Preparation of phthalates via carbonylation of o-dibromobenzenes in solutions of Pd catalysts and reactivity of Ar?Br bonds

Article abstract of DOI:10.1134/S1070363217100048

Carbonylation of o-dibromobenzene and its derivatives in the presence of palladium phosphine complexes with NaOAc or Et₃N additive leads to the formation of phthalates in high yield under mild conditions. Correlation NMR spectroscopy data and s

Full text of DOI:10.1134/S1070363217100048

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 10, pp. 2269–2275. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.R. Elman, A.M. Perepukhov, L.V. Ovsyannikova, A.V. Maksimychev, 2017, published in Zhurnal Obshchei Khimii, 2017, Vol. 87,
No. 10, pp. 1609–1615.
Preparation of Phthalates via Carbonylation
of o-Dibromobenzenes in Solutions of Pd Catalysts
and Reactivity of Ar−Br Bonds
a
b
a
b
A. R. Elman *, A. M. Perepukhov , L. V. Ovsyannikova , and A. V. Maksimychev
a
Rostkhim, ul. B. Sadovaya 1, str. 4, Moscow, 123995 Russia
*
e-mail: elmanar@yandex.ru
b
Moscow Institute of Physics and Technology (State University), Moscow, Russia
Received April 24, 2017
Abstract—Carbonylation of o-dibromobenzene and its derivatives in the presence of palladium phosphine
complexes with NaOAc or Et N additive leads to the formation of phthalates in high yield under mild
3
conditions. Correlation NMR spectroscopy data and semiempirical calculations have shown that the reactivity
of the C–Br bond is enhanced with the increase in the positive charge at the carbon atom, in line with the
results of kinetic experiments.
Keywords: carbonylation, o-dibromobenzene derivatives, palladium complex, Ar–Br bond reactivity
DOI: 10.1134/S1070363217100048
Aromatic polycarboxylic acids and their esters are
widely applied as monomers for the production of
thermostable fibers, liquid-crystalline polymers, protec-
tive coatings, dyes, plasticizers, and repellents as well
as in the synthesis of medicines and other valuable
products [1]. Furthermore, phthalic acid esters in the
synthesis of medicinal preparations of phthalocyanine
Liquid-phase catalytic carbonylation of aryl halide
via the ArX + 2CO + 2ROH = Ar(COOR) + 2HX
2
2
reaction (X being a halogen, R = Н or Alk) is among
the most promising approaches to the preparation of
phthalates and other derivatives of aromatic acids. In
contrast to conventional methods of alkylaromatic com-
pounds oxidation [4], the mentioned method exhibits
several important advantages such as high yield and
selectivity with respect to the target product, relatively
mild conditions, and high reaction rate. However, the
available reference data have mainly addressed
processes of carbonylation of aryl monohalides
(
Pc) structures used for photodynamic therapy and dia-
1
3
gnostics of tumors [2], promising C-labeled sub-
stances for various diagnostic issues [3] including dia-
gnostics of tumors by means of С NMR (Scheme 1)
1
3
are being developed.
(
Ar–X) leading to benzoic acid and its derivatives [5].
Scheme 1.
The data on the synthesis of aromatic poly-
*
NaOOC
*
COONa
carboxylic acids via carbonylation of aromatic poly-
halides as well as on the effects of the substituents on
the reactivity of the C–Х bonds have been fairly
scarce. For example, carbonylation of 1,2- and 1,4-di-
*
NaOOC
*
COONa
N
M
N
*
*
N
N
iodobenzenes in solutions of Pd(OAc) leads to phthalic
*
2
*
N
and terephthalic acids [6]. 1,8-Diiodonaphthalene can
be converted into diamides of 1,8-naphthalenedicar-
boxylic acid in the presence of the Pd(OAc) –PPh –
N
*
*
N
*
N
*
2
3
R NH catalytic system [7]. The reaction of substituted
2
*
NaOOC
2,4-dibromobenzophenone under СО atmosphere have
afforded diesters in 92% yield, the highest activity
being observed in the cases of catalytic systems based
*
COONa
*
*
NaOOC
COONa
2
269

2
270
ELMAN et al.
Scheme 2.
Br
Br
COOMe
COOMe
COOMe
CO, MeOH
CO, MeOH
Br
on PdCl –dppf [dppf = 1,1'-bis(diphenylphosphino)ferro-
cene] [8].
complex at the C–Br bond of the heteroaromatic ring
explains also the high yield of the products of amino-
carbonylation of 4,5-dibromo-2-methylpyridazin-3(2H)-
one [22].
2
Reactivity of various dichloropyridines in the
presence of Pd-phosphine systems and bases (NaOAc
and Et N) has been demonstrated in [9–11]. For
example, 5-methoxymethyl-2,3-dichloropyridine in the
Yet, in our point of view, the available reference
data are not sufficient for wide practical application of
carbonylation of aromatic polyhalides to obtain
aromatic polycarboxylic acids and their derivatives.
Moreover, the development of efficient synthesis of
3
presence of the Pd(OAc) –dppf–NaOAc system (146°С,
2
1
5 atm СО) has been converted in the diester with
selectivity 99% and yield 90% [11]. The complexes
with dppf have been found more active than these with
13
substituted phthalic esters labeled with the С isotope
1
3
1
,1'-bis(diphenylphosphino)butane (dppb) and other
[for example, RC
tion of
6
H
3
( COOMe)
С -phthalocyanines for medical diagnostics
n
2
] and further prepara-
13
diphosphines, and the nature of the substituent in the
aromatic ring [5-MeOCH or 5-MeOC(О)] practically
does not affect the product yield.
started in our earlier studies [2, 3] is of practical
importance. This work hence aimed to elucidate the
substituent effects on the reactivity of aromatic
bromine atoms using the example of liquid-phase
carbonylation of o-dibromobenzene and its tert-butyl
derivative and to clarify the nature of the activation of
the С–Br bonds in that substrate by the catalysts based
on palladium complexes.
2
The effect of the substituent on carbonylation of
substituted bromobenzenes affording butyl benzoates
has been shown in Ref. [12]: the yield of the ester in
the presence of the Pd(OAc) –dtbpx–Cs CO system
2
2
3
[dtbpx = bis(di-tert-butylphosphino)-o-xylene] (80°С,
2
.8 atm СО) has ranged between 36 and 95%; the
In the preliminary experiments, we elaborated the
conditions of carbonylation of aryl dibromides using
o-dibromobenzene as the example. The reaction was
acceptor substituents in the para-position with respect
to bromine activate the substrate as compared to the
donor ones, whereas the acceptors in the ortho-position
reduces the reactivity by 15%.
performed in methanol in the presence of the Pd(OAc)2–
PPh or Pd(OAc) –dppf catalytic systems; triethyl-
3
2
Peculiar data on the discussed matter have been
recently published [13, 14]. Ionic liquids noticeably
activate the Pd catalyst in carbonylation of substituted
bromobenzenes, and allow to reduce CO pressure to
amine or sodium acetate was used as the additive.
Chromato–mass spectrometry (GC/MS) analysis of the
reaction mixture revealed that the reaction gave
dimethyl phthalate, methyl 2-bromobenzoate being the
intermediate (Scheme 2).
1
atm [15, 16] and to reach high yields of benzoates
(
90–95%).
The results of the elaboration of the reaction
conditions are collected in the table. It was found that
It has been stated that the activation of aryl halides
ArX by Pd(0) complexes in the carbonylation reactions
14] occurs via the nucleophilic substitution
the Pd(OAc) –PPh –NaOAc catalytic system exhibited
2 3
[
good activity (exp. 1) only under severe conditions
(150°С, рСО = 60 atm): reduction of the pressure
resulted in the decrease in the yield of dimethyl
phthalate (from 100 to 65.2%, exp. 3), despite the
increase in the concentration of o-dibromobenzene.
0
mechanism [17, 18]. The anionic complex L Pd X‾
2
(
Х = Hlg or OAc) is the active form of the Pd(0)
complex (nucleophile), as confirmed by the data on the
increase in the catalyst activity by ionic liquids
0
+
forming the [L Pd X]‾[NR ] species [16]. Further-
The exchange of PPh
3
with dppf significantly
2
4
more, it has been shown that the oxidative addition
activation) of aryl halides to complexes of nickel and
enhanced the activity of the catalytic system and
allowed using milder conditions: for example, other
conditions being the same (exp. 3 and 9), the change of
the ligand led to the increase of dimethyl phthalate
fraction in the products mixture by almost 30% (to
(
cobalt occurs via the nucleophilic attack of the Ar–X
–
bond by anionic complexes L MX of these metals
n
[19–21]. The ease of the nucleophilic attack of the Pd
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

PREPARATION OF PHTHALATES VIA CARBONYLATION
Carbonylation of 1,2-dibromobenzene in dimethyl phthalate in the presence of Pd(OAc)
2271
2
2
Concentration, mol/L·10
Content in the products, %
Conversion
a
Exp. p,
no. atm
t,
°С
τ,
h
of o-dibromo-
additive benzene, %
o-dibromo-
benzene
o-dibro-
mobenzene
dimethyl
phthalate
b
Pd
L
monoester
PPh
10.6
10.4
11.9
3
–NaOAc
1
2
3
60
60
5
150
9.5
9.8
2.8
1.1
1.0
1.2
29.8
100.0
90.1
88.9
0
0
100.0
80.1
65.2
150 9.25
86.5
64.8
8.3
11.6
18.3
150
8.0
28.8
16.5
PPh
9.2
3 3
–Et N
4
5
6
7
8
60
5
150
150
130
8.0
8.0
8.0
25.7
25.7
26.4
26.4
26.4
0.9
0.9
0.9
0.9
1.6
77.2
77.2
60.3
60.3
60.3
100.0
100.0
100.0
68.1
0
0
0
0
3.6
0
100.0
96.4
100.0
42.3
0
9.1
9.4
5
0
3
130 5.67
130 4.83
9.4
32.9
100.0
24.7
0
1
13.6
dppf–NaOAc
9
5
2
2
150
100 7.25
100 5.0
9.0
28.8
28.8
28.8
1.5
1.7
1.7
0.9
0.9
1.8
60.9
60.5
62.6
95.1
80.4
91.4
5.6
18.9
10.0
0
94.4
69.7
83.3
1
1
0
1
11.4
6.7
3
dppf–Et N
1
1
1
1
1
2
3
4
5
6
2
1
100 1.33
100 4.33
100 0.67
100 1.08
100 1.58
26.4
26.4
26.4
26.4
24.7
1.5
1.5
1.5
2.7
2.2
1.9
1.6
1.7
3.1
2.0
60.3
60.3
60.3
60.3
54.5
98.3
99.1
73.2
99.9
99.8
1.8
1.0
1.0
4.3
12.4
0.6
0
97.3
94.7
55.9
99.3
99.8
0
31.7
0.2
1
2.5
0.2
a
b
2
Excess pressure (in Exp. 14, absolute pressure of СО was 1 atm). Pd(OAc) .
above 94%), and even upon further decrease in the
pressure and temperature (to 2 atm and 100°С, exp. 10
and 11) the fraction of dimethyl phthalate still
exceeded 83%, the amount of dppf being much lower
It should be noted that the selectivity of the process
could be enhanced (i.e. the fraction of the monoester in
the products mixture could be decreased) with the
increase in the dppf/Pd ratio and the CO pressure. For
example, the increase in the dppf/Pd ratio from 0.5 : 1
to 1 : 1 led to the decrease in the monoester fraction in
the products mixture from 11.4 to 6.7% (exp. 10 and
11), whereas the increase in рСО from 1 to 3.5 atm
(abs.) resulted in the decrease in the monoester fraction
from 12.4 to 0% (exp. 14–16).
than in the case of PPh (cf. exp. 3). The advantages of
3
the use of dppf were more clear in comparison of exp.
8
(the reaction did not occur) and 13 (dimethyl
phthalate fraction in the products was close to 95%).
Furthermore, triethylamine use as the base was ad-
vantageous over sodium acetate. For example, the
Pd(OAc) –dppf–Et N, 1 : 1 : 20 system (exp. 15)
2
3
allowed quantitative yield of dimethyl phthalate at
00°С and рСО 1 atm (excess) within 1 h. At the same
time, the catalyst turnover frequency under mild
conditions {TOF = [o-dibromobenzene]/([Pd]*τ)} was
increased approximately tenfold (exp. 1 and 15).
The conditions elaborated for carbonylation of o-
dibromobenzene were further used in the study of
reactivity of Br atoms in 4-tert-butyl-1,2-dibromo-
benzene. At the 4-tert-butyl-1,2-dibromobenzene :
1
Pd(OAc) : dppf : Et N ratio of 39 : 1 : 1 : 83 in the
2 3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

2
272
ELMAN et al.
Scheme 3.
t-Bu
t-Bu
13COOMe
13COOMe
13COOMe
t-Bu
Br
Br
t-Bu
13CO, MeOH
Br
Br
13CO, MeOH
meta-ester
13COOMe
para-ester
methanolic solution (100°С, pCO = 3 atm), the yield of
dimethyl 4-tert-butylphthalate was 98%. The GC/MS
analysis of the reaction mixture corresponding to the
incomplete process revealed that the reaction
intermediates were methyl esters of 2-bromobenzoic
acids with a tert-butyl substituent in the aromatic ring,
bonds in the ortho- and para-positions with respect to
the tert-butyl group of the starting 4-tert-butyl-1,2-
dibromobenzene. To do so, we performed the kinetic
experiments and determined the rate constants of the
formation of the intermediate and the final products.
Kinetics of carbonylation of 4-tert-butyl-1,2-dibromo-
+
+
m/z: 270, 272 [M] ; 255, 257 [M – CH ] ; 239, 241
benzene was studied under the following conditions:
3
+
+
–3
[
M – OCH ] ; 227, [M – C H ] . The presence of a
100°С, pCO 2 atm, [Pd(OAc) ] = 7×10 mol/L, 4-tert-
3
3
7
2
strong σ-donor substituent in the starting dibromo-
benzene led to the non-equivalence of the C–Br bond,
and the ratio of the concentrations of the intermediate
monoesters was at least 5 : 1.
butyl-1,2-dibromobenzene : Pd(OAc) : dppf : Et N =
46 : 1 : 1 : 98, methanol as solvent. Typical kinetic
curves are shown in Fig. 1.
2
3
The obtained kinetic curves of carbonylation of 4-
tert-butyl-1,2-dibromobenzene (Fig. 1a) revealed the
shape typical of the serial-parallel processes, and the
consumption of the starting dibromide followed the
first-order reaction kinetics (Fig. 1b) up to high
conversion (disregarding the short induction period).
The convergence of the material balance throughout
the process evidenced no formation of the non-
identified side products.
However, the obtained mass spectra did not allow
reliable elucidation of the position of tert-butyl group
in the aromatic ring of the intermediate monoesters;
therefore, their structures were determined by means of
correlation NMR spectroscopy of the reaction products
13
labeled with С (Scheme 3).
The NMR analysis allowed unambiguous assign-
ment of the three aromatic protons of each of the
1
1
reaction mixture components. The H– H COSY
spectrum contained the signals of spin-spin interaction
of the protons of the t-Bu group with the adjacent
protons (o-Н) of the aromatic ring. The heteronuclear
Basing on the obtained data and assuming the first-
order kinetics of consumption of the intermediate mono-
esters as well as stationary conditions for the concentra-
tion of the dissolved palladium complex, we derived
the kinetic model of the liquid-phase catalytic carbonyla-
tion of 4-tert-butyl-1,2-dibromobenzene (Scheme 4).
1
13
H– C HMBC spectrum contained the signals of the
spin-spin interaction of the protons (o-Н) of the
1
3
13
aromatic ring with the С atoms of the COOMe
group. Since the spectra contained the signals of only
one of the two monoesters (the major one), we con-
cluded that it was the major monoester that contained
the aromatic proton interacting with both tert-butyl and
the ester groups (i.e. positioned between them). Hence,
the major intermediate was identified as methyl 5-tert-
butyl-2-bromobenzoate, the product of substitution of
Br atom in the meta-position with respect to the tert-
butyl group of 4-tert-butyl-1,2-dibromobenzene.
The values of the reaction rate constants obtained
via optimization of the parameters for the kinetic
–3
model were as follows: k (3.8±0.4)×10 , k (0.8±0.4)×
1
2
–3
–3
–3
–1
1
0 , k (5.5±0.8)×10 , and k (21.8±16.0) ×10 min .
3
4
The built model described well the experimental data
see Fig. 1). The rate constants ratio k /k = 4.6 stages
(
1
2
of the monoesters formation evidenced the signifi-
cantly higher reactivity of the C–Br bond in the meta-
position with respect to the tert-butyl group than the
para-bond, that fact likely being related to the
localization of the positive charge at the meta-carbon
atom of 4-tert-butyl-1,2-dibromobenzene caused by
Elucidation of the structure of intermediate mono-
esters allowed the study of the reactivity of the C–Br
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

PREPARATION OF PHTHALATES VIA CARBONYLATION
(a) (b)
ln с
2273
τ, min
с, mol/L
1
2
3
4
τ, min
Fig. 1. Kinetics of carbonylation of 4-tert-butyl-1,2-dibromobenzene in methanol (a) and determination of the reaction order with
–
3
respect to 4-tert-butyl-1,2-dibromobenzene (b). [Pd(OAc)
2 2
] = 7×10 mol/L, 4-tert-butyl-1,2-dibromobenzene–Pd(OAc) –dppf–
Et N = 46 : 1 : 1 : 98, 100°С, pCO = 2 atm; (1) 4-tert-butyl-1,2-dibromobenzene, (2) dimethyl phthalate, (3) meta-ester, (4) para-
3
ester; (points) experiment, (lines) calculation using Scheme 4.
the +I-effect of the t-Bu group. Moreover, the k /k3
of the charge were well correlated with the rate constants
of carbonylation at the C–Br bonds determined earlier:
the Br atom in the para-position with respect to the
t-Bu group of 4-tert-butyl-1,2-dibromobenzene was the
4
value 4.0 for the stages of consumption of the
monoesters confirmed the enhancement of the
reactivity of the meta C–Br bond due to the additional
acceptor effect of the СООМе group in the para-ester
least reactive (k ), and the atom in the meta-position
2
(
Scheme 3).
with respect to the t-Bu group of methyl 4-tert-butyl-2-
bromobenzoate was the most reactive (k ). Those data
4
To verify the suggested increase in the positive
confirmed the suggestion of the activation of aryl
halides with the Pd complexes in the reactions of
carbonylation via nucleophilic substitution mechanism.
charge at the carbon atoms of the C–Br bonds in the
meta-position with respect to the t-Bu group of 4-tert-
butyl-1,2-dibromobenzene and the monoesters, we
calculated the partial charge using the CNDO method
with geometry optimization.
Br
Br
COOMe
+
0.08
+0.12
+0.06
Br _0.01
COOMe _0.05
_
Br
+0.14
+
_
0.01
.04
+
_
0.10
0.04
+0.02
+0.03
The obtained data revealed that the positive charge
at the aromatic C atoms of the C–Br bonds in the meta-
position with respect to the tert-butyl group of 4-tert-
butyl-1,2-dibromobenzene was significantly higher
than that in the para-position, facilitating the nucleo-
philic attack of the meta-bond Ar–Br with the active
Pd complex at the stage of the oxidative addition; the
same was held for the isomeric monoesters. The values
_
0
0.02 +0.01
+0.03
0.04
+
0.05
+0.08
t-Bu
t-Bu
t-Bu
Basing on the performed study, we elaborated an
efficient method of the synthesis of dimethyl 4-tert-
1
3
butyl[2,2'- C -carbonyl]phthalate [23] (Scheme 3) with
2
1
3
the degree of isotopic enrichment 99% ( C NMR data)
Scheme 4.
t-Bu
t-Bu
COOMe
k1
k
3
t-Bu
Br
Br
t-Bu
COOMe
COOMe
Br
Br
k2
k4
COOMe
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

2
274
ELMAN et al.
butyl-1,2-dibromobenzene.
REFERENCES
for the preparation of promising phthalocyanine drugs
used in the tumor diagnostics [2, 3].
In summary, it was found that the synthesis of
phthalic acid derivatives via carbonylation of aryl
dibromides in solutions of Pd complexes could occur
under mild conditions (80–100°С, 1–3 atm СО) with
high yield of the target products (at least 98%). As
exemplified by the tert-butyl-substituted o-dibromo-
benzene, the carbonylation reaction was accelerated
with the increase in the positive charge at the carbon
atoms of the C–Br bond. The obtained data allowed
prediction of the outcome of carbonylation of aryl
dibromides to optimize the synthesis of target
derivatives of aromatic polycarboxylic acids under
mild conditions with high yield.
1
2
3
. Ullmann’s Encyclopedia of Industrial Chemistry,
Weinheim: Wiley-VCH Verlag GmbH& Co. KGaA,
002, vol. 7, p. 113. doi 10.1002/14356007.a05_249
. Luk’yanets, Е.А., Fotodinamicheskaya terapiya i foto-
diagnostika (Photodynamic Therapy and Photodiagnostics),
2013, vol. 2, no. 3, p. 3.
. Elman, A.R., Korneeva, G.A., Noskov, Yu.G., Khan, V.N.,
Shishkina, E.Yu., Negrimovskii, V.M., Ponomarenko, E.P.,
Kononov, L.O., Bruk, L.G., Oshanina, I.V., Tomkin, O.N.,
and Kuz’min, S.G, Ross. Khim. Zh., 2013, vol. 57, no. 5,
p. 3.
2
4
. Lebedev, N.N., Khimiya i tekhnologiya osnovnogo
organicheskogo i neftekhimicheskogo sinteza (Chemistry
and Technology of Basic Organic and Petrochemical
Synthesis), Moscow: Khimiya, 1981, p. 351.
EXPERIMENTAL
5
. Brennführer, A., Neumann, H., and Beller, M., Angew.
Chem. Int. Ed., 2009, vol. 48, no. 23, p. 4114. doi
Quantitative analysis was performed using a
Kristallyuks-4000M gas chromatograph (flame ionization
detector, SE-54 phase, column 15 m × 0.32 mm, 2-meth-
oxyacetophenone as the internal standard). Chromato–
mass spectrometry analysis was performed using an
Agilent 6890N instrument (mass detector 5975,
column HP-5MS 30 m × 0.25 mm, EI, 70 eV). The
1
0.1002/anie.200900013
6. Pri-Bar, I. and Alper, H., J. Org. Chem., 1989, vol. 54,
no. 1, p. 36. doi 10.1021/jo00262a015
. Takács, A., Ács, P., and Kollár, L., Tetrahedron, 2008,
vol. 64, no. 6, p. 983. doi 10.1016/j.tet.2007.10.026
7
1
1
8. Tisserand, S., Baati, R., Nikolas, M., and Mioskowski, C.,
NMR correlation spectroscopy experiments Н– Н
J. Org. Chem., 2004, vol. 69, no. 25, p. 8982. doi
1
13
COSY and Н– С HMBC were performed using a
Varian Unity Inova 500M instrument (DMSO-d6
1
0.1021/jo049228l
9. Beller, M., Mägerlein, W., Indolese, A.F., and Fischer, C.,
9
9.8% as solvent, TMS as reference). The partial
Synthesis, 2001, no. 7, p. 1098. doi 10.1055/s-2001-14576
charge at the atoms of the substrates was calculated
using the CNDO method (HyperChem 8.0.3 software)
with optimization of the molecule geometry via the
Polak–Ribiere method [24].
1
0. Najiba, D., Carpentier, J.-F., Castanet, Y., Biot, C.,
Brocard, J., and Morteux, A., Tetrahedron Lett., 1999,
vol. 40, no. 19, p. 3719. doi 10.1016/S0040-4039(99)
0
0597-3
1
1
1. Bessard, Y. and Roduit, J.P., Tetrahedron, 1999, vol. 55,
The reactions were performed in a glass reactor
immersed in a steel autoclave to prevent contact the
autoclave material with the reaction mixture [25].
no. 2, p. 393. doi 10.1016/S0040-4020(98)01037-0
2. McNulty, J., Nair, J.J., Sliwinski, M., and Robertson, A.J.,
1
3
Tetrahedron Lett., 2009, vol. 50, no. 20, p. 2342. doi
When СО was used, it was fed from a small
container weighed with accuracy 0.01 g; after the
reaction was complete, the residual labeled gas was
collected in another container for further use and
1
0.1016/j.tetlet., 2009.02.200
1
3. Li, Y., Xue, D., Wang, C., Liu, Z.-T., and Xiao, J.,
Chem. Commun., 2012, vol. 48, p. 1320. doi 10.1039/
c2cc16611a
1
3
calculation of the material balance. СО was obtained
13
1
1
1
4. Kalck, P. and Urrutigoity, M., Inorg. Chim. Acta, 2015,
via reduction of СО (isotopic purity 99 mol%) as
2
vol. 431, p. 110. doi 10.1016/j.ica.2015.02.007
described elsewhere [26].
ACKNOWLEDGMENTS
5. McNulty, J., Nair, J.J., and Robertson, A.J., Org. Lett.,
2
007, vol. 9, no. 22, p. 4575. doi 10.1021/ol702081g
6. Calò, V., Gianniccaro, P., Nacci, A., and Monopoli, A.,
J. Organomet. Chem., 2002, vol. 645, nos. 1–2, p. 152.
doi 10.1016/S0022-328X(01)01401-2
This study was financially supported by the
Government of Moscow. Authors are grateful to
E.A. Luk’yanets and collaborators from State Science
Center “NIOPIK” for providing the sample of 4-tert-
17. Amatore, C. and Jutand, A., Acc. Chem. Res., 2000,
vol. 33, no. 5, p. 314. doi 10.1021/ar980063a
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017

PREPARATION OF PHTHALATES VIA CARBONYLATION
2275
1
1
8. Grigg, R. and Mutton, S.P., Tetrahedron, 2010, vol. 66,
and Kollár, L., Tetrahedron, 2012, vol. 68, no. 38,
p. 7855. doi 10.1016/j.tet.2012.07.030
no. 30, p. 5515. doi 10.1016/j.tet.2010.03.090
9. Collman, J.P., Hegedus, L.S., Norton, J.R., and
Finke, R.G. Principles and Applications of Organo-
transition Metal Chemistry, California: University
Science Books, Mill Valley, 1987.
0 Boyarskii, V.P., Larionov, E.V., Polyakova, S.M., Boyar-
skaya, I.A., and Zhesko, T.E., Russ. J. Gen. Chem., 2007,
vol. 77, no. 5, p. 915. doi 10.1134/S1070363207050179
1. Valaeva, V.N., Cand. Sci. (Chem.) Dissertation,
Мoscow, 2011.
2. Takács, A., Czompa, A., Krajovszky, G., Mátyus, P.,
2
2
3. Elman, А.R. and Ovsyannikova, L.V., RF Patent
2
470008, 2012; Byull. Izobret., 2012, no. 35.
4. HyperChem 8.0, Sophisticated Molecular Modeling
Environment. Hypercube, Inc., Gainesville (USA),
2
2
011. http://www. hyper.com.
2
5. Elman, A.R. and Smirnov, V.I., J. Environment. Sci.
Eng., 2011, vol. 5, no. 8, p. 1006.
2
2
26. Rupasov, S.I., Elman, A.R., and Batov, A.E., RF Patent
2319664, 2008; Byull. Izobret., 2008, no. 8.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 10 2017