Metal phthalocyanine-catalyzed addition of polychlorine-containing organic compounds to C=C bonds

Article abstract of DOI:10.1007/s11172-008-0377-0

Organopolychlorine compounds (CCl₄, CCl₃CO ₂Et, CCl₃CHO) add at the double bond of various olefins under the catalysis of the metal phthalocyanine complexes. A possibility of quantitative catalyst recovery was shown.

Full text of DOI:10.1007/s11172-008-0377-0

Russian Chemical Bulletin, International Edition, Vol. 58, No. 11, pp. 2393—2396, November, 2009
2393
Brief Communications
Metal phthalocyanineꢀcatalyzed addition
of polychlorineꢀcontaining organic compounds to С=С bonds
A. V. Ivanov,a A. Yu. Maksimov,b L. G. Tomilova,a,b and N. S. Zefirova,b
аInstitute of Physiologically Active Compounds, Russian Academy of Sciences,
142432 Chernogolovkа, Moscow Region, Russian Federation
bDepartment of Chemistry, M. V. Lomonosov Moscow State University,
Build. 3, 1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 0290. Eꢀmail: phthal_iv@mail.ru
Organopolychlorine compounds (CCl4, CCl3CO2Et, CCl3CHO) add at the double bond
of various olefins under the catalysis of the metal phthalocyanine complexes. A possibility of
quantitative catalyst recovery was shown.
Key words: phthalocyanines, olefins, polychlorineꢀcontaining organic compounds, tetrachloroꢀ
methane, Kharasch reaction, copper complexes, cobalt complexes.
of the present work is to study the catalytic activity of
phthalocyanines in the Kharasch reaction.
The addition of organic polyhalides to unsaturated
compounds (the Kharasch reaction) is a convenient and
satisfactorily developed method for functionalization of
organic compounds. The intermediate products obtained
can serve as precursors of higher carboxylic acids, amino
acids, and various heterocyclic compounds.
Copper and its salts,1—3, metal carbonyls,4—6 ferꢀ
rocene,7,8 etc. were used as catalysts of the process. Among
drawbacks of these catalysts is that they cannot be recovꢀ
ered after the reaction.
We found that in the presence of 0.1—1.0 mol.%
copper tetraꢀtertꢀbutylphthalocyanine or copper octaꢀ
butylphthalocyanine ССl4 adds to acrylonitrile to form
2,4,4,4ꢀtetrachlorobutyronitrile in a yield up to 65%
(Scheme 1). The reaction involving hexꢀ1ꢀene and
styrene proceeds similarly. As a result, 1,1,1,3ꢀtetraꢀ
chlorohexane and 1,1,1,3ꢀtetrachloroꢀ3ꢀphenylpropane,
respectively, are formed.
The reaction occurs on heating a mixture of the reacꢀ
tants in acetonitrile in a sealed vessel at 140 °С. An
attempt to carry out the process by refluxing the reactants
in acetonitrile or butyronitrile under atmospheric presꢀ
sure was unsuccessful: no addition products were formed.
At the same time, metal phthalocyanine complexes
are known to be used as catalysts of diverse organic reacꢀ
tions, for example, oxidation,9 reduction with sodium
boron hydride,10 Kabachnik—Fields reactions,11 and
chlorination of aromatic compounds.12,13 The purpose
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2316—2319, November, 2009.
1066ꢀ5285/09/5811ꢀ2393 © 2009 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009
Ivanov et al.
Scheme 1
Table 2. Yields of the addition products of
CCl4 to unsaturated substrates in the presꢀ
ence of Cu and Co tetraꢀtertꢀbutylphthaloꢀ
cyanines (0.5 mol.%)
Substrate
Yield (%)
t
t
Bu PcCu
Bu PcCo
R = CN (a), Bu (b), Ph (c)
Y = But4, Bun
NC—CH=CH2
Bu—CH=CH2
Ph—CH=CH2
65
76
72
64
84
69
8
The catalyst is quantitatively recovered after the target
compound was separated by the elution of the column
with polar solvents, which is seen from the weight of the
product, its unchanged electronic absorption spectrum,
and reproducible yields of the adducts when the phthaloꢀ
cyanine complex is used repeatedly.
Along with copper phthalocyaninates, we studied cataꢀ
lytic properties of planar and sandwich phthalocyanine
complexes and the free tetraꢀtertꢀbutylphthalocyanine
ligand. The results of CCl4 addition to hexꢀ1ꢀene in variꢀ
ous solvents in the presence of these additives are given in
Table 1.
As can be seen from Table 1, no adducts are formed in
the reaction of rareꢀearth metal diphthalocyanines and
the free ligand, which indicates that the reaction occurs
on the sterically accessible metal site of the catalyst. Note
that the addition in the presence of unsubstituted copper
phthalocyanine cannot be carried out, because the latter
is insoluble under the reaction conditions.
Cobalt tetraꢀtertꢀbutylphthalocyanine is an active cataꢀ
lyst along with the copper complexes, which was conꢀ
firmed for other unsaturated compounds as well. The
comparative yields of CCl4 addition to various substrates
in the presence of the copper and cobalt catalysts are
listed in Table 2.
The reactions described above concern terminal
olefins. In order to extend the range of involved olefins,
we studied the addition of CCl4 to cyclohexene under
the conditions determined earlier (sealed vessel, 140 °С,
8 h). The products were identified on the basis of GCꢀMS
data. The chromatograms of the reaction mixtures exhibit
three peaks with the retention times 12.5, 15, and 17 min
in a ratio of 1 : 2 : 1.5. The mass spectrum of the
first product contains peaks of the molecular ion of
[C7H10Cl4]+ with m/z 234, 236, 238, and 240, which corꢀ
responds to four chlorine atoms in the molecule. Thereꢀ
fore, this signal is assigned to adduct 3 of cyclohexene and
tetrachloromethane (Scheme 2). The mass spectra of
two other compounds contain signals with m/z 198, 200,
and 202 corresponding to the [C7H9Cl3]+ ion. However,
the second product contains predominantly light
fragments (m/z 80 for cyclohexadiene and m/z 78 for
benzene), which indicates that the structure contains
the trichloromethyl group. Based on these data, the strucꢀ
ture of 1ꢀtrichloromethylcyclohexene (4) can be ascribed
to the second product. Ions with m/z 162, 164, and 166
are observed in the mass spectrum of the latter compound
along with the molecular ion peak with m/z 198, 200,
and 202. This corresponds to the elimination of hydrogen
chloride from the molecular ion and indicate the allylic
migration of chlorine in 1ꢀtrichloromethylcyclohexene
(4), resulting in 1ꢀchloroꢀ2ꢀdichloromethylidenecycloꢀ
hexane (5).
Table 1. Yields of 1,1,1,3ꢀtetrachloroheptane (2b) with the use
of various metal complexes (0.5 mol.%) and solvents
Metal phthaloꢀ
cyanine
Yield 2b (%)
MeCN Propanꢀ2ꢀol CCl4*
Hexꢀ1ꢀene*
t
Bu PcCu
76
74
84
3
8
7
13
4
3
0
0
75
73
85
4
9
8
12
5
3
0
0
73
—**
78
3
10
6
11
4
3
64
—**
66
3
10
7
14
3
3
nPcCu
Bu
t
An increase in the reaction duration to 12 h and the
temperature decrease to 100—110 °С induce no substanꢀ
tial change in the composition of the products. Therefore,
it can be supposed that all the three compounds are formed
from the same precursor rather than consecutively (see
Scheme 2).
Note that we found no 1ꢀchlorocyclohexꢀ2ꢀene, which
is the byꢀproduct formed upon the addition of CCl4 to
cyclohexene in the presence of the CuCl complex with
triphenylphosphine.14,15
Bu PcCo
t
Bu PcNi
t
Bu PcPt
t
Bu PcPd
t
Bu PcMn
t
Bu PcCr
t
Bu PcZn
t
Bu PcH2
0
0
0
0
0
0
t
Bu Pc2Lu
t
Bu Pc2Eu
0
0
* An excess of the corresponding reactant was used as the solvent.
** Experiment was not carried out.
Under the conditions determined, chloroform does
not add to alkenes, whereas more reactive addends react

Synthesis of polychloro compounds
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009 2395
Scheme 2
We established that the phthalocyanine complexes
catalyze both the intermolecular and intramolecular
Kharasch reaction. The cyclization of allyl trichloroacetate
in the presence of copper and cobalt tetraꢀtertꢀbutylꢀ
phthalocyanines affords not 3,3,5ꢀtrichlorodihydropyranꢀ
2ꢀone (10) but 3,3ꢀdichloroꢀ4ꢀchloromethyldihydrofuranꢀ
2ꢀone (11), as in the presence of univalent copper salt3
(Scheme 5).
Scheme 5
in the process under study. For instance, we carried
out the addition of ethyl trichloroacetate (6) to acryloꢀ
nitrile and hexꢀ1ꢀene in 67 and 77% yields, respectively
(Scheme 3).
Scheme 3
This suggests that the addition of polychlorineꢀconꢀ
taining organic compounds to alkenes in the presence of
the phthalocyanine catalysts proceeds as a radical proꢀ
cess. Note that the addition of tetrachloromethane and
other addends to olefins is not inhibited by hydroquinone,
which makes it possible (with a sufficient probability) to
exclude the free radical mechanism of such a reaction.
This fact additionally indicates that the addition occurs in
the coordination sphere of the metal.
R = CN (a), Bu (b)
In the case of ethyl trichloroacetate addition to styꢀ
rene (1c) at the quantitative olefin conversion, a large
amount of resinous compounds are formed, which preꢀ
vents isolation of the target product.
Chloral reacts with acrylonitrile and allyl alcohol to
yield earlier described 2,2,4ꢀtrichloroꢀ5ꢀoxovaleronitrile
(8)1 and 2ꢀhydroxyꢀ3,3,5ꢀtrichlorotetrahydropyrane (9),2,4
respectively (Scheme 4).
In summary, a new efficient and easily recoverable
catalysts were found for the addition of organopolychlorine
compounds to carbon—carbon double bonds.
Experimental
Scheme 4
The 1Н and 13С NMR spectra were recorded on a Bruker
WPꢀ300 spectrometer relative to Me4Si, using СDCl3 as the
solvent. The GCꢀMS spectra were measured on a Finnigan MAT
INCOSꢀ50 instrument (EI, 70 eV), using nitrogen as a carrier
gas (30 cm3 min–1), glass columns 3500Ѕ3 mm with 5% ХЕꢀ60
on Inertonꢀsuper (0.20—0.25 mm), and the temperatureꢀ
programmed regime from 50 to 250 °С with a rate of 20 °С min–1
.
Thin layer chromatography was carried out on Silufol
UVꢀ254 plates (Merck).
All reagents used were highꢀpurity, reagent, and analytically
pure grade. Prior to use the solvents were distilled and (if
necessary) dried.
The phthalocyanine complexes were synthesized according
to procedures described earlier.16
Allyl trichloroacetate (10) was synthesized in 60% yield
according to a known procedure.3

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Ivanov et al.
Reaction of ССl4 with unsaturated compounds (general
procedure). A solution of an unsaturated compound (10 mmol),
a polychloro derivative (10 mmol), and a catalyst (0.01—0.10 g)
in acetonitrile (total volume 10 mL) was heated for 4—8 h at
140 °С in a sealed tube. After cooling, the tube was opened, and
the solvent and unreacted starting compounds were evaporated
in vacuo. The residue containing the target product and the
catalyst were purified by column chromatography (SiO2,
60—200 mesh). After the eluent was evaporated, the correꢀ
3,3ꢀDichloroꢀ4ꢀchloromethylꢀ4,5ꢀdihydroꢀ3Hꢀfuranꢀ2ꢀone
(11). The eluent for the chromatographic isolation of the adduct
was ethyl acetate—hexane (2 : 1, vol.). The yield was 67%.
1H NMR, δ: 4.65 (dd, 1 Н, CHО, 2J = 9.3 Hz, 3J = J = 7.1 Hz,
2J = 9.3 Hz); 4.23 (dd, 1 H, CHO, 3J = 8.8 Hz, J = 9.3 Hz); 3.99
(dd, 1 Н, CHCl, 3J = 4.6 Hz, 3J = 11.5 Hz); 3.75 (dd, 1 H,
CHCl, J = 7.1 Hz, J = 9.3 Hz); 3.32—3.41 (m, 1 Н, ССl2СН).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ00753)
and the Presidium of the Russian Academy of Sciences
(Program of Basic Research "Development of Methods of
Synthesis of Chemical Substances and Creation of New
Materials").
sponding adduct was obtained as a yellowish liquid. The yields
t
of the adducts are presented for the Bu PcCuꢀcatalyzed reaction.
After the adduct was isolated from the chromatographic column,
the catalyst was eluted with ethyl acetate, which allowed its
quantitative recovery to be performed.
2,4,4,4ꢀTetrachlorobutyronitrile (2a). The eluent for the
chromatographic isolation of the adduct was C6H6—hexane
(1 : 1, vol.). The yield was 65%. 1Н NMR, δ: 4.87 (dd, 1 Н, СHCl,
References
3
3J = 4.7 Hz, J = 8.7 Hz); 3.63 (dd, 1 Н, СН2, 2J = 15.2 Hz);
3.37 (dd, 1 Н, СН2). 13С NMR, δ: 115.8 (CN), 93.8 (CСl3),
59.1 (CH2), 37.95 (CHCl).
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1,1,1,3ꢀTetrachloroheptane (2b). The eluent for the chromꢀ
atographic isolation of the adduct was C6H6—hexane (1 : 1,
vol.). The yield was 76%. 1H NMR, δ: 4.27 (m, 1 Н, СHСl);
3
3.65 (dd, 1 H, ССl3—СH2, 2J = 15.5 Hz, Jvic = 5.5 Hz);
3.13 (dd, 1 H, ССl3—СH2, 3J = 4.6 Hz); 1.83—1.98 (m, 2 H,
СH2—СHСl); 1.27—1.58 (m, 4 Н, СН2—СН2); 0.95 (t, 3 Н,
Me, 3J = 7.3 Hz). 13C NMR, δ: 97.1 (ССl3), 62.5 (ССl3—СH2),
57.8 (СHСl), 38.9, 28.2, 22.1 (3 СH2), 14.0 (Me).
1,1,1,3ꢀTetrachloroꢀ3ꢀphenylpropane (2c). The eluent for
the chromatographic isolation of the adduct was C6H6—hexane
(1 : 1, vol.). The yield was 72%. 1H NMR, δ: 7.35—7.49 (m, 5 Н,
СН arom.); 5.33 (dd, 1 Н, CHCl); 3.65 (dd, 1 H, CCl3—СH2,
2J = 15.2 Hz, 3J = 5.5 Hz); 3.56 (dd, 1 H, CCl3—СH2,
3J = 6.4 Hz). 13C NMR, δ: 163.3 (С arom.), 140.5 (С arom.),
129.0 (С arom.), 127.5 (С arom.), 96.3 (CСl3), 62.8 (CH2), 58.4
(CHCl).
Ethyl 2,2,4ꢀtrichloroꢀ4ꢀcyanobutanoate (7a). The eluent
for the chromatographic isolation of the adduct was ethyl
acetate—hexane (1 : 2, vol.). The yield was 67%. 1H NMR, δ:
4.88 (dd, 1 Н, CHCl); 4.32 (q, 2 H, CH3CH2O); 4.20 (m, 1 Н,
CHCl); 3.11 (m, 2 H, CHCl—CH2—CCl2); 1.36 (t, 3 Н,
CH3CH2O).
Ethyl 2,2,4ꢀtrichlorooctanoate (7b). The eluent for the
chromatographic isolation of the adduct was C6H6—hexane
(1 : 1, vol.). The yield was 77%. 1H NMR, δ: 4.32 (q, 2 H,
CH3CH2O, 3J = 6.97 Hz); 4.20 (m, 1 Н, CHCl); 2.95 (ddd, 2 H,
CHCl—CH2—CCl2); 1.79 (m, 2 Н, СН2); 1.40 (m, 2 Н,
СН2СН2); 1.36 (t, 3 Н, СН3CH2O); 0.92 (t, 3 H, CH2CH2CH3,
3J = 6.4 Hz).
2,4,4ꢀTrichloroꢀ5ꢀoxopentanonitrile (8). The eluent for
the chromatographic isolation of the adduct was ethyl
acetate—hexane (3 : 1, vol.). The yield was 45%. 1H NMR, δ:
9.25 (s, 1 H, CHO); 4.88 (dd, 1 Н, CHCl, 3J = 6.2 Hz,
3J = 7.3 Hz); 3.00 (m, 2 H, CH2—CCl2).
16. E. G. Kogan, A. V. Ivanov, L. G. Tomilova, N. S. Zefirov,
Mendeleev Commun., 2002, 54.
2ꢀHydroxyꢀ3,3,5ꢀtrichlorotetrahydropyrane (9) was purified
by distillation in vacuo, b.p. 120 °C (0.12 Torr). The yield was
1
34%. H NMR, δ: 4.14 (s, 1 H, Нax(2)); 3.66 (m, 1 Н, Нax(4));
3.59 (m, 1 Н, Нax(5)); 2.68 (m, 1 Н, Нax(6)); 2.59 (m, 1 Н,
Received March 5, 2009;
Нeq(4)); 1.91 (m, 1 Н, Нeq(6)).
in revised form June 22, 2009