Chlorination of hydrocarbons with CCl4 catalyzed by complexes of Mn, Mo, V, Fe

Article abstract of DOI:10.1134/S1070428013110018

Catalytic chlorination of alkanes, cycloalkanes, and adamantane utilizing tetrachloromethane as the source of chlorine and applying catalysts containing manganese, molybdenum, vanadium, and iron activated with nitrile ligands, alcohols, and water was fulfilled. The optimum ratios of catalysts and reagents and the best reaction conditions were found for selective synthesis of chlorine-substituted hydrocarbons derivatives. Pleiades Publishing, Ltd., 2013.

Full text of DOI:10.1134/S1070428013110018

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1557−1566. © Pleiades Publishing, Ltd., 2013.
Original English Text © R.I. Khusnutdinov, N.A. Shchadneva, A.R. Bayguzina, T.M. Oshnyakova, Yu.Yu. Mayakova, U.M. Dzhemilev, 2013, published in Zhurnal
Organicheskoi Khimii, 2013, Vol. 49, No. 11, pp. 1583−1591.
Chlorination of Hydrocarbons with CCl4
Catalyzed by Complexes of Mn, Mo, V, Fe
R. I. Khusnutdinov, N. A. Shchadneva, A. R. Bayguzina, T. M. Oshnyakova,
Yu. Yu. Mayakova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
e-mail : ink@anrb.ru
Received October 18, 2012
Abstract—Catalytic chlorination of alkanes, cycloalkanes, and adamantane utilizing tetrachloromethane as the
source of chlorine and applying catalysts containing manganese, molybdenum, vanadium, and iron activated with
nitrile ligands, alcohols, and water was fulfilled. The optimum ratios of catalysts and reagents and the best reaction
conditions were found for selective synthesis of chlorine-substituted hydrocarbons derivatives.
DOI: 10.1134/S1070428013110018
is also topical we have prepared metal complex catalysts
based on compounds of Mn, Mo, V, and Fe providing the
possibility of alkanes and cycloalkanes chlorination using
tetrachloromethane as the halogen source.
Hydrocarbons chlorination with the use of tetrachlo-
romethane as the chlorine source is interesting as one of
the promising methods of an appropriate processing and
utilization of CCl4 and is important for manufacturing
practically valuable chlorinated hydrocarbons.
In the presence of manganese compounds [MnSO4,
MnCl2, MnO2, Mn(C17H35CO2)2, Mn(OAc)2, Mn(acac)3]
unbranched alkanes undergo the chlorination with ССl4,
and the conversion of the initial hydrocarbon decreases
with the growing length of its chain. The chlorination
of unbranced alkanes occurs under severe conditions
(200°С) not only at the methylene but also at the methyl
groups affording practically valuable 1-chloroalkanes
Iа–IVа in up to ~30% yield. The most active catalysts
formed from Mn(OAc)2 and Mn(acac)3 at adding to them
2–4 mol% of CH3CN. The alkane conversion, yields of
products, and isomers distribution is strongly affected by
the duration of the reaction. The optimum conditions for
obtaining monochlorinated alkanes are heating at 200°С
in the course of 8–10 h. The conversion of the initial al-
kane reached 70%. On increasing the reaction time to 20 h
the alkane conversion may reach 84%, but the selectivity
decreases due to the formation of a complex mixture of
di-, tri-, and polychlorinated alkanes.
The application of halomethanes (CCl4, CBr4, CHI3)
in the halogenation of hydrocarbons in the presence of
catalysts has been known for a long time. The adamantane
chlorination with tetrachloromethane in the presence of
anhydrous AlCl3 was described in [1]. Analogous reac-
tions are catalyzed by Lewis acids like SbCl5 and FeCl3
[2]. Recently it was suggested to perform the alkanes
halogenation with СХ4 (Х = Cl, Br, I) using phase trans-
fer catalysts [3], complexes of Rh [4], Pd [5], Pt [6], Cu
[7, 8], and Mn [9, 10]. In the mentioned publications the
catalytic chlorination with the use of CCl4 was investi-
gated by examples of a limited number of hydrocarbons
(hexane, cyclohexane, adamantane) [1–10]. The catalytic
bromination of hydrocarbons with СBr4 was carried out
in the presence of copper and nickel compounds [11].
Since the development of unconventional and environ-
mentally friendly processes of manufacturing organochlo-
rine compounds avoiding the use of gaseous chlorine is
urgent and promising and the problem of CCl4 utilization
The yields of 1-chloroalkanes Iа–IVа and 2-chloroal-
_
Mn(acac)3 CH3CN
RCH2CH3 + CCl4
RCH2CH2Cl + RCHClCH3
Ib_IVb
200oC, 8 h
Iа_IVа
R = C4H9 (Iа, Ib), C8H17 (IIа, IIb), C10H21 (IIIа, IIIb), C16H33 (IVа, IVb).
1557

KHUSNUTDINOV et al.
1558
kanes Ib–IVb depending on the alkane structure and the
reaction conditions are compiled in Table 1.
they can be selectively converted into the monochloro
derivatives at 200°С within 3 h.At longer heating (200°С,
5 h) a complete conversion of hydrocarbons was obtained
with the formation of a mixture of mono-, di-, tri-, and
tetrachloro derivatives with a random distribution of the
chlorine atoms in the ring (Table 2).
In the presence of the catalyst Mn(acac)3–CH3CN
cyclic hydrocarbons, cyclopentane, cyclohexane, and
cyclooctane, actively undergo chlorination. At the in-
complete conversion of the initial cycloalkane (80–90%)
Cl
_
_
Mn(acac)3 CH3CN
Mn(acac)3 CH3CN
(CH )
2 n + CCl4
(CH2)n
Clm
(CH2)n
200oC, 3 h
200oC, 5 h
n = 1, 2, 4; m = 2–4.
In continuation of the search for new catalytic systems
for alkanes chlorination using CCl4 as chlorine source
we found that molybdenum compounds were efficient
catalysts of this reaction, and their activity grew in the
series МоО3 < MoCl5 ≤ MoO2(C5H7O2)2 < Mo(CO)6.
most active catalyst) the hydrocarbon chlorination is
the main reaction direction, and the conversion of the
initial hydrocarbon, like in the case of Mn-containing
catalysts, depends on its structure and chain length. The
unbranched alkanes undergo chlorination both at the
methylene and methyl groups affording 1-chloro-alkanes
with the selectivity up to ~40% (at low conversions, with
At heating the alkane mixture with CCl4 at 140–160°С
in the presence of molybdenum hexacarbonyl (the
Table 1. Chlorination of aliphatic hydrocarbons at the use of CCl4 under the action of catalytic system Mn(acac)3– CH3CNа
Yield, %
Conversion
of alkane, %
Alkane
Catalyst
Reaction time, h
1-chloroalkane 2-chloroalkane Polychloroalkanes
Hexane
MnCl2
10
20
10
20
10
16
20
10
10
8
30
53
45
69
64
71
84
46
70
58
48
57
43
54
40
49
12
10
25
18
32
19
20
20
24
31
30
14
29
12
28
10
88
62
75
51
67
37
31
80
76
69
70
65
71
62
72
61
0
28
0
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Hexaneb
Hexanec
Hexane
Decane
Decane
Dodecane
Dodecane
Octadecane
Octadecane
а
MnCl2
Mn(OAc)2
Mn(OAc)2
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
Mn(acac)3
31
1
44
49
0
0
0
8
0
20
8
21
0
20
8
26
0
20
29
The ratio catalyst–CH3CN–alkane–CCl4 1 : 4 : 100 : 300, 200°C.
b Mn(acac)3–CH3CN–alkane–CCl4 1 : 4 : 100 : 100, 200°C.
c
Mn(acac)3–CH3CN–alkane–CCl4 1 : 4 : 100 : 500, 200°C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

CHLORINATION OF HYDROCARBONS
1559
Table 2. Chlorination of cycloalkanes with CCl4 under the action of catalytic system Mn(acac)3–CH3CNа
Yield, %
monochlorocycloalkanes polychlorocycloalkanes
Conversion
of cycloalkane, %
Cycloalkane
Reaction time, h
Cyclopentaneb
Cyclopentaneb
Cyclopentane
Cyclopentanec
Cyclopentane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclooctane
Cyclooctane
Cyclooctane
2.5
3
65
79
100
95
92
90
82
99
96
88
97
87
72
0
5
3
91
8
3
89
10
18
1
5
100
71
2
3
93
4
5
100
76
12
3
2
2
87
13
28
5
100
а
The ratio Mn(acac)3–CH3CN–cycloalkane–CCl4 1 : 4 : 100 : 300, 200°C.
b Mn(acac)3–CH3CN–cycloalkane–CCl4 1 : 4 : 100 : 100, 200°C.
c
Mn(acac)3–CH3CN–cycloalkane–CCl4 1 : 4 : 100 : 500, 200°C.
selectivity up to до 20%). The conversion of alkanes,
the yield of chlorinated derivatives, and the isomers
distribution depend on the duration of the reaction.At the
increase of the reaction time to 12 h the alkane conversion
may attain ~100%, but the selectivity is reduced due to the
formation of a complex mixture of tri- and tetrachloro-
substituted alkanes.
RO• and Cl•.
The main laws of the chlorination with the use of
halomethanes in the presence of molybdenum complexes
we explore by an example of hexane. The optimum molar
ratios of the catalyst components and reagents were
determined and the feasible conditions for the preparation
of 1- and 2-chlorohexanes were found (130–160°С,
3–6 h).
As a result of a targeted search for promoters, which
contained first of all organophosphorus and nitrogen-
containing organic ligands, we found that the activity
and selectivity of the action of the molybdenum-based
catalysts might be enhances by adding to them alcohols
(МеОН or EtOH). An important consequence of the
use of alcohols as promoters of the molybdenum-based
catalysts was the decrease in the reaction temperature to
130–150°С.
The increase in the concentration of CCl4 (hexane–
CCl4 1 : 3 × 5) resulted in the growing of the overall yield
of chloroalkanes Ia, Ib to 77%. The longer reaction time
(>12 h) is unwanted both for hexane and the higher alkane
(decane, dodecane), since the 1- and 2-chloroalkanes
suffer dehalogenation. Besides, the composition of
products gets more complex because of the formation of
3-chloroalkanes Ic–IIIc.
In order to reveal the reason of the feasible influence
of alcohol additives on the catalytic chlorination of
alkanes with CCl4 we investigated the composition of the
reaction mixture, where by the iodometric titration active
chlorine was detected [the concentration of the active
chlorine 5 min after the start of the reaction (150°С) was
1.5–2 mg/mL, and after 20 min, 3.5 mg/mL] showing
that the alcohols were oxidized with СCl4 to alkyl
hypochlorites. The detection of alkyl hypochlorites in the
reaction mixture allows an assumption on their probable
involvement into the process of alkane chlorination due
to the readiness of the generation from ROCl of radicals
The yields of 1-, 2-, and 3-chloroalkanes depending
on the alkane structure and the reaction conditions are
compiled in Table 3.
At the use of ethanol as the alcohol component besides
2-chlorohexane (Ib) acetaldehyde diethyl-acetal was
found in the products. At the increased concentration of
С2Н5ОН (hexane–ethanol, 1 : 4 × 8) the yield of the acetal
reached 88% due to the effect of HCl formed at the alcohol
oxidation with CCl4 into ethyl hypochlorite decomposed
with the liberation of HCl and acetic aldehyde. The
hexane conversion grew simultaneously.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

KHUSNUTDINOV et al.
1560
Mo(CO)6
RCH2CH2CH3 + CCl4 + CH3OH
RCH2CH2CH2Cl + RCH2CHClCH3 + RCHClCH2CH3
Iа_IIIа
140_160oC,
3_6 h
Ib_IIIb
Ic_IIIc
.R = C3H7 (Iа–Ic), C7H15 (IIа–IIc), C9H19 (IIIа–IIIc).
The results of hexane chlorination under the catalysis
with Мо(СО)6 using ethanol as promoter are presented
in Table 4.
at incomplete conversion of the initial cycloalkane
(60–80%) were selectively converted into monochloro
derivatives Vа, VIa (170°С, 3 h). At the longer heating
(170°С, 6 h) the conversion of cycloalkanes was virtually
complete, but a complex mixture formed of mono-, di-,
tri-, and tetrachloro derivatives with a fairly random
distribution of the chlorine atoms in the ring (Table 5).
The action of catalyst Мо(СО)6 in the presence
of CH3OH led to the efficient chlorination with CCl4
of cyclic hydrocarbons, in particular, cyclopentane,
cyclohexane, cyclooctane, and cyclododecane, which
Table 3. Chlorination aliphatic hydrocarbon using CCl4 in the presence of Mo(CO)6 and МеОН
Composition of reaction products, %
Molar ratio Мо(СО)6 –alkane–
ССl4 –СН3ОН
Reaction
conditions of alkane, %
Conversion
Alkane
1-chloroalkanes 2-chloroalkanes 3-chloroalkanes
(Iа–IIIа)
(Ib–IIIb)
98
98
97
78а
87
78
–
(Ic–IIIc)
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Hexane
Decene
1 : 200 : 600 : 2400
1 : 200 : 600 : 2400
1 : 200 : 600 : 2400
1 : 200 : 600 : 2400
1 : 200 : 600 : 2400
1 : 200 : 600 : 2400
1 : 200 : 600 : 0
130°С, 3 h
140°С, 3 h
150°С, 3 h
150°С, 6 h
160°С, 3 h
160°С, 4 h
150°С, 3 h
150°С, 6 h
150°С, 6 h
150°С, 6 h
140°С, 12 h
140°С, 6 h
140°С, 3h
140°С, 6 h
150°С, 6 h
150°С, 6 h
150°С, 6 h
140°С, 3 h
140°С, 6 h
140°С, 3 h
150°С, 6 h
150°С , 6 h
150°С, 6 h
140°С, 3 h
15
22
30
77
34
69
–
2
2
–
–
3
–
–
20
13
22
–
–
–
–
–
–
–
1 : 100 : 100 : 100
1 : 100 : 200 : 100
1 : 100 : 200 : 100
1 : 200 : 800 : 1200
1 : 200 : 800 : 1200
1 : 200 : 800 : 0
44
39
81
25
32
–
3
97
95
96
69
46
–
4
5
31
8
Decane
46
-
Decane
–
Decane
1 : 200 : 800 : 0
–
–
–
Decane
1 : 100 : 100 : 100
1 : 100 : 200 : 100
1 : 100 : 200 : 200
1 : 200 : 800 : 200
1 : 200 : 800 : 200
1 : 200 : 1600 : 2400
1 : 100 : 100 : 100
1 : 100 : 200 : 100
1 : 100 : 200 : 200
1 : 200 : 800 : 0
17
24
40
3
–
35
36
15
61
62
59
49
41
47
–
65
63
20
37
35
40
50
57
52
Decane
1
Decane
3
Dodecane
Dodecane
Dodecane
Dodecane
Dodecane
Dodecane
Dodecane
2
5
3
19
45
30
44
–
1
1
2
1
–
а The reaction mixture contained hexachloroethane (~2%).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

CHLORINATION OF HYDROCARBONS
1561
Table 4. Hexane chlorination with CCl4 in the presence of Мо(СО)6 and C2H5OH
Yield, %
Molar ratio
hexane–CCl4–С2Н5ОН– Мо(СО)6
Reaction conditions
Hexane conversion
Ib
Ic
200 : 200 : 200 : 1
200 : 200 : 200 : 1
200 : 200 : 400 : 1
200 : 400 : 1600 : 1
100 : 200 : 800 : 1
200 : 200 : 0 : 1
130°С, 6 h
130°С, 17 h
130°С, 6 h
160°С, 3 h
160°С, 3 h
130°С , 6 h
150°С, 12 h
130°С, 3 h
140°С, 3 h
160°С, 3 h
160°С, 4 h
150°С, 3 h
130°С, 6 h
130°С, 3 h
130°С , 6 h
28
42
26
28
23
8
89
86
88
69
77
100
72
80
88
78
81
81
80
77
78
11
14
12
28
33
–
100 : 300 : 1200 : 1
100 : 300 : 1200 : 1
100 : 300 : 1200 : 1
200 : 600 : 2400 : 1
200 : 600 : 2400 : 1
200 : 600 : 2400 : 1
200 : 200 : 400 : 1
200 : 200 : 1200 : 1
200 : 200 : 1200 : 1
28
25
39
61
66
32
31
28
19
28
20
12
22
19
19
20
23
22
Table 5. Cycloalkaneов chlorination with CCl4 in the presence of Мо(СО)6 and СН3ОНа
Composition of reaction products, %
Conversion of
cycloalkane, %
Cycloalkane
Reaction conditions
monochlorocycloalkanes polychlorocycloalkanes
Cyclopentane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclooctane
Cyclooctane
Cyclooctane
Cyclododecane
Cyclododecane
Cyclododecane
170°С, 6 h
130°С, 3 h
140°С, 3 h
150°С, 3 h
160°С, 3 h
170°С, 3 h
170°С, 1 h
170°С, 6 h
180°С, 2 h
170°С, 1 h
170°С, 6 h
180°С, 2 h
170°С, 1 h
170°С, 6 h
180°C, 2 h
87
42
60
64
69
75
53
97
81
49
95
89
30
82
90
58
~ 100
97
42
–
3
90
10
21
19
7
79
81
93
68
33
10
6
90
94
65
35
19
3
81
97
42
58
35
65
а The ratio Мо(СО)6– cycloalkane– ССl4– СН3ОН 1 : 100 : 400 : 800.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

KHUSNUTDINOV et al.
1562
[Mo]
_CHCl3
C2H5OH + CCl4
CH3CHO
C2H5OCl
_HCl
HCl
CH3CH(OC2H5)2
CH3CHO + 2C2H5OH
m = 1–4, n = 1, 2.
The addition to the reaction mixture of catalytic
proceed even at the prolonged heating (170°С, 20 h).
quantities of water caused an unexpected result:
At 170°С within 1 h monochlorocyclopentane (V)
and monochlorocyclohexane (VI) were obtained
in nearly quantitative yields. Cyclododecane under
similar conditions at 30% conversion formed
monochlorocyclododecane (VIII). The increased
duration of the reaction (165°С, 6 h) led to the formation
of exclusively polychlorinated products at the total
conversion of the initial cycloalkane.
In order to understand the feasible effect of water
on the course of the chlorination we examined the
composition of the reaction mixture [Mo(CO)6–CCl4–
H2O, 1 : 100 : 4] incubated at 170°С for 1 h. The
iodometric titration showed the presence in the reaction
mxture of active chlorine, and chloroform was found by
GLC. Therefore. presumably a reaction CCl4 + H2O →
HOCl + CHCl3 occurred.
The hypochloric acid is known to decompose easily
giving radicals НО• and Сl•. Apparently the formation of
HOCl is the reason of the increased yield of compounds
V, VI in the presence of water.
The water concentration is crucial. Thus, at the
addition of a stoichiometric amount of water with respect
to the hydrocarbon the cycloalkane chlorination did not
Cl
Clm
Mo(CO)6
Mo(CO)6
+ CCl4 + CH3OH
(CH2)n
170oC, 3 h
170oC, 6 h
97%
(CH2)n
(CH2)n
1
:
4
:
8
V, 70% (n = 1)
VI, 68% (n = 2)
We explored the preparative opportunities of the
catalytic chlorination with CCl4 cycloalkanes of more
complex structure, in particular, of adamantane, whose
chlorinated derivatives were widely used in preparation
of pharmaceuticals, diagnosticums, polymers possessing
thermal and chemical resistance [12].
_
3% Mo(CO)6 H2O, 1 : 4
+ CCl4
1 : 3
170oC, 8 h
Cl
IXa
At the use of water in a stoichiometric amount with
respect to adamantane the reaction proceeds under
milder conditions (150°С), but notwithstanding the high
conversion of adamantane (92%) the selectivity of the
chlorination sharply fell due to the formation of mono-
and polychlorinated (1,3-dichloro-, 1,3,5-trichloro-,
1,3,5,7-tetrachloro-) and oxygen-containing adamantanes
(adamantan-1-ol, adamantane-1,3-diol, adamantan-2-
one).
We formerly demonstrated the possibility of catalytic
chlorinationя of adamantane and its derivatives using CCl4
as chlorine source in the presence of Mn-, V-, and Мо-
containing catalysts promoted with alcohols and nitrile
ligands [13].
In the adamantane chlorination the promoting
effect of water was observed at the use of Mo- and
V-containing catalysts. The system Mo(CO)6–H2O, 1 :
4, catalyzed the selective chlorination of adamantane
in the node position. At 170°С in 8 h and adamantane
conversion of ~48% a single product was obtained,
1-chloroadamantane (IХa).
The best results were obtained at the adamantane
chlorination n the presence of the vanadium-containing
catalyst. At the addition to VO(acac)2 of a stoichiometric
amount of water 1-chloroadamantane (IХa) is formed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

CHLORINATION OF HYDROCARBONS
1563
mixture chloroform (the main reaction product) and
dichloromethane, indicating that the chlorination occurred
by replacing the hydrogen atom in adamantine molecule
predominantly in the node position.
selectively in 60% yield. At the 5–7-fold excess of CCl4
and water the complete conversion of adamantane was
attained, and the yield of chloroadamantane (IХa) grew
to 90%.
Thus, compound and complexes of Mn, Mo, V, and Fe
promoted with alcohols and water catalyze the chlorina-
tion of alkanes, cycloalkanes, and adamantine with CCl4
used as chlorine source.
Cl
Cl
VO(acac)2
160oC, 6 h
+ CCl4
+
Cl
The structure of compounds synthesized was estab-
lished by spectral methods, and by their comparison with
authentic samples and published data.
IXa
IXb
According to Kovacic et al. [2], one of the first cata-
lysts of adamantane chlorination with CCl4 was FeCl3.
We attempted to find whether alcohols and water would
work as promoters in the reaction under study with respect
to the iron compounds and complexes.
EXPERIMENTAL
13С NMR spectra were registered on a spectrometer
Bruker Avance-400 (operating frequency 100.62 МHz)
in CDCl3. Mass spectra were measured on an instrument
Shimadzu GCMS-QP2010Plus (capillary column SPB-5
30 m × 0.25 mm, carrier gas helium, ramp from 40 to
300°С at a heating rate 8 deg/min, vaporizer temperature
280°С, ion source temperature 200°С, ionizing energy
70 eV). Elemental composition of the samples was de-
termined on an analyzer Carlo Erba 1106.
The promoting effect of water with respect to
Fe(acac)3 and Fe(С5H5)2 proved to be insignificant. In the
presence of the catalytic system Fe(C5H5)2–H2О, 12 : 10,
the conversion of adamantane did not exceed 7%, а and
the only reaction product was 1-chloroadamantane (IХa).
Better results were obtained at promoting the iron-
containing catalysts with alcohols, methanol and etha-
nol, which considerably affect the yield as well as the
selectivity of the reaction. In the presence of the catalytic
system Fe(acac)3–CH3ОН, 1 : 30, at 160°С (6 h) the
single product of adamantane reaction with CCl4 was
1,3-dichloroadamantane (IХb).
The reaction progress was monitored and the purity of
compounds obtained was checked by GLC on an instru-
ment Shimadzu GC-9A, GC-2014 [column 2 m × 3 mm,
stationary phase silicone SE-30 (5%) on the carrier Chro-
maton N-AW-HMDS, ramp from 50 to 270°С at a heating
rate 8 deg/min, carrier gas helium (47 mL/min)].
Cl
General procedure of chlorination of alkanes and
cycloalkanes. (а) Into a pressure microreactor of stainless
steel of 17 mL capacity or into a glass ampule of 20 mL
capacity (the results of parallel runs materially coincide)
was charged 1 mmol of Mn(acac)3, 4 mmol of acetonitrile,
100 mmol of alkane or cycloalkane, and 300 mmol of
CCl4. The reactor was pressure-tight closed (the ampule
was sealed), and the reaction mixture was heated at 200°С
for 1–8 h. On the completion of the reaction the reactor
(ampule) was cooled to room temperature, opened, the
reaction mixture was filtered through a bed ofAl2O3. The
unreacted CCl4 was distilled off, the residue was distilled
in a vacuum or crystallized from ethanol.
_
Fe(acac)3 CH3OH
+ CCl4
160oC, 6 h
Cl
IXb, 98%
Fe(acac)3–AdH–CCl4–CH3OH, 0.03 : 1 : 2 : 1.
[Fe] = Fe(acac)3–C2H5OH, Fe(C5H5)2–C2H5OH;
Fe–AdH–CCl4–ROH, 0.035 : 1 : 2 : 1.
The replacement of methanol by ethanol resulted in
the selective formation of 1-chloroadamantane (IXа),
whose yield in the presence of the catalytic system
Fe(acac)3–C2H5ОН was 79%, and at the use of the
ferrocene-containing catalyst, 93%.
(b) Into a pressure microreactor of stainless steel of
17 mL capacity or into a glass ampule of 20 mL capacity
was charged 0.3 mmol of Mо(СО)6, 10 mmol of alkane (or
cycloalkane), 40 mmol of CCl4, 40–80 mmol of ethanol
(methanol), the reactor was pressure-tight closed (the
ampule was sealed), and the reaction mixture was heated
The experiments of adamantane chlorination using
CCl4 were carried out in sealed ampules or in a pressure
microreactor of stainless steel at 160–170°С over 1–6 h.
By means of GLC and GC-MS we found in the reaction
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KHUSNUTDINOV et al.
1564
at 130–180°С for 3–14 h.
(Irel, %) : 29 (32), 39 (10), 40 (8), 41 (60), 42 (29), 43
(100), 54 (10), 55 (48), 56 (26), 57 (82), 68 (8), 69 (32),
70 (13), 71 (28), 82 (5), 83 (13), 84 (6), 85 (12), 90 (13),
91 (66), 92 (7), 93 (19), 97 (7), 104 (5), 105 (14), 107
(5). Found, % : С 70.31; Н 12.27; Cl 17.42. С12Н25Cl.
Calculated, % : С 70.38; Н 12.31; Cl 17.31. М 204.78.
1-Chlorohexane (Iа). Yield 24%, bp 134°С (bp 133–
134°С [14]). Mass spectrum, m/z (Irel, %) : 29 (60), 32
(5), 39 (35), 41 (97), 42 (58), 43 (86), 53 (5), 54 (6), 55
(96), 56 (59), 57 (12), 69 (22), 90 (6), 90 (100), 92 (5),
93 (31). Found, % : С 59.68; Н 10.82; Cl 29.50. С6Н13Cl.
Calculated % : С 59.74; Н 10.86; Cl 29.40. М 120.60.
2-Chlorododecane (IIIb). Yield 71%, bp 121°С
(10 mm Hg). 13С NMR spectrum, δ, ppm: 14.15 (С12),
23.00 (С11), 26.83 (С1), 28.98 (С4), 28.99 (С5), 29.09
(С6), 29.11 (С7), 32.14 (С8), 32.21 (С9), 32.30 (С10),
38.93 (С3), 57.79 (С2). Mass spectrum, m/z (Irel, %) : 39
(20), 41 (100), 43 (98), 55 (85), 69 (59), 83 (37), 97 (29),
111 (20), 125 (7), 140 (5), 168 (12). Found, % : С 70.48;
Н 12.50; Сl 17.02. С12Н25Cl. Calculated, % : С 70.38;
Н 12.31; Cl 17.31. М 204.78.
2-Chlorohexane (Ib). Yield 77%, bp 133.5–134°С
(bp 133–134°С [14]). 13С NMR spectrum, δ, ppm: 15.17
(С6), 22.23 (С5), 27.77 (С1), 28.62 (С4), 38.81 (С3), 59.22
(С2), Mass spectrum, m/z (Irel, %) : 29 (49), 38 (5), 39
(30), 40 (12), 41(91), 42 (79), 43 (82), 53 (5), 54 (10),
55 (75), 56 (100), 57 (22), 58 (7), 63 (11), 84 (48), 85
(11). Found, % : С 59.66; Н 10.81; Cl 29.53. С6Н13Cl.
Calculated, % : С 59.74; Н 10.86; Cl 29.40. М 120.60.
1-Chlorodecane (IIa). Yield 8%, bp 105°С
(10 mm Hg) (bp 233°С [15]). Mass spectrum, m/z (Irel,
%) : 29 (38), 39 (14), 40 (13), 41 (70), 42 (31), 43 (100),
54 (11), 55 (53), 56 (25), 63 (7), 67 (7), 68 (7), 69 (67), 70
(60), 71 (16), 82 (10), 83 (24), 84 (25), 85 (7), 96 (6), 97
(25), 98 (14), 105 (7), 111 (18), 112 (11), 140 (5). Found,
% : С 67.48; Н 11.90; Cl 20.62. С10Н21Cl. Calculated, %
: С 67.96; Н 11.98; Cl 20.06. М 176.726.
3-Chlorododecane (IIIc). Yield 24%. Mass spectrum,
m/z (Irel, %) : 29 (51), 39 (14), 40 (13), 41 (89), 42 (43),
43 (100), 53 (7), 54 (23), 55 (93), 56 (87), 57 (67), 67
(10), 68 (20), 69 (81), 70 (66), 71 (22), 81 (6), 82 (20),
83 (51), 84 (35), 85 (10), 96 (13), 97 (36), 98 (18), 110
(8), 111 (22), 112 (10), 125 (11), 126 (5), 135 (7), 168
(8). Found, %: С 70.34; Н 13.25; Cl 16.41. С12Н25Cl.
Calculated, % : С 70.38; Н 12.31; Cl 17.31. М 204.78.
2-Chlorodecane (IIb). Yield 33%, bp 105°С
(10 mm Hg) (bp 238°С [15]). 13С NMR spectrum, δ, ppm
: 14.10 (С10), 22.73 (С9), 24.75 (С4), 26.00 (С1), 27.94
(С5), 28.32 (С6), 28.92 (С7), 31.95 (С8), 40.37 (С3), 57.26
(С2). Mass spectrum, m/z (Irel, %) : 29 (48), 39 (22), 40
(5), 41 (89), 42 (36), 43 (100), 53 (6), 54 (8), 55 (81), 56
(41), 63 (7), 67 (7), 68 (7), 69 (67), 70 (60), 71 (16), 82
(10), 83 (24), 84 (25), 85 (7), 96 (6), 97 (25), 98 (14),
105 (7), 111 (18), 112 (11), 140 (5). Found, % : С 67.48;
Н 11.90; Cl 20.62. C10H21Cl. Calculated, %: С 67.96;
Н 11.98; Cl 20.06. М 176.726.
1-Chlorooctadecane (IVа). Yield 28%, bp 126°С
(10 mm Hg) (bp 260°С [16]). 13С NMR spectrum, δ,
ppm: 13.63 (С18), 22.54 (С17), 28.65 (С2), 28.71 (С3),
28.80 (С4), 28.96 (С5), 29.00 (С6), 29.10 (С7), 29.19 (С8),
29.22 (С9), 29.34 (С10), 29.42 (С11), 29.49 (С12), 29.53
(С13), 29.56 (С14), 29.62 (С15), 29.69 (С16), 40.62 (С1).
Mass spectrum, m/z (Irel, %) : 39 (19), 41 (74), 43 (100),
55 (70), 57 (74), 69 (51), 83 (44), 97 (42), 111 (25), 125
(12), 139 (5), 153 (4), 167 (3), 224 (3), 252 (7). Found,
% : С 75.30; Н 12.20; Cl 12.50. C18H37Cl. Calculated,
% : С 74.82; Н 12.91; Cl 12.27. М 288.939.
3-Chlorodecane (IIc). Yield 15%. Mass spectrum,
m/z (Irel, %) : 29 (48), 39 (19), 40 (20), 41 (90), 42 (55),
43 (97), 53 (6), 54 (24), 55 (100), 51 (90), 52 (46), 67
(7), 68 (17), 69 (67), 70 (67), 71 (16), 82 (13), 83 (31),
84 (31), 85 (10), 96 (12), 97 (35), 98 (17), 110 (6), 111
(22), 112 (12), 140 (8). Found, % : С 67.90; Н 11.90;
Cl 20.20. C10H21Cl. Calculated, % : С 67.96; Н 11.98;
Сl 20.06. М 176.726.
2-Chlorooctadecene (IVb). Yield 72%, bp 120°С
(10 mm Hg). 13С NMR spectrum, δ, ppm : 13.57 (С18),
22.28 (С17), 25.34 (С4), 25.96 (С5), 26.10 (С6), 26.19 (С7),
26.27 (С8), 26.37 (С9), 26.44 (С10), 26.49 (С11), 26.51
(С1), 26.53 (С12), 26.57 (С13), 26.61 (С14), 26.68 (С15),
26.70 (С16), 40.36 (С3), 58.50 (С2). Mass spectrum, m/z
(Irel, %) : 39 (10), 41 (83), 43 (100), 55 (73), 57 (71), 69
(56), 83 (49), 97 (41), 111 (22), 125 (15), 139 (7), 153
(6), 252 (10). Found, % : С 74.18; Н 12.80; Cl 13.02.
C18H37Cl. Calculated, % : С 74.82; Н 12.91; Cl 12.27.
М 288.939.
1-Chlorododecane (IIIa). Yield 29%, bp 128°С (10
mm Hg) {130°С (15 mm Hg) [16]}. 13С NMR spectrum,
δ, ppm : 13.63 (С12), 22.54 (С11), 28.95 (С3), 28.98 (С2),
29.00 (С4), 29.16 (С5), 29.27 (С6), 29.40 (С7), 29.98 (С8),
30.00 (С9), 31.77 (С10), 40.75 (С1). Mass spectrum, m/z
Chlorocyclopentane (V). Yield 98%, bp 114°С
(bp 112°С [15]). 13С NMR spectrum, δ, ppm : 22.43
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CHLORINATION OF HYDROCARBONS
1565
(С3,4), 38.61 (С2,5), 60.13 (С1). Mass spectrum, m/z (Irel,
%) : [M]+ 102 (2), 41 (39), 42 (30), 51 (3), 53 (7), 55 (5),
62 (5), 67 (55), 68 (100), 69 (32), 75 (4), 76 (5). Found,
% : С 57.40; Н 8.63; Cl 33.97. C5H9Cl. Calculated, % :
С 57.42; Н 8.67; Cl 33.91. М 104.577.
a glass ampule of 20 mL capacity ( the results of paral-
lel runs materially coincide) under an argon atmosphere
was charged 0.01–0.1 mmol of Fe(C5H5)2, 0.02 mmol
of diethylamine, 1 mmol of adamantane (IX), 2 mmol
of CCl4, and 1 mmol of water воды. The reactor was
pressure-tight closed (the ampule was sealed), and the
reaction mixture was heated at 140°С for 6 h. On the
completion of the reaction the reactor (ampule) was
cooled to ~20°С, opened, the solvent was distilled off,
the residue was recrystallized from methanol.
Chlorocyclohexane (VI). Yield 79%, bp 140–141°С
(bp 142°С [14]). 1Н NMR spectrum, δ, ppm : 3.97 t (1Н,
СНCl), 1.77 m (10Н, 5СН2). 13С NMR spectrum, δ, ppm:
24.69 (С3,5), 25.08 (С4), 36.52 (С2), 36.59 (С6), 59.74
(С1). Mass spectrum, m/z (Irel, %) : [M]+ 118 (2), 83 (24),
82 (62), 81 (11), 68 (6), 67 (100), 66 (9), 56 (9), 55 (45),
54 (36), 53 (11), 51 (5), 43 (2), 42 (7), 41 (51), 40 (7),
39 (28), 38 (5). Found, % : С 60.65; Н 9.75; Cl 29.60.
С6Н11Cl. Calculated, % : С 60.75; Н 9.35; Cl 29.90.
М 118.604.
Chloroadamantane (IXа). Yield 90%, mp 165–
166°С {mp 166°C (ethanol) [13]}. 13С NMR spectrum, δ,
ppm : 31.49 (С3, С5, С7), 35.75 (С4, С6, С10), 47.77 (С2,
С8, С9), 68.21 (C1). Found, % : С 70.34; Н 8.84; Cl 20.82.
С10Н15Cl. Calculated, % : С 70.37; H 8.86; Cl 20.77.
Chlorocyclooctane (VII). Yield 82%, bp 60–62°С
(6 mm Hg) {bp 85–86°С (21 mm Hg) [17]}. 13С NMR
spectrum, δ, ppm : 23.86 (С3,7), 25.59 (С5), 28.19 (С4,6),
35.13 (С2,8), 62.13 (С1). Найде- но, % : С 65.60; Н 10.25;
Cl 24.15. C8H15Cl. Calculated, % : С 65.52; Н 10.31;
Cl 24.17.
1,3-Dichloroadamantane (IХb. Yield 98%, mp
130–132°С {mp 129.5–130°C (ethanol) [13]}. 13С NMR
spectrum, δ, ppm : 33.35 (С6), 33.65 (С5, С7), 45.71
(С4, С8, С9, С10), 56.51 (С2), 66.74 (C1, С3). Found, %
: С 58.54; Н 6.84; Cl 34.62. С10Н14Cl2. Calculated, % :
С 58.55; H 6.87; Cl 34.56.
Chlorocyclododecane (VIII). Yield 38%, bp 92–
94°С (3 mm Hg) {bp 87–90°С (0.4–0.5 mm Hg) [17]}.
13С NMR spectrum, δ, ppm : 24.87 (С3,11), 28.29 (С4,10),
28.82 (С5,6,7,8,9), 40.07 (С2,12), 62.64 (С1). Mass spectrum,
m/z (Irel, %) : [M]+ 200 (2), 39 (56), 40 (11), 41 (100), 42
(21), 43(11), 51 (10), 53 (34), 54 (28), 55 (55), 65 (25),
66 (11), 67 (78), 68 (22), 69 (20), 77 (28), 79 (54), 80
(24), 88 (27), 91 (15), 93 (18), 94 (14), 95 (36), 96 (16),
109 (23), 110 (4), 121 (22), 135 (13), 164 (6). Found, %:
С 71.28; Н 11.40; Cl 17.32. C12H23Cl. Calculated, % :
С 71.08; Н 11.44; Cl 17.48. М 202.764.
ACKNOWLEDGMENTS
The study was carried out under the financial support
of the Ministry of Education and Science of the Russian
Federation (State contract no. 02.740.11.0631).
REFERENCES
1. Stteter, V.H., Krause, M., and Last, W.D., Angew. Chem.,
1968, p. 970.
2. Kovacic, P. and Chang, J., J. Org. Chem., 1971, vol. 36,
p. 3138.
3. Schreiner, P.R., Lauenstein, O., Kolomitsin, I.V., and
Fokin, A.A., Angew. Chem., Int. Ed., 1998, vol. 37, p. 1895.
4. Vedernikov,A.N., Scharifullin, R.R., and Solomonov, B.N.,
Mendeleev Commun., 1996, p. 54.
5. Vedernikov,A.N., Kuramshin,A.I., Sayakhov, M.D., Soba-,
nov,A.A., and Solomonov, B.N., Russ. J. Org. Chem., 1997,
vol. 33, p. 39.
6. Vedernikov, A.N., Sayakhov, M.D., Zazybin, A.G., and
Solomonov, B.N., Russ. J. Org. Chem., 1998, vol. 34,
p. 812.
7. Golubeva, E.N., Nevskaya, S.M., Vorontsov, V.V., andAb-
drashitov, Ya.M., Izv. Akad. Nauk, Ser. Khim., 1997, 1835.
8. Smirnov, V.V., Nevskaya, S.M., and Golubeva, E.N., Neft-
ekhimiya, 2002, vol. 42, p. 22.
Chlorination of adamantane with tetrachloro-
methane in the presence of alcohols. Into a pressure
microreactor of stainless steel of 17 mL capacity or into
a glass ampule of 20 mL capacity ( the results of parallel
runs materially coincide) under an argon atmosphere was
charged 0.03 mmol of catalyst [Fe(acac)3, Fe(C5H5)2,
Fe2(CO)9], 1 mmol of adamantane, 2 mmol of CCl4, and
1 mmol of alcohol. The reactor was pressure-tight closed
(the ampule was sealed), and the reaction mixture was
heated at 160°С for 6 h. On the completion of the reaction
the reactor (ampule) was cooled to ~20°С, opened, the
solvent was distilled off, the residue was recrystallized
from methanol.
Chlorination of adamantane with tetrachloro-
methane in the presence of water. Into a pressure
microreactor of stainless steel of 17 mL capacity or into
9. Khusnutdinov, R.I., Shchadneva, N.A., Baiguzina, A.R.,
Lavrent’eva, Yu.Yu., and Dzhemilev, U.M., Izv. Akad. Nauk,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

KHUSNUTDINOV et al.
1566
Ser. Khim., 2002, p. 1919.
Lavrent’eva, Yu.Yu., Burangulova, R.Yu., and Dzhemi-
lev, U.M., Neftekhimiya, 2004, vol. 44, p. 148.
14. Fluka. Khimicheskie reaktivy dlya laboratornykh i anal-
iticheskikh rabot (Chemicals for Laboratory andAnalytical
Researches), Rossiya, 2009–2010, 1748 p.
15. Aldrich. Catalog. Handbook of Fine Ghemicals, 2009–
2010.
16. Dictionary of Organic Compounds, Buckingham, J., Ed.,
New York: London–Toronto: Chapman and Hall, 1982.
17. Asscher, M. and Vofsi, D., J. Am. Chem. Soc., 1961.
10. Khusnutdinov, R.I., Shchadneva, N.A., Baiguzina, A.R.,
and Dzhemilev, U.M., Izv. Akad. Nauk, Ser. Khim., 2002,
p. 979.
11. Smirnov, V.V., Zelikman, V.M., Beletskaya, I.P., Gol-
ubeva, E.N., Tsvetkov, D.S., Levitskii, M.M., and Ka-
zankova, M.A., Russ. J. Org. Chem., 2002, vol. 38, p. 1004.
12. Bagrii, E.I., Adamantany, poluchenie, svoistva, primenenie
(Adamantanes: Synthesis, Properties, Application), Mos-
cow: Nauka, 1989.
13. Khusnutdinov, R.I., Shchadneva, N.A., Baiguzina, A.R.,
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