First synthesis of cyclic organogermanium peroxides, 1,2,4,5,7,8-hexaoxa-3-germonanes

Article abstract of DOI:10.1016/j.jorganchem.2009.02.005

First, previously unknown, cyclic organogermanium peroxides, 1,2,4,5,7,8-hexaoxa-3-germonanes, were synthesized by the reaction of 1,1′-dihydroperoxydi(cyclododecyl)peroxide with (di)alkyl(aryl)dihalogengermanes. The new compounds have a higher tendency t

Full text of DOI:10.1016/j.jorganchem.2009.02.005

Journal of Organometallic Chemistry 694 (2009) 1786–1788
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Communication
First synthesis of cyclic organogermanium peroxides,
1,2,4,5,7,8-hexaoxa-3-germonanes
*
A.O. Terent’ev , M.M. Platonov, I.V. Krylova, M.P. Egorov, G.I. Nikishin
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
First, previously unknown, cyclic organogermanium peroxides, 1,2,4,5,7,8-hexaoxa-3-germonanes, were
synthesized by the reaction of 1,10-dihydroperoxydi(cyclododecyl)peroxide with (di)alkyl(aryl)dihalog-
engermanes. The new compounds have a higher tendency to undergo hydrolysis compared to silicon-
containing analogs.
Received 16 December 2008
Received in revised form 31 January 2009
Accepted 6 February 2009
Available online 21 February 2009
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Germanium
1,2,4,5,7,8-Hexaoxa-3-germonanes
Peroxides
Cycles
1,10-Dihydroperoxydi(cyclododecyl)
peroxide
1. Introduction
2. Results and discussion
Nine-membered cyclic peroxides, 1,2,4,5,7,8-hexaoxananes (A)
(Fig. 1), were synthesized for the first time in 1895 [1]. More than
a hundred years later, in 2008, we prepared 1,2,4,5,7,8-hexaoxa-3-
silonanes (B) (Fig. 1), which are silicon-containing analogs of com-
pounds A [2]. During the period of time between these publica-
tions, several tens of peroxides A were synthesized. The latter
compounds are of interest for organic and analytical chemistry
[3], materials science [4], and explosives manufacturing [5].
The present study is a continuation of our investigations on the
chemistry of cyclic peroxides [2,6]. We synthesized organogerma-
nium analogs of the structures A and B, 1,2,4,5,7,8-hexaoxa-3-ger-
monanes (C) (Fig. 1), which are the first cyclic organogermanium
peroxides. The aims of the present study were to develop proce-
dures for the synthesis of these peroxides and evaluate their stabil-
ity compared to Si analogs. The resulting peroxides were
characterized by NMR spectroscopy.
Organogermanium peroxides are poorly studied. About 20
mono-, di-, three-, and tetraperoxygermanes were documented
[7–11]. These compounds were synthesized by condensation
of hydroperoxides or hydrogen peroxides with halogermanes
[7–10], triphenylethoxygermane, or triphenylaminogermane [11].
The reaction of the sodium salt of tert-butyl hydroperoxide with
triphenylgermanium bromide produced tert-butylperoxytriphe-
nylgermanium [11].
Earlier we have developed a procedure for the synthesis of Si-
containing peroxides having the structure based on the
B
reaction of 1,10-dihydroperoxydi(cycloalkyl)peroxides with
(di)alkyl(aryl)dichlorosilanes in the presence of amines as accep-
tors for hydrogen chloride [2]. In the present study, we applied this
procedure to the synthesis of structurally similar Ge-
containing peroxides C. The latter compounds, 1,2,4,5,7,8-hexaoxa-
3-germonanes (3a–e), were prepared by the reaction of
1,10-dihydroperoxyperoxydi(cyclododecyl)peroxide
(1)
with
(di)alkyl(aryl)dihalogengermanes (2a–e) in the presence of trieth-
ylamine (Scheme 1 and Table 1).
Dichlorogermanes, unlike structurally similar dibromogerm-
anes, are less active in this synthesis. The reactions of 1,10-dihydr-
operoxide
1
with
dibutylgermanium
dichloride
and
methylphenylgermanium dichloride gave 3c and 3d in 8% and
11% yields, respectively. The analogous reaction of dibutylgermani-
um dibromide (2c) and methylphenylgermanium dibromide (2d)
afforded the target peroxides 3c and 3d in higher yields (37% and
31%, respectively). Peroxide 3a was synthesized in good yield
(59%) only from sterically unhindered dimethyldichlorogermane
(2a).
Experimentally, a key feature of the synthesis of 3 is that 1,10-
dihydroperoxyperoxide is initially mixed with (di)alkyl(aryl)diha-
logengermane followed by the addition of amine in an amount
equivalent to hydrohalic acid that is released. When three compo-
nents were mixed simultaneously, the target peroxides were
obtained in low yield due, apparently, to the formation of strong
* Corresponding author. Tel.: +7 499 135 64 28; fax: +7 495 135 53 28.
E-mail address: alterex@yandex.ru (A.O. Terent’ev).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.02.005

A.O. Terent’ev et al. / Journal of Organometallic Chemistry 694 (2009) 1786–1788
1787
Table 1
Structures and yields of 1,2,4,5,7,8-hexaoxa-3-germonanes (3a–e).a
O
O
O
O
O
O
3cb
3dc
3e
O
Ge
O
O
O
Si
Structure
3a
3b
9
9
9
O
O
O
O
O
Total reaction time (h)
Yield (%)
4
59
7
43
20
37
20
31
20
41
O
O
O
a
Reaction conditions: A mixture of 1,10-dihydroperoxydi(cyclododecyl)peroxide
1 (0.1 g, 0.23 mmol) and disubstituted dihalogengermane 2a–e (0.35 mmol) in
anhydrous THF (6 mL) was allowed to stand for 1 h. Then a solution of triethyl-
amine (0.71 mmol) in anhydrous THF (2 mL) was added, and the reaction mixture
was stirred at room temperature for 4–20 h.
A
B
С
Fig. 1. Structures of 1,2,4,5,7,8-hexaoxananes (A), 1,2,4,5,7,8-hexaoxa-3-silonanes
(B), 1,2,4,5,7,8-hexaoxa-3-germonanes (C).
b
The reaction with dibutylgermanium dichloride afforded 3c in 8% yield.
c
The reaction with methylphenylgermanium dichloride gave 3d in 11% yield.
complexes of amine with 1,10-dihydroperoxyperoxide (1) or
(di)alkyl(aryl)dibromogermanes (2).
prepared from methylphenylgermanium dibromide (2d) in two
steps involving the hydrolysis with a 20% aqueous NaOH solution
followed by the treatment of the product with 34% aqueous hydro-
chloric acid by analogy with the known procedure [13,16]. Elemen-
tal analysis of germanium was calculated from the mass of
germanium oxide after burning of organogermanium peroxides
under oxygen atmosphere in the presence of crushed quartz [18].
Attempts to synthesize 1,2,4,5,7,8-hexaoxa-3-germonanes by
the reactions of less stable peroxides, such as 1,10-dihydroperoxydi-
(cyclohexyl)peroxide or 1,10-dihydroperoxydi(cycloheptyl)perox-
ide, with dimethyldichloro- or diethyldibromogermane failed.
Germanium peroxides that were formed in these reactions under-
went considerable decomposition during the synthesis, which
was not the case with silicon analogs. [2] Unlike silicon-containing
cyclic peroxides, germanium peroxides more rapidly decompose
during storage and are readily hydrolyzed with atmospheric mois-
ture. The hydrolysis of organogermanium cyclic peroxides affords
the starting 1,10-dihydroperoxydi(cyclododecyl)peroxide 1 in high
yield.
3.1. Dibutylgermanium dibromide (2c)
1H NMR (250.13 MHz, CDCl3), d: 0.93 (t, 6H, CH3, J = 6.7 Hz),
1.37–1.82 (m, 12H, CH2). 13C NMR (62.9 MHz, CDCl3), d: 12.7
(CH3), 24.8, 26.4, 27.8 (CH2). Anal. Calc. for C8H18Br2Ge: C, 27.72;
H, 5.23; Br, 46.10; Ge, 20.95. Found: C, 27.91; H, 5.01; Br, 46.27;
Ge, 20.48%.
3. Experimental
Caution: Although we have encountered no difficulties in work-
ing 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.
3.2. Methylphenylgermanium dibromide (2d)
1H NMR (250.13 MHz, CDCl3), d: 1.71 (s, 3H, CH3), 7.56 (br.s., 3H,
CH), 7.78 (br.s., 2H, CH). 13C NMR (62.9 MHz, CDCl3), d: 11.7 (CH3),
128.9, 131.6, 131.7, 136.9 (CH2). Anal. Calc. for C7H8Br2Ge: C,
25.90; H, 2.48; Br, 49.24; Ge, 22.37. Found: C, 25.56; H, 2.74; Br,
49.11; Ge, 22.56%.
The NMR spectra were recorded on Bruker WM-250 and AM-
300 (250.13 and 300.13 MHz for 1H; 62.9 and 75.48 MHz for 13C)
spectrometers in CDCl3. Dialkyl(aryl)dihalogengermanes (dimeth-
ylgermanium dichloride (2a) [12], diethylgermanium dibromide
(2b) [13], dibutylgermanium dichloride [14], diphenylgermanium
dibromide (2e) [15], and diphenylgermanium dichloride [15])
were synthesized according to known procedures. 1,10-
Dihydroperoxydi(cyclododecyl)peroxide (1) was synthesized
according to the procedure described earlier [6]. Dibutylgermani-
um dibromide (2c) was prepared from dibutylgermanium dichlo-
ride in two steps involving the hydrolysis with a 20% aqueous
NaOH solution followed by the treatment of the product with
48% aqueous hydrobromic acid by analogy with the known proce-
dure [13,16]. Methylphenylgermanium dibromide (2d) was pre-
pared by the reaction of triphenylgermanium chloride with
MeMgBr followed by the treatment of methyltriphenylgermanium
that was formed in the first step with bromine by analogy with the
known procedure [17]. Methylphenylgermanium dichloride was
3.3. Methylphenylgermanium dichloride
1H NMR (250.13 MHz, CDCl3), d: 1.44 (s, 3H, CH3), 7.54 (m, 3H,
CH), 7.76 (m, 2H, CH). 13C NMR (62.9 MHz, CDCl3), d: 8.8 (CH3),
129.0, 131.7, 131.8, 136.3 (CH2). Anal. Calc. for C7H8Cl2Ge: C,
35.68; H, 3.42; Cl, 30.09; Ge, 30.81. Found: C, 35.77; H, 3.36; Cl,
30.14; Ge, 30.69%.
3.4. Procedure for the synthesis of 1,2,4,5,7,8,3-hexaoxagermonanes
(3a–e)
A
mixture of 1,10-dihydroperoxydi(cyclododecyl)peroxide
1
(0.1 g, 0.23 mmol) and (di)alkyl(aryl)dihalogengermane 2a–e
(0.35 mmol) in anhydrous THF (6 mL) was allowed to stand for
OOH
O O
OOH
O O
O O
Et3N
THF
X
R1
X
R2
+
Ge
O
O
R1
2a-e
1
Ge
R2
X = Cl, Br
3a-e
a: Х = Cl, R1=R2=Me; b: Х = Br, R1=R2=Et; c: Х = Br, R1=R2=Bu;
d: Х = Br, R1=Me, R2=Ph; e: Х = Br, R1=R2=Ph
Scheme 1. Synthesis of 1,2,4,5,7,8-hexaoxa-3-germonanes (3a–e).

1788
A.O. Terent’ev et al. / Journal of Organometallic Chemistry 694 (2009) 1786–1788
1 h. Then a solution of triethylamine (0.71 mmol) in anhydrous
THF (2 mL) was added. The reaction mixture was stirred at room
temperature for 4–20 h. The precipitate was filtered off, and the fil-
trate was concentrated to 1/5 of the initial volume. Then methanol
(15 mL) was added, the reaction mixture was cooled to ꢀ20 °C, and
the crystals of 3a–e that formed were filtered off and washed with
methanol (5 ꢁ 1 mL). Compounds 3a–e were dried in vacuo
(10 mm Hg) at room temperature for 1 h.
(75.48 MHz, CDCl3), d: 19.3, 19.5, 21.9, 22.2, 26.0, 26.2, 26.7
(CH2), 112.8 (OCO), 128.6, 130.9, 131.2, 134.6 (Car). Anal. Calc.
for C36H54GeO6: C, 65.97; H, 8.30; Ge, 11.08. Found: C, 65.79; H,
8.02; Ge, 11.24%.
Acknowledgments
This work is supported by the Program for Support of Leading
Scientific Schools of the Russian Federation (Grant No.
2942.2008.3) and the Grant of the President of the Russian Feder-
ation (No. MK-3515.2007.3).
3.5. 29,29-Dimethyl-13,14,27,28,30,31-hexaoxa-29-germadispiro
[11.2.11.5]hentriacontane (3a)
M.p. (MeOH) = 178–180 °C. 1H NMR (250.13 MHz, CDCl3), d:
0.61–0.82 (v, 6H, CH3), 1.24–1.92 (v, 44H, CH2). 13C NMR
(75.48 MHz, CDCl3), d: ꢀ2.0 (CH3), 19.5, 22.0, 22.3, 26.1, 26.2,
26.5 (CH2), 112.7 (C). Anal. Calc. for C26H50GeO6: C, 58.78; H,
9.49; Ge, 13.67. Found: C, 58.66; H, 9.11; Ge, 13.07%.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2009.02.005.
3.6. 29,29-Diethyl-13,14,27,28,30,31-hexaoxa-29-germadispiro
[11.2.11.5]hentriacontane (3b)
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