Catalytic olefination. Estimation of the reactivity of polyhaloalkanes

Article abstract of DOI:10.1007/s11178-005-0093-2

Global electrophilicity indices and carbon-halogen bond energies of a wide series of halogen derivatives were calculated in terms of the density functional theory (DFT). The calculated values were used to estimate the reactivity of halogen derivatives under conditions of catalytic olefination. Reactions of N-unsubstituted hydrazones with polyhaloalkanes in the presence of CuCl afforded substituted alkenes. The relation between the structure of polyhaloalkanes and their reactivity was studied using the reaction with 4-chlorobenzaldehyde hydrazone as an example. It was found that increase in the global electrophilicity index and decrease in the C-Hlg bond energy are accompanied by increase in the olefinating power of halogen derivatives.

Full text of DOI:10.1007/s11178-005-0093-2

Russian Journal of Organic Chemistry, Vol. 40, No. 12, 2004, pp. 1750–1756. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004,
pp. 1801–1807.
Original Russian Text Copyright © 2004 by Nenaidenko, Korotchenko, Shastin, Tyurin, Balenkova.
Dedicated to Full Member of the Russian Academy of Sciences
A.I. Konovalov on His 70th Anniversary
Catalytic Olefination. Estimation of the Reactivity
of Polyhaloalkanes
V. G. Nenaidenko1, V. N. Korotchenko1, A. V. Shastin2, D. A. Tyurin1, and E. S. Balenkova1
1 Faculty of Chemistry, Lomonosov Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
e-mail: nen@acylium.chem.msu.ru
2 Institute of Chemical Physics Problems, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received December 12, 2003
Abstract—Global electrophilicity indices and carbon–halogen bond energies of a wide series of halogen
derivatives were calculated in terms of the density functional theory (DFT). The calculated values were used
to estimate the reactivity of halogen derivatives under conditions of catalytic olefination. Reactions of
N-unsubstituted hydrazones with polyhaloalkanes in the presence of CuCl afforded substituted alkenes. The
relation between the structure of polyhaloalkanes and their reactivity was studied using the reaction with
4-chlorobenzaldehyde hydrazone as an example. It was found that increase in the global electrophilicity index
and decrease in the C–Hlg bond energy are accompanied by increase in the “olefinating” power of halogen
derivatives.
the catalytic olefination, promising procedures for the
preparation of dichloroalkenes [7], dibromoalkenes
[8], vinyl halides [9], and fluorine-containing unsatu-
rated compounds were developed [10]. In the present
work we examined the relative reactivity of various
polyhalogenated compounds and tried to find param-
eters which can be used to predict their reactivity.
The present work continues the series of our studies
on catalytic olefination. Building up of new carbon–
carbon bonds is one of the most important transforma-
tions in organic synthesis. Olefination of carbonyl
compounds, i.e., the conversion of C=O group into
double C=C bond has found increasing application in
the synthesis of substituted alkenes [1, 2]. Up to
now, numerous olefination methods utilizing various
reagents have been developed [1, 2]. Among these, the
Wittig reaction and its versions [3], Julia olefination
[4], and Peterson reaction [5] are used most widely
in the synthetic practice. However, these procedures
require large amounts of organometallic compounds,
and the reactions are carried out as a rule in an inert
atmosphere in dry solvents. Therefore, search for alter-
native methods for olefination of carbonyl compounds,
specifically catalytic ones, remains an important
problem. We have discovered a catalytic olefination
process which implies reaction of hydrazones with
geminal dihalo derivatives Hlg2CXY in the presence of
a catalytic amount of CuCl (Scheme 1) [6]. As a result,
hydrazones are converted into the corresponding
alkenes, and symmetric azines are formed as by-prod-
ucts. The discovered reaction is more advantageous
than the classical olefination methods, which makes it
a convenient tool in organic synthesis. On the basis of
Scheme 1.
R
R
O
NNH2
R'
Hlg2CXY, CuCl
R'
R
X
Y
R
R
+
N
N
+ N2
R'
R'
R'
Scheme 2 illustrates the general mechanism of the
catalytic olefination, proposed by us previously [7, 11].
The reaction is initiated by oxidation of CuCl with
halogen-containing compound CHlg2XY; copper(II)
thus formed oxidizes hydrazone to give diazoalkane.
The latter undergoes copper-catalyzed decomposition
with elimination of nitrogen, leading to copper–car-
bene complex A which is the key intermediate in
the catalytic olefination. Further transformations of
complex A follow two pathways. The reaction with
1070-4280/04/4012-1750 © 2004 MAIK “Nauka/Interperiodica”

CATALYTIC OLEFINATION.
1751
Scheme 2.
2H+
R
N2 CuLn
R'
R
N2
NNH2
R'
R
Hlg2CXY
CuLn
CuCl
Cu(II)
R'
A
R
X
Y
R
Hlg2CXY
HCHlgXY
CuLn
N2
R'
R'
Hlg2CXY
R
R
N
N
R'
R'
R
R'
Hlg
HlgCu
X
Y
B
CHlg2XY results in formation of substituted alkene
and regeneration of Cu(II) as catalyst (outer cycle).
Aldehyde (ketone) azine is formed as by-product via
reaction of the copper–carbene complex with another
diazoalkane molecule (inner cycle). Concomitant low-
valence copper compounds should be oxidized with
polyhaloalkanes to give products of partial reduction
of the latter.
On the basis of the proposed model of the reaction
of copper–carbene complexes with polyhaloalkanes we
performed calculations which allowed us to predict
with high accuracy chemo- and stereoselectivity in
the formation of alkenes [11]. In the present work we
applied this model to prediction of the olefinating
power of various halogen-containing compounds,
which are potential reagents for the catalytic olefina-
tion, by estimating their electrophilicity and the energy
of the carbon–halogen bond therein.
Both catalytic cycles, outer and inner, involve the
same states of copper catalyst. The ratio of the hydra-
zone transformation products, alkenes and azines,
depends on the relative contributions of concurrent
transformations of complex A. In keeping with the
proposed mechanism, the “olefinating” reactivity of
polyhaloalkanes should be determined by their reaction
with complex A, which leads to organocopper inter-
mediates B, i.e., by their ability to act as electron
acceptors, and by the strength of the carbon–halogen
bond which is broken as a result of oxidative addition
of the copper–carbene complex to the halogen-con-
taining reagent. Increase in the olefinating power of
polyhaloalkanes should lead to increase in the yield of
the target products (alkenes) and decrease in the yield
of by-products (azines), for these reaction pathways
compete with each other.
It is known that polyhaloalkanes behave as electro-
philes in reactions with electron donors [12]. Pre-
viously, qualitative correlations were revealed between
the reactivity of polyhaloalkanes and such parameters
as half-wave potential of electrochemical reduction,
electron affinity, bond energy, and energy of the lowest
unoccupied molecular orbital (LUMO) [13]. As a rule,
electron affinity rises with increase in the number of
halogen atoms (except for polyfluorinated compounds)
[14]. In the recent time, global electrophilicity index ω
is used to characterize the reactivity of chemical com-
pounds. It is a semiempirical parameter which reflects
the gain in energy upon electron transfer to the LUMO
of a molecule under study [15]. The global reactivity
index is calculated by the formula ω = µ2/2η, where µ
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

NENAIDENKO et al.
1752
Table 1. Global electrophilicity indices and energies of the lowest unoccupied (LUMO) and highest occupied molecular
orbitals (HOMO) of polyhaloalkanes
Reagent
–EHOMO, eV –ELUMO, eV
ω, eV
Reagent
–EHOMO, eV –ELUMO, eV
ω, eV
CBr3NO2
CCl3COCF3
CBr4
7.24
7.48
7.02
7.61
7.02
7.13
7.06
7.50
7.34
6.63
6.46
6.91
7.35
7.73
8.09
6.87
6.47
7.03
7.44
8.12
7.13
7.21
7.03
7.76
3.93
3.94
3.73
3.86
3.59
3.43
3.27
3.26
3.22
3.12
3.03
3.03
2.98
2.99
2.96
2.88
2.80
2.85
2.74
2.69
2.66
2.62
2.61
2.62
4.70
4.60
4.38
4.38
4.10
3.76
3.52
3.42
3.39
3.38
3.29
3.19
3.06
3.03
2.98
2.97
2.93
2.92
2.76
2.69
2.68
2.64
2.63
2.62
CH2BrCO2Me
CCl3SO2Me
CHCl2COOMe
CCl3CF3
6.57
7.41
6.92
7.84
6.15
7.49
7.46
7.42
7.30
6.70
6.38
7.19
7.53
6.97
8.04
6.34
8.08
6.31
8.55
7.37
6.68
9.42
7.09
2.58
2.57
2.51
2.52
2.46
2.43
2.43
2.38
2.35
2.34
2.30
2.25
2.25
2.24
2.18
2.21
2.15
2.13
1.50
1.52
1.33
0.36
0.84
2.62
2.57
2.52
2.52
2.51
2.43
2.43
2.39
2.35
2.34
2.31
2.26
2.26
2.24
2.23
2.21
2.21
2.13
1.79
1.69
1.50
1.32
1.26
CCl3NO2
CBr3Cl
CH2BrCOMe
CF3CHBrCl
CCl3CCl3
CCl3CCl2H
CCl3OMe
CCl3CONH2
PhCHBr2
CCl3CH2OH
CHCl3
CBr2Cl2
CCl3CHO
CHBr2CN
CBrCl3
CBr3COMe
CHBr2COMe
CHBr3
CBr2F2
CCl4
CH2Br2
CCl3CN
CCl2F2
CHBr2CO2Me
CHCl2COMe
CHBr2Cl
CH2BrCN
CHCl2CN
CHBr2SO2Me
CHBrCl2
CCl3CO2Me
CCl3F
CCl3CONMe2
CCl2FCClF2
PhCH2Br
CClF3
CH2Cl2
CH3Br
CH4
CH3Cl
is the electronic chemical potential [µ = 1/2(EHOMO
ELUMO)], and η is the chemical hardness (η = ELUMO
+
–
1/7.8×1/3×1/2×1) for chlorine, and (8.17×1/6.13×
1/6.8×1/3×1) for bromine. The calculated global elec-
trophilicity indices and C–Hlg bond energies showed
some relations with the reagent nature. The energy of
the carbon–halogen bond in halomethanes CHnHlg4–n
changes over a wide range, depending on the number
of the halogen atoms (Table 2). It is seen that the
energy of the C–Hlg bond decreases with rise in the
degree of halogenation; correspondingly, dissociation
of the carbon–halogen bond becomes easier. In going
from trihalomethanes CHBrnCl3–n to tetrahalomethanes
CBrnCl4–n the energy of the C–Br and C–Cl bonds
decreases by 8–10 kcal/mol.
E
HOMO). The parameter ω takes into account both
acceptor and donor properties of a molecule and cor-
relates well with the experimental data on the electro-
philicity of various compounds [15].
We calculated the energies of frontier molecular
orbitals (LUMO and HOMO), global electrophilicity
indices (Table 1), and energies of the carbon–halogen
bond (Table 2) for a series of halogen-containing com-
pounds in terms of the density functional theory (DFT)
using PBE 96 functional [16]; the calculations were
performed with the aid of PRIRODA software [17]. In
the DFT/PBE calculations we used a large basis set
consisting of contracted Gauss type basis functions
with the following contraction schemes: (5.3×1/3×
1/2×1) for hydrogen atoms, 7.7×1/5.3×1/3×1/2×1) for
carbon, (7.7×1/5.3×1/3×1/2×1) for fluorine, (8.12×
The calculation results suggest that the reactivities
of such tetrahalomethanes as CBr4, CBr2Cl2, and
CBrCl3 should be almost similar, for the reactivity of
these compounds is determined by the strength of the
weakest C–Br bond which is broken first upon
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

CATALYTIC OLEFINATION.
Table 2. Energies of C–Hlg bonds (kcal/mol) in polyhaloalkanes
1753
Reagent
CCl3COCCl3
CCl3COCF3
CCl3CN
C–Br
C–Cl
54.28
55.45
58.38
61.73
62.85
63.00
63.48
72.61
72.74
76.96
77.10
80.64
Reagent
PhCHBr2
CBr3OMe
PhCH2Br
CH2BrCN
CH2BrCOMe
CH2BrCO2Me
CH2BrNO2
CCl4
C–Br
56.30
59.44
63.14
62.28
65.83
65.93
68.78
C–Cl
CCl3CO2Me
CCl3CONH2
CCl3NO2
CCl3CONMe2
CH2ClCN
67.07
74.32
80.74
CCl3OMe
CCl3F
CH2ClCOMe
CH2ClCO2Me
CH2ClNO2
CBr3CN
CCl2F2
CBr2F2
66.93
63.19
63.28
63.31
CHBr3
46.91
49.35
44.13
50.76
50.86
49.56
53.67
CHBr2Cl
CHBrCl2
CHCl3
75.18
75.30
75.35
CBr3CO2Me
CBr3COCF3
CBr3CONH2
CBr3CONMe2
CBr3NO2
CH2Br2
71.15
CH2Cl2
82.51
65.82
CCl3CCl3
CCl3CCl2H
CBr4
66.47 (CCl3),
73.49 (CCl2H)
CBr3Cl
54.09
54.49
65.89
66.31
CCl3CF3
68.86
CBr2Cl2
CCl2FCClF2
76.33 (CCl2F),
82.95 (CClF2)
CBrCl3
54.87
66.71
oxidative addition of the copper–carbene complex. On
the other hand, the reactivity of CCl4 under conditions
of the catalytic olefination should be considerably
lower. Such trihalomethanes as CHBr3, CHBr2Cl, and
CHBrCl2 should also be characterized by similar reac-
tivities, for the energy of the C–Br bond in these com-
pounds is almost the same. The reactivity of chloro-
form (EC–Cl = 75.35 kcal/mol) and dihalomethanes
should be much lower than the reactivity of bromine-
containing trihalomethanes and CCl4.
The global electrophilicity indices of the corre-
sponding halogen derivatives increase in parallel with
decrease in the carbon–halogen bond energy; there-
fore, both these parameters equally predict the relative
reactivity.
In order to obtain experimental proofs for the hypo-
thesis that the global electrophilicity index and the
Scheme 3.
X
Y
H
NNH2
H
As applied to other halogen-containing compounds
of the general formula CHnHlg3–nG where G is a func-
tional group, introduction of electron-acceptor substit-
uents leads to an appreciable decrease in the energy of
the C–Cl and C–Br bonds. Replacement of chlorine
or bromine by fluorine increases the strength of the
carbon–halogen bond. In all CHnHlg3–nG compounds,
the C–Cl bond is slightly stronger than C–Br (by
several kcal/mol).
Hlg2CXY, CuCl
Cl
Cl
I
IIa–IIf
N
H
N
H
+
Cl
Cl
III
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

NENAIDENKO et al.
1754
Table 3. Reactions of polyhaloalkanes with 4-chloroben-
zaldehyde hydrazone (I)
Scheme 5.
CH2
Yield, %
Reagent
CH2Hlg2, CuCl
H
I
III
alkenea
ArCH=CBr2 (IIa)
ArCH=CCl2 (IIb)
ArCH=CCl2 (IIb)
ArCH=CHBr (IIc)
ArCH=CHCl (IId)
ArCH=CHCl (IId)
–
azine III overall
Cl
CBr4
89
71
82
67
44
0
07
20
17
26
52
52
78
63
21
21
96
91
99
93
96
52
78
63
84
41
Hlg = Cl, 78%; Br, 63%.
CBrCl3
CCl4
yields vinyl bromide IIc. No expected β-chlorostyrene
IId was detected in the reaction of hydrazone I with
chloroform (Scheme 4), presumably due to the low
global electrophilicity index and appreciably higher
C–Cl bond energy, as compared to tetrahalomethanes.
In this case, the only reaction product was aldehyde
azine III (yield 52%). Replacement of one chlorine
atom by bromine (CHBrCl2) gives rise to stereo-
selective formation of β-chlorostyrene (IId) in a good
yield, the E isomer prevailing. Thus the use of bromo-
dichloromethane as olefinating agent provides a con-
venient preparative procedure for the synthesis of
β-chlorostyrenes. Our experimental results convinc-
ingly prove that the strength of the carbon–halogen
bond is an important factor determining the reactivity
of polyhaloalkanes in the catalytic olefination.
CHBr3
CHBrCl2
CHCl3
CH2Br2
CH2Cl2
CCl3CF3
0
–
0
ArCH=CClCF3 (IIe) 63
CCl2FCClF2 ArCH=CFCClF2 (IIf) 20
a
Ar = 4-ClC6H4.
energy of the carbon–halogen bond can be used as
parameters for prediction of the behavior of polyhalo-
alkanes in the catalytic olefination and for estimation
of their olefinating power, we examined reactions of
a series of polyhaloalkanes with 4-chlorobenzaldehyde
hydrazone (I) as model compound (Scheme 3). The
reactions were performed in DMSO in the presence of
aqueous ammonia.
In all cases, the only products were the correspond-
ing alkenes IIa–IIf and 4-chlorobenzaldehyde azine
(III) (Table 3). The examined tetrahalomethanes
CBrnCl4–n turned out to be excellent olefinating agents,
and the corresponding β,β-dihalostyrenes were isolated
in high yields (71–89%); the yield of the target product
almost did not depend on the number of bromine
atoms in the reagent molecule. Compound III was
formed as the minor product, and the overall yield of
products II and III was nearly quantitative. In the
reaction with CBr4, dibromostyrene IIa was isolated,
and from bromotrichloromethane and CCl4 we obtain-
ed dichlorostyrene IIb.
Dihalomethanes CH2Hlg2 (Hlg = I, Br, Cl) turned
out to be inactive in the catalytic olefination, and the
expected 4-chlorostyrene was not detected (Scheme 5).
Isomeric Freons of the general formula C2Cl3F3 react
with 4-chlorobenzaldehyde hydrazone (I) to afford
fluorine-containing alkenes IIe and IIf. 1,1,1-Tri-
chloro-2,2,2-trifluoroethane CCl3CF3 (Freon 113a) is
much more reactive than isomeric CCl2FCClF2.
Alkene IIe was isolated in 63% yield, while the yield
of IIf was as poor as 20%. This is explained by the fact
that in the key olefination stage, i.e., insertion of the
copper–carbene complex at the carbon–halogen bond,
the reactivity of the trichloromethyl moiety is con-
siderably higher than the reactivity of the dichloro-
fluoromethyl group: the energy of the C–Cl bond in
CCl3CF3 is much lower while the global electro-
philicity index is higher than in CCl2FCClF2.
Bromoform can be used as C1 building block in
the catalytic olefination. Its reaction with hydrazone I
Thus the reactivity of polyhalogenated compounds,
predicted on the basis of the global electrophilicity
indices and carbon–halogen bond energies, is fully
consistent with the obtained experimental results.
Reagents possessing a higher global electrophilicity
index relative to chloroform (chlorine-containing com-
pounds) or methylene bromide (bromine-containing
reagents) should be active in the catalytic olefination,
and the corresponding alkenes should be formed.
Scheme 4.
H
Cl
H
CHBrCl2, CuCl
I
+
III (52%)
Cl
IId (44%)
CHCl3, CuCl
I
III (52%)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

CATALYTIC OLEFINATION.
1755
Table 4. Competing reactions of polyhaloalkanes with
4-chlorobenzaldehyde hydrazone (I)
Scheme 6.
Hlg2CX1Y1, Hlg2CX2Y2
CuCl
Ar
Ar
X1
Y1
Overall yield
of alkenes, %
NNH2
Reagents
CBr4/CCl4
Products (ratio)a
H
H
Ar
X2
Y2
65
98
72
63
74
84
IIa
CBr4/CHBr3
IIa/IIc (50/1)
IIb/IIc (6/1)
IIb/IIe (33/1)
IIc/IId (3/2)
IIa/IIb (2/3)
+
H
CCl4/CHBr3
CCl4/CCl3CF3
CHBr3/CHBrCl2
CBr4/CBrCl3
Ar = 4-ClC6H4.
We also examined the relative olefinating power of
a series of polyhaloalkanes. For this purpose, model
hydrazone I was treated with a mixture of halogenated
reagents under standard catalytic olefination conditions
(Scheme 6). Taking into account that each of the
polyhaloalkanes used is a good olefinating agent, the
relative reactivity can be estimated from the ratio of
two different alkenes formed as a result of the com-
peting reactions (Table 4). In the reaction of I with
a mixture of CBr4 and CCl4, the only product was
β,β-dibromostyrene (IIa). This means that the reac-
tivity of CBr4 is much higher than the reactivity of
CCl4, in keeping with the energies of the C–Cl and
C–Br bonds and global electrophilicity indices of the
reagents. Comparison of the reactivities of the pairs
CCl4/CCl3CF3 and CBr4/CHBr3 convincingly proves
higher reactivity of tetrahaloalkanes as compared to
trihaloalkanes. Bromoform and bromodichloromethane
showed comparable reactivities: β-bromostyrene (IIc)
and β-chlorostyrene (IId) were formed at a ratio of
3:2, which is consistent with fairly similar energies of
the C–Br bond in bromoform and bromodichloro-
methane. Analogous results were obtained with a mix-
ture of CBr4 and CBrCl3 in support of our assumption
that polyhalomethanes with similar energies of the
weakest carbon–halogen bond should be characterized
by similar reactivities. The examined polyhaloalkanes
can be arranged into the following series according to
their reactivity toward 4-chlorobenzaldehyde hydra-
zone (I) in the system DMSO–aqueous ammonia:
CBr4 ≈ CBrCl3 >> CCl4 > CHBr3 ≈ CHBrCl2 >
CCl3CF3. This series agrees with the calculated global
electrophilicity indices (Table 1) and C–Hlg bond
energies (Table 2).
a
Determined by 1H NMR spectroscopy.
EXPERIMENTAL
1
The H NMR spectra were recorded on a Varian
VXR-400 spectrometer at 400 MHz using CDCl3 as
solvent and tetramethylsilane as internal reference.
Kieselgel 60 F254 plates (Merck) were used for thin-
layer chromatography, and column chromatography
was performed on silica gel (63–200 mesh, Merck).
4-Chlorobenzaldehyde hydrazone (I) was synthesized
according to known procedure [7]. Commercial poly-
haloalkanes were used without additional purification.
Typical procedure for reactions of 4-chloroben-
zaldehyde hydrazone (I) with polyhaloalkanes in
DMSO. Aqueous ammonia, 0.68 ml (a 25% solution)
and 20 mg (0.2 mmol) of freshly purified copper(I)
chloride were added to a solution of 2 mmol (309 mg)
of freshly prepared hydrazone I in 2 ml of DMSO, and
10 mmol of the corresponding polyhaloalkane was
then added, maintaining the temperature at 20°C. The
mixture was stirred for 24 h, poured into 200 ml
of water, and extracted with methylene chloride (3×
20 ml). The extracts were combined, dried over
sodium sulfate, and evaporated, and the product was
isolated by column chromatography. In the reaction of
I with CBr4, the latter (3.32 g, 10 mmol) was pre-
liminarily dissolved in 8 ml of DMSO. The physical
properties and spectral parameters of the isolated com-
pounds were in agreement with published data [7–10].
Competing reactions with different polyhaloalkanes
were carried out in a similar way using a mixture of
the corresponding reagents (10 mmol each), and the
products were isolated as described above. The result-
ing mixtures of alkenes were not separated, and their
ratio was determined by 1H NMR spectrscopy.
Thus we have developed a model of alkene forma-
tion in the catalytic olefination, which makes it pos-
sible to estimate and predict the olefinating power of
halogen-containing compounds on the basis of their
global electrophilicity indices and energies of the
carbon–halogen bonds.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 03-03-32052a).
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NENAIDENKO et al.
10. Korotchenko, V.N., Shastin, A.V., Nenajdenko, V.G., and
1756
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004