Arenediazonium tetrachlorocuprates(II). Modified versions of the Meerwein and Sandmeyer reactions

Article abstract of DOI:10.1023/A:1015394423091

Chloroarylation of unsaturated compounds with arenediazonium chlorides in the presence of CuCl₂ as catalyst involves intermediate formation of arenediazonium tetrachlorocuprates(II) [ArN₂⁺] ₂ CuCl₄

Full text of DOI:10.1023/A:1015394423091

Russian Journal of Organic Chemistry, Vol. 38, No. 1, 2002, pp. 38 46. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 1, 2002,
pp. 47 55.
Original Russian Text Copyright
2002 by Obushak, Lyakhovich, Bilaya.
Arenediazonium Tetrachlorocuprates(II). Modified Versions
of the Meerwein and Sandmeyer Reactions
N. D. Obushak, M. B. Lyakhovich, and E. E. Bilaya
Ivan Franko Lviv National University, ul. Universitetskaya 1, Lviv, 79000 Ukraine
e-mail: obushak@pancha.lviv.ua
Received March 7, 2001
Abstract Chloroarylation of unsaturated compounds with arenediazonium chlorides in the presence of CuCl2
as catalyst involves intermediate formation of arenediazonium tetrachlorocuprates(II) [ArN+2]2 CuCl42 .
A procedure for preparative isolation of these intermediates was developed, and they were shown to be
efficient arylating agents. Reactions of [ArN2+]2 CuCl24 with unsaturated compounds gave the corresponding
Meerwein products; a mechanism was proposed for these reactions. In polar solvents arenediazonium tetra-
chlorocuprates(II) are converted into chloroarenes, presumably through a cyclic transition state.
Analysis of published data on decomposition of
arenediazonium salts in the presence of copper(I) or
copper(II) salts as catalyst shows that such reactions
involve intermediate formation of copper complexes
[1 6]. We previously found [6 10] that arenediazo-
nium salts react with unsaturated compounds in the
presence of copper(II) chloride to give CuCl2 com-
plexes with arenediazonium salts as primary products.
In some cases such complexes can be isolated from
that the procedure for preparation of coordination
compounds from arenediazonium salts and cobalt(II),
mercury(II), zinc, cadmium(II), iron(III), manga-
nese(II), and other metal chlorides takes advantage
of the poor solubility of these complexes in water in
the presence of excess chloride ions [14]. By contrast,
arenediazonium tetrachlorocuprates(II) are readily
soluble in water, and the procedure proposed in [12]
for synthesizing such complexes in nonaqueous
the reaction mixture. They were identified as arene- medium gives the target products as finely crystalline
diazonium tetrachlorocuprates(II) [ArN+2]CuCl42 .
Structurally related binary complexes of many metals
are well known; they are used in the synthesis of
organometallic compounds by the Nesmeyanov reac-
tion [11]. Binary complex salts of copper(II) and
arenediazonium chlorides have been studied poorly,
mainly by spectral methods [12 14]. The reason is
substances with reduced stability.
We have developed a convenient preparative
method for synthesizing arenediazonium tetrachloro-
cuprates(II). Initially, arenediazonium chlorides Ia Ii
were treated with iron(III) chloride in aqueous solu-
tion to obtain arenediazonium tetrachloroferrates(III)
IIa IIi. The subsequent exchange reaction of IIa IIi
Scheme 1.
I III, V, Ar = Ph (a), 3-MeC6H4 (b), 4-MeC6H4 (c), 2-MeOC6H4 (d), 4-MeOC6H4 (e), 3-BrC6H4 (f), 4-BrC6H4 (g),
2,4-Cl2C6H3 (h), 2,5-Cl2C6H3 (i); IV, Ar = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c).
1070-4280/02/3801-0038$27.00 2002 MAIK Nauka/Interperiodica

ARENEDIAZONIUM TETRACHLOROCUPRATES(II).
39
with CuCl2 in acetone or ethanol gave arenediazonium
tetrachlorocuprates(II) IIIa IIIi (Scheme 1).
Table 1. Yields, decomposition points, and N N fre-
quencies of arenediazonium tetrahalocuprates(II) IIIa IIIi
and IVa IVc
The use of less polar solvents is less efficient
because of the lower solubility of salts IIa IIi. Crys-
talline compounds IIIa IIIi are stable on storage;
they are readily soluble in water, sparingly soluble in
polar organic solvents, and insoluble in nonpolar sol-
vents (Tables 1, 2). It should be noted that 1-naphtha-
lenediazonium tetrachlorocuprate(II) [7] and analogous
complexes of unsubstituted and substituted 4,4 -bi-
phenylbisdiazonium salts [8] were synthesized by us
previously in aqueous acetone or aqueous alcohol.
The developed procedure was also used to prepare
arenediazonium tetrabromocuprates(II). The corre-
sponding arenediazonium tetrabromoferrates(III),
unlike their chlorine-containing analogs, did not
separate from solutions containing excess halide ions.
Compounds IVa IVc were obtained by reaction of
arenediazonium tetrachloroferrates(III) IIa, IIc, and
IIe with copper(II) bromide (as anionic complex;
Scheme 1). Salts IVa IVc were isolated as dark green
crystalline substances; their yields were considerably
lower than the yields of chlorine-containing analogs
III (Table 1). In addition, salts IV turned out to be
less stable than III, which makes it difficult to use
them as reagents.
Although salts IIIa IIIi are stable in the crystalline
state, in strongly polar media (DMF, DMSO, aqueous
acetone, or aqueous acetonitrile) they decompose
under mild conditions with liberation of nitrogen and
formation of chloroarenes Va Vi in 84 97% yield
(see Experimental). Dimethyl sulfoxide appeared to
be the most appropriate solvent ensuring specific
decomposition of salts IIIa IIIi. Copper(II) chloride
released from salts IIIa IIIi reacts with DMSO to
form insoluble complex VI [15]. Its formation favors
decomposition of IIIa IIIi under mild conditions
(Scheme 1). In such a way chloroarenes Va Vi were
obtained in high yields (see Experimental); thus de-
composition of arenediazonium tetrachlorocuprates(II)
Compound Yield,
Decomposition
point,
1
N N, cm
no.
%
C
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
83
88
93
91
97
84
94
79
81
26
58
50
86 87
92 93
2268
2251
2244
2244
2236
2253
2246
2242
2254
2262
2240
2235
100 101
121 122a
126 127
121 122
117 118
109 110
103 104
70 71
IVa
IVb
IVc
75 76
82 83
a
Published data [14]: mp 119 120 C.
IIIa IIIi can be regarded as an efficient version of
the Sandmeyer reaction.
We also examined decomposition of salts IIIa IIIi
in the presence of unsaturated compounds, namely
acrylic acid derivatives. Methyl, ethyl, and butyl
acrylates, methyl methacrylate, and acrylonitrile were
found to react with compounds IIIa IIIi at room
temperature, yielding chloroarylation products VIIa
VIIn (Scheme 2, Table 3).
The yields of adducts VIIa VIIn according to
Scheme 2 were higher than under usual conditions of
the Meerwein reaction (aqueous solution of arenedi-
azonium halide, aqueous acetone, catalytic amount
of CuCl2) [16]. The properties of compounds VIIa,
VIIg VIIl, and VIIn were consistent with published
data [17 19]; Table 4 contains boiling points, refrac-
tive indices, and elemental analyses of newly syn-
1
thesized compounds VIIb VIIf, and VIIm. The H
NMR spectra of such compounds were reported pre-
viously [18, 20].
Scheme 2.
Salts IIIa IIIi are identical to intermediate com-
plexes isolated by us in the reactions of arenediazo-
nium chlorides with unsaturated compounds, catalyzed
by copper(II) halides (Meerwein reaction). ESR study
of the reactions of arenediazonium tetrachlorocup-
rates(II) with styrene and acrylonitrile with the aid
of spin traps revealed formation of aralkyl radicals
ArCH2CHPh and ArCH2CHCN (as spin adducts with
nitrosodurene); however, no spin adducts derived
from aryl radicals were detected [21]. Obviously, aryl
For Ar, R, and R in VIIa VIIn, see Table 2.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 1 2002

40
OBUSHAK et al.
Table 2. Elemental analyses of arenediazonium tetrahalocuprates(II) IIIa IIIi and IVa IVc
Found, %
Cu
Calculated, %
Cu Hlg
Comp.
no.
Formula
C
H
Hlg
N
C
H
N
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
34.94 2.20 15.38 33.87 13.16
38.25 3.36 14.44 31.87 12.35
38.07 3.42 14.52 32.17 12.41
35.70 3.15 13.57 30.16 11.42
35.48 2.75 13.20 30.05 11.54
C12H10Cl4CuN4
C14H14Cl4CuN4
C14H14Cl4CuN4
C14H14Cl4CuN4O2
C14H14Cl4CuN4O2
C12H8Br2Cl4CuN4
C12H8Br2Cl4CuN4
C12H6Cl8CuN4
34.68
37.90
37.90
35.35
35.35
25.13
25.13
26.05
26.05
24.29
27.05
25.73
2.42
3.18
3.18
2.96
2.96
1.41
1.41
1.09
1.09
1.70
2.27
2.16
15.29 34.13 13.48
14.32 31.97 12.63
14.32 31.97 12.63
13.36 29.82 11.78
13.36 29.82 11.78
25.42 1.56 10.84 52.90
25.18 1.31 10.92 52.49
26.35 0.87 11.57 51.43
26.48 0.96 11.74 51.56
24.18 1.81 10.60 53.65
26.91 2.38 10.37 51.57
9.43
9.70
9.78
9.90
9.35
8.89
8.68
11.08 52.60
11.08 52.60
9.77
9.77
11.48 51.26 10.12
11.48 51.26 10.12
C12H6Cl8CuN4
IVa
IVb
IVc
C12H10Br4CuN4
C14H14Br4CuN4
C14H14Br4CuN4O2
10.71 53.86
10.22 51.43
9.44
9.01
8.57
26.03 2.20
9.66
49.28
9.72
48.91
radical reacts with the double bond inside the ac-
tivated triple complex without leaving the solvent
cage [2, 3]. Copper(II) salt was also used by us in
a modified version of the Meerwein reaction in DMF
and DMSO. These solvents are incapable of reducing
could generate aryl radicals by the reaction ArN+2 +
Cu+ Ar + N2 + Cu2+.
We believe that the catalytic activity of copper(II)
can be interpreted in terms of a radical ion mechanism
[10, 23 25]. It is supported by unusual pathways of
copper(II) to copper(I). On the other hand, the pos- the Meerwein reactions, e.g., replacement of the
halogen atom in halostyrenes by aryl group [25 27].
Radical cations were detected by UV spectroscopy in
sibility for the reaction CuCl2 + Me2CO
CuCl +
MeC(O)CH2Cl to occur in acetone was important
while interpreting the Meerwein reaction mechanism
[2, 16, 22], taking into account that just copper(I) ions
the system C C + Cu2+ [25]. Thus, previously
described examples of partial cis trans isomerization
of unreacted substrates, such as benzylideneacetone
[28] and maleic acid esters [29], may be explained by
rotation about the double bond in the corresponding
radical cation. cis trans Isomerizations due to loosen-
ing of the double bond in radical cations have been
well documented [30], and they can be regarded as
a criterion of radical ion mechanism [31]. With the
above in mind, Scheme 3 shows a possible general
mechanism of decomposition of arenediazonium salts
in the presence of unsaturated compounds, catalyzed
Table 3. Yields of alkyl 3-aryl-2-chloropropionates VIIa
VIIi and 3-aryl-2-chloropropionitriles VIIj VIIn
Comp.
no.
Yield,
%
Ar
R
R
VIIa
VIIb
VIIc
VIId
VIIe
VIIf
VIIg
VIIh
VIIi
VIIj
VIIk
VIIl
VIIm
VIIn
3-MeC6H4
4-MeC6H4
2-MeOC6H4
4-MeOC6H4
2,5-Cl2C6H3
2-MeOC6H4
3-MeC6H4
4-MeC6H4
4-MeOC6H4
3-MeC6H4
4-MeC6H4
2-MeOC6H4
2,5-Cl2C6H3
4-BrC6H4
H
H
H
H
H
H
H
Me
Me
H
H
H
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Et
CO2Bu
CO2Me
CO2Me
CN
41
56
42
70
69
44
42
59
60
42
72
40
66
61
by Cu(II) halides. The catalytic system Cu+
Cu2+
mediates electron transfer from olefin to diazonium
ion. The aryl radical thus formed reacts with the
double bond without leaving the activated complex
[arenediazonium tetrachlorocuprate(II) olefin or arene-
diazonium salt catalyst olefin] to give aryl-substi-
tuted alkyl radical B; just the latter is detected by
the ESR method [21]. Electron transfer from radical
B through copper(II) ion to radical cation A (formed
in the first cycle) results in formation of product C.
According to Scheme 3, some olefin molecules exist
as the corresponding radical cations which are capable
of changing their configuration.
CN
CN
CN
CN
H
H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 1 2002

ARENEDIAZONIUM TETRACHLOROCUPRATES(II).
41
Scheme 3.
Hlg = Cl, Br.
A question arises so as to whether our results and
the proposed reaction mechanism are consistent with
the data of [1, 2, 22, 32 34] where the catalytic activ-
ity of copper(I) chloride was substantiated. In most
of these publications copper(I) salts in statu nascendi
were noted to better catalyze the reaction; in other
words, copper(I) ions generated in situ are more effec-
tive than those added to the reaction mixture. Here,
one should keep in mind that most copper(I) salts in
aqueous solution give rise to a very low concentration
of Cu+ ions, for the latter undergo fast oxidation to
Cu2+ (K = [Cu2+]/[Cu+] 106) [35]. Primarily, this
concerns anionarylation of unsaturated compounds
[16, 33], catalyzed by copper salts other than copper
chlorides. Copper(I) chloride is stable in water; more-
over, the solubility of CuCl in acid solutions of arene-
diazonium chlorides (excess HCl) increases due to
formation of the complex ion [CuCl2] [36]. On the
other hand, CuCl undergoes oxidation to CuCl2 in
HCl-containing media: 2CuCl + 1/2O2 + 2HCl
2CuCl2 + H2O [37].
Copper(II) salts in aqueous solution form hexaaqua
ions [Cu(H2O)6]2+ in which water molecules can
readily be replaced by other ligands [35]. As a rule,
no more than four water molecules are replaced (inner
coordination sphere). In particular, addition of HCl,
HBr, LiCl, or LiBr to an aqueous solution of cop-
per(II) salt leads to formation of halide complexes
where redox interaction between copper(II) and halide
ions is possible. Provided that the other ligands, such
as acetone or olefins, are present, this interaction is
accompanied by halogenation of the organic ligand
[38, 39]. Presumably, ligand exchange and their inter-
actions play an important role in the chloroarylation
process [2, 33].
formation of mixed-ligand complex ion. Both catalytic
species participate in one-electron transfer process
(Scheme 3): Cu(II) oxidizes the substrate molecule,
while Cu(I) reduces diazonium ion. The formation of
radical cations A and radicals B indicates that two
catalytic cycles are operative, otherwise the formation
of radical B cannot be explained. In this case, the
following process would occur:
Salts IIIa IIIi turned out to be effective arylating
agents. This fact indirectly supports the active role
of tetrachlorocuprate ions in the chloroarylation, in
keeping with published data. According to [38, 40],
CuCl24 ion is more active than other copper(II)
species in reactions involving electron transfer. For
example, reactions of alkyl radicals with ligand
transfer (inner-sphere oxidation) in the presence of
tetrachlorocuprate ions are faster by an order of
magnitude than the same reactions catalyzed by Cu2+
[40, 41]. Aryl-substituted alkyl radicals B (Scheme 3)
are likely to react with CuCl24 more effectively in
the final stage. Olefins containing electron-acceptor
groups at the double bond are known to be more reac-
tive in the Meerwein reactions. Radicals derived from
such olefins are oxidized with ligand transfer, follow-
ing the inner-sphere mechanism [40, 42]. Presumably,
adduct C is formed by oxidation of radical B with
ligand transfer. An alternative path, outer-sphere
oxidation with electron transfer and formation of
carbocation, is less probable. The same also applies
to other catalytic addition processes [43], in particular
to those catalyzed by metal complexes and involving
ligand exchange [44]. In reactions of arenediazonium
Thus the catalytic activity of copper(I) and cop-
per(II) salts in the Meerwein reaction can be explained
in terms of two Cu+
Cu2+catalytic cycles and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 1 2002

42
OBUSHAK et al.
Table 4. Boiling points, refractive indices, and elemental analyses of compounds VIIb VIIf and VIIm
Found, %
Calculated, %
Comp.
no.
bp,
(2 mm)
C
n2D0
Formula
C
H
C
H
VIIb
VIIc
VIId
VIIe
VIIf
109 110
117 118
117 118
127 128
124 125
114 116
1.5234
1.5259
1.5254
1.5490
1.5239
1.5650
61.93
57.79
57.53
45.03
59.17
45.90
6.22
5.62
5.90
3.50
6.12
2.61
C11H13ClO2
C11H13ClO3
C11H13ClO3
C10H9Cl3O2
C12H15ClO3
C9H6Cl3N
62.12
57.77
57.77
44.89
59.38
46.09
6.16
5.73
5.73
3.39
6.23
2.58
VIIm
salts with styrene derivatives radicals B can be
oxidized, which is consistent with the data of [45].
The resulting carbocation reacts with external nucleo-
phile or eliminates a proton [46].
Taking into account the above stated, we propose
a mechanism of chloroarylation shown in Scheme 4.
In the first catalytic cycle tetrachlorocuprate(II) ion
mediates electron transfer from the olefin to diazo-
nium ion, yielding intermediate E. The formation of
such radical complex (ArSO2 and CuXn+, n = 0, 1)
was discussed in [47]. This is strongly supported by
the absence of aryl radicals (according to the ESR
data [21]) and their dimerization products, the corre-
sponding biaryls. However, in some cases the latter
are formed in small amounts [32]. It should be noted
that under analogous conditions, which exclude
formation of intermediates like E, biaryls are among
the major products. Here, intermediates are aryl-
copper(I) and diarylcopper(II) [48]. Some reagents
capable of generating aryl radicals but incapable of
forming complexes were ineffective in the reaction
under study [49, 50].
Intermediates D and E are -complexes of the
olefin with copper ion [2, 3, 50, 51]. It is interesting
that we succeeded in effecting cyanoarylation only
with 1,3-dienes [52]. Copper(I) cyanide does not form
-complexes [51, 53], but in reactions with dienes
oxidation of aryl-substituted alkyl radical B is possible
Scheme 4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 1 2002

ARENEDIAZONIUM TETRACHLOROCUPRATES(II).
43
due to electron transfer (rather than due to ligand tions and weak effect of substituent in the aromatic
transfer alone, F
arylation process.
C) [54], which favors cyano-
F can occur both with
ring, SN1 mechanism of replacement of diazo group
by chlorine also seems to be hardly probable. Bagal
et al. [56] proposed a mechanism of nucleophilic
substitution of diazo group, which does not involve
one-electron transfer stage. The reaction of diazonium
ion with base (X ) is treated as a cycle involving
two covalent products, ArN2X and (ArN2)2 [56]:
The transformation E
liberation of radical B and inside the complex. Taking
into account that radical B was detected by ESR spec-
troscopy, Scheme 4 shows the first version. However,
if elimination of radical B from the activated complex
is not the main reaction path, the second catalytic
cycle should follow a cryptoradical mechanism:
Here, ArN2X is an intermediate in the nucleophilic
substitution process, and (ArN2)2 is the main source
of aryl radicals. The equilibrium shifts toward forma-
tion of one of the above covalent products, depending
on their acid base and redox properties [56]. Cop-
per(II) salts shift the equilibrium toward formation of
ArN2X via complex formation with the latter, thus
reducing the probability of radical decomposition.
Salts IIa IIi can form complexes with two diazonium
species (Scheme 5). Stabilization of labile syn-diazo
compounds through formation of cyclic complexes
was reported previously [1, 57]. This mechanism
should be favored by polar solvents, as was observed
experimentally.
Active intermediate complexes containing different
ligands can react with each other [55], especially if
these complexes are labile. Apart from the above
factors, successful Meerwein reactions under condi-
tions allowing formation of other products are favored
by the unique (but not exclusive) role of copper(I)
and copper(II) halides which readily undergo redox
processes and catalyze not only addition process but
also decomposition of diazonium salts. The mecha-
nism of decomposition of salts IIIa IIIi attracts
interest. This reaction results in almost quantitative
formation of chloroarenes Va Vi, and it can be
regarded as a version of the Sandmeyer reaction,
although there is a strong difference: The Sandmeyer
reaction is catalyzed by copper(I) salts, whereas
decomposition of salts IIIa IIIi (which is fast and
efficient in various polar solvents) occurs in the
presence of copper(II) ions. It should be noted that no
free radical species were detected in this reaction by
ESR [21]. Taking into account mild reaction condi-
EXPERIMENTAL
The IR spectra of IIIa IIIi were recorded on
a Specord 75IR instrument in mineral oil.
Arenediazonium tetrachlorocuprates IIIa IIIi.
Arenediazonium chlorides Ia Ii were obtained by
diazotization of 0.1 mol of the corresponing amines,
following a standard procedure (HCl, NaNO2). A so-
lution of 81.1 g of FeCl3 6H2O in a minimal amount
of water was added to a solution of diazonium salt
Ia Ii in water at 5 C.
a. Concentrated hydrochloric acid was added drop-
wise with stirring at 0 5 C to a solution of IIa IIi
Scheme 5.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 1 2002

44
OBUSHAK et al.
(see above). Salts IIIa IIIi quantitatively precipitated
from the solution.
2. Ganushchak, N.I., Golik, V.D., and Migaichuk, I.V.,
Zh. Org. Khim., 1972, vol. 8, no. 11, pp. 2356 2361.
3. Ganushchak, N.I., Obushak, N.D., Koval’chuk, E.P.,
and Trifonova, G.V., Zh. Obshch. Khim., 1984,
vol. 54, no. 10, pp. 2334 2337.
b. A solution of 5.6 g of CuCl2 2H2O in 75 ml
of ethanol and 5 ml of concentrated hydrochloric acid
was added at 0 C to a solution of 65 mmol of salt
IIa IIi in 100 ml of acetone. The precipitate of salt
IIIa IIIi was filtered off, washed with diethyl ether,
and dried in air. An additional amount of IIIa IIIi
was precipitated from the filtrate by adding 150 ml
of diethyl ether.
Arenediazonium tetrabromocuprates(II) IVa
IVc. A solution of 1.1 g of copper(II) bromide in 5 ml
of ethanol and 2.5 ml of hydrobromic acid was added
at 0 C to a solution of 10 mmol of arenediazonium
tetrachloroferrate(III) IIa, IIc, or IIe in 10 ml of
acetone. The precipitate of salt IVa IVc was filtered
off, washed with diethyl ether, and dried in air. An ad-
ditional amount of salt IVa IVc was isolated from
the filtrate by precipitating with diethyl ether (10 ml).
4. Pfeil, E., Angew. Chem., 1953, vol. 65, no. 1,
pp. 155 158.
5. Galli, K., Chem. Rev., 1988, vol. 88, no. 5, pp. 765
792.
6. Obushak, N.D., Doctoral (Chem.) Dissertation, Lviv,
1999.
7. Obushak, N.D., Ganushchak, N.I., and Lyakho-
vich, M.B., Zh. Org. Khim., 1991, vol. 27, no. 8,
pp. 1757 1762.
8. Obushak, N.D., Lyakhovich, M.B., Fedorovich, I.S.,
and Ganushchak, N.I., Russ. J. Org. Chem., 1996,
vol. 32, no. 10, pp. 1471 1476.
9. Obushak, N.D., Lyakhovich, M.B., Fedorovich, I.S.,
and Ganushchak, N.I., Russ. J. Org. Chem., 1997,
vol. 33, no. 3, pp. 345 347.
Decomposition of arenediazonium tetrachloro-
cuprates(II) IIIa IIIi. Salt IIIa IIIi, 25 mmol, was
gradually added in portions to 50 ml of appropriate
solvent (DMSO, DMF, aqueous acetone, or aqueous
acetonitrile) while stirring at room temperature.
A vigorous reaction occurred with evolution of nitro-
gen. When DMSO was used as solvent, solvate com-
plex of copper(II) chloride with DMSO [15] was
formed. The precipitate of product VI was filtered
off, the filtrate was diluted with 50 ml of water and
extracted with diethyl ether, the extract was dried over
MgSO4, the solvent was removed, and the residue was
distilled under reduced pressure. Below are given
product number and yield, %: Va, 92; Vb, 96; Vc, 89;
Vd, 84; Ve, 94; Vf, 90; Vg, 92; Vh, 93; Vi, 97.
10. Obushak, M.D., Lyakhovych, M.B., and Ganu-
shchak, M.I., Tetrahedron Lett., 1998, no. 39,
pp. 9567 9570.
11. Nesmeyanov, A.N., Ber., 1929, vol. 62, no. 7,
pp. 1010 1018; Belov, B.I. and Kozlov, V.V., Usp.
Khim., 1963, vol. 32, no. 2, pp. 121 153.
12. Kazitsyna, L.A., Reutov, O.A., and Buchkov-
skii, Z.F., Zh. Obshch. Khim., 1961, vol. 31, no. 9,
pp. 2943 2950.
13. Kazitsyna, L.A., Kupletskaya, N.B., Ptitsyna, V.A.,
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