1,1´ꢀBishydroperoxydi(cycloalkyl) peroxides
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 5, May, 2005
1217
Complete Xꢀray diffraction data for 1,1´ꢀbishydroxyperoxyꢀ
di(cyclododecyl) peroxide (1c) were deposited with the Camꢀ
bridge Structural Database (CSDB).
1,1ꢀDihydroperoxycycloundecane (3b). The yield was 92%.
M.p. 80—82 °C (diethyl ether). Found (%): C, 60.42; H, 10.10.
C11H22O4. Calculated (%): C, 60.52; H, 10.16. 1H NMR
(250.13 MHz), δ: 1.28—1.63 (m, 16 H, CH2); 1.70—1.88 (m,
4 H, CH2); 9.30—9.49 (br.s, 2 H, OOH). 13C NMR (62.9 MHz),
δ: 21.3, 25.4, 26.3, 26.9, 27.7 (CH2); 115.4 (C).
1,1ꢀDihydroperoxycyclotridecane (3d). The yield was 94%.
M.p. 115—116.5 °C (diethyl ether). Found (%): C, 63.26;
H, 10.53. C13H26O4. Calculated (%): C, 63.38; H, 10.64.
1H NMR (300.13 MHz), δ: 1.25—1.60 (m, 20 H, CH2);
1.64—1.82 (m, 4 H, CH2); 9.35—9.43 (br.s, 2 H, OOH).
13C NMR (75.47 MHz), δ: 20.8, 25.5, 25.6, 26.8, 27.3, 28.6
(CH2); 115.1 (C).
(in the case of bis(hydroperoxide) 3d, to –20 °C), and kept in
the cold state for 1 h. Crystals of peroxides 1c—e that precipiꢀ
tated were filtered off, washed with water (3×5 mL), and diethyl
ether (2×2 mL) cooled to –20 °C, and evacuated at room temꢀ
perature and at 0.1 Torr for 1 h.
1,1´ꢀBishydroxyperoxydi(cyclododecyl) peroxide (1c).9,12 The
yield was 86%. M.p. 154—155.5 °C (CHCl3) (cf. lit. data9: m.p.
151—152 °C). Found (%): C, 66.80; H, 10.43. C24H46O6. Calꢀ
culated (%): C, 66.94; H, 10.77. 1H NMR (300.13 MHz), δ:
1.21—1.82 (m, 44 H, CH2); 9.78 (s, 2 H, OOH). 13C NMR
(75.47 MHz), δ: 19.40, 21.85, 22.12, 25.89, 26.20, 26.44 (CH2);
115.38 (C).
1,1´ꢀBishydroxyperoxydi(cyclotridecyl) peroxide (1d).8 The
yield was 64%. M.p. 127—128.5 °C (CHCl3) (cf. lit. data8: m.p.
128—129 °C). 1H NMR (300.13 MHz), δ: 1.20—1.78 (m, 48 H,
CH2); 9.35—9.42 (br.s, 2 H, OOH). 13C NMR (75.47 MHz), δ:
20.9, 25.2, 25.6, 26.5, 27.2, 28.6 (CH2); 111.4 (C).
1,1´ꢀBishydroxyperoxydi(cyclopentadecyl) peroxide (1e). The
yield was 84%. M.p. 113—115 °C (CHCl3). Found (%): C, 70.32;
H, 11.15. C30H58O6. Calculated (%): C, 70.00; H, 11.36.
1H NMR (300.13 MHz), δ: 1.20—1.78 (m, 56 H, CH2);
9.60—9.65 (br.s, 2 H, OOH). 13C NMR (75.47 MHz), δ: 21.4,
25.3, 25.4, 25.5, 26.0, 26.2, 27.9 (CH2); 115.6 (C).
1,1ꢀDihydroperoxycyclopentadecane (3e). The yield was 34%.
M.p. 116—118 °C (diethyl ether). Found (%): C, 65.37; H, 10.78.
C
15H30O4. Calculated (%): C, 65.66; H, 11.02. 1H NMR
(300.13 MHz), δ: 1.23—1.55 (m, 24 H, CH2); 1.59—1.80
(m, 4 H, CH2); 9.05—9.12 (br.s, 2 H, OOH). 13C NMR
(75.47 MHz), δ: 21.8, 26.5, 26.6, 26.9, 27.5, 29.3 (CH2);
115.1 (C).
Homocoupling of gemꢀbis(hydroperoxides) 3a,b in the presꢀ
ence of BF3•OEt2. Synthesis of 1,1´ꢀbishydroxyperoxydi(cycloꢀ
alkyl) peroxides 1a,b. Boron trifluoride diethyl etherate
(0.5 equiv.) was added to a solution of gemꢀbis(hydroxyꢀ
peroxy)cycloalkane 3 (2.3—3.4 mmol) in Et2O (10—20 mL).
The reaction mixture was stirred at room temperature for 1 h (in
the case of 3b, for 12 h), Et2O (20 mL) was added, and the
mixture was washed with water (4×5 mL). In the synthesis of
compound 1b, the reaction mixture was then washed with a 5%
NaOH solution (2×5 mL) and water (5 mL), and the ethereal
layer was dried (MgSO4) and concentrated. In the synthesis of
compound 1a, the ethereal layer was dried (MgSO4) and conꢀ
centrated, after which cyclohexanone, tetroxane 2a, and peroxꢀ
ide 1a were isolated by column chromatography (light petroꢀ
leum—diethyl ether, 95 : 5, as the eluent) (see Table 1). Cycloꢀ
hexanone and tetroxane 2a were identified by TLC using auꢀ
thentic samples. The residue prepared upon homocoupling of
bis(hydroperoxide) 3b was crystallized from diethyl ether and
peroxide 1b was obtained.
Xꢀray diffraction study of 1,1´ꢀbishydroxyperoxydi(cycloꢀ
dodecyl) peroxide (1c). Crystals of compound 1c (C24H46O6) are
monoclinic, M 430.61, at 213 K a = 10.398(8), b = 10.934(6),
c = 21.726(15) Å, β = 100.39(6)°, V = 2430(3) Å3, dcalc
=
1.177 g cm–3, µ = 0.082 mm–1, space group P2/n, Z = 4.
The intensities of 4676 independent reflections were meaꢀ
sured on a fourꢀcircle Syntex P21 diffractometer (λ(MoKα) =
0.71073 Å, graphite monochromator, θ/2θ scanning technique,
2θ
= 52°, data completeness was 89.6%). The equivalent
max
reflections were merged to obtain 4290 independent reflections
(Rint = 0.0822), which were used in subsequent calculations.
The structure was solved by direct methods. The nonꢀ
hydrogen atoms were refined anisotropically by the fullꢀmatrix
leastꢀsquares method against F2. The hydrogen atoms were placed
in calculated positions and refined using a riding model. The
final R factors were as follows: R1 = 0.0581 (calculated against F
for 2467 reflections with I > 2σ(I )), wR2 = 0.1306 (calculated
against F 2 for all 4290 reflections), 271 parameters were refined,
GOOF = 1.029. All calculations were carried out with the use of
the SHELXTLꢀ97 program package.15
1,1´ꢀBishydroxyperoxydi(cyclohexyl) peroxide (1a).14 The
yield was 36%. M.p. 80—81.5 °C (light petroleum) (cf. lit. data14
:
m.p. 81—82 °C). 1H NMR (300.13 MHz), δ: 1.43—1.68 (m,
12 H, CH2); 1.78—1.98 (m, 8 H, C—CH2); 9.42—9.62 (br.s,
2 H, OOH). 13C NMR (75.47 MHz), δ: 22.6, 25.5, 29.9 (CH2);
111.3 (C).
This study was financially supported by the Council
on Grants of the President of the Russian Federation
(Program for State Support of Leading Scientific Schools
of the Russian Federation, Grants NSh 02121.2003.3 and
NSh 1060.2003.3).
1,1´ꢀBishydroxyperoxydi(cycloundecyl) peroxide (1b). The
yield was 64%. M.p. 111—113 °C (diethyl ether). Found (%):
C, 65.58; H, 10.64. C22H42O6. Calculated (%): C, 65.64;
H, 10.52. 1H NMR (300.13 MHz), δ: 1.22—1.52 (m, 16 H,
CH2); 1.56—1.78 (m, 4 H, CH2); 9.23—9.32 (br.s, 2 H, OOH).
13C NMR (75.47 MHz), δ: 29.02, 27.5, 26.7, 26.5, 21.8 (CH2);
114.6 (C).
Homocoupling of gemꢀbis(hydroperoxides) 3c—e in the presꢀ
ence of BF3•OEt2. Synthesis of 1,1´ꢀbishydroxyperoxydi(cycloꢀ
alkyl) peroxides 1c—e (general procedure). Boron trifluoride diꢀ
ethyl etherate (0.6—1 equiv.) was added to a solution of
gemꢀbis(hydroxyperoxy)cycloalkane 3 (1.8—2.2 mmol) in Et2O
(10 mL). The reaction mixture was stirred for 1 h, cooled to 0 °C
References
1. P. Busch and P. R. Story, Synthesis, 1970, 181.
2. M. J. C. Harding and D. M. Whalen, Ind. Ing. Chem., Prod.
Res. Dev., 1975, 14, 232.
3. R. Story and P. Busch, in Advances in Organic Chemistry,
Ed. E. C. Taylor, Wiley, New York, 1972, Vol. 8, 67.
4. G. A. Razuvaev, V. S. Etlis, N. I. Kirillov, and E. M.
Samarina, Vysokomol. Soedin., 1961, 3, 1176 [Polym. Sci.
USSR, 1961, 3 (Engl. Transl.)].