolomitsyn, S. G. Krasutsky, P. Kiprof, Org. Lett.
439; e) D. M. Rubush, M. A. Morges, B. J. Rose, D. H.
Thamm, T. Rovis, J. Am. Chem. Soc. 2012, 134, 13554–13557;
ˇ
ˇ
2004, 6, 2539–2542; i) H. Hock, S. Lang, Ber. Dtsch. Chem.
f) I. N. Cvijeti c´ , Z. P. Zi zˇ ak, T. P. Stanojkovi c´ , Z. D. Jurani c´ ,
N. Terzi c´ , I. M. Opsenica, D. M. Opsenica, I. O. Jurani c´ , B. J.
Drakuli c´ , Eur. J. Med. Chem. 2010, 45, 4570–4577; g) D. M.
Rubush, M. A. Morges, B. J. Rose, D. H. Thamm, T. Rovis, J.
Am. Chem. Soc. 2012, 134, 13554–13557.
Ges. 1944, 77, 257–264; j) T. J. Fisher, P. H. Dussault, Tetrahe-
dron Lett. 2010, 51, 5615–5617; k) N. Kornblum, H. E.
De La Mare, J. Am. Chem. Soc. 1951, 73, 880–881; l) X. Gu,
W. Zhang, R. G. Salomon, J. Org. Chem. 2012, 77, 1554–1559;
m) A. O. Terent’ev, M. M. Platonov, A. V. Kutkin, Cent. Eur.
J. Chem. 2006, 4, 207–215; n) A. O. Terent’ev, M. M. Platonov,
A. S. Kashin, G. I. Nikishin, Tetrahedron 2008, 64, 7944–7948;
o) E. T. Denisov, I. B. Afanas’ev, Oxidation and Antioxidants
in Organic Chemistry and Biology, CRC Press, Boca Raton,
[6] a) T. Tokuyasu, S. Kunikawa, K. J. McCullough, A. Masuy-
ama, M. Nojima, J. Org. Chem. 2005, 70, 251–260; b) T. Toku-
yasu, S. Kunikawa, M. Abe, A. Masuyama, M. Nojima, H.-S.
Kim, K. Begum, Y. Wataya, J. Org. Chem. 2003, 68, 7361–
7367; c) A. Ahmed, P. H. Dussault, Org. Lett. 2004, 6, 3609–
3611; d) B. Barnych, B. Fenet, J.-M. Vatèle, Tetrahedron 2013,
69, 334–340; e) S. Gemma, S. Kunjir, S. S. Coccone, M. Brind-
isi, V. Moretti, S. Brogi, E. Novellino, N. Basilico, S. Parapini,
D. Taramelli, G. Campiani, S. Butini, J. Med. Chem. 2011, 54,
5949–5953.
[7] a) E. Buncel, A. G. Davies, J. Chem. Soc. 1958, 1550–1556; b)
Yu. A. Ol’dekop, F. Z. Livshits, J. Gen. Chem. USSR (Engl.
Transl.). 1974, 44, 2135–2137; Zh. Obshch. Khim. 1974, 44,
2174–2176; c) D. Brandes, A. Blaschette, Monatsh. Chem. 1975,
106, 1299–1306; d) Y. L. Fan, R. G. Shaw, J. Org. Chem. 1973,
38, 2410–2412.
2010; p) A. G. Griesbeck, M. Oelgemöller, F. Ghetti (Eds.)
CRC Handbook of Organic Photochemistry and Photobiology,
vol. 1, CRC Press, Boca Raton, 2012.
[
2] a) R. Matyá sˇ , J. Pachman, Primary Explosives, Springer, Hei-
delberg, 2013; b) J. Chen, W. Wu, A. J. McNeil, Chem. Com-
mun. 2012, 48, 7310–7312; c) F. Dubnikova, R. Kosloff, J.
Almog, Y. Zeiri, R. Boese, H. Itzhaky, A. Alt, E. Keinan, J.
Am. Chem. Soc. 2005, 127, 1146–1159; d) C. Denekamp, L.
Gottlieb, T. Tamiri, A. Tsoglin, R. Shilav, M. Kapon, Org. Lett.
2005, 7, 2461–2464; e) K. B. Landenberger, O. Bolton, A. J.
Matzger, Angew. Chem. Int. Ed. 2013, 52, 6468–6471; f) R. Ma-
tyá sˇ , R. Jirásko, A. Ly cˇ ka, J. Pachmá nˇ , Propellants Explos.
Pyrotech. 2011, 36, 219–224; g) H. Östmark, S. Wallin, H. G.
Ang, Propellants Explos. Pyrotech. 2012, 37, 12–23; h) A. O.
Terent’ev, M. M. Platonov, E. J. Sonneveld, R. Peschar, V. V.
Chernyshev, Z. A. Starikova, G. I. Nikishin, J. Org. Chem.
[8] E. J. Corey, M. M. Mehrotra, A. U. Khan, J. Am. Chem. Soc.
1986, 108, 2472–2473.
[9] a) W. Adam, A. Alzerreca, J.-C. Liu, F. Yany, J. Am. Chem.
Soc. 1977, 99, 5768–5773; b) H. Einaga, M. Nojima, M. Abe,
J. Chem. Soc. Perkin Trans. 1 1999, 2507–2512; c) L. Cointe-
aux, J.-F. Berrien, J. Mahuteau, M. E. Trân Huu-Dâu, L. Cicé-
ron, M. Danis, J. Mayrargue, Bioorg. Med. Chem. 2003, 11,
3791–3794.
[10] a) H.-S. Kim, K. Begum, N. Ogura, Y. Wataya, Y. Nonami, T.
Ito, A. Masuyama, M. Nojima, K. J. McCullough, J. Med.
Chem. 2003, 46, 1957–1961; b) Y. Ushigoe, A. Masuyama, M.
Nojima, K. J. McCullough, Tetrahedron Lett. 1997, 38, 8753–
8756; c) H.-S. Kim, K. Tsuchiya, Y. Shibata, Y. Wataya, Y.
Ushigoe, A. Masuyama, M. Nojima, K. J. McCullough, J.
Chem. Soc. Perkin Trans. 1 1999, 1867–1870.
[11] a) V. A. Yablokov, A. N. Sunin, N. V. Yablokova, A. V. Gan-
yushkin, J. Gen. Chem. USSR (Engl. Transl.). 1974, 44, 2405–
2408; Zh. Obshch. Khim. 1974, 44, 2446–2449; b) V. A. Yablo-
kov, A. V. Thomadze, N. V. Yablokova, Yu. A. Aleksandrov, J.
Gen. Chem. USSR (Engl. Transl.) 1979, 49, 1570–1572; Zh.
Obshch. Khim. 1979, 49, 1787–1790.
2007, 72, 7237–7243; i) A. O. Terent’ev, I. A. Yaremenko, V. A.
Vil’, I. K. Moiseev, S. A. Kon’kov, V. M. Dembitsky, D. O. Lev-
itsky, G. I. Nikishin, Org. Biomol. Chem. 2013, 11, 2613–2623.
3] a) R. D. Slack, A. M. Jacobine, G. H. Posner, Med. Chem.
Commun. 2012, 3, 281–297; b) C. W. Jefford, Curr. Top. Med.
Chem. 2012, 12, 373–399; c) N. Yadav, S. Chiranjeev, S. K.
Awasthi, RSC Adv. 2014, 4, 5469–5498; d) H. D. Hao, S.
Wittlin, W. Yikang, Chem. Eur. J. 2013, 19, 7605–7619; e) J. L.
Vennerstrom, H.-N. Fu, W. Y. Ellis, A. L. Ager, J. K. Wood,
S. L. Andersen, L. Gerena, W. K. Milhous, J. Med. Chem.
[
1992, 35, 3023–3027; f) V. Barton, S. A. Ward, J. Chadwick, A.
Hill, P. M. O’Neill, J. Med. Chem. 2010, 53, 4555–4559; g) P.
Ghorai, P. H. Dussault, C. Hu, Org. Lett. 2008, 10, 2401–2404;
h) J. Ruiz, B. Tuccio, R. Lauricella, M. Maynadier, H. Vial, C.
Andre-Barres, Tetrahedron 2013, 69, 6709–6720; i) X. Wang, Y.
Dong, S. Wittlin, S. A. Charman, F. C. K. Chiu, J. Chollet, K.
Katneni, J. Mannila, J. Morizzi, E. Ryan, C. Scheurer, J.
Steuten, J. Santo Tomas, C. Snyder, J. L. Vennerstrom, J. Med.
Chem. 2013, 56, 2547–2555; j) R. Maurya, A. Soni, D. Anand,
M. Ravi, K. S. R. Raju, I. Taneja, N. K. Naikade, S. K. Puri,
Wahajuddin, S. Kanojiya, P. P. Yadav, ACS Med. Chem. Lett.
[12]
a) T. Mukaiyama, N. Miyoshi, J.-I. Kato, M. Ohshima, Chem.
Lett. 1986, 1385–1388; b) A. Ramirez, K. A. Woerpel, Org.
Lett. 2005, 7, 4617–4620; c) A. Ahmed, P. H. Dussault, Tetra-
hedron 2005, 61, 4657–4670; d) P. Dai, P. H. Dussault, Org.
Lett. 2005, 7, 4333–4335; e) P. Dai, T. K. Trullinger, X. Liu,
P. H. Dussault, J. Org. Chem. 2006, 71, 2283–2292.
2013, 4, 165–169.
[
4] a) J. Keiser, V. Veneziano, L. Rinaldi, L. Mezzino, U. Duthaler,
G. Cringoli, Res. Vet. Sci. 2010, 88, 107–110; b) X. Shuhua,
M. Tanner, E. K. N’Goran, J. Utzinger, J. Chollet, R. Berg-
quist, M. Chen, J. Zheng, Acta Trop. 2002, 82, 175–181; c) K.
Ingram, I. A. Yaremenko, I. B. Krylov, L. Hofer, A. O. Ter-
ent’ev, J. Keiser, J. Med. Chem. 2012, 55, 8700–8711; d) J.
[13] a) V. A. Fomin, I. V. Petrukhin, J. Gen. Chem. USSR (Engl.
Transl.). 1997, 67, 580–588; Zh. Obshch. Khim. 1997, 67, 621–
630; b) D. A. Sapozhnikov, A. A. Sakharova, T. V. Volkova,
A. M. Nikulina, A. O. Terent’ev, D. A. Borisov, O. V. Afonich-
eva, E. V. Korostylev, Ya. S. Vygodskii, Bull. Russ. Acad. Sci.
Phys. 2010, 74, 1039–1042.
Keiser, K. Ingram, M. Vargas, J. Chollet, X. Wang, Y. Dong, [14] a) M. Taddei, A. Ricci, Synthesis 1986, 633–635; b) S. Seng-
J. L. Vennerstrom, Antimicrob. Agents Chemother. 2012, 56,
090–1092; e) J. Boissier, F. Cosledan, A. Robert, B. Meunier,
upta, V. A. Snieckus, Tetrahedron Lett. 1990, 31, 4267–4270;
c) L. Camici, P. Dembech, A. Ricci, G. Seconi, M. Taddei,
Tetrahedron 1988, 44, 4197–4206; d) G. A. Olah, T. D. Ernst,
J. Org. Chem. 1989, 54, 1204–1206.
1
Antimicrob. Agents Chemother. 2009, 53, 4903–4906; f) A. Ma-
ser, S. Wittlin, M. Rottman, T. Wanler, M. Kaiser, R. Brun,
Curr. Opin. Pharmacol. 2012, 12, 562–566.
[
15] a) A. Ramirez, K. A. Woerpel, Org. Lett. 2005, 7, 4617–4620;
b) B. Barnych, J.-M. Vatele, Synlett 2011, 13, 1912–1916; c) P.
Dai, T. K. Trullinger, X. Liu, P. H. Dussault, J. Org. Chem.
2006, 71, 2283–2292; d) X. Wang, Y. Dong, S. Wittlin, D.
[
5] a) R. H. van Huijsduijnen, R. Kiplin Guy, K. Chibale, R. K.
Haynes, I. Peitz, G. Kelter, M. A. Phillips, J. L. Vennerstrom,
Y. Yuthavong, T. N. C. Wells, PLoS One 2013, 8, e82962; b) D.
6
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
Synthesis of Nine-Membered Bicyclic Silyl Peroxides
Creek, J. Chollet, S. A. Charman, J. S. Tomas, C. Scheurer, C.
Snyder, J. L. Vennerstrom, J. Med. Chem. 2007, 50, 5840–5847;
e) P. Ghorai, P. H. Dussault, C. Hu, Org. Lett. 2008, 10, 2401–
p. 775–830; e) A. Ricci, G. Seconi, R. Curci, G. L. Larson, Adv.
Silicon Chem. 1996, 3, 63–104; f) A. G. Davies, Tetrahedron
2007, 63, 10385–10405; g) A. O. Terent’ev, M. M. Platonov,
D. O. Levitsky, V. M. Dembitsky, Russ. Chem. Rev. 2011, 80,
807–828.
2
404; f) C. E. Schiaffo, M. Rottman, S. Wittlin, P. H. Dussault,
ACS Med. Chem. Lett. 2011, 2, 316–319.
16] a) S. Gemma, S. Kunjir, S. S. Coccone, M. Brindisi, V. Moretti, [24] a) G. A. Razuvaev, V. A. Yablokov, A. V. Ganyushkin, V. E.
[
S. Brogi, E. Novellino, N. Basilico, S. Parapini, D. Taramelli,
G. Campiani, S. Butini, J. Med. Chem. 2011, 54, 5949–5953; b)
S. Gemma, F. Marti, E. Gabellieri, G. Campiani, E. Novellino,
S. Butini, Tetrahedron Lett. 2009, 50, 5719–5722.
Schklover, I. Zinker, Yu. T. Struchkov, Dokl. Chem. 1978, 242,
428–431; Dokl. Acad. Nauk. SSSR Ser. Khim. 1978, 242, 132–
135; b) R. Halle, L. A. Bock (Argus Chem. Co.) US 4161485,
1979; [Chem. Abstr. 1980, 92, 42836].
[
17] S. A.-L. Laurent, J. Boissier, F. Cosledan, H. Gornitzka, A.
Robert, B. Meunier, Eur. J. Org. Chem. 2008, 895–913.
18] H.-S. Kim, K. Begum, N. Ogura, Y. Wataya, Y. Nonami, T.
Ito, A. Masuyama, M. Nojima, K. J. McCullough, J. Med.
Chem. 2003, 46, 1957–1961.
[25] a) A. O. Terent’ev, M. M. Platonov, A. I. Tursina, V. V. Cherny-
shev, G. I. Nikishin, J. Org. Chem. 2008, 73, 3169–3174; b)
A. O. Terent’ev, M. M. Platonov, A. I. Tursina, V. V. Cherny-
shev, G. I. Nikishin, J. Org. Chem. 2009, 74, 1917–1922.
[26] A. V. Arzumanyan, R. A. Novikov, A. O. Terent’ev, M. M. Pla-
tonov, V. G. Lakhtin, D. E. Arkhipov, A. A. Korlyukov, V. V.
Chernyshev, A. N. Fitch, A. T. Zdvizhkov, I. B. Krylov, Y. V.
Tomilov, G. I. Nikishin, Organometallics 2014, 33, 2230–2246.
[27] a) W. Adam, R. Albert, Tetrahedron Lett. 1992, 33, 8015–8016;
b) T. Akasaka, M. Kako, S. Nagase, A. Yabe, W. Ando, J. Am.
Chem. Soc. 1990, 112, 7804–7806; c) T. Akasaka, K. Sato, M.
Kako, W. Ando, Tetrahedron Lett. 1991, 32, 6605–6608; d)
K. L. McKillop, G. R. Gillette, D. R. Powell, R. West, J. Am.
Chem. Soc. 1992, 114, 5203–5208; e) A. J. Millevolte, D. R.
Powell, S. G. Johnson, R. West, Organometallics 1992, 11,
1091–1095; f) W. Ando, M. Kako, T. Akasaka, S. Nagase, T.
Kawai, Y. Nagai, T. Sato, Tetrahedron Lett. 1989, 30, 6705–
6708; g) W. Ando, M. Kako, T. Akasaka, Y. Kabe, Tetrahedron
Lett. 1990, 31, 4177–4180; h) W. Ando, M. Kako, T. Akasaka,
S. Nagase, Organometallics 1993, 12, 1514–1522.
[28] a) P. A. Belyakov, V. I. Kadentsev, A. O. Chizhov, N. G. Kolo-
tyrkina, A. S. Shashkov, V. P. Ananikov, Mendeleev Commun.
2010, 20, 125–131; b) V. V. Kachala, L. L. Khemchyan, A. S.
Kashin, N. V. Orlov, A. A. Grachev, S. S. Zalesskiy, V. P. An-
anikov, Russ. Chem. Rev. 2013, 82, 648–685.
[29] a) A. O. Terent’ev, M. M. Platonov, Yu. N. Ogibin, G. I. Niki-
shin, Synth. Commun. 2007, 37, 1281–1287; b) A. O. Terent’ev,
A. V. Kutkin, M. M. Platonov, Z. A. Starikova, Y. N. Ogibin,
G. I. Nikishin, Russ. Chem. Bull. 2005, 54, 1214–1218.
Received: July 9, 2014
[
[
19] H.-S. Kim, T. Kaoru, S. Yasuharu, W. Yusuke, U. Yoshihiro,
M. Araki, N. Masatomo, K. J. McCullough, J. Chem. Soc. Per-
kin Trans. 1 1999, 1867–1870.
20] a) G. R. Jones, Y. Landais, Tetrahedron 1996, 52, 7599–7662;
b) I. Fleming, R. Henning, H. Plaut, J. Chem. Soc., Chem.
Commun. 1984, 29–31; c) I. Fleming, P. E. Sanderson, Tetra-
hedron Lett. 1987, 28, 4229–4232.
[
[21] a) K. Tamao, N. Ishida, M. Kumada, J. Org. Chem. 1983, 48,
2
120–2122; b) K. Tamao, N. Ishida, T. Tanaka, M. Kumada,
Organometallics 1983, 2, 1694–1696; c) K. Tamao, N. Ishida,
J. Organomet. Chem. 1984, 269, 37–39.
[
22] a) N. Sawwan, A. Greer, Chem. Rev. 2007, 107, 3247–3285; b)
C. S. Foote, J. Selverston Valentine, A. Greenberg, J. F. Lieb-
man(Eds.), Active Oxygen, in: Chemistry, Blackie Academic &
Professional, London, 1996; c) E. L. Clennan, R. P. L’Espere-
ance, Tetrahedron Lett. 1983, 24, 4291–4294; d) E. L. Clennan,
P. C. Heah, J. Org. Chem. 1983, 48, 2621–2622; e) E. L. Clen-
nan, J. P. Sram, A. Pace, K. Vincer, S. White, J. Org. Chem.
2002, 67, 3975–3978; f) E. L. Clennan, S. E. Hightower, A.
Greer, J. Am. Chem. Soc. 2005, 127, 11819–11826; g) A. L.
Baumstark, P. C. Vasquez, J. Org. Chem. 1992, 57, 393–395.
23] a) D. Brandes, A. Blaschette, J. Organomet. Chem. 1974, 78, 1–
[
4
7
8; b) Yu. A. Alexandrov, J. Organomet. Chem. 1982, 238, 1–
8; c) K. Tamao, Science of Synthesis (Ed.: M. G. Moloney),
Thieme, Stuttgart, Germany, 2002; d) W. Ando, in: Chemistry
of Peroxides (Ed.: Z. Rappoport), Wiley, Chichester, UK, 2006,
Published Online: ᭿
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7

Job/Unit: O42895
/KAP1
Date: 02-09-14 19:20:22
Pages: 8
A. O. Terent’ev et al.
FULL PAPER
Peroxides
Compounds containing two nine-mem-
bered peroxide rings bridged by an ethane,
ethene, or ethyne group are synthesized.
Each ring is formed by the replacement of
two geminal chlorine atoms at the silicon
atom with the hydroperoxide groups of one
peroxide molecule. The peroxides are iso-
lated by crystallization or silica gel fil-
tration; unexpectedly, all of these com-
pounds are extremely explosive.
A. V. Arzumanyan, A. O. Terent’ev,*
R. A. Novikov, V. G. Lakhtin,
V. V. Chernyshev, A. N. Fitch,
G. I. Nikishin .................................... 1–8
Six Peroxide Groups in One Molecule –
Synthesis of Nine-Membered Bicyclic Silyl
Peroxides
Keywords: Silanes / Peroxides / Energetic
materials / Cyclization
8
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0