Functionalization of alkanes and cycloalkanes by superelectrophiles 15. Carbonylation of cycloheptane, cyclooctane, and isomeric monoalkylcyclohexanes with CO in the presence of CBr4 · 2AlBr3 to form individual esters of tertiary car

Article abstract of DOI:10.1023/A:1015091731172

Cycloheptane, methylcyclohexane, cyclooctane, and ethylcyclohexane were selectively carbonylated with CO. The reactions of cycloalkanes with CO at -40 °C in the presence of the superelectrophilic system CBr₄ · 2AlBr₃ in CH₂

Full text of DOI:10.1023/A:1015091731172

2
394
Russian Chemical Bulletin, International Edition, Vol. 50, No. 12, pp. 2394—2400, December, 2001
Organic Chemistry
Functionalization of alkanes and cycloalkanes by superelectrophiles
5.* Carbonylation of cycloheptane, cyclooctane, and isomeric monoalkylcyclohexanes
with CO in the presence of CBr •2AlBr to form individual esters
1
4
3
of tertiary carboxylic acids of the cyclohexane series
«
I. S. Akhrem, L. V. Afanas´eva, P. V. Petrovskii, S. V. Vitt, and A. V. Orlinkov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
2
8 ul. Vavilova, 117813 Moscow, Russian Federation.
Fax: +7 (095) 135 5085. E-mail: cmoc@ineos.ac.ru
Cycloheptane, methylcyclohexane, cyclooctane, and ethylcyclohexane were selectively
carbonylated with CO. The reactions of cycloalkanes with CO at –40 °C in the presence of
the superelectrophilic system CBr •2AlBr in CH Br followed by treatment of the reaction
4
3
2
2
mixtures with alcohols afforded esters of 1-methylcyclohexanecarboxylic acid (in the reac-
tions of cycloheptane and methylcyclohexane) or esters of 1-ethylcyclohexanecarboxylic acid
(
in the reactions of cyclooctane and ethylcyclohexane) in 70—80% yields with respect to
CBr •2AlBr . The reaction of 1,3-dimethylcyclohexane at –40 °C and the reactions of
4
3
cyclooctane and ethylcyclohexane and at –20 °C proceeded nonselectively to form four
isomeric esters C H COOR.
8
15
Key words: tetrabromomethane, aluminum bromide, superelectrophiles, cycloheptane,
methylcyclohexane, cyclooctane, ethylcyclohexane, carbon monoxide, esters of 1-alkyl-
cyclohexanecarboxylic acids, functionalization, carbonylation.
The discovery of new systems which activate alkanes
alkanes and cycloalkanes have been subjected to selec-
2
under mild conditions gave impetus to extensive studies
on the synthesis of organic compounds from accessible
alkanes and cycloalkanes. Of one-step functionalization
reactions of saturated hydrocarbons, the reactions with
CO have considerable potential for organic synthesis.3
The insertion of CO into nonactivated C—H bonds of
hydrocarbons was carried out using transition metal
tive carbonylation. The selectivities of the reactions of
saturated hydrocarbons decrease as the length of the
hydrocarbon chain increases, which is associated with
the increase in the number of C—H bonds possessing
close reactivities. In addition, long-chain carbenium
ions, which are intermediates in electrophilic transfor-
mations of saturated hydrocarbons, are more readily
subjected to fragmentation than their lower homologs,
which results in low selectivities of the carbonylation
reactions. The stabilities of alkyl radicals involved in
radical reactions and of M—C bonds in organometallic
complexes,2
c,d,4
protic and aprotic superacids,
5
1a—d,2e
6
and radical species. However, only a limited number of
*
For previous communications, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2286—2291, December, 2001.
066-5285/01/5012-2394 $25.00 © 2001 Plenum Publishing Corporation
1

Selective carbonylation of cycloalkanes C —C8
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2395
6
5
complexes, which are responsible for carbonylation in
the presence of transition metal complexes, change in
the same direction.
philic reagent, i.e., the electrophilicity of the system
changes only slightly in the course of the reaction. It is
known that superelectrophilic systems containing
polyhalomethanes in combination with aluminum bro-
mide can efficiently generate carbenium ions from satu-
A decrease in selectivity with the increase in the
length of the hydrocarbon chain can be exemplified by
the reactions5c of n-alkanes C —C with CO in a
9
rated hydrocarbons and initiate selective carbonylation
6
8
HF—SbF medium. Carbonylation of hexane followed
of ethane,1a propane,1h butane, and pentane,1b which
prompted us to examine the possibility of selective
5
by hydrolysis of the reaction mixture afforded C -acids
7
with secondary and tertiary radicals and a mixture of
lower carboxylic acids with the total number of carbon
atoms from three to six. Under the same condi-
tions, heptane and octane gave exclusively destructive
carbonylation of cycloalkanes C —C and isomeric cyclo-
7 8
hexanes under the action of these systems.
Results and Discussion
5
c
carbonylation products, viz., C - and C -acids.
5
6
The selectivity of carbonylation of alkanes and
cycloalkanes would be expected to be higher in reactions
involving systems which exhibit high activity at low
temperatures. Indeed, under these conditions, fragmen-
tation of carbenium ions as well as decarbonylation of
At the temperature from –20 to –40 °C, the reaction
of cycloheptane with CO in the presence of the
superelectrophilic system CBr ·2AlBr (S) followed by
4
3
i
treatment of the reaction mixture with Pr OH gave
rise to the only carbonylation product, viz., ester 1
Scheme 1).
7
the resulting acylium cations are suppressed. It is known
(
that low temperature is favorable for the formation of
8
branched structures. Hence, one would expect that the
Scheme 1
reactions of saturated hydrocarbons with CO in the
presence of powerful superelectrophiles at low tempera-
tures will afford tertiary carboxylic acids or their deriva-
tives. It should be noted that the reactions involving
highly active systems proceed in high yields over a short
period in the presence of equimolar amounts of
electrophiles as well. Reduction of the latter with hydro-
carbons leads to a decrease in superelectrophilicity of
the system, which is favorable for preservation of
functionalization products. On the contrary, the reac-
tions with less reactive electrophiles proceed slowly at
higher temperatures and require an excess of an electro-
Me
1
2
) CO, CBr •2AlBr3
4
COOPri
i
) Pr OH
Me
1
The same product was obtained from methyl-
cyclohexane (Table 1). The mass spectrum of ester 1
Table 1. Carbonylation of cycloalkanes under the action of CO (1 atm.) initiated by the CBr •2AlBr system (S) in a solution
4
3
in CH Br
2
2
Run
Cycloalkane
RH
[RH] : [S]
T/°Ñ
t/h
Products of carbonylation and
subsequent alcoholysis with Pr OH
Yield
(mol.%)b
i
a
1
Cycloheptane
Ditto
1 : 1
1 : 1
1 : 1
1 : 1
1.2 : 1
2 : 1
2 : 1
2 : 1
1 : 1
1.2 : 1
1.2 : 1
1.2 : 1
1 : 1
1 : 1
1.2 : 1
1 : 1
–20
–40
–40
–40
–40
–20
–20
–20
–30
–40
–40
–40
–40
–40
–40
–40
0.5
1
2
0.5
1
0.5
0.7
1
1
1
0.5
1
1
1
1
1
1
1
36
40
82
67
74
74
46
47
27
73
67
68
48
40
69
90
2
3
4
» »
Methylcyclohexane
Ditto
5
6
7
Cyclooctane
Ditto
3a + 3b + 3c + 2 (5 : 3 : 4 : 1)
3a + 3b + 3c + 2 (4 : 2 : 4 : 1)
3a + 3b + 3c + 2 (3 : 2 : 3 : 1)
3a + 3b + 3c + 2 (5 : 3 : 4 : 1)
8
9 c
» »
» »
» »
» »
» »
» »
» »
1
1
1
1
1
1
1
0 d
3a + 3b + 3c + 2 (11 : 6 : 1 : 5)
1
2
2
2
2
2
3 c
4 e
5
2
1
0.5
Ethylcyclohexane
1,3-Dimethylcyclohexane
2
6
3a + 3b + 3c + 2 (11 : 5 : 8 : 1)
a
b
c
The ratio of the isomers is given in parentheses in order of increasing retention time; ester 2 has the largest TR.
With respect to S.
The CBr •3AlBr system was used instead of CBr •2AlBr .
4
3
4
3
d
e
The experiment was carried out under a CO pressure of 30 atm.
The CCl •3AlBr system was used instead of CBr •2AlBr .
4
3
4
3

2
396
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Akhrem et al.
5
3
6
2
7
CH3
10
CH3
1
4
Table 2. The H and 13C NMR spectroscopic data for ester
1
COOCH
8
(1)
9
CH3
1
1
Atom
δ (J/Hz)
1H
13C
Experiment
1.10 (s)
1.29 (d, 3J = 6.4)
1.10—2.10 (m)
1.10—2.10 (m)
1.10—2.10 (m)
5.00 (septet, 3J = 6.4)
—
—
Calculations
Experiment
Calculations
C(7)H3
C(10)H , C(11)H3
1.05
1.31
1.23—1.78
1.23—1.78
1.23—1.78
4.80
26.50
21.71
35.49
23.19
25.71
66.84
42.85
176.74
25.3±3.4
21.9±0.1
35.5±0.4
21.6±1.0
25.7±1.5
68.5±0.4
43.0±3.0
178.7±1.4
3
C(2)H , C(6)H2
2
C(3)H , C(5)H2
2
C(4)H2
C(9)H
C(1)
—
—
C(8)
+
(
8
m/z (Irel (%)): 184 [M] (3), 142 (11), 97 (95), 96 (15),
Scheme 2
1
7 (25), 81 (20), 69 (12), 67 (13), 55 (100)) and the H
and 13C NMR spectra presented in Table 2 prove the
structure of compound 1. The chemical shifts of the
signals observed in the NMR spectra of the esters syn-
thesized were compared with those calculated using the
ACD/C- and ACD/H-NMR programs.
Et
1) CO, CBr4•2AlBr3
COOPri
i
2
) Pr OH
Carbonylation of cycloheptane and methylcyclo-
Et
2
hexane proceeded rather smoothly; bromides C H Br
7
13
were obtained as by-products in 5—20% yields. These
compounds were identified as bromides based on the
GLC/MS data, viz., from the positions of the peaks in
the chromatograms and from the fact that the mass
(13), 101 (51), 81 (50), 69 (10), 57 (17), 55 (81), 53
(16). The experimental and calculated H and 13C NMR
spectroscopic data for ester 2 are given in Table 3.
The transformation products of cyclooctane also con-
1
+
spectra have the fragmentation ion peaks [M – Br]
+
(
m/z 97) and [M – HBr] (m/z 96) and rather intense
ion peaks at m/z 79—82.
tained a mixture of isomeric bromides C H Br whose
8 15
At –40 °C and 1 atm. of CO, cyclooctane also gave
virtually the only carbonylation product after alcoholy-
sis, viz., ester 2, in ∼ 70% yield (Scheme 2; see Table 1).
yield varied from 10 to 30% depending on the reaction
conditions. These isomers were identified as cycloalkyl
bromides based on the GLC/MS data. The isomers were
localized in a narrow chromatographic zone and the
mass spectra of each isomer have intense fragmentation
+
The mass spectrum of ester 2, m/z (Irel (%)): 198 [M]
(
5), 170 (10), 156 (15), 127 (15), 111 (90), 110 (51), 109
5
3
6
2
7
CH CH
2 3
8
1
2
CH3
1
4
Table 3. The H and 13C NMR spectroscopic data for ester
1
COOCH
(2)
CH3
9
10
1
1
Atom
δ (J/Hz)
1H
13C
Experiment
Calculations
Experiment
Calculations
C(8)H3
C(11)H , C(12)H3
0.93 (t, 3J = 8.0)
1.22 (d, 3J = 6.0)
1.00—2.10 (m)
1.00—2.10 (m)
1.00—2.10 (m)
1.00—2.10 (m)
0.83
1.31
8.41
21.75
33.82
23.30
26.09
33.40
66.66
46.93
175.59
9.6±1.2
21.9±0.1
34.8±4.0
21.7±0.8
26.6±1.0
28.0±4.9
68.5±0.4
47.3±2.5
178.1±1.4
3
C(2)H , C(6)H2
1.10—1.80
1.10—1.80
1.10—1.80
1.10—1.80
4.86
2
C(3)H , C(5)H2
2
C(4)H2
C(7)H3
C(10)H
C(1)
5.00 (septet, 3J = 6.0)
—
—
—
—
C(9)

Selective carbonylation of cycloalkanes C —C8
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2397
6
+
+
ion peaks at m/z 111 [M – Br] and 110 [M – HBr]
mides were obtained as by-products in 27% yield.
and rather intense ion peaks at m/z 79—82 (Br, HBr)
characteristic of bromides.
GLC/MS analysis showed that the reactions of
cyclooctane taken in an excess with respect to the
A decrease in selectivity of carbonylation as the pressure
of CO is increased has been described in the literature10
and has been attributed to rapid nonselective capture of
all carbocations in the reaction mixture in the presence
superelectrophile afforded isomeric cycloalkanes C H ,
of an excess of CO in the system. By contrast, only
carbenium ions, which are predominantly present in the
reaction mixture, are involved in the reaction if CO is
deficient.
8
16
which were identified as 1,3-dimethylcyclohexane (the
major component), 1,2- and 1,4-dimethylcyclohexanes,
ethylcyclohexane, and unconsumed cyclooctane based
on the NBS 75Ê library search. Two isomeric hydrocar-
bons C H were also present in small amounts. The use
The tertiary methylcyclohexyl cation (1´), which is a
precursor of acylium cation 1″ preceding ester 1
(Scheme 3), is generated from cycloheptane and
methylcyclohexane due to its substantially higher stabil-
ity as compared to the isomeric secondary cation 1´´´
8
14
of a higher excess of AlBr in the CBr —nAlBr system
3
4
3
(
n was changed from 2 to 3) led to a decrease in the
yield of ester 2 and an increase in the yield of bromides.
Ethylcyclohexane behaved analogously to cyclooctane
and also gave (at –40 °C) ester 2 with high selectivity
and in similar yield (see Scheme 2, Table 1).
Unlike methylcyclohexane and cycloheptane whose
reactions with CO proceeded selectively both at –40 °C
–
1
7
(the difference in the energies is ∼ 10 kcal mol ).
Scheme 3
AlBr3
AlBr3
and –20 °C, cyclooctane gave a mixture of four isomeric
CX3+AlBr3X–
CX3+Al Br X
–
CX4
2
6
i
esters C H COOPr in a ratio of 5 : 3 : 4 : 1 (GLC/MS)
8
15
even at –30 °C, ester 2 being formed in the lowest yield
∼ 8% of the total yield of the mixture of isomers). Based
CX3+
CO
PrOH
i
(
1
on the data from mass spectrometry, the other three
isomers, which were observed along with ester 2 in the
same chromatographic zone, have presumably the struc-
tures of esters of 1,2-, 1,3-, and 1,4-dimethylcyclo-
hexanecarboxylic acid (3). This conclusion was based on
the character of the mass spectra of the isomers. These
spectra have molecular ion peaks and similar sets of
fragmentation ion peaks, which differ only in intensities
CHX3
+
Me
1´
CO+
Me
Me
1´´
CX3+
+
(
see Experimental). The character of fragmentation of
CHX3
these compounds is in complete agreement with the
presence of the COOPr group (the presence of ion
peaks at m/z 156 [M – C H ] , 111 [M – COOPr] , 87
i
1´´´
+
+
3
6
+
[
COOPr] , etc.). The fact that the mass spectra of
The reaction of cyclooctane with an electrophile
affords the cyclooctyl cation (2´), which undergoes
isomerization into more stable tertiary carbenium ions
to give a series of dimethylcyclohexyl cations (3´) and
the ethylcyclohexyl cation (2´´). The addition of CO to
cations 3´ and 2´´ yields acylium cations 3´´ and 2´´´,
which are transformed into esters 3 and 2, respectively,
isomers 3 contain no fragmentation ion peaks at m/z 170
+
[
M – C H ] (unlike the mass spectrum of ester 2)
2 4
characteristic of the McLafferty rearrangement gives
grounds to exclude structures containing the ethyl group
in the cycloalkyl fragment. Hence, we had actually to
choose between dimethylcyclohexane and trimethylcyclo-
pentane derivatives. We rejected the fact that esters 3
belong to the trimethylcyclopentane series based on the
published data on their low thermodynamical stabilities
as compared to those of isomeric cyclohexane com-
pounds. The assignment of esters 3 to dimethylcyclo-
hexane derivatives is consistent with the formation of
analogous isomers upon carbonylation of 1,3-dimethyl-
cyclohexane (see below).
The reaction of cyclooctane with CO at –20 °C gave
rise to the same four isomers whose ratio depended only
slightly on the reaction time (0.5—1 h), the content of
ester 2 being only 8—11% of the total weight of the
mixture of esters. The reaction of cyclooctane with CO
at –40 °C under a CO pressure of 30 atm. afforded (in a
total yield of 73%) a qualitatively similar mixture of the
same isomeric esters containing ∼ 20% of ester 2. Bro-
i
under the action of Pr OH (Scheme 4).
Semiempirical PM3 quantum-chemical calculations
demonstrated that 2´´ is the most stable cation among all
the isomeric cations of the cyclohexane series. The
difference between the energy of the formation of cat-
–
1
ion 2´´ (∆H = 150.5 kcal mol ) and that of equally stable
f
–
1
dimethylcyclohexyl cations 3´ (∆H = 148.4 kcal mol )
f
–
1
is 2.1 kcal mol . It is known that a decrease in the
temperature is favorable for the shift of the equilibrium
to the most stable cation.7 This fact accounts for the
selective formation of ester 2 from cyclooctane at –40 °C.
At the same time, the resistance of the acylium cations
,8
to decarbonylation decreases as the stability of the de-
rived carbenium ions increases.8
,11
Cation 2´´´ (see
Scheme 4) is less resistant to decarbonylation than
isomeric ions 3´´ producing less stabilized carbocations 3´.

2
398
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Akhrem et al.
Scheme 4
methylcycloheptyl cation indicates that the latter under-
goes rapid isomerization into cations containing the
cyclohexane core.
2
Scheme 5
i
PrOH
Me
Me
1
) CO
COOR´
Et
Et
+
3
3´
+
CO
CO+
2) R´OH
a
1
2
) CO (b)
2
´
2´´
2´´´
) R´OH
CX3+
Me
Me
Me
Me
+
CX3
+
Me
Et
H
+
Me
5
´
3
´
c
CO –CO
Et
d
Me
Me
COOPri
+
i
PrOH
CO+
+
Me
Me
Me
1) CO
) R´OH
2
3
´´
3
2
At –40 °C, acylium cations 2´´´ and 3´´ are apparently
stable. As the temperature is raised from –40 to –30 °C,
the rate of decarbonylation of 2´´´ becomes noticeable.
Since this rate is higher for 2´´´ than for acylium cations
Isomerization reactions of cycloalkanes under the
action of Lewis acids accompanied by ring contraction
are well known.12 The regularities observed in the present
study agree with the published relative rate constants for
the contraction of the seven- and eight-membered rings
(25 and 16, respectively; the rate constant for the isomer-
ization of ethylcyclopentane into methylcyclohexane is
taken as 100%).13 It should be noted that cycloheptane
is quantitatively isomerized into methylcyclohexane,
whereas cyclooctane is completely transformed into a
mixture consisting of ethylcyclohexane (90%) and
dimethylcyclohexanes (10%).
3
´´, the major carbonylation products (3) are formed via
cations 3´ and 3´´.
Unlike the reactions of unsubstituted cycloalkanes
C and C and monoalkylcyclohexanes, carbonylation of
7
8
1
,3-dimethylcyclohexane proceeded nonselectively even
at –40 °C to give a four-component mixture containing
esters 2 and 3, which was identical with that generated
from cyclooctane (and ethylcyclohexane) at the tem-
perature in the range from –20 to –30 °C under an
atmospheric pressure of CO or at –40 °C under 30 atm.
of CO. The ratio of three isomers 3 was very close to
that observed in the reactions with cyclooctane per-
formed at –20 °C. However, the content of ester 2 was
only 4%. The total yields of the carbonylation and
bromination products were 90% and ∼ 10%, respectively.
The fact that carbonylation of 1,3-dimethylcyclohexane
proceeded nonselectively is apparently associated with
higher rates of intramolecular isomerizations of the
initially generated 1,3-dimethylcyclohexyl cation 5´
To our knowledge, carbonylation of cycloheptane,
cyclooctane, ethylcyclohexane, and 1,3-dimethyl-
cyclohexane has not been reported previously. Car-
bonylation of methylcyclohexane in a protic superacidic
medium (HF—SbF ) followed by hydrolysis of the reac-
5
tion mixture afforded5a a mixture of 1-methylcyclo-
hexanecarboxylic acid (10%) and isomeric methylcyclo-
hexanoic acids (90%). The reaction was accompanied
also by the ring opening to form isomeric hexanes.
Carbonylation of cyclooctene afforded 1-ethylcyclo-
hexanecarboxylic acid in 45% yield. This reaction gave
rise to high-molecular-weight carboxylic acids as the
major products.14 Carbonylation of methylcyclohexane
(
Scheme 5, reaction a) as compared to the rate of the
intermolecular addition of CO to cation 5´ (reaction b).5
Presumably, the formation of small amounts of ester 2
provides evidence that the ring contraction and expan-
sion in the cycloalkyl cations (reactions c and d) are
reversible. The absence of carbonylation products of the
c
under the action of CO in 98% H SO (or BF •H O) in
the presence of copper or silver salts (as sources of the
corresponding metal carbonyls) and olefins or alcohols
2
4
3
2

Selective carbonylation of cycloalkanes C —C8
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2399
6
(
as sources of the corresponding carbenium ions) af-
MS (EI, 70 eV), m/z (Irel (%)) of isomeric esters
i
+
cyclo-Me C H COOPr (3) (see Table 1, run 6): 3a, 198 [M]
forded 1-methylcyclohexanecarboxylic acid in 20—70%
yields.15 The drawback of this procedure is the necessity
of using copper or silver salts as well as olefins or
alcohols which generate the corresponding acids
in amounts comparable with the yield of the target
product.
2
6
9
(7), 156 (13), 139 (6), 138 (3), 129 (70), 116 (2), 113 (2), 111
(
(
(
(
91), 110 (17), 109 (28), 95 (34), 91 (6), 87 (88), 83 (21), 82
+
9), 70 (86), 69 (100), 67 (18), 55 (69); 3b, 198 [M] (9), 156
21), 139 (5), 138 (4), 129 (5), 115 (3), 112 (8), 111 (95), 110
24), 109 (14), 95 (21), 91 (67), 87 (24), 83 (20), 81 (12), 70
(82), 69 (100); 3c, 198 [M]+ (3), 157 (6), 156 (5), 139 (4), 129
To summarize, the use of superelectrophiles based
on polyhalomethanes allowed us to carry out selective
(8), 112 (9), 111 (100), 110 (22), 109 (9), 95 (24), 91 (5), 87
(5), 83 (3), 82 (5), 81 (8), 70 (10), 69 (99), 67 (14).
functionalization of cycloalkanes C and C and iso-
7
8
We thank A. L. Chistyakov for performing quantum-
chemical calculations for the dimethyl- and ethyl-
cyclohexyl cations.
meric monosubstituted cyclohexanes under the action of
CO. Thus, it was demonstrated that the range of satu-
rated hydrocarbons which can be subjected to selective
carbonylation is broader than has been assumed before.
At low temperature, carbonylation of cycloheptane,
cyclooctane, and isomeric monosubstituted cyclo-
hexanes affords compounds of the cyclohexane se-
ries containing the carbonyl group at the tertiary car-
bon atom.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 99-03-
3
3006).
References
1
. (a) A. V. Orlinkov, I. S. Akhrem, and S. V. Vitt, Mendeleev
Experimental
Commun., 1999, 198; (b) I. S. Akhrem, A. V. Orlinkov, and
S. V. Vitt, Tetrahedron Lett., 1999, 40, 5897; (c) I. S.
Akhrem, I. M. Churilova, A. V. Orlinkov, L. V. Afanas´eva,
S. V. Vitt, and P. V. Petrovskii, Izv. Akad. Nauk, Ser.
Khim., 1998, 947 [Russ. Chem. Bull., 1998, 47, 924 (Engl.
Transl.)]; (d) I. S. Akhrem, Top. Catal., 1998, 6, 27;
(e) I. S. Akhrem, A. V. Orlinkov, and S. V. Vitt, Inorg.
Chim. Acta, 1998, 280, 355; (f) A. V. Orlinkov, I. S.
Akhrem, L. V. Afanas´eva, E. I. Mysov, and M. E. Vol´pin,
Mendeleev Commun., 1997, 61; (g) A. V. Orlinkov, I. S.
Akhrem, S. V. Vitt, and M. E. Vol´pin, Tetrahedron Lett.,
1996, 37, 3363; (h) I. S. Akhrem, A. V. Orlinkov, L. V.
Afanas´eva, and M. E. Vol´pin, Izv. Akad. Nauk, Ser.
Khim., 1996, 1214 [Russ. Chem. Bull., 1996, 45, 1154
(Engl. Transl.)].
2. (a) G. A. Olah and G. K. S. Prakash, in The Chemistry of
Alkanes and Cycloalkanes, Part 13, Eds. S. Patai and
Z. Rappoport, Wiley-Intersci., Chichester, 1992, 624;
(b) G. A. Olah (Nobel Lecture), Angew. Chem., Int. Ed.
Engl., 1995, 13/14, 1393; (c) B. A. Arndtsen, R. G.
Bergman, T. A. Mobley, and T. H. Peterson, Acc. Chem.
Res., 1995, 28, 154; (d) C. L. Hill, Synlett, 1995, 127;
(e) I. S. Akhrem and A. V. Orlinkov, Izv. Akad. Nauk, Ser.
Khim., 1998, 771 [Russ. Chem. Bull., 1998, 47, 740 (Engl.
Transl.)].
Cycloalkanes C7 and C , CBr , and AlBr (Aldrich)
8
4
3
were used without additional purification. Dibromomethane
Aldrich) was dried with calcined MgSO4 and then distilled
over CaH2.
Qualitative and quantitative analysis of the reaction mix-
(
tures was carried out by GLC on a Finnigan 9001 chromato-
graph equipped with a flame ionization detector and a quartz
capillary column (30 m ½ 0.3 mm; DB-5.625 as the stationary
phase, helium as the carrier gas) in the linear temperature
programming mode. The GLC/MS analysis was performed on
an AEI 1073 instrument (70 eV) equipped with an analogous
capillary column. The H and 13C NMR spectra were recorded
1
on a Bruker AMX-400 spectrometer (400 MHz for 1H;
3
1
00 MHz for 1 C) in the JMODECHO mode with Me Si as
4
the internal standard.
The reactions of cycloheptane, methylcyclohexane,
cyclooctane, ethylcyclohexane, and 1,3-dimethylcyclohexane
with CO were carried out under an atmospheric pressure at the
temperature from –20 to –40 °C in the presence of
CBr •2AlBr or CCl •3AlBr (S) in a solution of CH Br or
4
3
4
3
2
2
CH Cl for 0.5—2 h. The molar ratio [RH] : [S] was varied
2
2
from 2 : 1 to 1 : 1. The yields of the products were determined
by GLC with the use of the internal standard (undecan-2-one)
taking into account the correction coefficient.
3. (a) H. Bahrman, Koch Reactions in New Syntheses with
Carbon Monoxide, Ed. J. Falbe, Springer-Verlag, Berlin,
1980, 372; (b) M. Koch and W. Haaf, Org. Synth.,
1964, 44, 1.
The samples for H and 13C NMR spectroscopy (CDCl3)
were prepared by concentrating ethereal extracts (without the
internal standard) in vacuo.
1
Carbonylation of cycloalkanes (general procedure). A solu-
4. (a) T. Sakakura, T. Sodeyama, K. Sasaki, and K. Wada,
J. Am. Chem. Soc., 1990, 112, 7221; (b) P. Margl, T. Ziegler,
and P. Blochl, J. Am. Chem. Soc., 1996, 118, 5412;
(c) K. I. Satoh, J. Watanabe, K. Takaki, and Y. Fujiwara,
Bull. Chem. Soc. Jpn., 1993, 63, 3755; (d) K. Nakata,
Y. Yamaoka, T. Miyata, Y. Taniguchi, K. Takaki, and
Y. Fujiwara, J. Organomet. Chem., 1994, 437, 329;
(e) Y. Fujiwara, K. Takaki, and Y. Taniguchi, Synlett,
1996, 591 (and references cited therein).
5. (a) R. Paatz and G. Weisgerber, Chem. Ber., 1967, 100,
984; (b) H. Hogeveen, J. Lukas, and C. Roobeck, J. Chem.
Soc., Chem. Commun., 1969, 920; (c) N. Yoneda,
Y. Takahashi, T. Fukuhara, and A. Suzuki, Bull. Soc.
tion of a mixture of CBr4 and anhydrous AlBr (taken in a
3
molar ratio of 1 : 2) in CH Br (1.5—2 mL per gram of AlBr )
2
2
3
was cooled with stirring to a temperature from –20 to –40 °C
and the flask was filled with gaseous CO to which the required
amount of cycloalkane was added (see Table 1). The reaction
mixture was stirred under conditions given in Table 1. Then
i
Pr OH (3 mL per gram of AlBr ) was added and the reaction
3
mixture was heated to 0 °C for 30 min. Then water was added
and the organic products were extracted with ether. The
extract was washed with water until the reaction became
neutral, dried with calcined MgSO , and analyzed by GLC
4
and GLC/MS.

2
400
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Akhrem et al.
Chem. Jpn., 1986, 59, 2819; (d) J.-C. Culmann, G. Cherry,
R. Lost, and J. Sommer, Tetrahedron Lett., 1989, 30, 701;
of Chemical Processes], Khimiya, Moscow, 1985 (in
Russian).
(
3
e) J. Sommer and J. Bukala, Acc. Chem. Res., 1993, 26,
70; (f) O. Farooq, M. Marcelli, G. K. S. Prakash, and
9. I. S. Akhrem, A. V. Orlinkov, and M. E. Vol´pin, J. Chem.
Soc., Chem. Commun., 1993, 671.
G. A. Olah, J. Am. Chem. Soc., 1988, 110, 864; (g) G. A.
Olah, Synthesis, 1992, 1090; (h) K. Takeuchi, F. Akiyama,
T. Miyazaki, I. Kitagawa, and K. Okamoto, Tetrahedron,
10. P. P. Gushchin, E. V. Lebedev, and T. E. Pivovarova,
Neftekhimiya [Petrochemistry], 1972, 12, 383 (in Russian).
11. A. V. Orlinkov, I. S. Akhrem, and M. E. Vol´pin, Usp.
Khim., 1991, 60, 1049 [Russ. Chem. Rev., 1991, 60, 920
(Engl. Transl.)].
12. M. B. Turova-Polyak and F. P. Sidel´nikova, Zh. Org.
Khim., 1941, 11, 817 [J. Org. Chem. USSR, 1941, 11 (Engl.
Transl.)].
13. A. A. Petrov, Khimiya naftenov [Chemistry of Naphthenes],
Nauka, Moscow, 1971, 191 pp. (in Russian).
14. H. Bahrman, Koch Reactions in New Syntheses with Carbon
Monoxide, Ed. J. Falbe, Springer-Verlag, Berlin, 1980, 395.
15. (a) Y. Souma and H. Sano, J. Org. Chem., 1973, 38, 3633;
(b) Y. Souma and H. Sano, Bull. Soc. Chim. Jpn., 1974, 47,
1714; (c) Y. Souma and H. Sano, Bull. Soc. Chim. Jpn.,
1976, 49, 3296.
1
987, 43, 701.
. (a) M. Lin and A. Sen, J. Chem. Soc., Chem. Commun.,
992, 892; (b) W. T. Boese and S. Goldman, Tetrahedron
6
1
Lett., 1992, 33, 2119; (c) W. T. Boese and S. Goldman,
J. Am. Chem. Soc., 1992, 114, 350; (d) C. L. Hill and B. S.
Jaynes, J. Am. Chem. Soc., 1995, 117, 4704; (e) R. R.
Ferguson and R. H. Crabtree, J. Org. Chem., 1991, 56,
5
503; (f) S. Kato, T. Iwakawa, S. Sakaguchi, and Y. Ishii,
J. Org. Chem., 1998, 63, 222; (g) I. Ryu and M. Soneda,
Angew. Chem., Int. Ed. Engl., 1996, 35, 1050.
7
8
. H. Hogeveen, in Advances in Physical Organic Chemistry,
Ed. V. Gold, Academic Press, London, 1973, 10, 29.
. (a) D. R. Stull, E. F. Westrum, and G. R. Sinke,
in Chemical Thermodynamics of Organic Compounds,
Wiley-Intersci., New York, 1969; (b) Yu. M. Zhorov,
Termodinamika khimicheskikh protsessov [Thermodynamics
Received December 26, 2000;
in revised form May 30, 2001