Liquid-phase synthesis of cyclic diene diepoxides using metal halides and hydrogen peroxide

Article abstract of DOI:10.1134/S1070428012100077

Optimal conditions were found for induced hydroxyhalogenation of cyclic dienes (tetrahydroindene, 4-vinylcyclohexene and 5-vinyl- and 5-cyclohexenylbicyclo[2.2.1]hept-2-enes) in the system [MHlg-HA or HHlg]-H ₂O₂ (or NaClO). Dehydrohalogenation of the chloro- and bromohydrins thus obtained with powdered potassium carbonate gave the corresponding diepoxy derivatives, and their hydrolysis led to mixtures of stereoisomeric tetrahydric alcohols. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012100077

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 10, pp. 1302–1308. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Kh.M. Alimardanov, O.A. Sadygov, N.I. Garibov, M.Ya. Abdullaeva, 2012, published in Zhurnal Organicheskoi Khimii, 2012,
Vol. 48, No. 10, pp. 1307–1312.
Liquid-Phase Synthesis of Cyclic Diene Diepoxides
Using Metal Halides and Hydrogen Peroxide
Kh. M. Alimardanov, O. A. Sadygov, N. I. Garibov, and M. Ya. Abdullaeva
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
pr. Khodzhaly 30, Baku, AZ 1025 Azerbaijan
e-mail: omar.sadiqov@gmail.com
Received November 17, 2011
Abstract—Optimal conditions were found for induced hydroxyhalogenation of cyclic dienes (tetrahydroin-
dene, 4-vinylcyclohexene and 5-vinyl- and 5-cyclohexenylbicyclo[2.2.1]hept-2-enes) in the system [MHlg–HA
or HHlg]–H2O2 (or NaClO). Dehydrohalogenation of the chloro- and bromohydrins thus obtained with
powdered potassium carbonate gave the corresponding diepoxy derivatives, and their hydrolysis led to
mixtures of stereoisomeric tetrahydric alcohols.
DOI: 10.1134/S1070428012100077
Development of efficient methods for the prepara-
tion of aliphatic and alicyclic diepoxides is important
from both theoretical and practical viewpoints. These
compounds are widely used as monomers in the manu-
facture of heat-resistant epoxy resins and specialty
rubbers [1–5]. Polyols and their esters, as well as
amino alcohols derived therefrom, are used in pharma-
cology, perfume and cosmetic industries [6, 7], and
manufacture of paint-and-lacquer materials [8].
In view of the above stated, search for more
efficient methods of synthesis of epoxy derivatives of
cyclic dienes is important now. From this viewpoint,
hydroxyhalogenation of the above hydrocarbons and
subsequent dehydrohalogenation of halohydrins thus
formed may provide an alternative synthetic approach
to mono- and diepoxides with a desired structure.
There are published data on the use of HCl–H2O2
(or HBr–H2O2) in hypohalogenation of unsaturated
compounds having only one double bond [20, 21]. We
previously showed that hypohalogenation of alkenyl-
arenes [21], enynes [22], alkyl cyclohexyl ketones
[23], and alkyl-, vinyl-, and allylacetylenes of the bi-
cyclo[2.2.1]heptene series can be performed, and the
corresponding epoxides can be synthesized [24, 25], in
aqueous solution of metal halides or hydrohalic acids.
The most common methods for the synthesis of
diepoxides are based on oxidation of diene hydro-
carbons with peroxo acids [5, 9, 10] or hydroperoxides
[11–13]. Analysis of numerous published data showed
that introduction of a second or third oxygen atom into
di- or polyene molecule requires more severe condi-
tions and is often complicated by secondary trans-
formations of the oxirane fragments [10].
The present article reports on the results of our
studies on the synthesis of halohydrins and diepoxides
from cyclic non-conjugated dienes, namely 4-vinyl-
cyclohexene (Ia), 3a,4,7,7a-tetrahydro-1H-indene (Ib),
5-vinylbicyclo[2.2.1]hept-2-ene (Ic), and 5-(cyclohex-
3-en-1-yl)bicyclo[2.2.1]hept-2-ene (Id, adduct of
4-vinylcyclohexene with cyclopentadiene), by one-pot
oxidation using a system generating electrophilic
reagents HOX (X = Cl, Br) (Scheme 1).
Selective diepoxidation of dienes has become pos-
sible after large-scale implementation of the synthesis
of epoxides from C2–C4 unsaturated hydrocarbons with
the use of hydroperoxides and transition metal com-
pounds [14]. However, despite extensive studies per-
formed in this field, the problem of selective epoxida-
tion of mono-, di-, and polycyclic dienes remains un-
resolved so far [15–18]. Attempted one-step diepoxida-
tion of dienes, including cyclic ones, under more
severe conditions were often accompanied by oligo-
merization, and the yields of the target compounds
were poor [19].
Treatment of dienes Ia–Id with dilute solutions of
metal or hydrogen halides in the presence of oxidants
under mild conditions (10–40°C) resulted in the forma-
tion of the corresponding halohydrins IIa–IId and
1302

LIQUID-PHASE SYNTHESIS OF CYCLIC DIENE DIEPOXIDES
1303
Scheme 1.
Hlg
Hlg
HO
OH
CH2
MHlg, HA, H2O2
Ia
IIa, IIIa
Hlg
Hlg
HO
MHlg, HA, H2O2
OH
Ib
IIb, IIIb
Hlg
Hlg
OH
MHlg, HA, H2O2
CH2
HO
Hlg
Ic
IIc, IIIc
Hlg
MHlg, HA, H2O2
HO
OH
Id
IId, IIId
M = H, Na, K, Co; A = HSO4–, NO3–, RSO3–; II, Hlg = Cl; III, Hlg = Br.
IIIa–IIId in fairly high yields (Scheme 1). Dehydro-
halogenation of IIa–IId and IIIa–IIId without isola-
tion in alkaline medium gave diepoxides IVa–IVd and
tetraols Va–Vd (Scheme 2).
metal halide or hydrohalic acid and oxidant, and
intensity of stirring (Tables 1, 2).
Initial dienes Ia–Id are poorly soluble in water;
therefore, the reaction in heterogeneous liquid–liquid
system occurs at the phase boundary. In a stationary
mode without strong stirring of the reaction mixture
(500–600 rpm), transfer of hypohalous acids generated
in situ from the aqueous phase to organic is consider-
ably hindered, and the yield is reduced. At 0–20°C the
oxidation involves mainly the double bond charac-
With a view to determine the relative reactivity of
the double bonds in the substrates we examined the
effect of various parameters on the reaction selectivity
and yield of chloro(bromo)hydrins. The rate of accu-
mulation of halohydrins in the reaction mixture
strongly depended on the temperature, concentration of
Table 1. Temperature effect on the yield of chloro(bromo)hydrins IIa–IId and IIIa–IIIda
Yield, %
Compound no.
0°C
10°C
20°C
30°C
40°C
50°C
IIa
40.6
36.5
37.8
32.6
34.6
31.7
36.7
33.5
48.4
43.6
44.5
40.8
42.8
38.6
43.6
41.8
76.5
72.4
74.6
71.5
72.6
67.5
73.6
68.7
86.4
81.5
82.0
79.0
80.0
78.4
78.5
73.8
89.6
86.5
86.6
85.7
87.0
84.0
85.6
81.8
80.7
74.6
81.0
74.6
68.0
64.8
71.0
68.0
IIIa
IIb
IIIb
IIc
IIIc
IId
IIId
a
Molar ratio substrate–MHlg (HHlg)–H2O2 (NaOCl) 0.1:0.24:0.24; HCl, 10%; HBr, 8%; NaBr or CoBr2, 10%; rate of addition of H2O2
10 g/h (NaOCl, 25 g/h); reaction time 7 h.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

ALIMARDANOV et al.
1304
Table 2. Effect of concentration of hydrohalic acid on the yield of chloro(bromo)hydrins IIa–IId and IIIa–IIId (40°C, ratio
substrate–MHlg–oxidant 1:0.24:0.24)
Yield, %
Concentration
of HCl, %
Concentration
of HBr, %
chlorohydrins
bromohydrins
IIa
IIb
IIc
IId
IIIa
IIIb
IIIc
IIId
06
10
15
25
36
78.0
89.6
72.5
54.6
42.4
74.6
86.6
70.4
50.8
40.5
79.0
87.0
71.6
51.5
41.6
71.5
85.4
64.5
46.4
38.6
76.5
86.5
72.0
48.5
42.0
36.0
71.6
85.7
70.0
46.0
40.0
34.0
70.5
84.0
73.0
43.6
38.0
31.0
68.0
81.8
64.5
44.0
39.0
32.8
06
08
15
25
33
46
terized by higher electron density, and the products are
the corresponding monohalohydrins. As the tempera-
ture rises from 20 to 40°C, the second double bond
also undergoes oxidation, and bis-halohydrins are ob-
tained. Raising the temperature to 50°C and higher
considerably reduces the yield as a result of increased
contribution of unproductive decomposition of hypo-
halous acids and oxidants (H2O2 and NaOCl).
chlorohydrins to 32%. Analogous results were ob-
tained with hydrobromic acid and its salts (NaBr,
CoBr2). The use of 8% aqueous HBr (NaBr) ensured
fairly high yields (up to 82%) of bromohydrins,
whereas the yield decreased to 35–50% when the con-
centration of HBr was higher than 8–10%; presumably,
this is the result of side formation of molecular halo-
gen (Cl2 and Br2) which is involved in other processes.
The reaction direction and the yield of chloro-
(bromo)hydrins also depended on the concentration of
hydrohalic acid or metal halide (Table 2). Fairly high
yields of chlorohydrins (up to 85%) were attained with
the use of 6–10% aqueous HCl. Further raising the
acid concentration (15–36%) reduced the yield of
The structure of chloro- and bromohydrins IIa–IId
and IIIa–IIId, as well as of diepoxides IVa–IVd and
tetraols Va–Vd obtained therefrom, was confirmed by
elemental analysis, IR and H NMR spectroscopy, and
independent synthesis, i.e., epoxidation of dienes Ia–
Id with a 30% solution of H2O2 and acetic acid in
1
Scheme 2.
OH
O
HO
HO
OH
KOH (NaOH), Et2O
O
15–22% NaOH (KOH)
IIa, IIIa
IVa
Va
Vb
OH
O
HO
HO
KOH (NaOH), Et2O
KOH (NaOH), Et2O
15–22% NaOH (KOH)
15–22% NaOH (KOH)
O
IIb, IIIb
IIc, IIIc
OH
OH
IVb
OH
O
HO
O
HO
HO
IVc
IVd
Vc
Vd
OH
O
O
KOH (NaOH), Et2O
15–22% NaOH (KOH)
IId, IIId
HO
OH
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

LIQUID-PHASE SYNTHESIS OF CYCLIC DIENE DIEPOXIDES
1305
the presence of chlorine-containing acidic cation ex-
changer Ku-2-8 (Cl 9.5%), the substrate–H2O2–AcOH
molar ratio being 1:1.2:0.5.
pounds and products were checked by TLC on Silufol
UV-254 plates and by GLC on an LKhM-8MD-5
chromatograph equipped with a thermal conductivity
detector [3000×0.3-cm column packed with 5% of
XE-60 on Chromaton N-AW-DMCS, oven temperature
140°C, carrier gas helium, flow rate 40 ml/min; or
8% of poly(ethylene glycol adipate) on Chromosorb W
(110–130 mesh), carrier gas nitrogen, oven tempera-
ture 160°C (for products)].
The IR spectra of IIa–IId and IIIa–IIId contained
absorption bands at 3615, 3625, 3550, 3200 and 1150,
1100, 850–650 cm–1, typical of secondary and tertiary
O–H groups and C–Cl (C–Br) bonds, respectively,
while bands assignable to vibrations of double C=C
bonds in cyclohexene (680, 1650 cm–1) or bicyclo-
heptene fragments (720, 1670, 3030 cm–1) were absent.
The IR spectra of IIa, IIc, IIIa, and IIIc lacked
absorption bands at 910, 990, and 3040 cm–1, typical
of vinyl group.
Halohydrins IIa–IId and IIIa–IIId (general
procedure). A 26–30% solution of hydrogen peroxide
(0.25 mol) in water or dioxane or a 18.5% solution of
NaOCl (containing 110 mol/l of active chlorine) was
added dropwise (10 g/h) under stirring to a mixture of
0.2 mol of diene Ia–Id and 0.25 mol of a 6–8% solu-
tion of MBr (or HBr) or a 8–10% solution of MCl (or
HCl), adjusted to a required temperature (0–40°C).
The mixture was stirred for 5.5–7 h until complete
consumption of the oxidant (according to the data of
redox titration). Chloro- and bromohydrins thus ob-
tained were then converted into the corresponding
diepoxides by adding potassium (or sodium) hydroxide
to the reaction mixture.
Compounds IIa–IId and IIIa–IIId displayed in the
1H NMR spectra signals from CH protons at δ 3.46–
3.49 ppm and a broadened singlet at δ 4.78–4.81 ppm
due to CHOH fragment in the bicycloheptane or cyclo-
pentane fragment or side hydroxyethyl group.
Both chloro- and bromohydrins IIa–IId and IIIa–
IIId readily underwent dehydrohalogenation to the
corresponding diepoxides IVa–IVd on heating with
powdered KOH (yield 79–96%), whereas treatment of
these compounds with aqueous alkali afforded 80–94%
of tetraols Va–Vd (Scheme 2).
The organic phase containing compound II or III
was separated, the aqueous phase was extracted with
diethyl ether (2×50 ml), and the extracts were com-
bined with the organic phase, neutralized with a 10%
solution of sodium carbonate, dried over magnesium
sulfate, and evaporated to isolate isomeric halohydrins
IIa–IId and IIIa–IIId.
Thus chloro- and bromohydrins derived from cyclic
dienes can be used to obtain the corresponding di-
epoxides and various polyfunctionalized derivatives of
alicyclic hydrocarbons.
EXPERIMENTAL
2(1)-Chloro-4-(1-chloro-2-hydroxyethyl)cyclo-
hexan-1(2)-ol (IIa) was obtained from 21.6 g
(0.2 mol) of diene Ia. Yield 36.8 g (86%), mp 61–
64°C. IR spectrum, ν, cm–1: 3625, 1150, 1100 (CH–
The IR spectra were recorded from thin films on
a UR-20 spectrometer. The H NMR spectra were
1
measured from solutions in carbon tetrachloride on
a Bruker spectrometer operating at 300 MHz; hexa-
methyldisiloxane was used as internal reference. Initial
1
OH, CH2–OH), 830, 745, 665 (C–Cl) [27]. H NMR
spectrum, δ, ppm: 3.47 t (1-H), 3.51 t (2-H), 3.76 br.s
(8-OH), 3.91 d (7-H), 4.60 br.s (1-OH) [28, 29].
Found, %: C 45.12; H 6.72; Cl 33.41. C8H14Cl2O2.
Calculated, %: C 45.07; H 6.57; Cl 33.33.
5-vinylnorbornene [bp 60–61°C (6.5 mm), d420
=
1.4819, nD20 = 0.8867] was prepared by thermal conden-
sation of buta-1,3-diene with cyclopentadiene [26].
4-Vinylcyclohexene (purity 99.1%, bp 130°C, d420 =
2(1),5(6)-Dichloroperhydroindene-1(2),6(5)-diol
(IIb) was obtained from 24 g (0.2 mol) of diene Ib.
Yield 36.9 g (82%), mp 136–140°C. IR spectrum, ν,
cm–1: 3625, 3550, 3200, 1100 (CH–OH), 850, 830,
0.8363, nD20 = 1.4648) and bicyclo[4.3.1.01.6]nona-3,8-
diene (purity 99.3%, bp 148°C, d420 = 0.8344, nD20
=
1.4658) were isolated by fractional distillation of
a mixture of 70% of 4-vinylcyclohexene and 30% of
bicyclo[4.3.1.01.6]nona-3,8-diene. 5-(Cyclohex-3-enyl)-
1
745, 660 (C–Cl). H NMR spectrum, δ, ppm: 1.43 d
(2-H), 1.49 d (1-H), 1.41–1.83 m (6H, CH2), 3.47 d
(8-H), 3.51 d (7-H), 3.53 t (3-H), 3.56 d (4-H),
3.71 br.s (8-OH), 4.70 br.s (3-OH). Found, %: C 48.23;
H 6.38; Cl 31.83. C9H14Cl2O2. Calculated, %: C 48.0;
H 6.22; Cl 31.56.
bicyclo[2.2.1]hept-2-ene [bp 99–101°C (4 mm), d420
=
0.9768, nD20 = 1.5158] was prepared by condensation of
cyclopentadiene with 4-vinylcyclohexene [19]. The
purity and isomeric composition of the initial com-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

ALIMARDANOV et al.
1306
3(2)-Chloro-5-(1-chloro-2-hydroxyethyl)bicyclo-
3(2)-Bromo-5-[3(4)-bromo-4(3)-hydroxycyclo-
hexyl]bicyclo[2.2.1]heptan-2(3)-ol (IIId) was ob-
tained from 34.8 g (0.2 mol) of diene Id. Yield 54.3 g
(74%), mp 182–187°C. IR spectrum, ν, cm–1; 3625,
[2.2.1]heptan-2(3)-ol (IIc) was obtained from 24 g
(0.2 mol) of diene Ic. Yield 36.0 g (80%), mp 98–
101°C. IR spectrum, ν, cm–1: 3625, 3615, 1150, 1100
1
1
(CH–OH, CH2–OH), 830, 745, 660 (C–Cl). H NMR
1100 (CH–OH), 750, 680–670 (C–Br). H NMR spec-
spectrum, δ, ppm: 1.23–1.56 m (4H, CH2), 1.78 t
(4-H), 2.72 d (5-H), 3.46 t (2-H), 3.49 t (3-H), 3.50 d
(8-H), 3.63–3.88 d.d (2H, 9-H), 3.76 br.s (9-OH),
4.78 br.s (2-OH). Found, %: C 48.12; H 6.33;
Cl 31.70. C9H14Cl2O2. Calculated, %: C 48.0; H 6.22;
Cl 31.56.
trum, δ, ppm: 0.89 d (2′-H, 6′-H), 1.11 d (5′-H), 1.58 t
(2′-H, 6′-H), 1.79 t (5′-H), 3.32 t (4′-H), 4.78 br.s
(4′-OH), 4.79 t (3′-H), 1.23–1.55 m (5H, 1-H, CH2),
1.83 t (4-H), 3.46 d (3-H), 3.58 d (2-H), 4.80 br.s
(2-OH). Found, %: C 42.43; H 5.51; Br 43.46.
C13H20Br2O2. Calculated, %: C 42.39; H 5.43;
Br 43.48.
3(2)-Chloro-5-[3(4)-chloro-4(3)-hydroxycyclo-
hexyl]bicyclo[2.2.1]heptan-2(3)-ol (IId) was obtained
from 34.8 g (0.2 mol) of diene Id. Yield 43.8 g (79%),
mp 158–161°C. IR spectrum, ν, cm–1: 3625, 3615,
Compounds IVa–IVd and Va–Vd (general proce-
dures). a. Powdered potassium hydroxide, 8.5 g
(0.075 mol), was added under stirring to a solution of
0.025 mol of compound IIa–IId or IIIa–IIId in 50 ml
of diethyl ether, cooled to 8–10°C. The mixture was
stirred for 2.5 h at 20°C, the solvent was distilled off,
and the residue was subjected to vacuum distillation or
chromatography on aluminum oxide (using hexane as
eluent) to isolate mixtures of isomeric mono- and
diepoxides.
1
1100 (CH–OH), 830, 745, 660–650 (C–Cl). H NMR
spectrum, δ, ppm: 0.89 d (2′-H, 6′-H), 1.11 d (5′-H),
1.57 t (2′-H, 6′-H), 1.79 t (5′-H), 3.32 t (4′-H), 4.77 br.s
(4′-OH) 4.79 t (3′-H), 1.23–1.55 m (4H, CH2), 1.73 t
(4-H), 3.45 d (2-H), 3.49 d (3-H), 4.76 br.s (2-OH).
Found, %: C 56.08; H 7.24; Cl 25.57. C13H20Cl2O2.
Calculated, %: C 55.97; H 7.17; Cl 25.45.
2(1)-Bromo-4-(1-bromo-2-hydroxyethyl)cyclo-
hexan-1(2)-ol (IIIa) was obtained from 21.6 (0.2 mol)
of diene Ia. Yield 49.2 g (82%), mp 116–120°C. IR
spectrum, ν, cm–1: 3625, 3615, 1150, 1100 (CH–OH,
b. Compound IIa–IId or IIIa–IIId was treated
(without preliminary isolation from the reaction mix-
ture; see above) with a cold (5–10°C) 20–22% aqueous
solution of sodium hydroxide; mixtures of isomeric
compounds Va–Vd were isolated as described in [11].
1
CH2–OH), 745, 660–650 (C–Br). H NMR spectrum,
δ, ppm: 1.46–1.98 m (6H, CH2), 3.49 t (2-H), 3.59 d
(1-H), 3.86–4.11 d.d (2H, 8-H), 4.76–4.78 br.s (2H,
OH). Found, %: C 31.96; H 4.8; Br 53.12. C8H14Br2O2.
Calculated, %: C 31.79; H 4.64; Br 52.98.
5-(Oxiran-2-yl)-2-oxabicyclo[4.1.0]heptane (IVa)
was synthesized from 5.3 g (0.025 mol) of IIa. Yield
3.2 g (92%), bp 49–51°C (10 mm), nD20 = 1.4738, d420 =
1.0917. IR spectrum, ν, cm–1: 3010–3028 (C–H) [27];
1(2),5(6)-Dibromoperhydroindene-2(1),6(5)-diol
(IIIb) was obtained from 24.0 g (0.2 mol) of diene Ib.
Yield 43.6 g (79%), mp 173–176°C. IR spectrum, ν,
cm–1: 3625, 3550, 3200, 1100 (CH–OH), 830, 750, 660
1
1260, 1250, 945, 840 (oxirane). H NMR spectrum, δ,
ppm: 1.31–1.71 m (6H, CH2), 1.74 d (5-H), 2.38 d.d
and 2.63 d.d (9-H), 2.87 q (1-H, 3-H), 5.52 d (8-H)
[28, 29]. Found, %: C 68.82; H 8.71. C8H12O2. Cal-
culated, %: C 68.57; H 8.57.
1
(C–Br). H NMR spectrum, δ, ppm: 1.46 d (2-H),
1.49–1.98 m (6H, CH2), 3.33 br.s (8-OH), 3.49 d
(7-H), 3.52 d (4-H), 3.63 t (3-H), 4.78 br.s (3-OH).
Found, %: C 34.43; H 4.52; Br 51.04. C9H14Br2O2.
Calculated, %: C 34.39; H 4.46; Br 50.96.
2,7-Dioxatetracyclo[6.3.2.01.305.1006.8]undecane
(IVb) was synthesized from 9.6 g (0.025 mol) of IIb.
Yield 3.3 g. According to the GLC data, the product
contained 84.2% of diepoxide IVb [bp 73–75°C
(10 mm), nD20 = 1.4908, d240 = 1.1062] and 15.8% of
monoepoxide [bp 53–55.5°C (14 mm), nD20 = 1.5188,
d240 = 0.9812]. IR spectrum, ν, cm–1: 1265, 1260, 930,
940, 860, 865 (oxirane ring fused to the six-membered
ring), 850–835 (oxirane ring fused to the five-mem-
3(2)-Bromo-5-(1-bromo-2-hydroxyethyl)bicyclo-
[2.2.1]heptan-2(3)-ol (IIIc) was obtained from 24.0 g
(0.2 mol) of diene Ic. Yield 49.2 g (78%), mp 160–
163°C. IR spectrum, ν, cm–1: 3615, 1115, 1100 (CH–
1
OH, CH2–OH), 750, 680 (C–Br). H NMR spectrum,
δ, ppm: 1.23–1.54 m (4H, CH2), 3.48 t (2-H), 3.50 t
(3-H), 3.53 d (8-H), 3.63–3.89 d.d (2H, 9-H), 4.76 br.s
(9-OH), 4.78 br.s (2-OH). Found, %: C 34.47; H 4.54;
Br 51.16. C9H14Br2O2. Calculated, %: C 34.39; H 4.46;
Br 50.96.
1
bered ring). H NMR spectrum, δ, ppm: 1.39–1.77 m
(6H, CH2), 2.82 q (1-H, 3-H), 3.53–3.51 d (6-H, 8-H).
Found, %: C 71.15; H 7.93. C9H12O2. Calculated, %:
C 71.05; H 7.89.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

LIQUID-PHASE SYNTHESIS OF CYCLIC DIENE DIEPOXIDES
1307
6-(Oxiran-2-yl)-3-oxatricyclo[3.2.1.02.4]octane
(IVc) was synthesized from 7.9 g (0.025 mol) of IIIc.
Yield 3.5 g (93%), mp 42–44°C, bp 111–113°C
(10 mm), d420 = 1.1182; the product crystallized in
a receiver. IR spectrum, ν, cm–1: 1265, 1260, 940, 850
4. Wu, S., Jorgensen, J.D., and Soucek, M.D., Polymer,
2000, vol. 41, p. 81.
5. Wang, Z., Xie, M., Zhoo, Y., Yu, Y., and Fang, S.,
Polymer, 2003, vol. 44, p. 923.
6. Kheifits, L.A. and Dashunin, V.M., Dushistye veshche-
stva i drugie produkty dlya parfyumerii (Fragrance
Substances and Other Materials for Perfumery),
Moscow: Khimiya, 1994.
1
(oxirane). H NMR spectrum, δ, ppm: 1.24–1.56 m
(4H, CH2), 1.74–1.86 t (1-H, 5-H, 6-H), 2.53 d.d
(9-H), 2.39–2.65 d.d (10-H), 2.77 q (2-H, 4-H). Found,
%: C 70.95; H 8.5 C9H12O2. Calculated, %: C 71.05;
H 7.89.
7. Mashkovskii, K.L., Lekarstvennye sredstva (Medicines),
Moscow: Novaya Volna, 2002, 15th ed., vols. 1, 2.
8. Livshchits, R.M. and Vobrvinskii L.A., Zameniteli
rastitel’nykh masel v lakokrasochnoi promyshlennosti
(Vegetable Oil Substitutes in Paint-and-Lacquer
Industry), Moscow: Khimiya, 1987.
9. Prilezhaeva, E.N., Reaktsiya Prilezhaeva. Elektrofil’noe
okislenie (Prilezhaev Reaction. Electrophilic Oxidation),
Moscow: Nauka, 1974; Kas’yan, L.I., Seferova, M.F.,
and Okovityi, S.I., Alitsiklicheskie epoksidnye soedi-
neniya. Metody sinteza (Alicyclic Epoxy Compounds.
Methods of Synthesis), Dnepropetrovsk: Dnepropetr.
Gos. Univ., 1996.
6-(7-Oxabicyclo[4.1.0]hept-3-yl)-3-oxatetracyclo-
[3.2.1.02.4]octane (IVd) was synthesized from 9.2 g
(0.025 mol) of IIId. Yield 4.8 g (94%), bp 96–98°C
(1 mm), nD20 = 1.5182, d420 = 1.1084. IR spectrum, ν,
1
cm–1: 1265, 1260, 858, 840 (oxirane). H NMR spec-
trum, δ, ppm: 1.25–1.77 m (9H), 2.81 q (2-H, 4-H),
2.89 q (2H). Found, %: C 76.03; H 8.10. C13H18O2.
Calculated, %: C 71.05; H 7.89.
4-(1,2-Dihydroxyethyl)cyclohexane-1,2-diol (Va)
was synthesized from 5.3 g (0.025 mol) of IIa. Yield
3.7 g (87%), mp 128–133°C. Found, %: C 54.51;
H 8.97. C8H16O4. Calculated, %: C 54.54; H 9.09.
10. Guiard, S., Giorgi, M., Santelli, M., and Parrain, J.-L.,
J. Org. Chem., 2003, vol. 68, p. 3319.
11. Tolstikov, G.A., Reaktsiya gidroperoksidnogo okisleniya
(Hydroperoxide Oxidation), Moscow: Nauka, 1976.
Perhydroindene-1,2,5,6-tetraol (Vb) was synthe-
sized from 7.9 g (0.025 mol) of IIIb. Yield 4.1 g
(88%), mp 164–168°C. Found, %: C 57.46; H 8.56.
C9H16O4. Calculated, %: C 57.45; H 8.57.
12. Nozhnin, I.A., Mel’nik, L.V., Egorova, L.M., and Kryu-
kov, S.I., Neftekhimiya, 1997, vol. 37, no. 2, p. 160.
13. Leonov, V.N., Katalizatory epoksidirovaniya olefinov
organicheskimi gidroperoksidami (Catalysts for Olefin
Epoxidation with Organic Hydroperoxides), Moscow:
TsNIIENeftekhim, 1993.
14. Landau, R., Brown, D., Russel, J.L., and Collar, R.,
Book of Synopses, 7th World Petroleum Congress,
Mexico, 1967.
15. Sheng, M.N. and Zajacek, J.G., J. Org. Chem., 1970,
vol. 35, p. 1839.
16. Lazurin, E.A., Voronenkov, V.V., and Osokin, Yu.G.,
5-(1,2-Dihydroxyethyl)bicyclo[2.2.1]heptane-2,3-
diol (Vc) was synthesized from 3.6 g (0.025 mol) of
IIc. Yield 4.3 g (91%), mp 160–164°C. IR spectrum, ν,
cm–1: 3625, 3615, 1150, 1100 (CH–OH, CH2–OH).
1H NMR spectrum, δ, ppm: 3.24 d (2-H, 3-H), 3.29
(8-H), 3.56–3.81 t (2H, 9-H), 4.78 br.s (CH2OH),
4.81 br.s (CHOH). Found, %: C 57.43; H 8.56.
C9H16O4. Calculated, %: C 57.47; H 8.51.
Usp. Khim., 1997, vol. 46, p. 1739.
17. Antonova, T.N., Izv. Vyssh. Uchebn. Zaved., Ser. Khim.
Khim. Tekhnol., 2008, vol. 51, no. 4, p. 38.
5-(3,4-Dihydroxycyclohexyl)bicyclo[2.2.1]hep-
tane-2,3-diol (Vd) was synthesized from 7.9 g
(0.025 mol) of IIId. Yield 5.4 g (89%), mp 218–
222°C. Found, %: C 64.46; H 9.17. C13H22O2. Calcu-
lated, %: C 64.47; H 9.09.
18. Kas’yan, L.I., Kas’yan, A.O., Okovityi, S.I., and Tara-
bara, I.N., Alitsiklicheskie epoksidnye soedineniya. Re-
aktsionnaya sposobnost’ (Alicyclic Epoxy Compounds.
Reactivity), Dnepropetrovsk: Dnepropetr. Gos. Univ.,
2003.
19. Alimardanov, Kh.M., Sadygov, O.A., Gadzhiev, T.A.,
Abdullaeva, M.Ya., Asirova, R.B., and Babaev, N.R.,
Prots. Neftekhim. Nefteper., 2007, no. 5, p. 66.
20. Muganlinskii, F.F., Treger, Yu.A., and Lyushin, M.M.,
Khimiya i tekhnologiya galogenorganicheskikh soedi-
nenii (Chemistry and Technology of Organohalogen
Compounds), Moscow: Khimiya, 1991.
21. Sadygov, O.A. and Alimardanov, Kh.M., Russ. J. Org.
Chem., 2007, vol. 43, p. 1661.
REFERENCES
1. Paquin, A.M., Epoxydverbindungen und Epoxydharze,
Berlin: Springer, 1958.
2. Korshak, V.V., Termostoikie polimery (Heat-Resistant
Polymers), Moscow: Nauka, 1969.
3. Kameyama, A., Watanabe, Sh., Kobayashi, E., and
Nishikubo, T., Macromolecules, 1992, vol. 25, no. 9,
p. 2307.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

ALIMARDANOV et al.
1308
22. Veliev, M.G., Sadygov, O.A., Alimardanov, Kh.M., and
Shatirova, M.I., Russ. J. Org. Chem., 2007, vol. 43,
p. 1604.
23. Sadygov, O.A. and Alimardanov, Kh.M., Russ. J. Org.
Chem., 2009, vol. 45, p. 166.
26. Plate. A.F. and Belikova, N.A., Zh. Obshch. Khim.,
1960, vol. 30, p. 3945.
27. Bellamy, L.J., The Infra-red Spectra of Complex
Molecules, London: Methuen, 1958.
28. Ionin, B.I. and Ershov, B.A., YaMR spektry v orga-
nicheskoi khimii (NMR Spectra in Organic Chemistry),
Leningrad: Khimiya, 1967.
24. Sadygov, O.A., Alimardanov, Kh.M., and Abba-
sov, M.F., Russ. J. Gen. Chem., 2009, vol. 79, p. 1698.
25. Veliev, M.G., Sadygov, O.A., Shatirova, M.I., and Ali-
mardanov, Kh.M., Russ. J. Org. Chem., 2008, vol. 44,
p. 1282.
29. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion, New York: Wiley, 1972.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012