Synthesis and heteroelectrocyclization of unsymmetrically substituted diazomalonamides

Article abstract of DOI:10.1023/B:RUCB.0000042291.70287.2d

A selective procedure was developed for the synthesis of 1,2,3-triazoles and unsymmetrically substituted diazomalonamides. Cyclization of unsymmetrically substituted diazomalonamides to 1,2,3-triazoles was studied by the method of intramolecular competiti

Full text of DOI:10.1023/B:RUCB.0000042291.70287.2d

Russian Chemical Bulletin, International Edition, Vol. 53, No. 6, pp. 1305—1310, June, 2004
1305
Synthesis and heteroelectrocyclization of
unsymmetrically substituted diazomalonamides ✾
Yu. Yu. Morzherin,ꢀ Yu. O. Subbotina, Yu. I. Nein, M. Yu. Kolobov, and V. A. Bakulev
Urals State Technical University,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Eꢀmail: morjerine@htf.ustu.ru
A selective procedure was developed for the synthesis of 1,2,3ꢀtriazoles and unsymmetrically
substituted diazomalonamides. Cyclization of unsymmetrically substituted diazomalonamides
to 1,2,3ꢀtriazoles was studied by the method of intramolecular competitive reactions. The
kinetic and thermodynamic characteristics of the process were determined. Quantumꢀchemiꢀ
cal calculations for the monorotatory electrocyclic and nonrotatory heteroelectrocyclic mechaꢀ
nisms of cyclization were carried out. NꢀAryldiazomalonamides undergo cyclization according
to the heteroelectrocyclic mechanism, whereas cyclization of Nꢀalkyldiazomalonamides proꢀ
ceeds by the monorotatory mechanism. The experimental constant of competition between
these processes is (1.3—8.3)•103 (DMSOꢀd6) and (45.2—72.4)•103 (CD3OD).
Key words: 1,2,3ꢀtriazoles, diazo compounds, method of intramolecular competitive reacꢀ
tions, cyclization, quantumꢀchemical calculations, thermodynamic stability, rate constant.
ogy5,10 as colorꢀsensitive reagents, metal corrosion inꢀ
hibitors, and light stabilizers for polymers.
Chemistry of aliphatic diazo compounds has been exꢀ
tensively developed over the last several decades.1—4
Diazoalkanes bearing the carbamoyl group in the α posiꢀ
tion are of particular interest. These compounds were
used for the synthesis of 1,2,3ꢀtriazole derivatives, which
have found wide application in synthetic organic chemisꢀ
try, technology, and medicine.5,6 Compounds of this class
attract considerable interest because of their biological
activity.7—9 For example, the 1,2,3ꢀtriazole ring is inꢀ
volved as a structural fragment in many βꢀlactam antiꢀ
biotics (for example, in Tazobactam or Cefatrizine).
1,2,3ꢀTriazoles have also found extensive use in technolꢀ
However, cyclization pathways of unsymmetrical
diazomalonamides to isomeric 5ꢀhydroxyꢀ1,2,3ꢀtriazoles
are scantily studied. Earlier, we have demonstrated11 that
the transformation of diazoacetamides into 5ꢀhydroxyꢀ
1,2,3ꢀtriazoles can occur by two different mechanisms,
viz., as either the classical electrocyclic process or the
1,5ꢀheteroelectrocyclic process, depending on the subꢀ
stituent at the nitrogen atom of the carboxamide group.
In the present study, we examined regioselective cyꢀ
clization of unsymmetrical diazomalonamides 1a—c to
1,2,3ꢀtriazoles 2a—c or 3a—c (Scheme 1).
Scheme 1
Results and Discussion
Unsymmetrical diazomalonamides were synthesized
according to two methods: 1) by diazotization of 2ꢀaminoꢀ
malonamides 4a—c, which were prepared from malonꢀ
amides 5a—c through oximes 6a—c (Scheme 2) in a total
yield of 20—45%; 2) by diazo transfer4 to malonamides
5a—c (Scheme 3).
The reaction of amides 5a—c with tosyl azide generꢀ
ates diazo compounds 1. Under basic conditions,5 the
latter could undergo cyclization at the alkylamide or
arylamide group to give isomeric triazoles 2 or 3. We
demonstrated that under basic conditions, the arylamide
group in compound 1 is more reactive than the alkylamide
group. Only 1ꢀarylꢀ1,2,3ꢀtriazolates 7a—c were isolated
in good yield, whereas the isomeric product was not deꢀ
R = Me (a), OMe (b), Br (c)
K1 = k–1/k1 = [1]/[2], K2 = k–2/k2 = [1]/[3], K = [3]/[2].
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1252—1257, June, 2004.
1066ꢀ5285/04/5306ꢀ1305 © 2004 Plenum Publishing Corporation

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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 6, June, 2004
Morzherin et al.
Scheme 2
Table 1. 1H NMR spectra (DMSOꢀd6) of compounds 1a—c,
2a—c, and 3a—c
Comꢀ
pound
δ
Me
ArH (d)
R (s)
2.26
NH
1a
1b
2.82 (d)
7.66, 7.38
9.80 (s),
10.40 (q)
9.90 (s),
10.40 (q)
8.60 (q)
10.50 (q)
10.60 (q)
8.36 (br.s)
9.82 (s)
3.09 (d)
7.76, 7.00
3.92
1c
2a
2b
2c
3a
3b
3c
2.77 (d)
2.77 (d)
3.02 (d)
2.83 (br.s)
3.72 (s)
3.78 (s)
3.74 (s)
7.53, 7.48
7.40, 7.12
7.78, 7.05
7.81, 7.77
7.61, 7.11
7.75, 7.05
7.77, 7.50
—
2.26
3.82
—
2.38
3.96
—
9.80 (s)
10.24 (s)
sorption band12,13 of the diazo group at 2250 cm–1. The
characteristics of these compounds are identical to those
of compounds prepared by diazotization of 2ꢀaminoꢀ
malonamides 4a—c. Therefore, we developed a new
regioselective procedure for the synthesis of isomeric
1ꢀarylꢀ1,2,3ꢀtriazoles 2, 1ꢀalkylꢀ1,2,3ꢀtriazoles 3, and
unsymmetrically substituted diazomalonamides 1 by the
Cornforth rearrangement.
The kinetics and the equilibrium for the rearrangeꢀ
ment of 1ꢀarylꢀ1,2,3ꢀtriazoles 2a—c into diazomalonꢀ
amides 1a—c and 1ꢀmethylꢀ1,2,3ꢀtriazoles 3a—c were
studied by 1H NMR spectroscopy in CD3OD and
DMSOꢀd6 at 50 °C. We demonstrated (Table 3) that the
ternary equilibrium is shifted toward 1ꢀalkylꢀ1,2,3ꢀtriꢀ
azoles 3a—c. The use of CD3OD instead of DMSO as the
solvent leads to better stabilization of diazo compound 1
(see Table 3). Based on the results of our study, comꢀ
pounds 1—3 can be arranged in the order of decreasing
thermodynamic stability as follows: 1ꢀmethylꢀ1,2,3ꢀtriꢀ
azoles 3 > diazomalonamides 1 > 1ꢀarylꢀ1,2,3ꢀtriazoles 2.
R = Me (a), OMe (b), Br (c)
tected by TLC. The 1H NMR spectra of heterocycles
7a—c show signals of aromatic protons (and the substituꢀ
ent in the aromatic ring, Table 1) at δ 7.00—8.00, a oneꢀ
proton quartet of the NHMe proton at δ 10.00—10.50,
and a threeꢀproton doublet of the NHMe group at
δ 2.80—3.00.
After treatment of aqueous solutions of compounds
7a—c with concentrated hydrochloric acid, 1ꢀarylꢀ1,2,3ꢀ
triazoles 2a—c were isolated in good yields. Refluxing of
solutions of compounds 2a—c in toluene for 10 h afforded
1ꢀmethylꢀ1,2,3ꢀtriazoles 3a—c (in 60—80% yields) as preꢀ
cipitates. Diazomalonamides 1a—c were isolated from
the filtrate in 20—30% yields upon cooling. The IR specꢀ
tra of diazo compounds 1a—c have a characteristic abꢀ
Scheme 3
R = Me (a), OMe (b), Br (c)

Unsymmetrical diazomalonamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 6, June, 2004
1307
Table 2. 13C NMR spectra (DMSOꢀd6) of compounds 1a—c, 2a—c, and 3a—c
Comꢀ
pound
δ
C(1)
C(2)
C(3)
C(4)
C(5), C(6), C(7), C(8)
R
1a
1b
1c
2a
2b
2c
3a
3b
3c
26.1
26.9
26.1
25.2
26.0
25.2
31.8
31.9
31.7
162.6
162.3
162.4
160.3
160.1
162.4
156.7
159.9
152.2
64.8
65.0
65.3
105.2
110.1
115.2
116.5
115.2
114.9
160.3
160.8
160.4
153.2
154.0
153.0
162.3
161.3
158.8
137.90, 135.75, 129.26, 119.55
139.9, 130.7, 125.2, 121.5
137.6, 131.4, 121.5, 114.9
138.03, 132.69, 129.73, 122.00
138.0, 132.9, 129.7, 122.0
134.5, 132.2, 123.4, 120.8
133.81, 132.20, 130.62, 129.60
137.8, 132.0, 129.6, 120.6
138.1, 131.6, 121.7, 115.3
20.4
55.0
—
20.6
56.0
—
20.8
55.2
—
Table 3. Ternary equilibrium of diazomalonamides 1a—c and
triazoles 2a—c and 3a—c in DMSOꢀd6 and CD3OD (in parenꢀ
theses)
C (%)
3
2
80
60
40
20
Comꢀ
pound
Content (%)
Equilibrium constants
1
2
3
K1
K2
K
a
b
c
6.6
4.1
89.3
(87.6)
88.6
(88.6)
84.7
1.610
(7.267)
1.111
(6.125)
2.558
0.07391
(0.1244)
0.06772
(0.1106)
0.1299
21.78
(58.40)
16.41
(55.38)
19.70
(10.9) (1.5)
6.0 5.4
(9.8) (1.6)
11.0 4.3
(13.8) (0.8)
1
0
20
40
60
80
100
τ/min
Fig. 1. Concentration dependence of compounds 1a (1), 2a (2),
and 3a (3) on the reaction time in CD3OD.
(85.4) (17.25)
(0.1616) (106.8)
The rate constants k1, k2, k–1, and k–2 (see Scheme 1)
can be calculated from the equilibrium constants K1, K2,
and K according to Eqs (3)—(6) (Table 5). These equaꢀ
tions were derived analogously to those reported earlier.11
The typical kinetic curves for the rearrangements unꢀ
der study are shown in Fig. 1. It should be noted that the
concentration of diazo compounds 1a—c changes only
slightly in the course of the process. However, the obꢀ
served constant of formation of 1ꢀmethylꢀ1,2,3ꢀtriazoles
3a—c is substantially smaller than the constant of disapꢀ
pearance of 1ꢀarylꢀ1,2,3ꢀtriazoles 2a—c (Table 4). Thereꢀ
fore, the kinetic equations can be reduced to Eqs (1)
and (2) using the stationary state method.14
(3)
k–2 ≈ kdis/(1 + K + K1)
k2 = k–2/K2
(4)
(5)
(6)
(1)
(2)
k–1 = k1K1
Therefore, we demonstrated that cyclization of the
diazo group at the arylamide group occurs much more
Table 4. Observed constants of disappearance (kdis) of 1ꢀarylꢀ1,2,3ꢀtriazoles 2a—c and constants of appearance (kapp) of 1ꢀalkylꢀ
1,2,3ꢀtriazoles 3a—c in DMSOꢀd6 and CD3OD
Comꢀ
pound
kdis (2a—c)
kapp (3a—c)
DMSOꢀd6
kdis•106/s–1 r2
CD3OD
kdis•107/s–1
DMSOꢀd6
kapp•107/s–1 r2
CD3OD
kapp•107/s–1
r2
r2
a
b
c
22.30 0.05
18.98 0.08
25.33 0.07
0.9992
0.9989
0.9987
56.61 0.04
65.40 0.05
112.0 0.6
0.9993
0.9991
0.9994
85.45 0.05
89.91 0.07
71.19 0.09
0.9989
0.9991
0.990
6.848 0.008
9.179 0.005
6.137 0.005
0.9994
0.9991
0.9992

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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 6, June, 2004
Morzherin et al.
Table 5. Calculated constants of cyclization of unsymmetrically substituted diazomalonamides 1a—c to triazoles 2a—c
and 3a—c
Comꢀ
pounds
1—3
DMSOꢀd6
CD3OD
k1•102
k–1•102
k2•106
k–2•106
k1/k2
k1•102
k–1•102
k2•107
k–2•107
k1/k2
s–1
s–1
a
b
c
5.57
1.95
6.98
8.97
2.16
17.9
12.4
15.1
8.39
0.914
1.02
1.09
4500
1290
8320
3.61
1.82
4.01
26.2
11.2
69.2
6.82
9.46
5.54
0.849
1.05
0.896
52800
19300
72400
rapidly than that at the alkylamide group. The constant of
competition between these processes is (1.3—72.4)•103
(see Table 5). The difference in the activation energy is
should be noted that the calculations for the gas phase by
both the PM3 and DFT methods showed no difference
for the alkyl and aryl derivatives. In both cases, the
heteroelectrocyclic mechanism is preferable to the electroꢀ
cyclic one.
4.6—7.3 kcal mol–1
.
We carried out semiempirical quantumꢀchemical calꢀ
culations (PM3 method)15—17 and the density functional
theory (DFT) at the BLYP/6ꢀ31G(d) level18 for the
electrocyclic (I) and heteroelectrocyclic (II) (Scheme 4)
mechanisms of cyclization of diazomalonamides. The acꢀ
tivation energy for the electrocyclic (with rotation about
the terminal nitrogen atoms) mechanism of cyclization of
both Nꢀarylꢀ and Nꢀalkylamides (see Scheme 4, path A) is
32—34 (BLYP/6ꢀ31G(d)) and 36—41 kcal mol–1 (PM3)
(the rate constant is 3•10–9—1•10–14 s–1). The activaꢀ
tion energy for the heteroelectrocyclic mechanism (no
rotation about the terminal bonds occurs, and a new
σꢀbond is formed with the involvement of the lone elecꢀ
tron pair and the unoccupied orbital located orthogonal
Substituents in the aryl residue have different effects
on cyclization of the diazo group at the nitrogen atom of
the carbamoyl group containing an aromatic or alkyl subꢀ
stituent. Electronꢀwithdrawing substituents accelerate cyꢀ
clization at the anilide nitrogen atom and, on the conꢀ
trary, decelerate cyclization at the nitrogen atom of the
methylcarbamoyl group (see Table 5). This is attributable
to the fact that in the case of the electrocyclic mechaꢀ
nism, where a new σ bond is formed with the involvement
of orbitals of the π system, a decrease in the electron
density in the π system due to the presence of πꢀconjuꢀ
gated electronegative substituents hinders cyclization. In
the case of the heteroelectrocyclic mechanism, where a
new σ bond is formed due to interactions of orbitals loꢀ
cated perpendicular to the π system, this conjugation faꢀ
cilitates the electron density redistribution in the π sysꢀ
tem, which has no effect on the cyclization process (the
π system is not involved in the formation of a σ bond) and
only contributes to stabilization of the transition aromatic
to the π system in the plane of the molecule19—26
)
of cyclization of diazomalonamides is 18—22
(BLYP/6ꢀ31G(d)) and 22—24 (PM3) kcal mol–1 (the
rate constant is 1.2•10–2—5•10–4 s–1). These values agree
well with the experimental rate constants k1 and k2 deterꢀ
mined in the study of the equilibrium (see Table 5). It
Scheme 4

Unsymmetrical diazomalonamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 6, June, 2004
1309
B. A solution of triazole 2a—c (10 mmol) in toluene (50 mL)
was refluxed for 10 h and then cooled. Triazole 3a—c was filꢀ
tered off. The filtrate was concentrated in vacuo and the residue
containing malonamide 1a—c was triturated in hexane.
1ꢀArylꢀ5ꢀhydroxyꢀNꢀmethylꢀ1,2,3ꢀtriazoleꢀ4ꢀcarboxamides
(2a—c). Sodium 1ꢀarylꢀ4ꢀ(Nꢀmethylcarbamoyl)ꢀ1,2,3ꢀtriazolꢀ
5ꢀolate (7) (10 mmol) was dissolved in water (10 mL) and the
solution was acidified with concentrated hydrochloric acid to
pH 3—4 at 0—10 °C. The precipitate that formed was filtered off
and dried over P2O5 in vacuo.
state, thus decreasing the activation energy of cyclization
proceeding by the heteroelectrocyclic mechanism. If the
lone electron pair of the nitrogen atom of the carbamoyl
group is involved in π conjugation, electronꢀwithdrawing
substituents will decelerate cyclization. If the carbamoyl
group is in the tautomeric oxyimine form, the lone elecꢀ
tron pair of the nitrogen atom is orthogonal to the π system
and the electronꢀwithdrawing substituents promote the
reaction.
NꢀArylꢀ5ꢀhydroxyꢀ1ꢀmethylꢀ1,2,3ꢀtriazoleꢀ4ꢀcarboxamides
(3a—c). A solution of triazole 2a—c (10 mmol) in toluene
(50 mL) was refluxed for 10 h and then cooled. Triazole 3a—c
was filtered off, dried over P2O5 in vacuo, and crystallized from
ethanol.
It can be concluded that cyclization of unsymmetriꢀ
cally substituted diazomalonamides also proceeds by two
different mechanisms, viz., by the pseudopericyclic
mechanism for aryl derivatives and the monorotatory
mechanism for alkyl derivatives. This provides an explaꢀ
nation for the fact that only one isomer is formed in the
diazo transfer to malonamides 5a—c. Since the rate of
cyclization of the diazo group at the carboxamide fragꢀ
ment containing the aryl substituent is higher than that at
the fragment containing the alkyl substituent, only 1ꢀarylꢀ
1,2,3ꢀtriazolꢀ5ꢀolate 2 is produced. The formation of
triazolꢀ5ꢀolates proceeds irreversibly and, consequently,
isomeric 1ꢀalkylꢀ1,2,3ꢀtriazolꢀ5ꢀolate is not generated.
To summarize, we have developed a new selective
procedure for the synthesis of diazomalonamides and
1,2,3ꢀtriazoles. The kinetic data for cyclization of diazoꢀ
malonamides to isomeric 1,2,3ꢀtriazoles are consistent
with the electrocyclic mechanism for cyclization of
Nꢀalkyldiazomalonamides and the heteroelectrocyclic
mechanism for cyclization of Nꢀaryldiazomalonamides.
Table 6. Characteristics of compounds 1—4, 6, and 7
Comꢀ Yield M.p.
Found
Calculated
Molecular
formula
(%)
N
poꢀ
(%) /°C
und
C
H
1a
1b
1c
2a
2b
2c
3a
3b
3c
4a
4b
4c
6a
6b
6c
7a
7b
7c
86a,
80
57.0
5.4
24.0 C11H12N4O2
12b (decomp.) 56.89 5.21 24.12
90a,
8b (decomp.) 53.22 4.87 22.57
75a,
94 40.5 3.2 19.0 C10H9BrN4O2
10b (decomp.) 40.43 3.05 18.86
75
53.6
5.0
22.3 C11H12N4O3
95
93
98
72
62
80
45
59
36
64
59
65
87
82
78
126
135
186
139
156
189
96
57.0
56.89 5.21 24.12
53.3 4.9 22.6 C11H12N4O3
53.22 4.87 22.57
40.5 2.9 18.9 C10H9BrN4O2
40.43 3.05 18.86
56.6 5.5 24.2 C11H12N4O2
56.89 5.21 24.12
53.2 5.0 22.7 C11H12N4O3
53.22 4.87 22.57
40.5 3.1 18.9 C10H9BrN4O2
40.43 3.05 18.86
60.0 7.0 19.2 C11H15N3O2
59.71 6.83 18.99
55.5 6.4 17.8 C11H15N3O3
55.69 6.37 17.71
41.5 4.5 14.9 C10H12BrN3O2
41.98 4.23 14.69
56.2 5.4 17.9 C11H13N3O3
56.16 5.57 17.86
52.5 5.5 16.5 C11H13N3O4
52.59 5.22 16.72
39.8 3.8 13.9 C10H10BrN3O3
40.02 3.36 14.00
48.6 4.6 20.6 C11H11N4NaO2
48.53 4.81 20.58 •H2O
45.3 4.6 19.3 C11H11N4NaO3
45.84 4.55 19.44 •H2O
35.3 3.4 16.3 C10H8BrN4NaO2
35.63 2.99 16.62 •H2O
5.1
24.1 C11H12N4O2
Experimental
The 1H and 13C NMR spectra were recorded at 400 and
100 MHz, respectively, on a Bruker AMX 400 instrument in
DMSOꢀd6 or CD3OD with Me4Si as the internal standard.
The electronꢀimpact mass spectra were obtained on a Varian
MAT 311A instrument (40—200 °C, 70 eV). The IR spectra
were measured on a URꢀ25 spectrometer in KBr pellets. The
course of the reactions and the purity of the compounds synꢀ
thesized were monitored by TLC on Silufol UVꢀ254 plates in
chloroform and the ethyl acetate—hexane (3 : 1), chloroꢀ
form—ethanol (9 : 1), and chloroform—ethanol—ammonia
(25%) (60 : 11 : 1) systems. All solvents were purified before use
according to standard procedures.
Kinetics and equilibrium. A 0.11 M solution of compounds
2a—c in DMSOꢀd6 or CD3OD was placed in an NMR tube and
the tube was heated in a thermostat at 60 °C. The NMR specꢀ
trum was recorded at equal intervals. The concentration of the
compounds was monitored by the integral intensity of the sigꢀ
nals for the protons of the aromatic ring and the methyl group.
The observed rate constant of the reaction was calculated using
the linear regression programs.
68
115
196
205
215
>250
>250
>250
NꢀArylꢀN´ꢀmethylꢀ2ꢀdiazomalonamides (1a—c). A. A soluꢀ
tion of sodium nitrite (0.345 g, 5 mmol) in water (10 mL) was
added dropwise with stirring to a solution of 2ꢀaminoꢀNꢀarylꢀ
N´ꢀmethylmalonamide 4a—c (5 mmol) in 1 M HCl (40 mL)
at 0 °C. The reaction mixture was stirred for 20 min. The preꢀ
cipitate that formed was filtered off and dried over P2O5 in vacuo.
a Method A.
b Method B.

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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 6, June, 2004
Morzherin et al.
2ꢀAminoꢀNꢀarylꢀN´ꢀmethylmalonamides (4a—c). NꢀArylꢀ2ꢀ
hydroxyiminoꢀN´ꢀmethylmalonamide 6 (10 mmol) was added
to a suspension of aluminum amalgam (0.4 g, 1.48 mmol) in
diethyl ether (50 mL) at 0 °C. The reaction mixture was stirred
at 0—5 °C for 2 h. Then water (10 mL) was added. The mixture
was stirred for 30 min and then filtered. Amine 4 was extracted
from the precipitate with hot ethanol (3×50 mL). The combined
extracts were concentrated to dryness. The residue was trituꢀ
rated and crystallized from ethanol.
NꢀArylꢀ2ꢀhydroxyiminoꢀN´ꢀmethylmalonamides (6a—c).
Ethyl nitrite (0.83 mL, 0.75 g, 10 mmol) was added in one
portion to a suspension of malonamide 5a—c (5 mmol) in soꢀ
dium ethoxide, which was prepared from anhydrous ethanol
(50 mL) and sodium (0.115 g, 5 mmol), at 0—5 °C. The reaction
mixture was stirred at this temperature for 2 h and concentrated
in vacuo to dryness. Water (50 mL) was added to the residue.
Unconsumed malonamide 5 was filtered off and the filtrate was
acidified to pH 3. The precipitate was filtered off and crystalꢀ
lized from ethanol.
Schaadt, D. Stapert, and B. H. Yagi, J. Med. Chem., 2000,
43, 953.
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Sodium 1ꢀarylꢀ4ꢀ(Nꢀmethylcarbamoyl)ꢀ1,2,3ꢀtriazolꢀ5ꢀolates
(7a—c). A solution of tosyl azide (3.94 g, 20 mol) in ethanol
(5 mL) was added dropwise to a suspension of malonamide
4a—c (20 mmol) in sodium ethoxide, which was prepared from
anhydrous ethanol (100 mL) and sodium (0.460 g, 20 mmol),
at 0 °C. The reaction mixture was stirred at 0—5 °C for 2 h and
concentrated in vacuo to dryness. The residue was suspended in
water (50 mL). The precipitate containing tosylamide was filꢀ
tered off and the filtrate was concentrated to dryness. The prodꢀ
uct was dried over P2O5 in vacuo.
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Gaussian, Inc., Pittsburgh (PA), 2003.
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This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 02ꢀ03ꢀ
96421aꢀUral and 04ꢀ03ꢀ96104aꢀUral) and the US Civilꢀ
ian Research and Development Foundation (CRDF,
Grants RC1ꢀ2393ꢀEKꢀ02 and RECꢀ005).
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Received December 29, 2003;
in revised form April 9, 2004