Reaction of diethyl esters of 1-acylamino-2,2-dichlorovinylphosphonic acids and their analogs with the Lawesson's reagent

Article abstract of DOI:10.1134/S1070363210100105

Diethyl esters of 1-acylamino-2,2-dichlorovinylphosphonic acids and their analogs upon heating with the Lawesson's reagent are converted into the earlier unknown substituted 1,3-thiazol-4-ylthiophosphonates in high yields.

Full text of DOI:10.1134/S1070363210100105

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 10, pp. 1937–1940. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.V. Popil’nichenko, K.M. Kondratyuk, R.N. Solomyannyi, V.S. Brovarets, 2010, published in Zhurnal Obshchei Khimii, 2010,
Vol. 80, No. 10, pp. 1626–1629.
Reaction of Diethyl Esters
of 1-Acylamino-2,2-dichlorovinylphosphonic Acids
and Their Analogs with the Lawesson’s Reagent
S. V. Popil’nichenko, K. M. Kondratyuk, R. N. Solomyannyi, and V. S. Brovarets
Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 1, Kiev, 02660 Ukraine
e-mail: brovarets@bpci.kiev.ua
Received November 19, 2009
Abstract—Diethyl esters of 1-acylamino-2,2-dichlorovinylphosphonic acids and their analogs upon heating
with the Lawesson’s reagent are converted into the earlier unknown substituted 1,3-thiazol-4-ylthiophos-
phonates in high yields.
DOI: 10.1134/S1070363210100105
Earlier the reactions of diethyl esters of 1-acyl-
amino-2,2-dichlorovinylphosphonic acids I prepared
from tetrachloroethylamides of carboxylic acids and
triethylphosphite [1] with amines, hydrazines, sodium
hydrogen sulfide have been studied. As a rule they lead
to 4-phosphorylated derivatives of 5-amino- and 5-
mercapto-1,3-oxazoles [2–6].
In this work the reaction of compounds I and their
analogs II with the Lawesson’s reagent was first
studied and shown to lead to the earlier unknown
diethyl esters of 2-aryl-5-chloro-1,3-thiazol-4-ylthio-
phosphonic acids (see the sequences of transformations
I → III → V → VII and II → IV → VI → VIII,
respectively, on the scheme) (Table 1).
Table 1. Yields, constants, and elemental analysis of compounds I, II, VII–IX
Found, %
Calculated, %
Comp. Yield,
mp, °С
Formula
no.
%
(solvent)
Cl
N
P
S
–
Cl
N
P
S
–
84
71
78
80
82
77
82
58
61
65
67
51
53
174–176 (EtOH)
17.49
7.75
3.56
2.89
2.66
3.12
5.28
5.04
3.83
4.02
3.98
7.84
3.14
5.03
7.11
C13H15Cl2N2O6P
17.85
7.05
7.80
Id
97–99 (ethyl acetate)
107–109 (ethyl acetate)
115–117 (ethyl acetate)
144–146 (ethyl acetate)
182–184 (ethyl acetate)
160–162 (ethyl acetate)
73–75 (EtOH)
8.21
15.28
14.86
21.72
7.42
7.49
7.05
6.29
6.92
6.09
6.43
8.74
8.91
8.53
8.02
6.12
5.95
7.18 C20H23ClNO4PS
6.63 C19H20Cl2NO4PS
6.82 C20H22Cl2NO4PS
6.83 C19H19Cl3NO4PS
6.31 C20H22ClN2O6PS
6.27 C19H19Cl2N2O6PS
18.62 C13H15ClNO2PS2
17.56 C14H17ClNO2PS2
16.91 C13H14Cl2NO2PS2
16.12 C13H14ClN2O4PS2
19.08 C19H18Cl2NO2PS3
20.44 C20H21N2O4PS3
8.06
15.40
14.95
21.50
7.31
3.18
3.04
2.95
2.83
5.78
5.54
4.03
3.87
3.66
7.13
2.86
5.83
7.04
6.73
6.53
6.26
6.39
6.13
8.91
8.56
8.10
7.88
6.32
6.45
7.29
6.97
IIа
IIb
6.76
IIc
6.48
IId
6.61
IIe
13.91
10.09
9.91
14.03
10.19
9.80
6.35
IIf
18.44
17.72
16.78
16.32
19.61
20.02
VIIа
VIIb
VIIc
VIId
VIIIа
VIIIb
79–81 (EtOH)
103–105 (EtOH)
18.25
8.88
18.55
9.03
95–97 (EtOH)
88–90 (С6Н6)
14.87
–
14.46
–
93–95 (С6Н6)
1937

1938
POPIL’NICHENKO et al.
Table 1. (Contd.)
Comp. Yield,
Found, %
Calculated, %
mp, °С
Formula
no.
VIIIc
IXа
IXb
IXc
%
57
41
47
43
49
54
57
(solvent)
Cl
N
P
S
Cl
N
P
S
97–99 (С6Н6)
80–83а (EtOH)
131–133 (EtOH)
108–110 (EtOH)
110–112 (EtOH)
144–146 (EtOH)
151–153 (EtOH)
6.98
5.91
6.86
19.06 C19H18ClN2O4PS3
13.44 C14H16N2S
7.08
5.59
6.18
19.20
–
12.08
11.91
11.17
10.26
10.11
14.82
–
–
–
–
–
–
–
11.46
11.37
10.84
10.76
9.98
–
–
–
–
–
–
13.12
13.02
12.41
12.32
11.42
11.01
–
13.36 C13H14N2OS
12.21 C15H18N2S
–
–
–
–
–
12.72 C14H16N2OS
11.13 C13H13ClN2OS
11.22 C13H13N3O3S
IXd
IXe
12.92
–
12.63
–
14.42
IXf
a
Melting point corresponds to the literature data [8].
The Lawesson’s reagent produced complex action
The structure of compounds VII and VIII is
consistent with the data of the IR and 1H NMR spectra,
which prove that the reaction of substrates I and II
with the Lawesson’s reagent proceeds with the
participation of the acylamine moieties (Table 2).
Thus, in the IR spectra of compounds VII and VIII the
absorption bands at 1600–1700 and 3050–3500 cm–1,
which are characteristic of the starting compounds, are
on compounds I and II since not only thionation of
the carbonyl and the phosphoryl groups occurs with
the formation of the intermediate products III and
IV or their prototropic tautomers V and VI but
also their subsequent cyclocondensation with the
participation of the dichlorovinyl or chlorovinyl
fragments.
P(O)(OEt)2
P(S)(OEt)2
Cl
P(S)(OEt)2
Cl
P(S)(OEt)2
Cl
_HCl
HN
HN
N
N
RL(exess)
R
Cl
R
R
R
S
O Cl
Ia_d
S Cl
SH Cl
VIIa_VIId
Va_Vd
IIIa_IIId
X
NH (excess)
Δ
ArSH/Et3N
N
N
R
S
X
IXa_IXf
P(O)(OEt)2
P(S)(OEt)2
SAr
P(S)(OEt)2
SAr
S Cl
IVa_IVc
P(S)(OEt)2
HN
N
HN
_HCl
RL(exess)
N
R
SAr
R
R
SAr
O Cl
Ia_If
R
SH Cl
S
VIa_VIc
VIIIa_VIIIc
I, VII: R = Ph (a), 4-MeC6H4 (b), 4-ClC6H4 (c), 3-O2NC6H4 (d); II: R = Ph, Ar = 4-MeC6H4 (a), 4-ClC6H4 (b); R = 4-
MeC6H4, Ar = 4-ClC6H4 (c); R = 4-ClC6H4, Ar = 4-ClC6H4 (d); R = 3-O2NC6H4, Ar = 4-MeC6H4 (e), 4-ClC6H4 (f); VIII:
R = Ar = 4-ClC6H4 (a); R = 3-O2NC6H4, Ar = 4-MeC6H4 (b), 4-ClC6H4 (c); IX: R = Ph; X = CH2 (a), O (b); R = 4-MeC6H4,
S
S
X = CH (c), O (d); R = 4-ClC H , X = CH (e);
RL = MeO
P
S
P
OMe
2
6
4
2
S
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

REACTION OF DIETHYL ESTERS
Table 2. Spectral data of compounds I, II, VII–IX
1939
Comp.
no.
31Р NMR spectrum,
δ, ppm (DMSO-d6)
1Н NMR spectrum, δ, ppm (ДМСО-d6)
IR spectrum (KBr), ν, cm–1
1246 (P=O), 1673 (C=O), 3085–3205 (NHass)
1.20 m (6Н, 2СН3), 4.09 m (4Н, 2СН2), 7.73–8.51 m (4Harom),
_
Id
10.33 s (1H, NH)
1.23 m (6Н, 2СН3), 4.10 m (4Н, 2СН2), 7.48–7.97 m (9Harom), 9.10, 10.00 (1:1)a 1232 (P=O), 1667b (C=O), 3080–3205
10.04 s, 10.15 s (1H, NH) (NHass
1.21 m (6Н, 2СН3), 4.12 m (4Н, 2СН2), 7.51–7.96 m (8Harom), 8.82, 9.90 (1:3)a 1242 (P=O), 1662b (C=O), 3050–3200
10.18 s, 10.21 s (1H, NH) (NHass
VIIbc 1.34 t (6Н, 2СН3), 2.36 s (3H, CH3), 4.26 m (4Н, 2СН2),
7.35–7.77 m (4Harom
1.34 t (6Н, 2СН3), 4.25 m (4Н, 2СН2), 7.63–7.90 m (4Harom
IIb
)
IId
)
69.90
69.70
1620–1700, 3050–3500 (no bands)
)
)
1600–1700, 3050–3500 (no bands)
VIIc
VIId
1.35 t (6Н, 2СН3), 4.27 m (4Н, 2СН2), 7.81–8.62 m (4Harom
)
66.80
71.00
1600–1700, 3050–3500 (no bands)
1600–1700, 3050–3500 (no bands)
VIIIbd 1.35 t (6Н, 2СН3), 2.36 s (3H, CH3), 4.27 m (4Н, 2СН2),
7.32–8.52 m (8Harom
3.14–3.75 m (8H, 4CH2), 7.13 s (1H, C4–H thiazole), 7.33–
7.75 m (5Harom
1.58–3.12 m (10Н, 5СН2), 2.34 s (3Н, СН3), 6.91 s (1H, C4–H
thiazole), 7.20–7.58 m (4Harom
2.34 s (3Н, СН3), 3.10–3.75 m (8H, 4CH2), 7.00 s (1H, C4–H
thiazole), 7.21–7.60 m (4Harom
3.13–3.76 m (8H, 4CH2), 7.06 s (1H, C4–H thiazole), 7.43–
7.72 m (4Harom
3.18–3.76 m (8H, 4CH2), 7.17 s (1H, C4–H thiazole), 7.72–
8.49 m (4Harom
a Integral intensities are given in parentheses. b Band with a shoulder. c Mass spectrum: m/z 362 (M+). d Mass spectrum: m/z 481 (M+).
)
_
_
_
_
_
1600–1700, 3050–3500 (no bands)
1600–1700, 3050–3500 (no bands)
1600–1700, 3050–3500 (no bands)
1600–1700, 3050–3500 (no bands)
1600–1700, 3050–3500 (no bands)
IXb
IXc
IXd
IXe
IXf
)
)
)
)
)
absent. At the same time, mass spectra and elemental
analysis confirm the presence of two (compounds VII)
or three (compounds VIII) sulfur atoms. The presence
of the thiophosphoryl group in these products is proved
by the signals in the 31Р NMR spectra at 69–71 ppm
characteristic of the P=S bond [7].
at δ 1.58–3.76 ppm, as well as singlet signals at δ
6.91–7.17 ppm, which belong to the Н4 proton of the
thiazole ring. Besides, one of these compounds IXa
was earlier prepared by alternative protocol [8] that
unequivocally proves the structure of compounds IX
as well as their precursors VII and analogs VIII.
It should be noted that the mobility of the chlorine
atoms in compounds VII is low, therefore it is not
replaced by the action of thiols or amines at long
heating in ethanol. However, when refluxed in
piperidine or morpholine without solvent, compounds
VII suffer replacement of chlorine by the residue of
the nitrogen base, and, moreover, the carbon-
phosphorus bond is ruptured so that the derivatives of
5-aminothiazole without substituents in the 4 position
of the ring are formed.
EXPERIMENTAL
IR spectra were recorded on a Vertex 70 spec-
trometer in KBr, 1Н and 31Р NMR spectra were
registered on a Varian VXR-300 spectrometer at 300
and 81 MHz, respectively, in DMSO-d6, with TMS as
an internal standard. Mass spectra were taken on an
Agilent 1100/DAD/MSD VL G1965 instrument.
Melting points were measured on a Fisher-Johns unit.
Diethyl esters of 1-acylamino-2,2-dichlorovinyl-
phosphonic acids (Iа–Ic) were prepared as described
in [1].
The structure of compounds IX is confirmed by
their H NMR spectra, where characteristic signals of
the piperidine and the morpholine protons are observed
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

1940
POPIL’NICHENKO et al.
Diethyl ester of 1-(3-nitrobenzoylamino-2,2-di-
chlorovinylphosphonic acid (Id) was synthesized by
the scheme used for compounds Iа–Ic [1].
2-Aryl-5-piperidino(morpholino)-1,3-thiazoles
(IXа–IXf). To 0.01 mol of compound VIIа–VIId
20 ml of piperidine or morpholine was added, the
mixture was refluxed for 4 h, the excess of piperidine
or morpholine was removed in a vacuum, the residue
was treated with water, the precipitate was filtered off,
and compounds IXа–IXf were purified by crystal-
lization.
Diethyl esters of 2-arylthio-1-acylamino-2,2-di-
chlorovinylphosphonic acids (IIa–IIf). To the solu-
tion of 0.01 mol of compound Iа–Id in 30 ml of aceto-
nitrile 0.01 mol of 4-methylthiophenol or 4-chloro-
thiophenol and equimolar amount of triethylamine
were added, and the mixture was left overnight at room
temperature. Triethylamine hydrochloride was filtered
off, the solvent was removed in a vacuum, the residue
was treated with water, the precipitate was filtered off,
and compounds IIа–IIf were purified by crystallization.
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Diethyl esters of (2-aryl-5-chloro-1,3-thiazol-4-
yl)thiophosphonic acids (VIIа–VIId). To the solution
of 0.01 mol of compound Iа–Id in 50 ml of dry
dioxane 0.02 mol of the Lawesson’s reagent was
added, the mixture was refluxed for 6 h, the solvent
was removed in a vacuum, the residue was treated with
water, then with 20% aqueous sodium hydroxide to
remove the unreacted Lawesson’s reagent. The
precipitate was filtered off and compounds VIIа–VIId
were purified by crystallization.
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Diethyl esters of (2-aryl-5-arylthio-1,3-thiazol-4-
yl)thiophosphonic acids (VIIIа–VIIIc) were prepared
similarly to thiazoles VIIа–VIId from compounds
IId–IIf.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010