Addition of CCl4 to olefins catalyzed by chromium and ruthenium complexes: The influence of water as a nucleophilic additive

Article abstract of DOI:10.1134/S0965544109040136

The feasibility of the addition of CCl₄ to linear and cyclic olefins and dienes in the presence of chromium and ruthenium complexes was established. The influence of water as a nucleophilic additive and the influence of the olefin nature, the c

Full text of DOI:10.1134/S0965544109040136

ISSN 0965-5441, Petroleum Chemistry, 2009, Vol. 49, No. 4, pp. 331–338. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © R.I. Khusnutdinov, N.A. Schadneva, T.M. Oshnyakova, U.M. Dzhemilev, 2009, published in Neftekhimiya, 2009, Vol. 49, No. 4, pp. 349–356.
Addition of CCl4 to Olefins Catalyzed by Chromium
and Ruthenium Complexes: The Influence
of Water as a Nucleophilic Additive
R. I. Khusnutdinov, N. A. Schadneva, T. M. Oshnyakova, and U. M. Dzhemilev
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
e-mail: ink@anrb.ru
Received July 07, 2008
Abstract—The feasibility of the addition of CCl4 to linear and cyclic olefins and dienes in the presence of chro-
mium and ruthenium complexes was established. The influence of water as a nucleophilic additive and the influ-
ence of the olefin nature, the catalyst central atom, and its ligand environment on the reaction selectivity and
product yields were investigated. It was shown that the addition of water to chromium and ruthenium catalysts
leads to the hydrolysis of the chloromethyl group in the resulting 1,1,1,3-tetrachloro derivatives, yielding the
corresponding hydroxy derivatives and increasing the selectivity for the formation of (1 + 1) adducts, which is
caused by the formation of hypochlorous acid playing the role of a coactivator of the addition of CCl4 to alk-
enes.
DOI: 10.1134/S0965544109040136
Group VI–VIII transition metal complexes are severe conditions (150–170°ë, 6 h) are required for the
known as effective catalysts for the telomerization of generation of HOCl. The concentration of HOCl
unsaturated compounds with halomethanes (CHnX4 – n
,
formed is small (0.9–1.2 mg/ml); however, it is deter-
X = Cl, Br, I; n = 0–2) and its particular case, the addi- minable not only by iodometry, but also by UV spec-
tion of CHnX4 – n to multiple bonds [1].
troscopy from the absorbance at the maximum in the
region of 229–236 nm, which is characteristic of
hypochlorous acid [4, 5].
An important advantage of metal complex catalysts
(MCs) for telomerization is the possibility of increasing
their activity and selectivity by insertion of nucleo-
philic activators into the catalyst structure [1]. The
range of nucleophilic activators is sufficiently wide and
includes not only the traditional “neutral” ligands
(PPh3, nitriles, tertiary amines, DMFA, HMPTA), but
also compounds containing an “acidic” hydrogen atom
(alcohols, primary and secondary amines), which are
able to participate directly in the radical generation and
telomerization initiation processes due to the presence
of O–H and N–H bonds [1].
It should be pointed out that the direct participation
of alcohols in the generation of radicals has been
proven and involves their catalytic oxidation with CCl4
into alkyl hypochlorites (ROCl), which readily decom-
pose to form the free radicals RO• and •Cl [2].
In this work, we attempted to use water as a nucleo-
philic activator of metal complex telomerization cata-
lysts. The study was impelled by the unusual finding
that the reaction of CBr4 with H2O in the presence of
molybdenum complexes leads to hypobromous
acid [3].
Later, we found that compounds of chromium or 200 × 0.3 cm column; the stationary phase 5% SE-30
(Cr(acac)3, Cr(HCO2)2) and ruthenium (Ru(OH)Cl3, supported on Chromaton N-AW-HMDS, temperature
Ru(PPh3)3Cl2) catalyze a similar reaction of water with programming from 50 to 280°ë at a rate of 8°C/min)
CCl4 to form hypochlorous acid. It should be noted that and helium as the carrier gas using heptane, decane, or
EXPERIMENTAL
The reactions of alkenes with CCl4 were carried out
in the presence of the following reagent-grade transi-
tion metal compounds: Cr(acac)3, Ru(PPh3)3Cl2,
Ru(OH)Cl3, and CuCl2, which were used after addi-
tional drying under a vacuum. The following substrates
having 99.8% purity were used: hexene-1, heptene-1,
octene-1, decene-1, cyclopentene, cyclohexene,
cyclooctene, norbornene, norbornadiene, tetracy-
clo[4.3.0.02,4.03,7]nonene-8, 7,1'-spirocyclopropanenor-
bornene, cyclododecatriene-1,5,9, allyl acetate, and
cis-1,4-diacetoxybutene-2. The olefins and dienes were
dried over calcined zeolite 3A and distilled before use.
The nitriles and CCl4 were purified and dried according
to the standard procedures.
The reaction products were analyzed by using the
1
following methods: GLC, H and 13C NMR, IR spec-
trometry, and gas chromatography–mass spectrometry.
The composition of the reaction mixtures was analyzed
by GLC with a Chrom-5 chromatograph (120 × 0.3 cm
331

332
KHUSNUTDINOV et al.
1,1,1,3-tetrachlorononane as an internal standard (with 93(46), 96(24), 103(17), 104(41), 105(10), 109(24),
the area correction factor). The IR spectra were 111(20), 117(7), 122(41), 123(15), 124(24), 129(41),
recorded with a UR-20 spectrophotometer in KBr tab- 131(15), 165(24), 167(17). Found, %: C, 38.19; H,
lets or white oil mulls in the region 550–3500 cm–1. The 5.93; Cl, 48.39. Calculated for C7H13Cl3O, %: C, 38.23;
1H and 13C NMR spectra were taken with a Jeol FX90Q H, 5.96; Cl, 48.37; O, 7.44.
spectrometer operating at 90 MHz and 22.5 MHz,
respectively, in CDCl3 solutions; the chemical shifts (δ)
are given in ppm with respect to TMS. The mass spectra
(EI, 70 eV) were taken with a Finnigan MAT 112 S
instrument in the electron impact mode with an ioniza-
tion energy of 70 eV and a source temperature of 22°ë.
1,1,1,3-Tetrachlorooctane (1b). Yield 45%. Bp
108–109°C/10 Pa. 13C NMR spectrum (CDCl3, TMS,
δ, ppm): 97.09(ë1); 62.41 (C2); 55.32 (C3); 39.07 (C4);
31.09 (C5); 25.69 (C6); 22.49 (C7); 13.98 (C8). Found,
%: C, 38.09; H, 5.55; Cl, 56.36. Calculated for
C8H14Cl4, %: C, 38.12; H, 5.60; Cl, 56.28.
General procedure for CCl4 addition to olefins.
Into a stainless steel microautoclave (V = 17 ml) or a
glass ampule (V = 20 ml), 0.1 mmol of Cr(acac)3
(Ru(PPh3)3Cl2 or Ru(OH)Cl3), 10 mmol of an olefin,
10 mmol of CCl4, and 200 mmol of water were placed;
the autoclave (ampule) was sealed and the reaction
mixture was heated with continuous stirring at 130–
170°ë for 4–6 h.
After completion of the reaction, the autoclave
(ampule) was cooled to room temperature and
unsealed, the reaction mixture was filtered through a
silica gel layer (eluent—hexane : ether = 1 : 1), the sol-
vent was distilled off, and the residue was distilled
under a vacuum.The reaction of CCl4 with olefins in the
presence of the cocatalyst CuCl2 and ligands (CH3CN,
ë6H4(CN)2) was carried out according to the same pro-
cedure.
Carbon tetrachloride hydrolysis procedure. Into
a stainless steel microautoclave (V = 17 ml), 0.1 mmol
of Cr(acac)3 (Ru(PPh3)3Cl2 or Ru(OH)Cl3), 10 mmol of
CCl4, and 200 mmol of water were placed, the auto-
clave was sealed and heated by stirring at 170°ë for 6 h.
After completion of the reaction, the autoclave was
cooled to room temperature. The released gases CO2
and HCl were passed through a freshly prepared 0.1 M
Ca(OH)2 solution.
Published data: bp 109–110°C/10 Pa [6].
3-Hydroxy-1,1,1-trichlorooctane (3b).Yield 23%.
Bp 110°C/8 Pa. 13C NMR (CDCl3, TMS, δ, ppm):
97.09 (C1); 57.69 (C2); 70.81 (C3); 38.09 (C4); 31.67
(C5); 25.78 (C6); 22.13 (C7); 13.86 (C8). Found, %: C,
41.02; H, 6.39; Cl, 45.48. Calculated for C8H15Cl3O, %:
C, 41.13; H, 6.47; Cl, 45.54; O, 6.86.
1,1,1,3-Tetrachlorononane (1c). Yield 44%. Bp
105–106°C/9 Pa. 13C NMR (CDCl3, TMS, δ, ppm):
97.12 (C1); 62.41 (C2); 57.66 (C3); 39.10 (C4); 31.64
(C5); 28.58 (C6); 25.97 (C7); 22.55 (C8); 14.06 (C9).
Mass spectrum, m/z (Jrel, %): M+ (absent), 39(23),
40(14), 41(87), 42(43), 43(100), 51(5), 53(10), 54(22),
55(70), 56(34), 57(26), 63(5), 67(14), 68(11), 69(44),
70(49), 71(5), 75(8), 77(6), 79(5), 80(5), 81(22), 82(5),
83(17), 85(6), 89(6), 90(6), 91(7), 95(10), 96(30),
97(12), 101(6), 103(5), 108(6), 109(16), 111(12),
115(10), 121(17), 122(12), 132(7), 157(11), 185(5),
187(5). Found, %: C, 40.55; H, 6.09; Cl, 53.36. Calcu-
lated for C9H16Cl4, %: C, 40.63; H, 6.06; Cl, 53.31.
3-Hydroxy-1,1,1-trichlorononane (3c). Yield
22%. Bp 111–112°C/7 Pa. 13C NMR (CDCl3, TMS, δ,
ppm): 97.05 (C1); 57.69 (C2); 71.03 (C3); 38.09 (C4);
31.67 (C5); 28.78 (C6); 25.95 (C7); 22.55 (C8); 14.09
(C9). Found, %: C, 43.59; H, 7.11; Cl, 42.91. Calcu-
lated for C9H17Cl3O, %: C, 43.65; H, 7.13; Cl, 42.96; O,
5.81.
1,1,1,3-Tetrachloroundecane (1d). Yield 41%. Bp
94–95°C/1 Pa. IR (ν, cm–1): 670, 675 (CCl), 760
(CCl3). 13C NMR spectrum (CDCl3, TMS, δ, ppm):
94.02 (C1); 63.60 (C2); 58.89 (C3); 35.64 (C4); 32.20
(C5); 28.31 (C6); 27.71 (C7); 23.87 (C8); 25.97 (C9);
22.61 (C10), 14.03 (C11). Found, %: C, 44.85; H, 6.96;
Cl, 48.19. Calculated for C11H20Cl4, %: C, 44.92; H,
6.85; Cl, 48.23.
3-Hydroxy-1,1,1-trichloroundecane (3d) Yield
22%. Bp 96–97°C/0.8 Pa. IR (ν, cm–1): 760 (CCl3),
3600 (OH). 13C NMR (CDCl3, TMS, δ, ppm): 97.15
(C1); 57.70 (C2); 71.01 (C3); 38.12 (C4); 31.67 (C5);
28.33 (C6); 27.70 (C7); 23.87 (C8); 25.78 (C9); 22.13
(C10), 13.86 (C11). Found, %: C, 47.88; H, 7.65; Cl,
38.53. Calculated for C11H21Cl3O, %: C, 47.92; H,
7.68; Cl, 38.59; O, 5.81.
The isolated products had the following characteris-
tics.
1,1,1,3-Tetrachloroheptane (1a). Yield 47%. Bp
79°C/9 Pa. Mass spectrum, m/z (Jrel, %): å+ (none),
29(48), 39(27), 41(100), 42(59), 43(29), 49(3), 52(5),
55(57), 56(7), 57(25), 63(11), 85(7), 68(27), 69(61),
75(16), 76(14), 77(11), 83(45), 89(14), 91(11), 93(34),
103(18), 104(48),105(9), 106(16), 109(25), 111(16),
114(25), 116(16), 122(43), 123(14), 124(30), 125(11),
129(45), 131(14), 165(32), 167(18). Found, %: C,
35.27; H, 4.99; Cl, 59.74. ë7ç12Cl4. calculated, %: C,
35.33; H, 5.08; Cl, 59.59.
Published data: bp 82°C/10 Pa [6].
3-Hydroxy-1,1,1-trichloroheptane (3a). Yield
23%. Bp 80–81°C/10 Pa. 13C NMR (CDCl3, TMS, δ,
ppm): 97.08(ë1); 57.71(C2); 70.82(ë3); 38.10(ë4);
31.67(ë5); 23.04(ë6). 14.03(ë7). Mass spectrum, m/z
(Jrel, %): å+ (none), 29(41), 38(5), 39(29), 40(7),
trans-1-Trichloromethyl-2-chlorocyclopentane
41(100), 42(46), 43(22), 51(10), 55(37), 57(15), 61(7), (4). Yield 75%. Bp 94–95°C/1 Pa. IR (ν, cm–1): 670,
62(5), 63(7), 65(7), 67(5), 68)17), 69(49), 75(17), 675 (CCl), 760 (CCl3). 13C NMR (CDCl3, TMS, δ,
76(10), 83(46), 85(7), 87(10), 89(7), 90(5), 91(7), ppm): 61.28 (C1); 71.11 (C2); 30.99 (C3); 24.61 (C4);
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ADDITION OF CCl4 TO OLEFINS CATALYZED
333
38.51 (C5); 101.84 (C6). Found, %: C, 32.28; H, 3.59;
endo-2-Hydroxy-exo-3-(trichloromethyl)tetracy-
Cl, 64.13. Calculated for C6H8Cl4, %: C, 32.46; H, clo[4.3.0.02,4.03,7]nonane (15). Yield 98%. 13C NMR
3.63; Cl, 63.91.
(CDCl3, TMS, δ, ppm): 51.05 (C1); 70.91 (C2); 63.52
(C3); 50.33 (C4); 32.52 (C5, C6); 47.20 (C7); 39.19 (C8);
12.13 (C9); 95.59 (C10). Found, %: C, 44.63; H, 4.48;
Cl, 39.99. Calculated for C9H11Cl3O, %: C, 44.74; H,
4.59; Cl, 44.03; O, 6.64.
endo-2-Hydroxy-3-exo-(trichloromethyl)-7,1'-
{spirocyclopropanebicyclo[2.2.1]heptane} (17). Yield
76%. 13C NMR (CDCl3, TMS, δ, ppm): 50.99 (C1, C4);
73.45 (C2); 62.97 (C3); 22.59 (C5); 24.64 (C5); 40.73
(C7); 5.17 (C8); 10.41 (C9); 92.87 (C10). Found, %: C,
47.48; H, 4.95; Cl, 41.52. Calculated for C10H12Cl3O3,
%: C, 47.18; H, 4.75; Cl, 41.78; O, 6.29.
Published data: bp 92°C/0.6 Pa [6].
trans-1-Trichloromethyl-2-chlorocyclohexane (6).
Yield 25%. Bp 73–74°C/1 Pa. 1H NMR (δ, ppm): 1.30–
2.52 m (8H, CH2), 2.84 m (1H, HCCCl3), 4.49 m (1H,
HCCl). Found, %: C, 35.56; H, 4.23; Cl, 60.21. Calcu-
lated for C7H11Cl4, %: C, 35.62; H, 4.27; Cl, 60.11.
Published data: bp 72–73°C/0.5 Pa [6].
trans-1-Hydroxy-2-(trichloromethyl)cyclohex-
ane (7). Yield 25%. Bp 75°C/0.2 Pa. IR (ν, cm–1): 670,
675, 760, 840, 985, 1360, 1450, 1470, 2850, 2960,
3600. 13C NMR (CDCl3, TMS, δ, ppm): 79.75 (C1);
61.76 (C2); 34.58 (C3); 26.80 (C4); 24.35 (C5); 33.81
(C6); 100.82 (C7). Found, %: C, 38.56; H, 4.99; Cl,
48.83. Calculated for C7H11Cl3O, %: C, 38.64; H, 5.09;
Cl, 48.90; O, 7.37.
trans-1-Trichloromethyl-2-chlorocyclooctane (9).
Yield 85%. Bp 102°C/0.5 Pa. IR (ν, cm–1): 690, 760,
830, 975, 1240, 1445, 1470, 2860, 2950. Found, %: C,
40.65; H, 5.28; Cl, 54.07. Calculated for C9H14Cl4, %:
C, 40.94; H, 5.34; Cl, 53.72.
exo-5-Chloro-exo-3-(trichloromethyl)tricy-
cle[2.2.1.02,6]heptane (18).Yield 50%. Bp 83–85°C/1 Pa.
1H NMR (CDCl3, δ, ppm): 3.91 c (1H, H5), 2.82 c (1P,
H3), 2.55 c (1H, H4), 2.37 d (1H, H7'), 2.02 d (1H, H7''),
1.80–1.65 m (3H, H1, H2, H6). 13C NMR spectrum
(CDCl3, TMS, δ, ppm): 15.39 (C1); 19.98 (C2); 65.41
(C3); 42.38 (C4); 63.81 (C5); 15.75 (C6); 26.20 (C7);
100.06 (C8). Mass spectrum, m/z (Jrel, %): M+ (none),
32(5), 38(8), 29(25), 50(16), 51(38), 63(7), 65(18),
67(5), 68(7), 69(8), 73(8), 75(14), 77(22), 78(12),
79(53), 87(10), 91(52), 100(8), 101(29), 192(14),
103(18), 109(17), 111(17), 112(10), 113(30), 115(11),
121(23), 122(100), 123(20), 124(61), 125(10),
126(12), 127(12), 137(14), 145(7), 147(13), 172(10),
173(29), 175(19), 208(6), 209(11), 211(11). Found, %:
C, 38.70; H, 3.18; Cl, 58.12. Calculated for C8H8Cl4,
%: C, 39.06; H, 3.28; Cl, 57.66.
endo-5-Chloro-exo-3-(trichloromethyl)tricy-
cle[2.2.1.02,6]heptane (19).Yield 50%. Bp 82–83°C/1 Pa.
1H NMR (CDCl3, δ, ppm): 4.08 c (1H, H5), 3.61 c (1P,
H3), 2.49 c (1H, H4), 2.37 d (1H, H7'), 1.80–1.65 m (3H,
H1, H2, H6), 1.46 c (1H, H7'). 13C NMR (CDCl3, TMS,
δ, ppm): 13.76 (C1); 19.98 (C2); 63.97 (C3); 42.51 (C4);
65.41 (C5); 18.65 (C6); 28.38 (C7); 100.77 (C8). Mass
spectrum, m/z (Jrel, %): M+ (none), 32(5), 38(7), 39(19),
50(11), 51(29), 65(12), 66(8), 68(7), 75(11), 77(16),
78(14), 79(100), 80(10), 91(29), 101(17), 102(11),
103(13), 109(8), 111(10), 113(14), 114(28), 116(8),
121(10), 122(43), 124(29), 137(12), 139(6), 147(7),
173(14), 175(10). Found, %: C, 38.85; H, 3.21; Cl,
57.94. Calculated for C8H8Cl4, %: C, 39.06; H, 3.28;
Cl, 57.66.
Published data: bp 97–116°C/10 Pa [6].
trans-1-Hydroxy-2-(trichloromethyl)cyclooctane
(10). Yield 10%. Bp 110°C/1 Pa. IR (ν, cm–1): 760
(CCl3), 3600 (OH). 13C NMR (CDCl3, TMS, δ, ppm):
79.77 (C1); 61.86 (C2); 35.68 (C3); 26.86 (C4); 29.62
(C5); 26.43 (C6); 24.35 (C7); 33.82 (C8); 101.92 (C9).
Found, %: C, 43.89; H, 6.07; Cl, 43.35. Calculated for
C9H15Cl3O, %: C, 44.01; H, 6.15; Cl, 43.31; O, 6.53.
Cyclooctanol (11).Yield 5%. Bp 104–105°C/20 Pa.
IR spectrum (ν, cm–1): 3600 (OH). Found, %: C, 74.63;
H, 12.44. Calculated for C8H16O, %: C, 74.94; H,
12.58.
Published data: bp 97–116°C/10 Pa [7].
endo-2-Hydroxy-exo-3-(trichloromethyl)bicy-
clo[2.2.1]heptane (12). Yield 80%. Bp 98–99°C/1.5
Pa. 13C NMR (CDCl3, TMS, δ, ppm): 44.63 (C1); 71.89
(C2); 63.29 (C3); 42.19 (C4); 30.66 (C5); 21.77 (C6);
35.68 (C7); 101.42 (C8). Mass spectrum, m/z (Jrel, %):
M+ (absent), 29(5), 36(7), 38(5), 39(22), 41(12), 51(7),
53(5), 65(7), 66(5), 67(35), 68(19), 75(7), 77(17),
79(7), 81(5), 85(5), 88(6), 91(6), 93(46), 99(5),
109(10), 111(10), 129(100), 130(10), 132(34), 139(7),
175(12), 177(7). Found, %: C, 41.69; H, 4.71; Cl,
49.37. Calculated for C8H11Cl3O, %: C, 41.85; H, 4.83;
Cl, 46.34; O, 6.98.
exo-2-Hydroxybicyclo[2.2.1]heptane (13). Yield 37.73 (C11); 37.73 (C12); 104.98 (C13). Found, %: C,
20%. Mp 125–126°C (ethanol). Mass spectrum, m/z 49.28; H, 5.72; Cl, 45.00. Calculated for C13H18Cl4, %:
(Jrel, %): M+ 112(2), 29(49), 31(12), 39(46), 40(10), C, 49.39; H, 5.74; Cl, 44.87.
41(49), 42(12), 43(22), 44(7), 53(15), 55(24), 56(7),
57(24), 66(44), 67(61), 68(39), 70(10), 71(7), 77(7),
1-Chloro-2-(trichloromethyl)cyclododecadiene-
5,9 (21). Yield 24%. 13C NMR (CDCl3, TMS, δ, ppm):
66.09 (C1); 67.55 (C2); 31.05 (C3); 33.89 (C4); 153.48
(C5); 131.44 (C6, C9); 32.23 (C7, C8); 129.05 (C10);
1-Hydroxy-2-(trichloromethyl)cyclododecadi-
ene-5,9 (22). Yield 6%. 13C NMR (CDCl3, TMS, δ,
ppm): 71.56 (C1); 65.63 (C2); 34.34 (C3); 39.27 (C4);
153.48 (C5); 131.44 (C6, C9); 32.23 (C7, C8); 129.05
79(100), 80(7), 81(12), 83(22), 84(7), 94(83), 95(7),
97(7), 111(2), 112(2).
Published data: mp 124–126°C, bp 176–177°C [8]. (C10); 30.73 (C11); 39.06 (C12); 104.98 (C13). Found, %:
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KHUSNUTDINOV et al.
C, 52.31; H, 6.39; Cl, 35.70. C13H19Cl3O. Calculated, 79(100), 81(31), 83(7), 85(26), 87(19), 96(9), 98(6),
%: C, 52.45; H, 6.43; Cl, 35.73; O, 5.39.
109(18), 111(11), 113(4), 121(26), 122(4), 123(21),
125(6), 130(32), 132(31), 134(9), 143(5), 145(5),
151(12), 153(8), 156(5), 157(32), 158(12), 159(32),
160(10), 161(11), 162(3), 186(4), 187(7), 188(4),
189(6). Found, %: C, 28.99; H, 2.90; Cl, 68.11. Calcu-
lated for C5H6Cl4, %: C, 28.88; H, 2.91; Cl, 68.21.
2,4,4,4-Tetrachlorobutyl acetate (23). Yield 12%.
Bp 83–84°C/0.2 Pa. 13C NMR (CDCl3, TMS, δ, ppm):
66.39 (C1); 58.02 (C2); 53.17 (C3); 95.15 (C4); 170.36
(C5); 20.35 (C6). Found, %: C, 28.68; H, 3.53; Cl,
55.39. Calculated for C6H8Cl4O2, %: C, 28.37; H, 3.18;
Cl, 55.85; O, 12.06.
2-Hydroxy-4,4,4-trichlorobutyl acetate (24).
Yield 37%. Bp 85–87°C/0.4 Pa. 13C NMR (CDCl3,
TMS, δ, ppm): 58.41 (C1); 66.06 (C2); 53.17 (C3);
96.70 (C4); 170.36 (C5); 20.35 (C6). Found, %: C,
22.84; H, 4.53; Cl, 50.02. Calculated for C6H9Cl3O3, %:
C, 22.72; H, 4.29; Cl, 50.29; O, 22.70.
RESULTS AND DISCUSSION
In this work, the characteristic features of the addi-
tion reactions of CCl4 to structurally different olefins
catalyzed by Cr and Ru complexes in the presence and
absence of water were studied.
1,1,1,5-Tetrachloropent-3Z-ene (27). Yield 78%.
The Cr(acac)3-catalyzed reaction of CCl4 with α-
Mass spectrum, m/z (Jrel, %): M+ 222(2), 41(18), olefins (1-hexene, 1-heptene, 1-octene, and 1-decene)
44(11), 49(15), 50(14), 51(30), 60(6), 61(11), 62(12), leads to (1 + 1) adducts—1,1,1,3-tetrachloroalkanes
63(75), 64(3), 69(6), 73(7), 75(14), 76(4), 77(6), (1a–1d).
Cl
Cr(acac)3
R
+ CCl
+
:
+ C Cl
2 6
4
R
170°C, 6 h
98%
R
CCl3
2
Cl
1
(2–3%)
1a–d
2a–d
R = n-C3H7 (1‡), n-C4H9 (1b), n-C5H11 (1c), n-C7H15 (1d)
At 170°C, the reaction proceeds at a noticeable rate conversion of α-olefins decreases (~60–70%), whereas
and takes 6 h for completion. Along with (1 + 1) adducts the selectivity for telomers 1a–1d) increases, and the pro-
(1a–1d), the allyl substitution products 3-chloro-1-alk- cess does not stop at the step of formation of 1,1,1,3-tetra-
enes (2a–2d) (~30%) and a negligible amount of chloroalkanes 1a–1d, since the latter undergo partial
hexachloroethane (2–3%) were found in the reaction mix- hydrolysis under the reaction conditions to give
ture. When the reaction is run in the presence of water, the 3-hydroxy-1,1,1-trichloroalkanes (3a–3d).
Cl
OH
Cr(acac)3
62–70%
+ CCl + H O
+
:
4
2
R
R
CCl3
2
R
CCl3
1
1‡–d
3‡–d
R = n-C3H7 (3‡), n-C4H9 (3b), n-C5H11 (3c), n-C7H15 (3d)
It should be pointed out that the formation of phthalonitrile) into the catalytic system (molar ratio
hydroxy derivatives 3a–3d is unexpected, since, unlike [Cr(acac)3] : [RCN] = 1 : 2) led to a substantial increase
the trichloromethyl group, the chloromethyl group is in the yield of the (1 + 1) adducts and lowered the reac-
inert towards water even in the presence of strong acids, tion temperature (140–150°C, 6 h). If the reaction is
according to published data, and enters into the substi- conducted in the presence of a large excess of water, the
tution reactions only with strong nucleophiles, such as olefin conversion decreases to 50% and the selectivity
ammonia, amines, alcoholates, and mercaptides [6]. It for 3-hydroxy-1,1,1-trichloroheptane (3a) increases by
was found that the introduction of nitriles (acetonitrile, a factor of 2.5.
PETROLEUM CHEMISTRY Vol. 49 No. 4 2009

ADDITION OF CCl4 TO OLEFINS CATALYZED
335
+ H2O
Cr(acac)3–C6H4(CN)2
CCl3
CCl3
+ CCl + H O
+
:
4
2
150°C, 6 h
50–80%
Cl
OH
3‡
1
4
1‡
On the basis of the set of experiments, the following [CuCl2] : CH3CN] = 1 : 1 : 2), the yield of trans-1-
optimal reaction conditions and most preferable reac- trichloromethyl-2-chlorocyclopentane (4) increased to
tant concentrations were found: 150–160°C, 6 h, 75%, whereas the hydrochlorination product was not
[Cr(acac)3] : [CH3CN] : [olefin] : [CCl4] : [H2O] = 1 : isolated in this case. If the reaction is conducted in the
2 : 100 : 100 : 2000.
presence of the CuCl–CH3CN catalyst system, the yield
of telomer 4 does not exceed 10%, and most of the
amount of cyclopentene is transformed into the poly-
mer. The conclusion about the trans configuration of 4
has been made on the basis of its 13C NMR data and by
their comparison with those of authentic samples [6].
The yields and product compositions were deter-
mined by the isolation of the desired compounds, as
well as by means of the GLC and GC–MS techniques.
The telomer structures were determined on the basis of
the 13C NMR data. For example, the structure of
1,1,1,3-tetrachloroundecane (1d) was assigned to the
product of the reaction of 1-decene with carbon tetra-
chloride, which displayed signals at δ 97.06 ppm
(CCl3) and 57.66 ppm (CHCl), and the hydrolysis prod-
uct displaying characteristic signals at δ 97.15 ppm
(CCl3) and 71.01 ppm (CHOH) was identified as 3-
hydroxy-1,1,1-trichloroundecane (3d).
The addition of CCl4 to cycloolefins in the presence
of water is characterized by some specific features. The
product yields and process selectivity are dependent on
the cycloolefin molecular structure, the reaction condi-
tions, the catalyst nature, and the ligand environment.
For example, the reaction of cyclopentene with CCl4
proceeds at 140°C for 6 h with a conversion of 50% to
Cl
Cr(acac)3–CuCl2–CH3CN
+ CCl4 + H2O
140°C, 6 h
75%
CCl3
4
The hydrochlorinating agent in the reagent CCl4–
H2O–Cr(acac)3 is HCl, which is produced by the hydrol-
ysis of CCl4. As it was shown by a blank experiment,
heating the mixture of CCl4 and water in an autoclave at
170°C during 6 h led to the hydrolysis of about 5% of
CCl4 with the release of HCl and CO2.
Under the above conditions, CCl4 adds to cyclohex-
yield two products, trans-1-trichloromethyl-2-chloro- ene to form trans-1-trichloromethyl-2-chlorocyclohex-
cyclopentane (4) and chlorocyclopentane (5), in the ane (70% yield). When Ru(PPh3)3Cl2 is used instead of
4 : 1 ratio, respectively. No hydrolysis products were the Cr–Cu-containing catalyst, the complete conversion
detected. As a result of further research, it was found of cyclohexene is observed to give three adducts: trans-
that copper compounds, in particular, CuCl and CuCl2, 1-trichloromethyl-2-chlorocyclohexane (6), trans-1-
had a promoting effect on Cr(acac)2. In the presence of hydroxy-2-trichloromethylcyclohexane (7), and chlo-
these copper compounds as a cocatalyst ([[Cr(acac)3] : rocyclohexane (8) in a 1 :1 : 2 ratio.
CCl3
Cl
CCl3
OH
Cl
Ru(PPh)3Cl2
+ CCl + H O
+
:
+
:
4
2
150°C, 6 h
∼100%
7
8
6
1
1
2
The addition of CCl4 to cyclooctene was accomplished (10) (10%) and a small amount of cyclooctanol (11) (~5%)
have been detected in the reaction mixture. In the presence
of the Ru(OH)Cl3–MeCN (1 : 25) catalyst system, the
cyclooctene conversion decreases (~30%); however, the
amount of hydrolysis product 10 increases (ratio [9] : [10] =
1 : 2).
with the use of the Cr(acac)3–CH3CN (1 : 10) catalyst sys-
tem. The reaction goes to the complete olefin conversion to
give trans-1-trichloromethyl-2-chlorocyclooctane (9)
(85%) as the main product. Along with 9, its hydrolysis
product
trans-1-hydroxy-2-trichloromethylcyclooctane
PETROLEUM CHEMISTRY Vol. 49 No. 4 2009

336
KHUSNUTDINOV et al.
CCl3
OH
CCl3
OH
Cr(acac)3–CH3CN
+ CCl + H O
+
+
:
4
2
160°C, 5 h
~100%
Cl
9
10
11
:
8.5
1
0.5
The conclusion about the trans configuration of the
substituents in compounds 7 and 10 follows from their
13C NMR data. The carbon atoms bearing the trichlo-
romethyl group resonate at 61.76 and 61.86 ppm, and
the carbon atoms having the OH group produce signals
at 79.75 and 79.77 ppm, which are typical of the trans
configuration of these substituents [9].
The Cr(acac)3-catalyzed reaction of CCl4 with nor-
bornene at 150°C in the presence of water goes to a
~100% olefin conversion over 5 h to give 2-endo-
hydroxy-3-exo-trichloromethylbicyclo[2.2.1]heptane
(12) and the hydration product exo-norborneol (13) in a
ratio of 4 : 1. The addition of acetonitrile to Cr(acac)3
(1 : 10) makes it possible to lower the reaction temper-
ature to 130°C, with the yield of 12 increasing to 90%.
CCl3
150°C, 5 h
~100%
OH
+
OH
12
Cr(acac)3
13
13
+ CCl + H O
4
2
:
4
1
1
CCl3
+ CH3CN
OH
+
130°C, 6 h
~100%
OH
12
:
9
The
substituted
norbornene
tetracy- lectivity and neither a hydrochlorination nor a hydra-
clo[4.3.0.02,4.03,7]nonene (14) readily reacts with tion product. The reaction of 7-spirocyclopropane-
CCl4 in the presence of Cr(acac)3 or Cr(acac)3– norbornene proceeds in similar manner, yielding
MeCN and gives only adduct 15 with a high regiose- adduct 17.
CCl3
Cr(acac)3
+ CCl + H O
4
2
150°C, 6 ˜
98%
OH
14
15
CCl
Cr(acac)3
3
+ CCl + H O
4
2
150°C, 6 h
76%
OH
17
16
PETROLEUM CHEMISTRY Vol. 49 No. 4 2009

ADDITION OF CCl4 TO OLEFINS CATALYZED
337
The conclusion about the substituent configuration
in compounds 12, 15, and 17 has been made on the
basis of their 13C NMR data. Thus, the carbon atoms
bearing the CCl3 substituent in 12, 15, and 17 resonate
at 63.29, 63.52, and 62.97 ppm, and the carbon atoms
bearing the hydroxyl group produce signals at 71.89,
73.45 and 70.91 ppm, thereby unambiguously indicat-
ing that the trichloromethyl and hydroxyl groups are
It has been found that the addition of CCl4 to norbor-
nadiene, catalyzed by Cr(acac)3–MeCN or
Ru(OH)Cl3–MeCN, at 130°C during 4 h leads to two
isomers
of
3-trichloromethyl-5-chlorotricy-
clo[2.2.1.02,6]heptane (18, 19) in a 1 : 1 ratio, differing
by the orientation of the chlorine substituent, as is con-
firmed by their 13C NMR data and a comparison with
in the exo and the endo position, respectively [9, 10]. authentic samples [6].
Cr(acac)3–CH3CN
(or Ru(OH)Cl3–CH3CN)
+ CCl + H O
+
4
2
CCl3
130°C, 4 h
Cl
CCl3
~100%
Cl
18
19
:
1
1
In the presence of the aforementioned catalysts, the and 1-hydroxy-2-trichloromethyl-5,9-cyclododecatri-
addition of CCl4 to cyclododecatriene (20) leads to 1- ene (22) with a total yield of ~30%.
trichloromethyl-2-chloro-5,9-cyclododecatriene (21)
CCl3
Cl
CCl3
OH
Cr(acac)3–CH3CN
+ CCl + H O
+
4
2
130°C, 6 h
28%
20
21
22
:
4
1
Functionalized olefins also can enter into the (25). With the use of the two-component Cr(acac)3–
Cr(acac)3-catalyzed telomerization reaction with CCl4. CuCl2 · 2H2O catalytic system, the complete conver-
For example, the reaction of allyl acetate with CCl4 at sion of allyl acetate is reached; however, the yield of 24
130°C for 6 h proceeds with the conversion of ~60% drops to 23% because of the formation of a polymer as
and high regioselectivity to give the (1 + 1) adduct the main product. The use of triethylamine as an acti-
1,1,1,3-tetrachlorobutyl acetate (23), its hydrolysis vating ligand blocks the formation of higher oligomers
product 3-hydroxy-1,1,1-trichlorobutyl acetate (24), and results in 23), (24, and 25 in the equimolar ratio
and the hydration product 2-hydroxypropyl acetate with a 100% conversion of the olefin.
Cl
OH
OH
+
+
61%
OAc
OAc
OAc
OAc
CCl3
CCl3
23
24
25
1 : 3 : 1
OH
Cr(acac)3
CuCl2
~100%
+ CCl + H O
+
ppolymer
4
2
130°C, 6 h
OAc
23%
CCl3
CuCl2–Et3N
~100%
(23)
1
+
:
(24)
1
+
:
(25)
1
PETROLEUM CHEMISTRY Vol. 49 No. 4 2009

338
KHUSNUTDINOV et al.
The reaction of CCl4 with 1,4-diacetoxy-2Z-ene process results in the replacement of both of the acetate
(26) in the presence of Cr(acac)3 proceeds in a nontriv- substituents with the Cl and CCl3 group, rather than
ial manner. Judging from the structure of 1,1,1,5-tetra- going towards the addition of CCl4 to the multiple
chloropent-3Z-ene (27) resulted from the reaction, the bond.
Cr(acac)3
+ CCl4 + H2O
140°C, 6 h
Cl
CCl3
OAc
OAc
26
27
90%
2. R. I. Khusnutdinov, N. A. Shchadneva, A. R. Baiguzina,
et al., Izv. Akad. Nauk, Ser. Khim., No. 11, 1919 (2002).
Thus, the addition of water has a substantial effect
on the telomerization reaction of CCl4 with olefins in
the presence of Cr and Ru-containing catalysts. On the
one hand, water increases the selectivity for (1 + 1)
adducts. On the other hand, water takes part in the
hydrolysis reaction of the trichloromethyl group of the
resulting tetrachloro derivatives.
3. R. I. Khusnutdinov, N. A. Shchadneva, R. Yu. Burangu-
lova, et al., Zh. Org. Khim. 43, 625 (2007).
4. I. Kh. Bikbulatov, F. Kh. Valitov, A. G. Gromova, et al.,
KhPKh 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. R. I. Khusnutdinov, N. A. Shchadneva, A. R. Baiguzina,
et al., Neftekhimiya 44, 382 (2004) [Pet. Chem. 44, 350
(2004)].
ACKNOWLEDGMENTS
The work was supported by the Russian Foundation
for Basic Research, project no. 08-03-97005, and the
Ministry of Education and Science of Russia, grant no.
NSh 7470.2006.3.
7. P. S. Skell and R. F. Harris, J. Am. Chem. Soc. 87, 5806
(1965).
8. Aldrich. A Handbook of Chemicals and Laboratory
Equipment (Russia, 2003–2004).
9. J. K. Whitesell and M. A. Minton, Stereochemical Anal-
ysis of Alicyclic Compounds C-13 NMR Spectroscopy
(New York, 1985).
REFERENCES
1. R. Kh. Freidlina, F. K. Velichko, S. S. Zlotskii,
D. L. Rakhmankulov, and A. B. Terent’ev, Radical 10. R. Grigg, J. Devlin, A. Ramasubbu, et al., J. Chem. Soc.,
Telomerization (Khimiya, Moscow, 1988) [in Russian].
Perkin Trans. 1, No. 7, 1515 (1987).
PETROLEUM CHEMISTRY Vol. 49 No. 4 2009