Telomerization of Z,Z-cyclooctadiene with halomethanes catalyzed by chromium, copper, and molybdenum compounds in the presence of water

Article abstract of DOI:10.1134/S0965544111060107

The telomerization of 1Z,5Z-cyclooctadiene with halogenated methanes (CCl₄, CBrCl₃, CHCl₃, CH₂Cl ₂) mediated by chromium, copper, and molybdenum complexes has been investigated. It has been shown that the use of water as a nucleophilic additive promotes the formation of 1,4- and 1,5-epoxycyclooctanes and anti-8-(trichloromethyl)bicyclo[3.2.1]octan-exo-2-ol. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S0965544111060107

ISSN 0965ꢀ5441, Petroleum Chemistry, 2011, Vol. 51, No. 6, pp. 435–441. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © R.I. Khusnutdinov, N.A. Shchadneva, T.M. Oshnyakova, U.M. Dzhemilev, 2011, published in Neftekhimiya, 2011, Vol. 51, No. 6, pp. 443–449.
Telomerization of Z,ZꢀCyclooctadiene with Halomethanes Catalyzed
by Chromium, Copper, and Molybdenum Compounds
in the Presence of Water
R. I. Khusnutdinov, N. A. Shchadneva, T. M. Oshnyakova, and U. M. Dzhemilev
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences, Ufa, Russia
eꢀmail: ink@anrb.ru
Received November 20, 2010
Abstract—The telomerization of 1Z,5Zꢀcyclooctadiene with halogenated methanes (CCl4, CBrCl3, CHCl3,
CH2Cl2) mediated by chromium, copper, and molybdenum complexes has been investigated. It has been
shown that the use of water as a nucleophilic additive promotes the formation of 1,4ꢀ and 1,5ꢀepoxycycloocꢀ
tanes and antiꢀ8ꢀ(trichloromethyl)bicyclo[3.2.1]octanꢀexoꢀ2ꢀol.
DOI: 10.1134/S0965544111060107
It is known that complexes of Group VI–VIII tranꢀ was confirmed by iodometric titration (0.05–
sition metals are effective catalysts for the radical 0.3 mg/ml) and UV spectroscopy (229–236 nm)
telomerization of unsaturated compounds with haloꢀ [4, 5].
genated methanes and a particular case of it: the addiꢀ
tion of CHnX4 (X = Cl, Br, or I;
ethanes to the double bond [1].
n = 0–2) halomꢀ
– n
EXPERIMENTAL
An important feature and advantage of metal cataꢀ
lysts is the possibility of enhancing the activity and
selectivity of their action by introducing nucleophilic
coinitiators into their structure, since their variety is
The reactions of 1,5ꢀCOD with halomethanes
CCl4, CBrCl3, CHCl3, CH2Cl2) were conducted in
(
the presence of reagentꢀgrade transition metal comꢀ
plexes: Cr(acac)3, Cr(CO)6, Cr(HCO2)3, Mo(CO)6,
and CuCl2 · 2H2O, which were used after recrystallizaꢀ
tion and vacuum drying. 1,5ꢀCyclooctadiene was
dried over calcined zeolite 3A and distilled before use.
The halomethanes, pyridine, and acetonitrile were
purified and dehydrated according to standard proceꢀ
dures [6].
The reaction products were analyzed by GLC, 1Н
and 13C NMR, and GC–MS techniques. The chroꢀ
matographic analysis of the products was performed
on a Chromꢀ5 instrument (column length, 1.2 m or
wide and includes both “neutral” ligands (PPh3
,
nitriles, tertiary amines, DMF, HMPA) and comꢀ
pounds with a labile hydrogen atom (alcohols, primary
and secondary amines) [1].
We have previously reported that effective catalysts
for the telomerization of olefins and dienes with CCl4
are Mo and Cr complexes activated by water, which
acts as a nucleophilic coinitiator [2, 3]. The activating
effect of water is due to its participation in the generaꢀ
tion of hypochlorous acid (HOCl), which is prone to
radical decomposition according to the following
scheme:
2 m
Chromaton NꢀAWꢀHMDS; carrier gas, helium; proꢀ
grammed temperature rise from 50 to 280 at a rate
of C/min) using an internal standard (octane,
octanolꢀ1, 1,1,1,3ꢀtetrachlorononane). H and 13C
× 3 mm; stationary phase, SEꢀ30 silicone (5%) on
[catalist]
–CHCl
°С
H2O + CCl4
HOCl
3
8°
1
In this work, we studied the interaction of 1Z
,5Zꢀ
cyclooctadiene (1,5ꢀCOD) with halomethanes mediꢀ NMR spectra were recorded on a Bruker Avanceꢀ
ated by metal catalysts in the presence of water as the 400Q instrument operating at 100.62 and
nucleophilic coinitiator. The interest in 1,5ꢀCOD is 400.13 MHz, respectively, in CDCl3; chemical shifts
due to the fact that it has been found to undergo a variꢀ
(δ) are given in ppm. Mass spectra were taken on a
ety of unusual transformations in the reactions with Finnigan MAT 112 S GC–MS instrument in the elecꢀ
CCl4 and water in the presence of catalytic systems tron ionization mode at an ionization energy of 70 eV
based on Cr, Mo, and Cu compounds and coordinaꢀ and an ion source temperature of 22°С. The elemental
tion complexes. As in the previous studies, the reacꢀ composition of the products was determined with a
tion of water with CCl4 in the presence of chromium Karlo Erba Model 1106 analyzer. The Rf values for
(
(
Cr(acac)3, Cr(CO)6, Cr(HCO2)3) or molybdenum compounds (
3
), (
4), and (8) were determined on Siluꢀ
Mo(CO)6) complexes yields hypochlorous acid, as fol 200
× 200 UV 256 TLC plates.
435

436
KHUSNUTDINOV et al.
General Procedure for Addition of Halomethanes
to 1Z,5ZꢀCyclooctadiene
The
clo[4.2.1]nonane (
) were isolated by column chromatography. The
mixture of and was eluted with diethyl ether on a
200 10 mm column, packed with silica gel
(40/100
pounds
fractionating vacuum distillation.
The isolated products had the following characterꢀ
istics.
isomeric
compounds
9ꢀoxobicyꢀ
3) and 9ꢀoxobicyclo[3.3.1]nonane
(
4
A stainless steel microautoclave (
V = 17 ml) or a
3
4
glass ampoule ( = 10 ml) was charged with 0.1 mmol
V
×
of Cr(acac)3 (Cr(HCO2)3, Cr(CO)6, or Mo(CO)6),
10 mmol of 1,5ꢀCOD, 10 mmol of CCl4 (CBrCl3,
CHCl3, CH2Cl2), and 200 mmol of water. The autoꢀ
clave was tightly closed (ampoule, sealed) and the
μ
m) to have a bed height of 100 mm. Comꢀ
9,
10 11, and 13 were isolated in pure form by
,
reaction mixture was heated at 140–150°С for 6 h with
continuous stirring. The autoclave (ampoule) was
cooled and unsealed. To separate the catalyst, the
reaction mixture was filtered through an alumina
2ꢀ(Trichloromethyl)ꢀendoꢀ6ꢀchloroꢀcisꢀbicyꢀ
clo[3.3.0]octane (2). Yield 75%. Bp 94–95°C/133 Pa.
1H NMR spectrum (CDCl3,
δ, ppm): 1.70–2.30 (m,
(Brockmann II, neutral) bed in a glass column (50
×
10 mm) with a tapered end plugged with a cotton ball
to prevent the adsorbent from loss and eluted with a
1 : 1 hexane–ether blend; the solvent was distilled off;
and the residue was distilled in a vacuum.
Heating CHCl3 or CH2Cl2 with 1Z,5Z ꢀcyclooctaꢀ
diene over the catalysts in the presence or absence of
8H, 4CH2), 2.70–2.90 (m, 3H, 2CH, CHCCl3), 4.14
(s, 1H, CHCl). 13C NMR spectrum (CDCl3,
, ppm):
45.62 (С1), 65.40 (С2), 32.13 (С3), 31.24 (С4), 55.97
(С5), 69.05 (С6), 34.90 (С7), 30.07 (С8), 103.53 (С9)
Mass spectru,
, rel. %): M+ (absent), 225
(5)/224 (2), 200 (8), 198 (10), 191 (14), 189 (20), 163
(8), 153 (30), 149 (57), 145 (25), 143 (83), 127 (8), 117
(24), 107 (100), 91 (20), 81 (43), 79 (85), 67 (22), 65
(13), 53 (11), 51 (11), 41 (13). Found, %: C 41.52, H
4.64, Cl 53.84. Calculated for C9H12Cl4, %: C 41.25,
H 4.62, Cl 54.13. Published data: Bp 70°C/13.30
Pa [7].
δ
.
m/z (I
water at 150–160°С for 6 h with continuous stirring
did not lead to significant transformations of the reacꢀ
tants, which were recovered unchanged from the reacꢀ
tion mixture.
The reaction of CCl4 with 1Z,5Z ꢀcyclooctadiene in
the presence of CuCl2 ⋅ 2Н2О and experiments with
admixed ligands were carried out in a similar fashion.
9ꢀOxobicyclo[4.2.1]nonane (3). Yield 30%. Rf
1
(diethyl ether) 0.71. H NMR spectrum (CDCl3,
δ
,
ppm): 1.25–1.38 (m, 2H, СН2), 1.46–1.56 (m, 2H,
General Procedure for Addition of Halomethanes
to 1Z,5ZꢀCyclooctadiene in the Presence
of Nitrogen Compounds
CH2), 1.38–1.57 (s, 8H, 4CH2), 4.30–4.45 (m, 2H,
CH–O–CH). 13C NMR spectrum (CDCl3,
δ, ppm):
77.52 (С1, С4), 31.34 (С2, С3), 35.92 (С5, С8), 24.24
(С6, С7)). Found, %: C 76.10, H 11.20. Calculated for
C8H141O, %: C 76.14, H 11.18, O 12.68. Published
A stainless steel microautoclave (
V = 17 ml) or a
glass ampoule ( = 10 ml) was charged with 0.1 mmol
V
of Cr(acac)3 (Cr(HCO2)3, Cr(CO)6 or Mo(CO)6),
10 mmol of 1,5ꢀCOD, 10 mmol of CCl4 (CBrCl3,
CHCl3, CH2Cl2), 200 mmol of water, and 10 mmol of
a nitrogen compound; the autoclave was tightly closed
(ampoule, sealed); and the reaction mixture was
data: H NMR (δ, ppm): 1.30–2.10 (m, 12H, CH2),
4.50 (m, 2H, CH–O–CH) [8].
9ꢀOxobicyclo[3.3.1]nonane (4). Yield 20%. Rf
(diethyl ether) 0.42. 1H NMR spectrum (CDCl3,
δ,
ppm): 1.38–1.56 (m, 4H, 2CH2), 1.48–1.66 (m, 8H,
4CH2) 3.80
3.95 (m, 2H, CH–O–CH). 13C NMR
spectrum (CDCl3,
heated at 140–150°С for 6 h with continuous stirring.
⎯
The reaction mixture was treated as described above,
using a 1 : 1 hexane–dichloromethane blend as an eluꢀ
ent. The solvent was distilled off, and the residue was
distilled in a vacuum or chromatographed on a silica
gel column with diethyl ether eluting.
δ
, ppm): 66.90 (С1, С5), 29.51 (С2,
С4, С6, С8), 19.01 (С3, С7). Found, %: C 76.16, H
11.17. С8Н14О. Calculated for, %: C 76.14; H 11.18; O
12.68.
Published data: 13C NMR (CDCl3,
δ, ppm): 66.5
(С1, С5), 29.3 (С2, С4, С6, С8), 18.8 (С3, С7) [9].
antiꢀ8ꢀ(Trichloromethyl)ꢀexoꢀ2ꢀ
chlorobicyclo[3.2.1]octane Hydrolysis Procedure
Mixture of 1,3ꢀcyclooctadiene (5) and bicyꢀ
clo[3.3.0]octene (6). Yield 30%. Ratio (5) : (6) = 1 : 1.
Bp 20–30°C/1600 Pa. 13C NMR spectrum (CDCl3,
ppm) for
125.94 (С1, С4), 129.32 (С2,С3), 23.15 (С5,
С8), 28.46 (С6, С7); for 40.60 (С1), 134.44 (С2),
6:
δ,
A stainless steel microautoclave (
charged with 0.1 mmol of Cr(acac)3, 0.1 mmol of
CuCl2 2Н2О 10 mmol of antiꢀ8ꢀ(trichloromethyl)ꢀ
V = 17 ml) was
5:
⋅
131.13 (С3), 40.09 (С4), 40.99 (С5), 35.65 (С6), 25.18
(С7), 32.28 (С8). Found, %: C 88.80, H 11.17. Calcuꢀ
lated for C16H24, %: C 88.82, H 11.18. Published data:
exoꢀ2ꢀchlorobicyclo[3.2.1]octane, 10 mmol of CCl4,
and 200 mmol of water, and the mixture was heated at
150°С for 6 h with continuous stirring. After compleꢀ
Bps 140–146 (
5ꢀChlorocycloocteneꢀ1 (7). Yield 10%. Bp 30–
, ppm):
vent was distilled off, and the residue was distilled in a 129.34 (С1), 129.57 (С2), 25.32 (С3), 38.77 (С4), 62.52
vacuum.
(С5), 36.62 (С6), 24.13 (С7), 26.05 (С8). Found, %: C
5) and 130–133°C (6) [10].
tion of the reaction, the autoclave was cooled and
unsealed, the reaction mixture was filtered through an
alumina layer (eluent, hexane : ether = 1 : 1), the solꢀ 32°C/133 Pa. 13C NMR spectrum (CDCl3,
δ
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TELOMERIZATION OF Z,ZꢀCYCLOOCTADIENE WITH HALOMETHANES
437
66.40, H 04.09, Cl 24.56. Calculated for C8H13Cl, %: 1H NMR spectrum (CDCl3,
δ, ppm): 1.19–2.22 (m,
C 66.43, H 9.06, Cl 24.51.
8H, 4CH2), 2.23–2.29 (m, 1H, CHCCl3), 2.30–2.45
(m, 2H, 2CH), 4.21 (s, 1H, CHBr). 13C NMR specꢀ
4ꢀCycloocteneꢀ1ꢀol (8). Yield 3%.
R
f (diethyl ether)
0.42. 13C NMR spectrum (CDCl3,
δ
, ppm): 72.45 (С1),
trum (CDCl3,
(С3), 31.86 (С4), 56.67 (С5), 56.79 (С6), 35.86 (С7),
δ
, ppm): 45.72 (С1), 69.09 (С2), 32.06
37.04 (С2), 22.77 (С3), 129.29 (С4), 130.02 (С5), 25.57
(С6), 24.62 (С7), 36.22 (С8). Found, %: C 76.15, H
11.15. Calculated for C8H14O, %: C 76.14, H 11.18, O
31.56 (С8), 103.51 (С9). Mass spectrum,
m/z (I, rel.
%): M+ 306 (15), 191 (18), 189 (22), 155 (25), 153
(74), 127 (20), 125 (35) 117 (100), 109 (23), 91 (31),
81 (12), 79 (50), 67 (36), 41 (32). Found, %: C 35.30,
12.68. Published data: 13C NMR (CDCl3,
δ, ppm):
72.26 (72.26 (С1), 37.17 (С2), 22.58 (С3), 129.15 (С4),
129.89 (С5), 25.42 (С6), 24.70 (С7), 36.07 (С8)) [11].
antiꢀ8ꢀ(Trichloromethyl)ꢀexoꢀ2ꢀchlorobicyꢀ
clo[3.2.1]octane (9). Yield 34%. Bp 95–97°C/133 Pa.
H
4.01, Br 26.02, Cl 34.67. Calculated for
C9H12BrCl3, %: C 35.27, H 3.95, Br 26.07, Cl 34.71.
transꢀ5ꢀBromoꢀ6ꢀ(trichloromethyl)cyclooctꢀ1ꢀene
13C NMR spectrum (CDCl3,
δ
, ppm): 50.00(С1);
1
(13). Yield 19%. Bp 100–103
°
С/133 Pa. H NMR
56.05(С2); 32.13(С3); 28.04(С4, C7); 35.07(С5); 31.03
(С6); 65.73(С8); 103.54(С9). Mass spectrum,
spectrum (CDCl3,
δ
, ppm.) 1.20–2.27 (m, 4H,
m/z (I,
2СН2), 2.75–2.85 (m, 2H, CH2), 2.85–2.95 (m, 2H,
2CH), 2.98–3.20 (m, 1H, CHCCl3), 5.08 (s, 1H,
CHBr), 5.60–5.70 (m, 1H, HC=C), 5.89–5.96 (m,
rel. %): M+ (absent), 225 (2)/224 (2), 197 (10), 191
(15), 189 (17), 155 (66), 153 (24), 149 (41), 145 (27),
143 (78), 129 (17), 117 (17), 115 (44), 111 (15), 109
(28), 108 (10), 107 (100) 92 (44), 81 (73), 80 (20), 79
(98), 78 (10), 77 (34), 75 (20), 67 (39), 66 (12), 65
(24), 54 (24), 53 (22), 51 (22), 41 (41). Found, %: C
41.28, H 4.50, Cl 54.22. Calculated for C9H12Cl4, %:
C 41.25, H 4.62, Cl 54.13.
1H, HC=C). 13C NMR spectrum (CDCl3,
δ, ppm):
131.43 (C1), 129.98 (C2), 23.24 (C3), 37.59 (C4), 55.43
(C5), 58.06 (C6), 30.28 (C7), 22.65 (C8), 104.84 (C9).
Mass spectrum, m/z (I
, rel.%): M+ (absent), 191 (25),
189 (37), 155 (36), 153 (100), 127 (23), 125 (27), 117
(82), 109 (32), 91 (31), 81 (31), 79 (42), 67 (25), 41
(19). Found, %: C 35.25, H 3.97, Br 26.09, Cl 34.69.
Calculated for C9H12BrCl3, %: C 35.27, H 3.95, Br
26.07, Cl 34.71.
antiꢀ8ꢀ(Trichloromethyl)bicyclo[3.2.1]octanꢀexo
ꢀ
2ꢀol (10). Yield 34%. Bp 97–100°C/133 Pa. 13C NMR
spectrum (CDCl3,
30.86(С3) 28.04(С4)
103.54(С9). Mass spectrum (EI, 70 eV),
δ
, ppm): 46.13(С1, С5) 70.02(С2)
,
29.21(С6); 27.75(C7) 64.95(С8)
,
,
,
,
,
m/z (I, rel.
%): [M]+ (absent), 198 (15), 191 (17), 189 (24), 153
(32) 151 (41), 149 (61), 145 (24), 143 (71), 142 (15),
117 (17), 115 (17), 111 (20), 109 (20), 107 (76), 91
(22), 85 (20), 81 (100), 80 (27), 79 (78), 78 (7), 77
(24), 75 (12), 67 (39), 65 (20), 57 (24), 55 (27), 54
(29), 53 (20), 51 (22), 44 (22), 43 (20), 42 (10), 41
(51), 39 (49). Found, %: C 44.35, H 5.40, Cl 43.50.
Calculated for C9H12Cl3O, %: C 44.38, H 5.38, Cl
43.67; O 6.57.
RESULTS AND DISCUSSION
We studied the interaction of polyhalogenated methꢀ
anes
cyclooctadiene mediated by chromium (Cr(acac)3,
Cr(HCO2)3, Cr(CO)6) and molybdenum (Mo(CO)6
((CCl4, CBrCl3, CHCl3, CH2Cl2) with 1Z,5Zꢀ
)
catalysts in the absence or presence of water. Thus, the
heating of 1,5ꢀCOD CCl4 in the presence of Crꢀconꢀ
taining catalysts (Cr(acac)3, Cr(CO)6) at 150оС for 6 h
gives
2ꢀ(trichloromethyl)ꢀendoꢀ6ꢀchloroꢀcisꢀbicyꢀ
clo[3.3.0]octane (2) with a yield of 70–78%, while the
endoꢀ2ꢀBromoꢀ6ꢀ(trichloromethyl)ꢀcisꢀbicyꢀ
clo[3.3.0]octane (11). Yield 59%. Bp 103–105°C/133 Pa. rest of the diene is converted into a polymer.
Cr(acac) (1 mol %
3
)
CCl3
conversion of
1, 100%
yield of , 70%
2
+ CCl4
150°C, 6 h
Cr(CO) (1 mol %
6
)
conversion of
1
100%
Cl
78%
yield of 2,
(
1
)
(2)
The structure of compound
2 was established on structure of 2ꢀ(trichloromethyl)ꢀendoꢀ6ꢀchloroꢀcisꢀ
1
the basis of H NMR spectra and their comparison
with published data [7, 12]. In particular, the presence
bicyclo[3.3.0]octane (
When water is added ([Cr(acac)3] : [1,5ꢀCOD] :
CCl4] : [H2O] = 1 : 100 : 100 : 2000) the yield of
decreases to 42–50%, but higher oligomers are not
2).
1
of the singlet signal in the H NMR spectrum at
4.14 ppm suggests that the hydrogen atom at C6 is in
[
2
the exoꢀposition relative to the hydrogen atom at the
carbon junction atom (C5); i.e., the compound has the produced in this case.
PETROLEUM CHEMISTRY Vol. 51
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438
KHUSNUTDINOV et al.
Cr(acac)
3
42%
CCl3
+ CCl4 + H O
2
150°C, 6 h
Cr(CO)
50%
6
Cl
(1)
(2)
If the reaction is carried out in the presence of Mo(CO)6 under the same conditions, the yield of
the selectivity decreases because of the formation of 9ꢀoxobicyclo[4.2.1]nonane ( ) and 9ꢀoxobicyꢀ
clo[3.3.1]nonane ( ).
2 is 37%, but
3
4
CCl3
Mo(CO)
150°C, 6 h
6
O
O
+
+
:
+ CCl4 + H O
2
conversion of 1
, 43%
Cl
(
1
)
(
2
)
(
3)
(4
)
:
19
2
1
Based on the results of a set of experiments, preꢀ
ferred catalyst and reactant concentrations were deterꢀ
mined as [catalyst] : [1,5ꢀCOD] : [CCl4] : [H2O] = 1 :
100 : 100 : 2000. Although a large excess of water
reduces the yield of 2ꢀ(trichloromethyl)ꢀendoꢀ6ꢀ
It was found that the admixture of copper(II)
chloride (CuCl2 2H2O) as a cocatalyst to Cr(acac)3
promotes the change of the reaction route toward
the formation of 9ꢀoxobicyclo[4.2.1]nonane (
and 9ꢀoxobicyclo [3.3.1]nonane ( ) with a total
yield of 40%. When Cr(acac)3 is replaced by
Cr(HCO2)3 in the catalyst system, the yield of and
increases to 50%.
⋅
3
)
4
chloroꢀcisꢀbicyclo[3.3.0]octane
selectivity for nevertheless can reach 100% on the
Crꢀcontaining catalysts or 86% in the presence of
Mo(CO)6
(2), the reaction
2
3
.
4
Cr(acac) (1
%)
mol
O
O
3
40%
+
:
⋅
150
2H O (1 mol %)
°
+ CCl4 + H O CuCl
2
2
C, 6 h
2
1.2
1
Cr(HCO ) (1
2 3
50%
%)
mol
(
1.5
3)
+
:
(
4)
1
As the temperature is elevated to 160
reaction of 1Z,5Zꢀcyclooctadiene isomerization to
°
С
, the side 1,3ꢀcyclooctadiene (
5) and bicyclo[3.3.0]octꢀ2ꢀene
(
6) is observed.
Cr(acac) – CuCl
⋅ 2H O
2 2
3
160
O
O
+
:
+
+
+ CCl4 + H O
2
°C, 6 h
52%
(1
)
(3
)
2.5
(4
)
1.8
(
1.2
5
)
(
6)
:
1
The CuCl2
⋅
2H2Oꢀcatalyzed reaction of 1,5ꢀCOD
4
, but the product composition is further complicated
with H2O in the presence of CCl4 also results in
3
and by the formation of 5ꢀchlorocycloocteneꢀ1 (
7):
Cl
+
CuCl
150
⋅ 2H O
°C, 6 h
2 2
O
O
+ CCl4 + H O
+
:
+
:
+
:
2
73%
(1
)
(3
)
2.7
(
4
)
(
5
)
(6)
1.7
(7)
1.2
1
1.7
Regarding the mechanism of formation of 9ꢀoxobicyꢀ
(4), the process apparently begins from the hydration of
clo[4.2.1]nonane ( ) and 9ꢀoxobicyclo[3.3.1]nonane 1,5ꢀCOD yielding 4ꢀcycloocteneꢀ1ꢀol (
3
8). The hydraꢀ
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TELOMERIZATION OF Z,ZꢀCYCLOOCTADIENE WITH HALOMETHANES
439
tion of 1,5ꢀCOD is facilitated by HCl generated from 13–15 mg/ml was confirmed by titration). At the final
CCl4 and water by the action of chromium and copper stage, the intramolecular addition of the OH group to the
complexes (formation of HCl with a concentration of double bond takes place [13]:
OH
[Cu]
O
O
+ H2O
+
(1)
(3)
(8
)
(4)
The structure of 9ꢀoxobicyclo[4.2.1]nonane (
3
)
As is seen from the table, the addition of acetoniꢀ
trile leads to either complete (in the case of
and 9ꢀoxobicyclo[3.3.1]nonane (4) was established on
the basis of 13C NMR spectra and published data
[8, 9]. For example, a compound that exhibits a signal
with the chemical shift at 66.90 ppm (CH–O–CH)
was assumed to have the 9ꢀoxobicyclo[3.3.1]nonane
Cr(acac)3⎯CuCl2
Mo(CO)6) catalyst deactivation; thus, compound
⋅
2H2O) or partial (in the case of
is
2
not produced (run 6) or forms with a yield of 20%
(run 7).
The reaction of 1,5ꢀCOD with CCl4 in water at
structure 4.
140
Мо(CO)6–CuCl2
mation of , but its yield does not exceed 50%. The
reaction of 1,5ꢀCOD with CCl4 in water in the presꢀ
ence of the Cr(CO)6– CuCl2 2H2O catalyst system
has a 93% selectivity for at a 1,5ꢀCOD conversion of
°
С
for 6 h over the Cr(CO)6–CuCl2
⋅ 2H2O or
The use of nitrogen compounds (NCs) (triethyꢀ
lamine, acetonitrile, DMF) as a nucleophilic agent and
cosolvent ([water] : [NC] ratio = 20 : 1) under the reacꢀ
⋅
2H2O system also leads to the forꢀ
2
tion conditions of 150
thyl)ꢀendoꢀ6ꢀchloroꢀcisꢀbicyclo[3.3.0]octane (
yield of 75%. In addition, the reaction temperature in the
case of nitrogen compounds can be lowered to 140
(table).
°С
and 6 h gives 2ꢀ(trichloromeꢀ
⋅
2) with a
2
53%. Similarly, a portion of the diene (~7%) converts
into the polymer, and the remainder is recovered
unchanged from the reaction.
°
С
CCl3
Cr(CO) – CuCl
⋅ 2H O
2 2
6
140
+ CCl4 + H O
2
°
C, 6 h
conversion
(1
) 53%
Cl
(1
)
(2)
conversion 93%
total yield 49%
The reaction of 1,5ꢀCOD with CCl4 mediated by chloroꢀcisꢀbicyclo[3.3.0]octane (
the Cr(acac)3–CuCl2 2H2O catalyst system in (trichloromethyl)ꢀexoꢀ2ꢀchlorobicyclo[3.2.1]octaꢀ
water proceeds in an interesting manner. In this ne ( ) is produced with a 2 : 9 ratio of 4 : 1 and a
2) and antiꢀ8ꢀ
⋅
9
case, a mixture of 2ꢀ(trichloromethyl)ꢀendoꢀ6ꢀ total yield of 57%:
CCl3
Cl3C
Cl
– CuCl
140°C, 6 h
57%
⋅ 2H O
2 2
+ CCl4 + H OCr(acac)
3
+
2
(
2
)
(
9
)
Cl
(1)
:
4
1
Such a reaction yielding bicyclo[3.2.1]octane derivaꢀ tion of
9
is also due to the isomerization of 2ꢀ(trichloꢀ
romethyl)ꢀendoꢀ6ꢀchloroꢀcisꢀbicyclo[3.3.0]octane ( ),
and the catalyst is hydrogen chloride (in concentration of
2
tives is exemplified by 1,5ꢀCOD chlorination on the
SbCl5 catalyst in ССl4 as described in [14]. Uemura et al.
[14] have suggested that the bicyclo[3.2.1]octane derivaꢀ
tives are produced as a result of isomerization of the
13–14 mg/ml), which, along with the Cr(acac)3–CuCl2
2H2O catalyst system, initiates this transformation.
⋅
dichloro derivatives of bicyclo[3.3.0]octane on SbCl5
which is a strong Lewis acid. Most likely, the formaꢀ ligand into the Cr(acac)3–CuCl2
,
The introduction of acetonitrile as an activating
2H2O catalytic sysꢀ
⋅
PETROLEUM CHEMISTRY Vol. 51
No. 6
2011

440
KHUSNUTDINOV et al.
Yield of 2ꢀ(trichloromethyl)ꢀendoꢀ6ꢀchloroꢀcisꢀbicyclo[3.3.0]octane (2) depending on the nature of nitrogen compound
Run no.
Catalyst system
NC
Reaction conditions
Product yield, %
1
2
3
6
7
8
Cr(acac)3–CuCl2
⋅
2H2O
Triethylamine
150
140
140
150
150
140
°
°
°
°
°
°
C, 6 h
C, 6 h
C, 6 h
C, 6 h
C, 6 h
C, 6 h
75
55
56
0
''
''
Cr(HCO2)3–CuCl2
⋅
2H2O
''
Acetonitrile
''
Cr(acac)3–CuCl2
Mo(CO)6
⋅
2H2O
20
18
Cr(acac)3–CuCl2
⋅
2H2O
DMF
The catalyst to reactants ratio is[Cr] or [Mo]: [CuCl · 2H O] : [1,5ꢀCOD] : [CCl ] : [H O] : [NC] = 1 : 1 : 100 : 100 : 2000 : 100.
2 2 4 2
tem ([Cr(acac)3] : [CuCl2
10) has two important consequences: the complete robicyclo[3.2.1]octane (
absence of compounds with the bicyclo[3.3.0]octane thyl)bicyclo[3.2.1]octanꢀexoꢀ2ꢀol (10), which is forꢀ
structure from the reaction products and the formaꢀ mally a hydrolysis product of
⋅
2H2O] :
[
CH3CN] = 1 : 1 : tion, along with antiꢀ8ꢀ(trichloromethyl)ꢀexoꢀ2ꢀchloꢀ
), of antiꢀ8ꢀ(trichloromeꢀ
9
9:
Cl3C
Cl3C
– CuCl
⋅ 2H O – CH CN
2 2 3
+ CCl4 + H OCr(acac)
Cl
OH
3
+
:
2
140°C, 6 h
68%
(
9
1
)
(
10)
(1)
1
Earlier, it was suggested that alcohol 10 can form by The configuration of
partial hydrolysis of adduct [3]. However, we failed to of the chemical shifts of carbon atoms and their matching
hydrolyze under the given reaction conditions. with those of authentic samples [15].
9and 10 was determined on the basis
9
9
Therefore, it is reasonable to assume that alcohol 10
results from the simultaneous interaction of 1,5ꢀCOD
with CCl4 and water or HOCl in the presence of
According to published data [16–18], the reaction
of 1,5ꢀCOD with CBrCl3 under conditions of radical
initiation with benzoyl peroxide leads to a mixture
of 2ꢀbromoꢀ6ꢀ(trichloromethyl)bicyclo[3.3.0]octane
Cr(acac)3–CuCl2
⋅
2H2O–CH3CN
.
The structure of telomers
9
and 10 was established on
(
11
)
and 2ꢀ(bromodichloromethyl)ꢀ6ꢀchlorobicyꢀ
the basis of 13C NMR data. Thus, the spectrum of antiꢀ8ꢀ clo[3.3.0]octane (12). The outcome of the Cr(acac)3–
(trichloromethyl)ꢀexoꢀ2ꢀchlorobicyclo[3.2.1]octane (
displays signals at 56.05 and 103.54 ppm characteristic of CBrCl3 in the presence of water at 140
the –CHCl and –CCl3 groups, respectively, and the specꢀ different. In this case, a mixture of endoꢀ2ꢀbromoꢀ6ꢀ
trum of antiꢀ8ꢀ(trichloromethyl)bicyclo[3.2.1]octanꢀexo
2ꢀol (10) contains signals at 70.02 and 103.54 ppm, charꢀ transꢀ5ꢀbromoꢀ6ꢀ(trichloromethyl)ꢀcyclooctene 1 (13
acteristic of the –CHOH and –CCl3 groups, respectively. in a 3 : 1 ratio was produced with a yield of 78%:
9)
СuCl2
⋅
2H2Oꢀcatalyzed reaction of 1,5ꢀCOD with
°C
for 6 h turned
ꢀ
(trichloromethyl)ꢀcisꢀbicyclo[3.3.0]octane (11) and
)
CCl3
Br
CCl3
– CuCl
⋅ 2H O
2 2
+ CBrCl3 + H O Cr(acac)
3
+
2
140°C, 6 h
78%
Br
(11
)
(13)
:
3
1
The use of Cr(CO)6 or Mо(CO)6 in an analogous (trichloromethyl)ꢀcisꢀbicyclo[3.3.0]octane
reaction leads to the formation of endoꢀ2ꢀbromoꢀ6ꢀ andtransꢀ5ꢀbromoꢀ6ꢀ(trichloromethyl)cycloocteneꢀ1ꢀ
(11)
PETROLEUM CHEMISTRY Vol. 51
No. 6
2011

TELOMERIZATION OF Z,ZꢀCYCLOOCTADIENE WITH HALOMETHANES
441
ene (13), and the reaction temperature is lowered to ature leads to polymerization of 1Z,5Zꢀcyclooctadiꢀ
130
°
С
in this case. A further increase in the temperꢀ ene:
Mo(CO)
6
34%
CCl3
Br
+
+ CBrCl3 + H O
2
130°C, 6 h
CCl3
Cr(CO)
65%
6
Br
(1
)
(11
)
(13)
:
4
1
4. I. Kh. Bikbulatov, F. Kh. Valitov, A. G. Gromova, et al.,
The yields of the compounds were determined by
isolating the desired products and by GLC (internal
standard 1,1,1,3ꢀtetrachlorononane). The structure of
telomers 11 and 12 was established on the basis of
13C NMR data and by matching with authentic comꢀ
pounds prepared according to the published proceꢀ
dures [7, 19]. For example, the spectrum of 2ꢀbromoꢀ
6ꢀ(trichloromethyl)bicyclo[3.3.0]octane (11) exhibits
signals at 56.79 ppm (CHBr) and 103.51 ppm (CCl3),
and that of transꢀ5ꢀbromoꢀ6ꢀ(trichloromethyl)
cyclooctꢀ1ꢀene (13) displays signals at 55.43 ppm
(CHBr) and 104.84 ppm (CCl3) together with the sigꢀ
nals at 131.42 (C1) and 129.98 ppm (C2) characteristic
of carbon atoms at the double bond.
Zh. Prikl. Khim. (St. Petersburg) 58, 2499 (1985).
5. B. P. Nikol’skii, V. G. Krunchak, T. V. L’vova, et al.,
Dokl. Akad. Nauk SSSR 191, 1324 (1970).
6. H. Becker, W. Berger, H. Domschke, et al., Organikum
(VEB Deutscher Verlag die Wissenschaften, Berlin,
1976), vol. 2.
7. Y. Shvo and R. Green, J. Organomet. Chem. 675, 77
(2003).
8. N. I. Kapustina, A. Yu. Popkov, and G. I. Nikishin, Izv.
Akad. Nauk SSSR, Ser. Khim., No. 11, 2538 (1988).
9. R. J. Waseman and H. O. Krabbenhoft, J. Org. Chem.
42, 2240 (1977).
10. P. R. Stapp and R. F. Kleinschmidt, J. Org. Chem. 30
,
Neither chloroform nor methylene chloride reacts
with 1,5ꢀCOD under these conditions.
3006 (1965).
11. K. G. Penman, W. Kiching, and A. P. Wells, J. Chem.
Soc., Perkin Trans. 1, 721 (1991).
ACKNOWLEDGMENTS
12. A. S. Dneprovskii, A. N. Kasatochkin, V. P. Boyarskii,
This work was supported by the Federal Agency for
et al., Zh. Org. Khim. 42, 1142 (2006).
Science
and
Innovations,
State
Contract
13. A. C. Cope and P. E. Peterson, J. Am. Chem. Soc. 81
,
no. 02.740.11.0631.
1643 (1959).
14. S. Uemura, A. Onoe, and M. Okano, Bull. Chem. Soc.
Jpn. 50, 1078 (1977).
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PETROLEUM CHEMISTRY Vol. 51
No. 6
2011