Addition of water and carbon tetrachloride to cyclododecene in the presence of chromium catalysts

Full text of DOI:10.1134/S1070428008080241

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 8, pp. 1240–1242. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © T.M. Oshnyakova, N.A. Shchadneva, R.I. Khusnutdinov, U.M. Dzhemilev, 2008, published in Zhurnal Organicheskoi Khimii, 2008,
Vol. 44, No. 8, pp. 1252–1253.
SHORT
COMMUNICATIONS
Addition of Water and Carbon Tetrachloride to Cyclododecene
in the Presence of Chromium Catalysts
T. M. Oshnyakova, N. A. Shchadneva, R. I. Khusnutdinov, and U. M. Dzhemilev
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received April 16, 2008
DOI: 10.1134/S1070428008080241
Synthetic transformations of cyclododecene (I)
have been studied in sufficient detail [1]. This com-
pound has become accessible due to development of
large-scale manufacture of cyclododeca-1,5,9-triene by
trimerization of butadiene over titanium- and nickel-
containing catalysts. An important product of trans-
formations of cyclododecene (I) is cyclododecanol (II)
which is used as starting material for the synthesis of
dodecanedioic acid, dodecane-1,12-diol, and ω-do-
decalactam [1, 2]. The latter are widely used in the
manufacture of polyesters, polyamides, Nylon-12, and
high-quality plasticizers [1, 2]. Several methods for the
synthesis of cyclododecanol (II) from cyclododecene
(I) are known, in particular those based on epoxidation
followed by catalytic reduction with hydrogen [3] and
on treatment with three-fold excess of 96% H2SO4
with subsequent hydrolysis [4].
methylcyclododecane (III) is formed as a result of
addition of carbon tetrachloride at the double bond of
cyclododecene (I); the yield of compound III does not
exceed 5%.
The use of mineral acids (H2SO4, H3PO4, HCl) as
promoter instead of acetic acid did not improve the
reaction outcome. On the other hand, we found that
copper compounds such as CuCl and CuCl2·2H2O, act
as promoters with respect to Cr(acac)3, but the yield of
cyclododecanol (II) did not exceed 35% in the pres-
ence of catalysts containing these copper salts. Chro-
mium(III) formate Cr(HCO2)3 and hexacarbonyl-
chromium(0) Cr(CO)6 also showed a catalytic activity
comparable with that of Cr(acac)3.
On the basis of the results of a series of experi-
ments we determined the optimal conditions and reac-
tant concentrations: temperature 180°C, reaction time
6 h, concentration ratio [Cr(acac)3]–[AcOH]–[I]–
[CCl4]–[H2O] 1:3:100:100:2000. The conversion of
cyclododecene (I) initially increases, reaches its maxi-
mum value (72%) in 6 h, and then decreases, indicat-
ing that the process is reversible. This was confirmed
experimentally: under the above conditions cyclodo-
decanol (II) underwent dehydration with formation of
cyclododecene (I) as a 3:2 mixture of E and Z isomers
The present communication reports on the direct
hydration of cyclododecene (I, a mixture of E and Z
isomers at a ratio of 3:1) with water in carbon tetra-
chloride in the presence of the catalytic system
Cr(acac)3–AcOH (1 :3). The reaction takes 6 h at
180°C and gives cyclododecanol (II) in an overall
yield of 67% (Scheme 1). The conversion of olefin I
is ~72%. Apart from alcohol II, 1-chloro-2-trichloro-
Scheme 1.
Cr(acac)3–AcOH (1:3)
180°C, 6 h
OH
+
H2O + CCl4
I (E :Z = 1:3)
II
1240

ADDITION OF WATER AND CARBON TETRACHLORIDE TO CYCLODODECENE
1241
Scheme 2.
Cr(acac)3, 180°C, 6 h
CCl3
CCl3
OH
+
H2O
+
CCl4
II
+
+
Cl
I
III
IV
tetrachloride, and 200 mmol of water. The reactor was
hermetically closed (the ampule was sealed) and
heated for 6 h at 180°C under stirring. It was then
cooled to room temperature and opened, and the mix-
ture was extracted with methylene chloride (3×5 ml).
The extracts were combined, the solvent was distilled
off, and the residue was subjected to column chroma-
tography on aluminum oxide of Brockmann activity
grade II using methylene chloride–hexane (1:1 by
volume) as eluent.
(yield ~75%). Apart from compound I, the reaction
mixture contained chlorocyclododecane and cyclodo-
decanone.
According to published data, dehydration of cyclo-
dodecanol (II) catalyzed by p-toluenesulfonic acid
occurs at 250–270°C [5]. Lowering of the reaction
temperature to 180°C in the system CCl4–H2O–
Cr(acac)3–AcOH is likely to result from the effect of
the catalyst. It should be noted that the formation of
cyclododecene (I) as a mixture of E and Z isomers was
not surprising. An analogous pattern is observed in the
synthesis of cyclododecene (I) by different methods,
specifically by dehydrochlorination of chlorocyclodo-
decane [6] and by dehydration of cyclododecanol (II)
in the presence of p-toluenesulfonic acid [5]. There-
fore, the use of pure E and Z isomers as initial com-
pounds seems to be unreasonable.
Cyclododecanol (II). Yield 67%, mp 79–80°C
(from MeOH); published data [5]: mp 77.6–78.5°C
(from petroleum ether). 13C NMR spectrum (CDCl3),
δC, ppm: 64.66 (C1), 33.96 (C2, C12), 27.48 (C3, C11),
28.42 (C4, C10), 29.95 (C5, C6, C7, C8, C9). Found,
%: C 77.98; H 13.09. C12H24O. Calculated, %:
C 78.19; H 13.12.
Unlike selective dehydration of cyclododecene (I)
in the presence of chromium-containing catalyst pro-
moted by acetic acid, the main pathway in the reaction
catalyzed by Cr(acac)3 without promoter is addition of
carbon tetrachloride at the double bond of olefin I. In
this case, the process is accompanied by partial hydrol-
ysis of the adduct, 1-chloro-2-trichloromethylcyclo-
dodecane (III), to give 2-trichloromethylcyclodo-
decan-1-ol (IV) (Scheme 2). The conversion of cyclo-
dodecene (I) reaches 62%, and the yields of II, III,
and IV are 12, 28, and 20%, respectively. When the
reaction was carried out using a large excess of water
to ensure complete hydrolysis of III, the conversion of
olefin I decreased to 15%, while the product composi-
tion remained almost unchanged. Other chromium
compounds, such as Cr(CO)6 and Cr(HCO2)3, also
catalyzed the process, but their catalytic activity was
lower than that of Cr(acac)3.
1-Chloro-2-(trichloromethyl)cyclododecane (III).
Yield 28% (isolated by column chromatography).
13C NMR spectrum (CDCl3), δC, ppm: 58.89 (C1),
59.29 (C2), 32.68 (C3), 26.01 (C4), 32.13 (C5), 26.27
(C6, C7, C8, C9, C10), 26.98 (C11), 40.17 (C12), 91.58
(C13). Found, %: C 48.57; H 6.88; Cl 44.55. C13H22Cl4.
Calculated, %: C 48.77; H 6.93; Cl 44.30.
2-Trichloromethylcyclododecan-1-ol (IV). Yield
20% (isolated by column chromatography). 13C NMR
spectrum (CDCl3), δC, ppm: 77.97 (C1), 59.28 (C2),
32.13 (C3), 24.83 (C4), 31.61 (C5), 26.98 (C6, C7, C8,
C9, C10), 26.01 (C11), 34.76 (C12), 91.58 (C13). Found,
%: C 51.69; H 7.62; Cl 35.28. C13H23Cl3O. Calculated,
%: C 51.75; H 7.68; Cl 35.26.
The products were analyzed by gas–liquid chroma-
tography using Tsvet-102 and Chrom-5 instruments;
flame ionization detector, 1.2-m × 3-mm column
packed with 5% of SE-30 on Chromaton N-AW-
HMDS (0.125–0.160 mm), carrier gas helium
(50 ml/min), oven temperature programming from 50
to 220°C. The 13C NMR spectra were recorded on
a Jeol FX-90Q spectrometer at 22.5 MHz; the chem-
ical shifts were measured relative to tetramethylsilane.
The reactions were carried out in 20-ml glass am-
pules or in a 17-ml stainless-steel high-pressure micro
reactor. The reactor (or ampule) was charged with
0.1 mmol of Cr(acac)3 (in the synthesis of cyclodo-
decanol, 0.3 mmol of acetic acid was also added),
10 mmol of cyclododecene (I), 10 mmol of carbon
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

OSHNYAKOVA et al.
1242
2. Freidlin, G.N., Alifaticheskie dikarbonovye kisloty (Ali-
phatic Dicarboxylic Acids), Moscow: Khimiya, 1978,
p. 264.
The elemental compositions were determined on
a Carlo Erba 1106 analyzer.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 08-03-97005) and by the Ministry of Education
and Science of the Russian Federation (project
no. NSh 7470.2006.3).
3. Zakharkin, L.I. and Korneva, V.V., Dokl. Akad. Nauk
SSSR, 1960, vol. 132, p. 1078.
4. Mueller, K.A., Kirchgof, W., and Franke, W., FRG Patent
Appl. no. 1103326, 1962; Chem. Abstr., 1962, vol. 56,
p. 8593.
5. Normant, H. and Maitte, P., Bull. Soc. Chim. Fr., 1960,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008