Formation of N-cyclopropylhydrazones by azo coupling of cyclopropyldiazonium with aliphatic CH acids

Article abstract of DOI:10.1023/A:1024429232345

Decomposition of N-cyclopropyl-N-nitrosourea under the action of K ₂CO₃ or KOH containing 15-20% of H₂O at 0-7 °C gives rise to cyclopropyldiazonium, which reacts with some β-diketones, methyl cyanoacetate, or malonodinitr

Full text of DOI:10.1023/A:1024429232345

Russian Chemical Bulletin, International Edition, Vol. 52, No. 4, pp. 993—997, April, 2003
993
Formation of Nꢀcyclopropylhydrazones by azo coupling
of cyclopropyldiazonium with aliphatic CH acids
ꢀ
Yu. V. Tomilov, I. V. Kostyuchenko, E. V. Shulishov, and G. P. Okonnishnikova
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 6390. Eꢀmail: tom@ioc.ac.ru
Decomposition of NꢀcyclopropylꢀNꢀnitrosourea under the action of K2CO3 or KOH conꢀ
taining 15—20% of H2O at 0—7 °C gives rise to cyclopropyldiazonium, which reacts with some
βꢀdiketones, methyl cyanoacetate, or malonodinitrile to form the corresponding cycloꢀ
propylhydrazones. The latter compounds are analogous to products of azo coupling and isomerꢀ
ization of aryldiazonium ions with the aboveꢀmentioned substrates. These transformations
provide the first example of azo coupling of the cyclopropyldiazonium ion in the series of
activated aliphatic CH acids.
Key words: cyclopropylnitrosourea, diazocyclopropane, cyclopropyldiazonium, funcꢀ
tionalized Nꢀcyclopropylhydrazones, competitive reactions.
Decomposition of NꢀalkylꢀNꢀnitrosoamides under the
action of bases is one of the methods, which are most
generally used for the synthesis of aliphatic diazo comꢀ
pounds.1 The generation of diazocyclopropanes from the
corresponding NꢀcyclopropylꢀNꢀnitrosoureas or Nꢀcycloꢀ
propylꢀNꢀnitrosocarbamates follows the same pathway.
In spite of the fact that all diazocyclopropanes are very
unstable, their in situ formation can be judged by chemiꢀ
cal trapping techniques, in particular, by the 1,3ꢀdipolar
cycloaddition to some unsaturated compounds.2 The reꢀ
actions of aliphatic diazo compounds assuming generaꢀ
tion of diazonium ions are generally accompanied by
elimination of the nitrogen molecule followed by transꢀ
formations of the resulting carbocations.3,4 Nevertheless,
it appeared that the cyclopropyldiazonium ions can unꢀ
dergo transformations, which are highly competitive with
deazotization. Thus, the intermediate formation of the
cyclopropyldiazonium ion (1) is evidenced from the reacꢀ
tions of NꢀcyclopropylꢀNꢀnitrosourea (2) with dimethylꢀ
amine or ethylamine, which give cyclopropyltriazenes5
and typical azo coupling products in reactions involving
certain hydroxynaphthalenes,6,7 spiro(2ꢀpyrazolineꢀ5,1´ꢀ
cyclopropanes),8 or 8ꢀhydroxyquinoline7 as azo comꢀ
ponents.
the latter, when reacting at the activated C—H bond of
the methyl or methylene fragment (for example, in the
reactions of phenyldiazonium chloride with nitromethane
or acetylacetone), generally produce isomeric arylhydrꢀ
azones rather than azo compounds. Hence, in the case of
trapping of ion 1 by compounds containing an activated
methylene group, the reactions would also be expected to
afford the corresponding cyclopropylhydrazones.
Actually, the reaction of nitrosourea 2 with solid
K2CO3 containing ∼20% of H2O in the presence of penꢀ
taneꢀ2,4ꢀdione (3a) in CH2Cl2 at 0—7 °C gave rise to
lowꢀmelting crystalline 3ꢀcyclopropylhydrazonopentaneꢀ
2,4ꢀdione (4) in 84% yield (Scheme 1). The yield of
cyclopropylhydrazone substantially decreased in the reꢀ
actions with the use of either anhydrous K2CO3 or aqueous
Scheme 1
With the aim of extending the range of compounds,
which can trap the cyclopropyldiazonium ion (1), we exꢀ
amined alkaline decomposition of nitrosourea 2 in the
presence of selected aliphatic CH acids, viz., βꢀdiketones,
methyl cyanoacetate, or malonodinitrile, which exhibit
properties of typical azo components in reactions with
aromatic diazo compounds.9,10 It should be noted that
Y = Me (3a, 4); 2ꢀthienyl (3b, 5)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 941—945, April, 2003.
1066ꢀ5285/03/5204ꢀ993 $25.00 © 2003 Plenum Publishing Corporation

994
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 4, April, 2003
Tomilov et al.
Table 1. Yields of cyclopropylhydrazone 4 upon decomposition
of nitrosourea 2 under different conditions (5 °C)
cyclopropylamino substituent in minor isomer Eꢀ7 is also
oriented toward the CN group.
Base
(B)
Solvent
2 : 3a : B t/h Y *
Scheme 2
(%)
K2CO3 + H2O (20%)
CH2Cl2
1.2 : 1 : 2.5 2.5 84
KOH + H2O (15%) CH2Cl2—MeOH 1.2 : 1 : 2.5 0.5 82
(4 : 1)
LiOH•H2O
CH2Cl2
CH2Cl2
CH2Cl2
MeCN
1 : 1 : 3
1 : 1 : 3
1 : 1 : 2
1 : 1 : 2
1
1
5
3
78
40
38
10
K2CO3 + H2O (50%)
K2CO3 (anhydrous)
K2CO3 + H2O (20%)
* The yield with respect to the isolated product.
solutions of K2CO3 or KOH (Table 1). A decrease in the
yield of compound 4 is attributable to the fact that deꢀ
composition of nitrosourea 2 in the presence of anhyꢀ
drous K2CO3 proceeded very slowly, whereas decomposiꢀ
tion with the use of aqueous solutions of the base proꢀ
ceeded, on the contrary, vigorously, which was characꢀ
terized by substantial deazotization of intermediate diꢀ
azonium ion 1 under the action of H2O.
Under the action of a methanolic solution of KOH,
the percentage of isomer Eꢀ7 in the resulting mixture of
hydrazones Zꢀ7 and Eꢀ7 in CH2Cl2 increased. According
1
1
In the H and 13C NMR spectra of compound 4 in
to the H NMR spectroscopic data, the ratio between
CDCl3, the signals of the protons of the methyl groups
differ by 0.19 and 4.9 ppm, respectively, which is indicaꢀ
tive of their nonequivalence due to a fixed position of the
cyclopropylamine substituent with respect to the C=N
bond. The signal of the proton of the NH fragment is
observed at low field (δ 13.6) due to the formation of an
intramolecular hydrogen bond with the carbonyl O atom.
Decomposition of nitrosourea 2 under the action of
K2CO3 in CH2Cl2 in the presence of diketone 3b using
the reagent molar ratio of 1.2 : 2.5 : 1 also proceeded rather
efficiently to give 2ꢀcyclopropylꢀ1ꢀ(2ꢀthienyl)hydrazonoꢀ
butaneꢀ1,3ꢀdione (5) in ∼75% yield with respect to the
isolated product (see Scheme 1), ∼20% of the startꢀ
isomers Zꢀ7 and Eꢀ7 changed from ∼5 : 1 to ∼1 : 3.3 after
stirring for 36 h. After treatment of the reaction mixture
with diethyl ether, isomer Eꢀ7 was isolated in the indiꢀ
vidual form as beige needleꢀlike crystals. The repeated
treatment of a solution of isomer Eꢀ7 in CH2Cl2 with a
methanolic solution of KOH again gave rise to isomer
Zꢀ7, but isomer Eꢀ7 did remain the major product. After
storage of the reaction mixture for 4 days, the ratio beꢀ
tween isomers Zꢀ7 and Eꢀ7 was ∼1 : 6, which is, apparꢀ
ently, most close to the equilibrium state under the reacꢀ
tion conditions used. Therefore, isomer Eꢀ7 is the most
stable product in the presence of strong bases, whereas
azo coupling gives rise to isomer Zꢀ7 as the major prodꢀ
uct irrespective of whether K2CO3 or KOH in a ∼4 : 1
CH2Cl2—MeOH mixture is used for the generation of
cyclopropyldiazonium 1 from nitrosourea 2.
Unlike CH acids 3a—d, dimethyl malonate and acꢀ
etoacetic ester were not involved in azo coupling with
cyclopropyldiazonium 1 under the same reaction condiꢀ
tions. In the last two cases, nitrosourea 2 decomposed,
but dimethyl malonate or acetoacetic ester used as trapꢀ
ping agents were recovered.
Taking into account that the formation of products of
azo coupling of cyclopropyldiazonium 1 with activated
CH acids, in particular, with compounds 3a—d, and the
formation of the products of 1,3ꢀdipolar cycloaddition of
diazocyclopropane (8), for example, with acrylonitrile or
methyl methacrylate,11 proceeded under the same condiꢀ
tions of decomposition of nitrosourea 2, it was of interest
to examine the possibility of the simultaneous trapping of
intermediates 1 and 8 by the corresponding substrates.
1
ing diketone 3b remaining unconsumed. The H and
13C NMR spectra of the reaction product have one set of
signals corresponding to one of the possible isomers (preꢀ
sumably, to isomer 5 in which the cyclopropylamino fragꢀ
ment forms an intramolecular hydrogen bond with the
acetyl group).
Under analogous conditions, cyclopropyldiazonium 1
generated in situ reacted with malonodinitrile (3c) or meꢀ
thyl cyanoacetate (3d) to give the corresponding cycloꢀ
propylhydrazones 6 or 7 in 56—60% yields (Scheme 2).
The latter reaction afforded a mixture of isomeric hydrꢀ
azones Zꢀ7 and Eꢀ7 in a ratio of ∼5 : 1 (according to the
data on the integral intensities of the signals of the methoxy
1
groups in the H NMR spectrum). In addition, the specꢀ
trum has two broadened signals of the NH group at δ 11.7
and 8.3 corresponding to two different isomers. Since the
spectrum of symmetrically substituted hydrazone 6 has a
signal of the NH group at δ 8.5, it can be assumed that the

Coupling of the cyclopropyldiazonium ion
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 4, April, 2003
995
For this purpose, we studied decomposition of nitrosoꢀ
urea 2 in the presence of pentanedione 3a and acryloniꢀ
trile or methyl methacrylate using 2, 3a, and the unsaturꢀ
ated compound in a molar ratio of 1 : 4 : 4. The reaction
was carried out in CH2Cl2 by adding 2 equiv. of K2CO3
containing ∼20% of H2O at 5 °C for 2 h. After the removal
of an excess of 3a and unsaturated compounds from the
mixtures obtained in both reactions, the residues conꢀ
mide, although the latter readily gave the corresponding
spiro(1ꢀpyrazolineꢀ3,1´ꢀcyclopropanes)13—15 upon deꢀ
composition of nitrosourea 2 with sodium methoxide.
These results are in agreement with the earlier explanaꢀ
tion12 provided for the substantial shift of the equilibrium
to diazocyclopropane 8 in the presence of strong bases,
which is responsible for an increase in the rate of 1,3ꢀdiꢀ
polar cycloaddition dependent on the concentrations of
the starting reagents.
1
tained (according to H NMR spectroscopy) both hydrꢀ
azone 4 and a 1,3ꢀdipolar cycloaddition product, viz.,
pyrazoline 9 or pyrazoline 10 in the case of acrylonitrile
(4 : 9 ≈ 1 : 2.4) or methyl methacrylate (4 : 10 ≈ 1 : 2.2),
respectively (Scheme 3). However, the examination of
the competitive reactions of diazocyclopropane 8 with an
equimolar mixture of acrylonitrile and methyl methacryꢀ
late performed under the same conditions demonstrated
that acrylonitrile is ∼18 times more active than methyl
methacrylate. Apparently, these results are attributed, on
the one hand, to a low current concentration of diazo
compound 8 under the reaction conditions used (i.e., to
the shift of equilibrium to diazonium ion 1)12 and, on the
other hand, to a substantially lower rate of azo coupling of
diazonium 1 with pentanedione 3a compared to the rate
of 1,3ꢀdipolar cycloaddition of diazocyclopropane to the
aboveꢀmentioned acrylates.
In the above discussion of the possibility of azoꢀcouꢀ
pling, we considered cyclopropyldiazonium ion 1 as an
intermediate. However, it is not inconceivable that
cyclopropyldiazohydrate (11) serves as the reactive speꢀ
cies in this process, because only anions of weak acids,
–
viz., HCO3 and NCO–, or the hydroxide ion itself can
serve as counterions for cyclopropyldiazonium 1 (unlike
direct diazotization of aromatic amines). In addition, the
anions of aliphatic CH acids 3a—d can also be considered
as counterions. For example, this can give rise to a tight
ion pair, which is rapidly transformed into azo comꢀ
pounds 12 and then into more stable hydrazones 4—7
(Scheme 4).
Scheme 4
Scheme 3
It should be emphasized that intermediates 1 and 8 are
very unstable species and their successful trapping deꢀ
pends substantially on the nature of the substrates used.
In particular, the low reactivity of the trapping agent is,
apparently, responsible for the absence of azo coupling
products in the case of acetoacetic ester or dimethyl malꢀ
onate as well as for the absence of 1,3ꢀdipolar cycloaddiꢀ
tion products upon decomposition of nitrosourea 2 with
potassium carbonate in the presence of such unsaturꢀ
ated compounds as norbornene, styrene, or vinyl broꢀ
Therefore, decomposition of NꢀcyclopropylꢀNꢀ
nitrosourea with bases makes it possible to generate
cyclopropyldiazonium intermediates, which can be inꢀ
volved in azo coupling with some active CH acids analoꢀ
gously to the processes taking place in the series of aroꢀ
matic diazo compounds. As a result, cyclopropylhydrꢀ
azones, which cannot virtually be prepared according to
other methods, become readily accessible. Depending on

996
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 4, April, 2003
Tomilov et al.
malonodinitrile (3c) (0.27 g, 4 mmol), nitrosourea 2 (0.62 g,
4.8 mmol), and K2CO3 (1.65 g). After separation of the reaction
mixture by preparative TLC (SiO2, Et2O—benzene, 1 : 3), hydrꢀ
azone 6 was obtained in a yield of 0.30 g (56%) as yellow crysꢀ
tals, m.p. 67—69 °C, Rf 0.80. Found (%): C, 53.98; H, 4.74;
N, 41.29. C6H6N4. Calculated (%): C, 53.72; H, 4.51; N, 41.77.
1H NMR (CDCl3), δ: 0.95 (m, 4 H, CH2CH2); 3.20 (m, 1 H,
CH); 8.6 (br.s, 1 H, NH). 13C NMR (CDCl3), δ: 6.8 (CH2CH2);
33.8 (CH); 84.5 (C(2)); 108.3 and 112.3 (2 CN). Partial MS,
m/z (Irel (%)): 134 (4) [M]+, 133 (4) [M – H]+, 106 (30), 86
(57), 84 (92), 41 (100) [C3H5]+.
the nature of the trapping agents, either diazocyclopropane
or cyclopropyldiazonium and cyclopropyldiazohydrate
can be involved in the reactions performed under the
same conditions to give 1,3ꢀdipolar cycloaddition adducts
with unsaturated compounds or azo coupling products,
respectively. Hence, cyclopropyldiazonium intermediates
are related to both aliphatic and aromatic diazo comꢀ
pounds.
Experimental
Methyl (cyclopropylhydrazono)cyanoacetate (7). Potassium
carbonate (1.65 g) was added to a mixture of methyl cyanoacetate
(3d) (0.40 g, 4 mmol) and nitrosourea 2 (0.62 g, 4.8 mmol) in
CH2Cl2 (12 mL) at 5—7 °C. The reaction mixture was vigorꢀ
ously stirred for 2 h and then filtered. To remove unconsumed
ester 3d, the filtrate was treated with a 5% KOH solution (5 mL)
and then the aqueous layer was neutralized with a 5% aqueous
HCl solution and extracted with CH2Cl2 (3×5 mL). The organic
layer was dried with Na2SO4 and concentrated in vacuo to obꢀ
tain a viscous liquid as a mixture of isomeric hydrazones Zꢀ7 and
Eꢀ7 (∼5 : 1) in a yield of 0.41 g (∼60%). Found (%): C, 50.07;
H, 5.58; N, 24.80. C7H9N3O2. Calculated (%): C, 50.29; H, 5.43;
N, 25.14. 1H NMR for Zꢀ7 (CDCl3), δ: 0.92 (m, CH2CH2);
3.19 (m, CH); 3.81 (s, OMe); 11.7 (br.s, NH). 13C NMR for
Zꢀ7 (CDCl3), δ: 6.3 (CH2CH2); 33.8 (CH); 52.2 (OMe);
101.9 (C(2)); 115.7 (CN); 162.9 (CO). Partial MS,
m/z (Irel (%)): 167 (4) [M]+, 166 (4) [M – H]+, 108 (100) [M –
COOMe]+.
Isomerization of hydrazones Zꢀ7 and Eꢀ7. A 6% KOH soluꢀ
tion in MeOH (3 mL) was added to a solution of hydrazones Zꢀ7
and Eꢀ7 (∼5 : 1) (0.30 g) in CH2Cl2 (5 mL) and the reaction
mixture was stirred at 20 °C for 36 h. The solvents were evapoꢀ
rated in vacuo. The residue was washed with CH2Cl2 (5 mL),
treated with a 5% HCl solution (5 mL), and extracted with
CH2Cl2 (3×5 mL). The organic layer was dried with Na2SO4,
the solvent was removed in vacuo (according to results of
1H NMR spectroscopy of the residue, the ratio between isomers
Zꢀ7 and Eꢀ7 was ∼1 : 3.3). The residue was treated with Et2O
(2 mL) at –15 °C to obtain hydrazone Eꢀ7 in a yield of 0.14 g as
beige needleꢀlike crystals, m.p. 88—90 °C. Found (%): C, 50.51;
H, 5.59; N, 25.02. C7H9N3O2. Calculated (%): C, 50.29; H, 5.43;
N, 25.14. 1H NMR (CDCl3), δ: 0.92 (m, CH2CH2); 3.19
(m, CH); 3.88 (s, OMe); 8.3 (br.s, NH). 13C NMR (CDCl3), δ:
6.7 (CH2CH2); 33.1 (CH); 52.7 (OMe); 103.0 (C(2)); 110.7
(CN); 161.4 (CO). An analogous procedure was repeated for
individual hydrazone Eꢀ7. After 4 days, the ratio between isoꢀ
mers Zꢀ7 and Eꢀ7 (according to the 1H NMR spectroscopic
data) was ∼1 : 6, signals of other compounds being virtually abꢀ
sent in the spectrum.
The 1H and 13C NMR spectra were recorded on Bruker
ACꢀ200 (200 and 50.3 MHz, respectively) and Bruker AMꢀ300
(300 and 75.5 MHz) spectrometers for solutions in CDCl3 conꢀ
taining 0.05% of Me4Si as the internal standard. The mass specꢀ
tra were obtained on a Finnigan MAT INCOSꢀ50 instrument
(EI, 70 eV, direct inlet). The IR spectra were measured on a
Bruker IFSꢀ113v spectrometer in CCl4. The starting CH acids
3a,c,d (highꢀpurity grade) were used without additional purifiꢀ
cation. βꢀDiketone 3b (see Ref. 16) and NꢀcyclopropylꢀNꢀ
nitrosourea12,13 were synthesized according to known proꢀ
cedures. Potassium carbonate (reagent grade) used in the
experiments contained (according to the results of drying)
∼20% of H2O. The TLC analysis was carried out on silica gel
(0.040—0.063 mm, Merck).
3ꢀCyclopropylhydrazonopentaneꢀ2,4ꢀdione (4). Potassium
carbonate (1.65 g) was added to a mixture of pentanedione 3a
(0.40 g, 4 mmol) and NꢀcyclopropylꢀNꢀnitrosourea (2) (0.62 g,
4.8 mmol) in CH2Cl2 (15 mL) at 5—7 °C and the reaction
mixture was vigorously stirred at this temperature for 2.5 h.
Then the reaction mixtue was filtered, the solvent was removed
in vacuo, and the residue was crystallized from hexane at –15 °C.
Hydrazone 4 was obtained in a yield of 0.56 g (84%) as yellow
crystals, m.p. 32—34 °C. Found (%): C, 57.42; H, 7.48; N, 16.52.
C8H12N2O2. Calculated (%): C, 57.13; H, 7.19; N, 16.66.
1H NMR (CDCl3), δ: 0.98 (m, 4 H, CH2CH2); 2.30 and 2.49
(both s, 2×3 H, 2 Me); 3.20 (br.ddt, 1 H, CH, Jcis ≈ 10.2 and
7.5 Hz, Jtrans ≈ 4.0 Hz); 13.6 (br.s, 1 H, NH). 13C NMR (CDCl3),
δ: 6.5 (CH2CH2); 26.4 (C(1)); 31.3 (C(5)); 33.9 (CH);
133.2 (C(3)); 196.7 and 196.8 (C(2) and C(4)). Partial MS,
m/z (Irel (%)): 168 (1.5) [M]+, 167 (1.5) [M – H]+, 125 (38)
[M – COMe]+, 43 (100) [COMe]+.
2ꢀCyclopropylhydrazonoꢀ1ꢀ(2ꢀthienyl)butaneꢀ1,3ꢀdione (5).
Hydrazone 5 was prepared according to the aboveꢀdescribed
procedure from 1ꢀ(2ꢀthienyl)butaneꢀ1,3ꢀdione (0.67 g, 4 mmol)
(3b), nitrosourea 2 (0.62 g, 4.8 mmol), and K2CO3 (1.65 g).
After recrystallization from hexane, hydrazone 5 was obtained
in a yield of 0.71 g (75%) as orange crystals, m.p. 45—47 °C.
Found (%): C, 55.64; H, 5.27. C11H12N2O2S. Calculated (%):
C, 55.92; H, 5.12. 1H NMR (CDCl3), δ: 0.97 and 1.04 (both m,
2×2 H, CH2CH2); 2.57 (s, 3 H, Me); 3.28 (m, 1 H, CH); 7.12
(dd, 1 H, H(4), J = 4.9 Hz, J = 3.7 Hz); 7.60 (dd, 1 H, H(5),
J = 4.9 Hz, J = 1.2 Hz); 7.94 (dd, 1 H, H(3), J = 3.7 Hz,
J = 1.2 Hz); 13.6 (br.s, 1 H, NH). 13C NMR (CDCl3), δ: 6.9
(CH2CH2); 30.8 (Me); 33.8 (CH); 127.0 (C(4´)); 132.3 (C(2));
134.1 and 134.2 (C(3´) and C(5´)); 141.0 (C(2´)); 181.7 (C(1));
197.5 (C(3)). Partial MS, m/z (Irel (%)): 236 (1.5) [M]+, 235 (1)
[M – H]+, 193 (19) [M – COMe]+, 111 (100) [(C4H3S)CO]+.
2ꢀ(Cyclopropylhydrazono)malonodinitrile (6). Hydrazone 6
was prepared according to the aboveꢀdescribed procedure from
Competitive formation of cyclopropylhydrazone 4 and
spiro(pyrazolinecyclopropanes). Potassium carbonate (165 mg)
containing ∼20% of H2O was added in one portion to a mixture
of acrylonitrile (106 mg, 2.0 mmol) or methyl methacrylate
(200 mg, 2.0 mmol), acetylacetone (200 mg, 2.0 mmol), and
nitrosourea 2 (70 mg, 0.5 mmol) in CH2Cl2 (7 mL) at 5 °C. The
reaction mixture was stirred for 2 h and filtered. The solvent and
the starting compounds, including acetylacetone, were removed
in vacuo. The residues obtained in both cases were analyzed by
1H NMR spectroscopy. In the case of acrylonitrile, compound 4
and pyrazoline 9 were generated in a ratio of ∼1 : 2.4. In the case

Coupling of the cyclopropyldiazonium ion
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 4, April, 2003
997
of methyl methacrylate, the ratio between compound 4 and
pyrazoline 10 was ∼1 : 2.2.
8. Yu. V. Tomilov, I. V. Kostyuchenko, E. V. Shulishov, and
O. M. Nefedov, Izv. Akad. Nauk, Ser. Khim., 1997, 532
[Russ. Chem. Bull., 1997, 46, 511 (Engl. Transl.)].
9. S. M. Parmerter, in Organic Reactions, Ed. R. Adams, John
Wiley, New York, 1959, 10, p. 1.
10. Yu. P. Kitaev and B. I. Buzykin, Gidrazony [Hydrazones],
Nauka, Moscow, 1974, p. 26 (in Russian).
11. Yu. V. Tomilov, I. V. Kostyuchenko, I. P. Klimenko, and
O. M. Nefedov, The 12th Europ. Symp. on Organic Chemisꢀ
try, Groningen, The Netherlands, 2001, P2ꢀ107.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 02ꢀ03ꢀ33365
and 00ꢀ15ꢀ97387) and by the Complex Program of Scienꢀ
tific Research of the Russian Academy of Sciences "New
Principles and Methods for Construction and Directed
Synthesis of Compounds with Desired Properties."
12. W. Kirmse and H. Schutte, Chem. Ber., 1968, 101, 1674.
13. Yu. V. Tomilov, E. V. Shulishov, and O. M. Nefedov, Izv.
Akad. Nauk SSSR, Ser. Khim., 1991, 1057 [Bull. Acad. Sci.
USSR, Div. Chem. Sci., 1991, 40, 939 (Engl. Transl.)].
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Averkiev, M. Yu. Antipin, and O. M. Nefedov, Izv. Akad.
Nauk, Ser. Khim., 1999, 1328 [Russ. Chem. Bull., 1999, 48,
1316 (Engl. Transl.)].
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Received December 10, 2002;
in revised form February 10, 2003