Reactions of dimethyl 2-chloroethynylphosphonate with 1-substituted 5-oxo-1H-1,2,3,4-tetrazoles

Article abstract of DOI:10.1134/S107036321411019X

Addition of 1-substituted tetrazol-5-ones to dimethyl 2-chloroethynylphosphonate occurred regioselectively to form new geminally substituted bis(4-R-5-oxo-4,5-dihydro-1H-tetrazol-1-yl)ethenylphosphonates with 65- 92% yield.

Full text of DOI:10.1134/S107036321411019X

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 11, pp. 2160–2166. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © Yu.V. Mel’nikova, L.V. Myznikov, A.V. Dogadina, N.I. Svintsitskaya, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84,
No. 11, pp. 1863–1869.
Reactions of Dimethyl 2-Chloroethynylphosphonate
with 1-Substituted 5-Oxo-1H-1,2,3,4-tetrazoles
Yu. V. Mel’nikovaa, L. V. Myznikova, A. V. Dogadinab, and N. I. Svintsitskayab
a St. Petersburg State University of Technology and Design, St. Petersburg, Russia
b St. Petersburg State Institute of Technology (Technical University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: nsvincickaya@mail.ru
Received September 29, 2014
Abstract—Addition of 1-substituted tetrazol-5-ones to dimethyl 2-chloroethynylphosphonate occurred regioselectively
to form new geminally substituted bis(4-R-5-oxo-4,5-dihydro-1H-tetrazol-1-yl)ethenylphosphonates with 65–
92% yield.
Keywords: alkenylphosphonate, 5-oxo-1H-1,2,3,4-tetrazole, 2-chloroethynylphosphonate, nucleophilic addition,
N,O-binucleophile, X-ray diffraction
DOI: 10.1134/S107036321411019X
Alkenylphosphonates have been widely used to
produce biologically active compounds [1–4], flame
retardants [5], polymer additives [6]; they have found
interesting applications as reagents in organic synthesis
[7–9]. One of the most convenient approaches to
synthesize compounds of this class is nucleophilic
addition to the double bond. 2-Chloroethynylphos-
phonate has revealed high reactivity towards different
mono- and binucleophiles [10]. Nature of the nucleo-
philes defines regiochemistry of nucleophilic addition
to chloroacetylenephosphonate. In particular, reaction
with mononucleophilic reactants occurred via replace-
ment of the chlorine atom followed by addition of the
second nucleophile molecule to form geminally
disubstituted alkenylphosphonates [11]. The reaction
with bifunctional nucleophiles such as 1,2-alkanediols,
ethanolamine, o-aminophenol, and o-phenylenedi-
amine proceeded via substitution of chlorine atom
followed by nucleophilic attack of the second nucleo-
philic site at the same carbon atom to give phos-
phorylated 1,3-oxalanes, 4,5-dihydrooxazoles, benz-
oxazoles, and benzimidazoles, respectively [12].
Another direction of the reaction was observed in
the case of reacting 2-chloroethynylphosphonate with
1-substituted 5-thio-1,2,3,4-tetrazole under base catalysis
in a protic solvent. The reaction resulted in formation
of vicinally disubstituted alkenylphosphonates with
yields of 80–90% [13] (Scheme 1).
Some of the prepared dimethyl Z-1,2-bis[(1Н-1,2,3,4-
tetrazol-5-yl)sulfanyl]ethenylphosphonates showed high
antifungal activity comparable to that of fluconazole,
the latter being widely used in medical practice for
treatment of various fungal infections.
It was of interest to introduce structural analogs of
5-thio-1,2,3,4-tetrazoles, 1-substituted 5-oxo-1,2,3,4-
tetrazoles, into the reaction with 2-chloroethynylphos-
phonate. 1-Phenyl- (Ia), 1-benzyl- (Ib), 1-(2-chloro-
phenyl)- (Ic), 1-(4-nitrophenyl)- (Id), and 1-(2,4-
dinitrophenyl)-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ones
Scheme 1.
R
(MeO)2(O)P
S
H
N
t-BuOK
N
N
S
+
2
S
(MeO)2(O)P
Cl
MeOH
R
N
R
N
N
N
N
H
N N
N N
2160

REACTIONS OF DIMETHYL 2-CHLOROETHYNYLPHOSPHONATE
2161
Scheme 2.
Me
O
S
S
Me2SO4
NaOH
H2O, Δ
NaOH
EtOH
R
R
R
HN
HN
HN
N=C=S + NaN3
R
N
N
N
N
N
N
N
N
N
Ia–Ie
R = Ph (Iа), Bn (Ib), 2-Cl-C6H4 (Ic), 4-NO2-C6H4 (Id), 2,4-NO2-C6H3 (Ie).
Scheme 3.
N
R
R
R
N
N
N
N
(MeO)2(O)P
H
K2CO3
MeCN
N
N
O
O
+
2
O
(MeO)2(O)P
Cl
N
N
H
N
N
N
IIa–IIe
R = Ph (IIа), Bn (IIb), 2-Cl-C6H4 (IIc), 4-NO2-C6H4 (IId), 2,4-NO2-C6H3 (IIe).
Scheme 4.
N
N
R
(MeO)2(O)P
Cδ−
N
N
O
O
δ−
K2CO3
MeCN
K2CO3
MeCN
δ+
R
(MeO)2(O)P
H
N
R
N
(MeO)2(O)P C C N
O
O
N
HN
Cδ+
N
N
N
N
N
H
Cl
N
N
N
R
O
N
N
N
R
(Ie) were used as binucleophilic reagents. They were
obtained starting from isothiocyanate according to the
procedure adopted from [14–16] (Scheme 2).
The reaction progress was monitored by 31P NMR
spectroscopy. Completion of the reaction was re-
cognized by disappearance of the signal of starting
chloroacetylenephosphonate at –6 ppm and by appe-
arance of the signal of tetrazolyl-substituted alkenyl-
phosphonates IIa–IIe at 10–12 ppm.
The reaction of dimethyl 2-chloroethynylphos-
phonate with the substituted NH-tetrazol-5-ones was
found to proceed regioselectively to afford the geminally
disubstituted alkenylphosphonates IIa–IIe with 65–
87% yield. The reactions were carried out in
anhydrous acetonitrile using two-fold molar excess of
1-R-NH-tetrazol-5-one by stirring the reaction mixture
during 16–20 h at room temperature in the presence of
K2CO3 as acceptor of evolving hydrogen chloride.
The proposed reaction pathway includes two stages.
The first step involves nucleophilic attack of NH group
of the 1-R-tetrazol-5-one molecule at the C2 carbon
atom, leading to substitution of the labile chlorine
atom and to formation of the corresponding dimethyl-
(4-R-5-oxo-4,5-dihydro-1Н-teterazol-1-yl)ethynylphos-
phonate (Scheme 4).
At the next step, addition of the second molecule of
1-R-tetrazol-5-one occurs to produce geminally disub-
stituted bis(4-R-5-oxo-4,5-dihydro-1H-tetrazol-1-yl)-
ethenylphosphonates.
According to [17], under those reaction conditions
the 1-substituted 5-oxo-1H-1,2,3,4-tetrazoles reacted
exclusively as non-dissociated (neutral) molecules
(Scheme 3).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

2162
MEL’NIKOVA et al.
Table 1. NMR spectral data of compounds IIa–IIe
δН, ppm (JНР, Hz)
δС, ppm (JНР, Hz)
PCH= (1JCР)
Comp.
no.
m/z
δP, ppm
[M + Na]+
CH3OP (3JНР) PCH= (2JНР)
CH3OP (2JСР)
=CCl (2JCР)
IIа
IIb
IIc
IId
IIe
3.79 d (12.0)
3.63 d (11.5)
3.83 d (11.5)
3.85 d (12.0)
3.72 d (12.0)
6.94 d (4.0)
6.78 d (3.5)
6.97 d (4.0)
6.98 d (4.7)
6.89 d (4.0)
53.35 d (6.0)
109.58 d (189.2) 133.21 d (8.8)
106.53 d (190.5) 132.98 d (9.0)
107.49 d (189.8) 133.33 d (9.4)
108.88 d (189.2) 132.52 d (9.1)
107.84 d (188.7) 131.91 d (9.0)
11.98
12.17
11.98
11.20
10.98
479.5487
507.3924
547.9891
569.0637
659.3368
53.20 d (5.4)
53.44 d (5.4)
53.52 d (5.4)
52.72 d (5.7)
Noteworthily, reaction of chloroacetylenephosphonate
with 1-substituted 5-thio-1,2,3,4-tetrazoles under similar
conditions led to preferential formation of the cycliza-
tion products; only traces of linear vicinally disub-
stituted alkenylphosphonates were detected by spec-
troscopy [13]. In the latter case, unlike the reaction of
tetrazol-5-ones, the nucleophilic attack occurred
exclusively via the sulfur atom, and the nitrogen atom
was not involved into the reaction.
phosphonates IIa–IIe, the molecular ions [M + Na]+
peaks were found (Table 1).
X-Ray diffraction data of isolated dimethyl {2,2-bis-
[4-(2-chlorophenyl)-5-oxo-4,5-dihydro-1Н-tetrazol-1-
yl]ethenyl}phosphonate IIc unambiguously confirmed
the formation of geminally disubstituted alkenephos-
phonates (see figure). The compound crystallized in
the triclinic (P-1) space group with two molecules in
the asymmetric unit cell (Table 2). The bond lengths
and angles coincided with those typically found in
similar compounds and are listed in Tables 3–5.
Structure of compounds IIa–IIe was confirmed by
1
13
31
IR, H, C, and P NMR spectroscopy, mass spectro-
metry, and X-ray diffraction data. Main parameters of
1H, 13C, and 31P NMR spectra are summarized in Table 1.
In conclusion, nucleophilic addition of 1-substituted
NH-tetrazol-5-ones to dimethyl ester of 2-chloro-
ethynylphosphonic acid proceeds via regioselective
attack of NH site of the tetrazole at the C2 carbon atom
to form geminal bis(4-R-5-oxo-4,5-dihydro-1Н-tetera-
zol-1-yl)ethenylphosphonates. The obtained tetrazolyl-
substituted alkenylphosphonates are promising synthons
for preparation of tetrazolyl-containing phosphonates
with potentially wide range of biological activity.
1
In H NMR spectra of alkenylphosphonates IIa–
IIe, the protons of РОСН3 fragment resonated as a
3
doublet in the range of 3.63–3.85 ppm, JHP 11.5 Hz.
The methine proton of PCH moiety manifested as a
characteristic doublet signal in weak field (6.78–
6.98 ppm, 2JHP 3.0–3.5).
In 13C NMR spectra of IIa–IIe, a signal of the C1
carbon atom adjacent to the phosphorus atom appeared
as a doublet at δC 106.53–108.88 ppm split at phosphorus
nucleus with coupling constants of 1JСP 189.2–190.5 Hz,
typical of phosphonates with sp2-hybridized carbon
atom. The C2 carbon atom resonated as a weak doublet
EXPERIMENTAL
NMR spectra of the solutions in CDCl3 were
recorded with a Bruker Avance 400 spectrometer
[400.13 (1Н), 100.61 (13С), 161.98 MHz (31Р)] relative
to internal TMS (1Н, 13С) or external 85% H3PO4 (31Р)
reference. IR spectra were recorded using a Shimadzu
FTIR-8400S spectrometer (KBr pellets). Mass spectra
(HRMS-ESI) were recorded with a Bruker MicrOTOF
spectrometer. Melting points were determined on a
Kofler bench (VEB Wдgetechnik Rapido, РНМК
81/2969). X-Ray diffraction analysis was performed
using a Bruker APEX II CCD diffractometer. TLC
analysis was carried out on Merck Kieselgel 60F254
plates with a UV light developing.
2
signal in the range of 132.52–133.33 ppm, JСP 8.8–
9.4 Hz. An upfield doublet at about 53 ppm (2JСP 4.7–
5.4 Hz) corresponded to carbon atoms of PОСН3 groups.
The chemical shifts of phosphorus were found at δP
11.20–12.17 in the spectra of adducts IIa–IIe. IR
spectra of compounds IIa–IIe contained strong absorp-
tion bands assigned to stretching of phosphoryl group
(1247–1257 cm–1), of double carbon–carbon bond
(1630–1640 cm–1), and of double C=O bond (1686–
1696 cm–1). In the mass spectra (HRMS-ESI) of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

REACTIONS OF DIMETHYL 2-CHLOROETHYNYLPHOSPHONATE
Synthesis of 1-substituted NH-tetrazol-5-ones
2163
(general procedure). 0.058 mol of substituted isothio-
cyanate and about 60 mL of water were added upon
stirring to a solution of 0.087 mol of sodium azide in
50 mL of water. The reaction mixture was refluxed
during 1.5 h. The reaction progress was monitored
with TLC (hexane–EtOAc, 8 : 2). After the reaction
was complete, the reaction mixture was acidified with
conc. hydrochloric acid to pH ≈ 1. The formed pre-
cipitate was filtered off, dried in air, and recrystallized
from a large amount of water with the hot filtration.
Dimethylsulfate (0.024 mol) was added dropwise to
a solution of 0.015 mol of the so obtained 1-R-
tetrazole-5-thione in 50 mL of 5% sodium hydroxide
solution. The reaction mixture was stirred at room
temperature during 2 h. The reaction progress was
monitored with TLC (hexane–EtOAc, 1 : 1). After the
reaction was complete, the reaction mixture was
extracted three times with ethyl acetate, the extract was
washed sequentially with water, saturated sodium
chloride solution, and water; then it was dried over
Na2SO4 and evaporated. Crude 5-methylsulfanyl-1-R-
tetrazole was used without further purification.
General view of the molecule of dimethyl {2,2-bis[4-(2-
chlorophenyl)-5-oxo-4,5-dihydro-1H-tetrazol-1-yl]ethenyl}-
phosphonate IIc
reaction mixture was acidified with conc. hydrochloric
acid to pH ≈ 1. The formed precipitate was filtered off.
The filtrate was extracted with ethyl acetate, dried over
Na2SO4, and evaporated. The residue was recrystal-
lized from ethyl acetate.
A solution of 40 mL of ethanol and 0.066 mol of
sodium hydroxide was added to 0.0125 mol of 5-
methylsulfanyl-1-R-tetrazole upon stirring. The
reaction mixture was refluxed during 2 h. The reaction
progress was monitored with TLC (hexane–ethyl
acetate 1 : 1). After the reaction was complete, the
Synthesis of bis(4-R-5-oxo-4,5-dihydro-1H-tetra-
zol-1-yl)ethenylphosphonate (general procedure).
2.8 mmol of potassium carbonate and 5 mmol of 1-R-
Table 2. Crystallographic data of adduct IIc
Parameter
Formula
Value
Parameter
Value
C18H15Cl2N8O5P2
525.25
Z
2
1.549
М
dcalc, g/cm
T, K
100(2)
F(000)
536
Crystal system
Space group
a, Å
Triclinic
Р-1
μ, mm−1
3.711
7.04–153.44
23553
2θmax, deg
9.5300(3)
9.7408(3)
Reflections collected
b, Å
Independent reflections
4711 (0.0513)
(Rint)
c, Å
12.8595(3)
94.011(2)
Parameters
R1[I > 2σ(I)]
wR2 (all data)
GOF
309
α, deg
β, deg
γ, deg
V, Å3
0.0438
0.1095
1.198
100.164(2)
105.086(3)
1126.05(6)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

2164
MEL’NIKOVA et al.
Table 3. Bond lengths (Å) in the molecule of compound IIc
Bond
d
Bond
d
Bond
d
Cl19–C7
P21–O33
P21–O31
P21–O22
P21–C20
Cl34–C25
O30–C17
1.726(3)
1.463(2)
1.564(2)
1.573(2)
1.792(3)
1.733(3)
1.209(3)
O18–C5
N15–N14
N13–C17
N13–N14
N13–C12
N3–N2
1.205(3)
1.270(3)
1.389(3)
1.375(3)
1.409(3)
1.274(3)
1.379(3)
C20–C12
C7–C6
1.325(4)
1.385(4)
1.388(4)
1.382(4)
1.383(4)
1.388(4)
1.388(4)
C7–C8
C6–C11
C24–C24
C24–C29
C8–C9
N1–C5
N4–N3
N4–C5
N4–C12
1.367(3)
1.393(3)
1.412(3)
N1–N2
N1–C6
O31–C32
1.368(3)
1.429(3)
1.448(4)
C10–C11
C10–C9
O29–C28
1.390(4)
1.383(4)
1.386(4)
N16–N15
N16–C17
N16–C24
1.371(3)
1.378(3)
1.424(3)
O22–C23
C26–C25
C26–C27
1.448(4)
1.390(4)
1.384(4)
C27–C28
1.384(4)
Table 4. Bond angles (deg) in the molecule of compound IIc
Angle
O33P21O31
O33P21O22
O33P21C20
O31P21O22
O31P21C20
O22P21C20
N3N4C5
ω
Angle
ω
Angle
ω
111.51(12)
115.97(12)
113.97(12)
102.76(12)
107.90(12)
103.75(12)
111.49(19)
120.4(2)
127.8(2)
111.7(2)
121.5(2)
126.6(2)
108.5(2)
125.8(2)
111.5(2)
121.2(2)
107.7(2)
127.6(2)
N2N1N5
N2N1C6
111.8(2)
120.6(2)
122.74(18)
119.3(2)
129.7(2)
129.9(2)
100.4(2)
108.6(2)
129.8(2)
129.8(2)
100.4(2)
107.8(2)
119.0(3)
122.5(2)
119.50(19)
120.4(2)
120.1(2)
120.0(2)
C11C6N1
C11C6C7
119.5(2)
120.4(2)
120.1(2)
119.8(2)
120.1(3)
120.5(2)
120.7(2)
118.8(2)
112.1(2)
124.4(2)
123.5(2)
118.9(2)
119.8(3)
119.6(3)
119.3(3)
121.1(2)
120.8(2)
119.9(3)
C32O31P21
C23O22P21
O18C5N4
O18C5N1
N1C5N4
C26C25Cl34
C24C25Cl34
C24C25C26
C25C24N16
C25C24C29
C29C24N16
N13C12N4
C20C12N4
C20C12N13
C7C8C9
C9C10C11
C6C11C10
C28C29C24
C28C27C26
C10C9C8
N3N4C12
N3N2N1
C5N4Cl2
O30C17N16
O30C17N13
N16C17N13
N15N14N13
C27C26C25
C12C20P21
C6C7Cl19
C6C7C8
N15N16C17
N15N16C24
C17N16C24
N14N15N16
C17N13C12
N14N13C17
N14N13C17
N2N3N4
C8C7Cl19
C7C6N1
C5N1C6
C27C28C29
tetrazol-5-one were added to a solution of 2.5 mmol of
2-chloroacetylenephosphonic acid dimethyl ester in
7 mL of acetonitrile. The reaction mixture was stirred
during 16–20 h at room temperature. Then the
inorganic salt was filtered off, and the solvent was
removed. The residue was recrystallized from iso-
propyl alcohol.
Dimethyl [2,2-bis(5-oxo-4-phenyl-4,5-dihydro-
1H-1,2,3,4-tetrazol-1-yl)ethenyl]phosphonate (IIa).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

REACTIONS OF DIMETHYL 2-CHLOROETHYNYLPHOSPHONATE
Table 5. Torsion angles (τ) in the molecule of the compound IIc
2165
Angle
τ
Angle
τ
Angle
τ
Сl19C7C6N1
Cl19C7C6C11
Cl19C7C8C9
P21C20C12N4
P21C20C12N13
Cl34C25C24N16
Cl34C25C24C29
N4N3N2N1
N16N15N14N13
N16C24C29C28
N15N16C17O30
N15N16C17N13
N15N16C24C25
N15N16C24C29
N3N4C5O18
O22P21C20C12
C5N4N3N2
C5N4C12N13
C5N4C12C20
C5N1N2N3
C5N1C6C7
C5N1C6C11
N2N1C5N4
N2N1C5O18
N2N1C6C7
С20P21O22C23
C7C6C11C10
C7C8C9C10
C6N1C5N4
C6N1C5O18
C6N1N2N3
0.0(4)
178.0(2)
–178.8(2)
–173.29(19)
7.5(4)
139.7(2)
0.4(3)
–66.5(3)
1.4(5)
–171.6(2)
9.1(4)
0.3(4)
–178.4(2)
2.9(4)
–0.7(3)
–90.3(3)
91.7(3)
0.9(3)
–0.7(4)
178.6(2)
–0.4(4)
0.4(4)
C6C7C8C9
177.4(2)
–0.2(3)
C25C26C27C28
C25C24C29C28
C24N16N15N14
C24N16C17O30
C24N16C17N13
C24C29C28C27
C2N4N3N2
C12N4C5O18
C12N4C5N1
C12N13C17O30
C12N13C17N16
C12N13N14N15
C8C7C6N1
0.2(3)
–177.8(3)
90.5(3)
–87.5(3)
–2.0(3)
114.0(3)
–64.2(3)
2.4(3)
1.0(4)
179.1(2)
–178.2(3)
3.2(3)
–176.5(2)
–4.0(4)
177.4(2)
–0.2(4)
–173.6(2)
–8.6(4)
172.7(2)
11.9(4)
–169.5(2)
169.3(2)
–178.5(2)
–0.5(4)
0.6(5)
N2N1C6C11
C17N16N15N14
C17N16C24C25
C17N16C24C29
C17N13N14N15
C17N13C12N4
C17N13C12C20
N14N13C17O30
N14N13C17N16
N14N13C12N4
N14N13C12C20
C26C25C24N16
C26C25C24C29
C26C27C28C29
–72.4(3)
109.5(3)
177.9(3)
–0.8(3)
N3N4C5N1
–121.4(3)
57.9(4)
178.0(3)
–3.4(3)
73.8(3)
–107.0(3)
–179.2(2)
–1.1(4)
–0.5(4)
–39.2(3)
N3N4C12N13
N3N4C12C20
O33P21O31C32
O33P21O22C23
O33P21C20C12
N1C6C11C10
O31P21O22C23
O31P21O20C12
1.3(3)
–178.0(2)
–165.1(2)
59.3(3)
C8C7C6C11
12.6(3)
C11C10C9C8
C27C26C25Cl34
C27C26C25C24
179.4(3)
–178.8(3)
–111.8(2)
70.0(3)
–178.0(2)
0.4(4)
O22P21O31C32
C20P21O31C32
C9C10C11C6
–1.4(5)
1
2
1
Yield 87%, white crystals, mp 158°С. Н NMR spec-
trum, δ, ppm: 3.79 d (6Н, ОСН3, 3JHP 12.0 Hz), 6.94 d
53.20 d (ОСН3, JСP 5.4 Hz), 106.53 d (=СН, JСP
190.5 Hz), 127.84 and 128.44 (СНm, С6Н4), 128.42
and 128.83 (СНp, С6Н4), 128.88 and 129.01 (СНo,
(1Н, =СН, JHP 4.0 Hz), 7.39 t and 7.46 t (4Н, СНm,
2
3JНН 8.0 Hz), 7.48 t (2Н, СНп, 3JНН 8.0 Hz), 7.82 d and
7.91 d (4Н, СНо, 3JНН 8.0 Hz). 13С NMR spectrum, δС,
ppm: 53.35 d (ОСН3, 2JСP 6.0 Hz), 109.58 d (=СН, 1JСP
189.8 Hz), 128.16 and 128.65 (СНm, С6Н4), 129.42
С6Н4), 133.21d (=С, JСP 8.8 Hz), 133.43 and 134.08
2
(Сipso, С6Н4), 132.98 d (=С, JСP 9.0 Hz), 147.52 and
2
149.22 (С=О). 31Р NMR spectrum, (CDCl3): δР
12.17 ppm.
and 129.58 (СНo,p, С6Н4), 133.21 d (=С, JСP 8.8 Hz),
2
Dimethyl {2,2-bis[4-(2-chlorophenyl)-5-oxo-4,5-
dihydro-1H-1,2,3,4-tetrazol-1-yl]ethenyl}phosphonate
(IIc). Yield 85%, white crystals, mp 154°С. Н NMR
spectrum, δ, ppm: 3.83 d (6Н, ОСН3, JHP 11.5 Hz),
133.53 and 134.14 (Сipso, С6Н4), 146.05 and 147.66
(С=О). 31Р NMR spectrum, (CDCl3): δР 11.98 ppm.
1
3
Dimethyl [2,2-bis(4-benzyl-5-oxo-4,5-dihydro-1H-
1,2,3,4-tetrazol-1-yl)ethenyl]phosphonate (IIb). Yield
65%, yellowish oil. 1Н NMR spectrum, δ, ppm: 3.63 d
(6Н, ОСН3, 3JHP 11.5 Hz), 4.97 s and 5.06 s (4Н, СН2),
2
6.97 d (1Н, =СН, JHP 4.0 Hz), 7.49 m (8Н, С6Н4Cl).
13С NMR spectrum, δС, ppm: 53.44 d (ОСН3, 2JСP
1
5.4 Hz), 107.49 d (=СН, JСP 189.8 Hz), 127.94 and
2
6.78 d (1Н, =СН, JHP 3.5 Hz), 7.27 m (10Н, С6Н5).
128.06 (С5, С6Н4Cl), 128.98 and 129.38 (С3, С6Н4Cl),
129.72 and 130.38 (С2, С6Н4Cl), 130.81 and 131.00
13С NMR spectrum, δС, ppm: 48.73 and 48.96 (СН2),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

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MEL’NIKOVA et al.
(С6, С6Н4Cl), 131.85 and 132.27 (С4, С6Н4Cl), 132.04
2. Holstein, S.A., Cermak, D.M., Wiemer, D.F., Lewis, K.,
and Hohl, R., J. Bioorg. Med. Chem., 1998, vol. 6,
p. 687. DOI: 10.1016/S0968-0896(98)00034-0.
2
and 132.14 (С1, С6Н4Cl), 133.33 d (=С, JСP 9.4 Hz),
146.46 and 148.35 (С=О). 31Р NMR spectrum
(CDCl3): δР 11.98 ppm.
3. Lazrek, H.B., Rochdi, A., Khaider, H., Barascut, J.L.,
Imbach, J.L., Balzarini, J., Witvrouw, M., Pannecouque, C.,
and De Clerq, E., Tetrahedron, 1998, vol. 54, p. 3807.
DOI: 10.1016/S0040-4020(98)00107-0.
Dimethyl {2,2-bis[4-(4-nitrophenyl)-5-oxo-4,5-di-
hydro-1H-1,2,3,4-tetrazol-1-yl]ethenyl}phosphonate
1
(IId). Yield 84%, white crystals, mp 173°С. Н NMR
4. Harnden, M.R., Parkin, A., Parratt, M.J., and Perkins, R.M.,
J. Med. Chem., 1993, vol. 36, p. 1343. DOI: 10.1021/
jm00062a006.
3
spectrum, δ, ppm: 3.85 d (6Н, ОСН3, JHP 12.0 Hz),
2
6.98 d (1Н, =СН, JHP 4.7 Hz), 8.22 d and 8.27 d (4Н,
3
3
СНm, JНН 8.0 Hz), 8.41 d and 8.43 d (4Н, СНo, JНН
8.0 Hz). 13С NMR spectrum, δС1, ppm: 53.52 d (ОСН3,
2JСP 5.4 Hz), 108.88 d (=СН, JСP 189.2 Hz), 119.17
and 119.32 (СНm, С6Н4NO2), 125.19 and 125.37 (СНo,
5. Welch, C.M., Gozalez, E.J., and Guthrie, J.D., J. Org.
Chem., 1961, vol. 26, p. 3270. DOI: 10.1021/jo01067a057.
6. Jin J.I., US Patent 74-496233, 1978; C. A., 1979, no. 90,
153010m.
2
С6Н4NO2), 132.52 d (=С, JСP 9.1 Hz), 138.22 and
7. Cristau, H.-J., Pirat, J.-L., Drag, M., and Kafarski, P.,
Tetrahedron Lett., 2000, vol. 41, p. 9781. DOI: 10.1016/
S0040-4039(00)01723-8.
138.90 (Сipso, С6Н4NO2), 145.55 and 146.55 (СНp,
С6Н4NO2), 146.91 and 147.22 (С=О). 31Р NMR
spectrum (CDCl3): δР 11.20 ppm.
8. Inoue, H., Tsubouchi, H., Nagaoka, Y., and Tomioka, K.,
Tetrahedron, 2002, vol. 58, p. 83. DOI: 10.1016/S0040-
4020(01)01089-4.
Dimethyl {2,2-bis[4-(2,4-dinitrophenyl)-5-oxo-4,5-
dihydro-1H-1,2,3,4-tetrazol-1-yl]ethenyl}phosphonate
1
9. Ranu, B.C., Guchhait, S.K., and Ghosh, K.J., Org. Chem.,
(IIe). Yield 74%; white crystals, mp 185°C. Н NMR
3
1998, vol. 63, p. 5250. DOI: 10.1021/jo980128n.
spectrum, δ, ppm: 3.72 d (6Н, ОСН3, JHP 12.0 Hz),
6.89 d (1Н, =СН, 2JHP 4.0 Hz), 8.15 d (2Н, С6Н3, 3JНН
10. Petrov, A.A., Dogadina, A.V., Ionin, B.I., Garibina, V.A.,
and Leonov, A.A., Russ. Chem. Rev., 1983, vol. 52,
no. 11, p. 1030.
3
8.0 Hz), 8.80 d (2Н, С6Н3, JНН 8.0 Hz), 8.89 s (2Н,
С6Н3). 13С NMR spectrum, δС, ppm: 52.72 d (ОСН3,
1
2JСP 5.7 Hz), 107.84 d (=СН, JСP 188.7 Hz), 122.71
11. Garibina, V.A., Leonov, A.A., Dogadina, A.V., Ionin, B.I.,
and Petrov, A.A., Zh. Obsch. Khim., 1985, vol. 55,
no. 9, p. 1994.
and 123.25 (С6, С6Н3), 125.67 and 125.79 (С5, С6Н3),
2
131.91 d (=С, JСP 9.0 Hz), 139.67 and 139.99 (С1,
С6Н3), 140.86 and 141.24 (С3, С6Н3), 142.17 and
142.77 (С2, С6Н3), 145.63 and 146.77 (С4, С6Н3), 146.94
and 147.75 (С=О).
12. Garibina, V.A., Leonov, A.A., Dogadina, A.V., Ionin, B.I.,
and Petrov, A.A., Zh. Obsch. Khim., 1987, vol. 57,
no. 7, p. 1481.
13. Erkhitueva, E.B., Dogadina, A.V., Khramchikhin, A.V.,
and Ionin, B.I., Tetrahedron Lett., 2013, vol. 54, no. 38,
p. 5174. DOI: 10.1016/j.tetlet.2013.07.032.
ACKNOWLEDGMENTS
14. Han, S.Y., Lee, J.W., Kim, H.-J., Kim, Y.-J., Lee, S.W.,
and Gyoung, Y.S., Bull. Korean Chem. Soc., 2012,
vol. 33, no. 1, p. 55.
This work was financially supported by the Russian
Foundation for Basic Research (project no. 14-03-
31445_mol_a)
15. Lieber, E., and Ramachandran, J., Canad. J. Chem.,
1959, vol. 37, p. 101.
REFERENCES
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17. Ostrovskii, V.A. and Koren, A.O., Heterocycles, 2000,
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Schutz, D., Spiess, B., and Bourguigon, J.-J., J. Org.
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