Reaction of trifluoro-N-(oxo-λ4-sulfanylidene)methanesulfonamide with pyrazolidin-3-ones

Article abstract of DOI:10.1134/S107042801704025X

Trifluoro-N-(oxo-λ⁴-sulfanylidene)methanesulfonamide reacted with 1-phenylpyrazolidin-3-one and 4-methyl-1-phenylpyrazolidin-3-one to give 1-phenyl-1,2-dihydro-3H-pyrazol-3-ones. A probable oxidation mechanism was proposed.

Full text of DOI:10.1134/S107042801704025X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 4, pp. 632–633. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © B.A. Shainyan, L.L.Tolstikova, 2017, published in Zhurnal Organicheskoi Khimii, 2017, Vol. 53, No. 4, pp. 624–625.
SHORT
COMMUNICATIONS
Reaction of Trifluoro-N-(oxo-λ4-sulfanylidene)methane-
sulfonamide with Pyrazolidin-3-ones
B. A. Shainyan* and L. L.Tolstikova
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*e-mail: bagrat@irioch.irk.ru
Received February 22, 2017
Abstract—Trifluoro-N-(oxo-λ4-sulfanylidene)methanesulfonamide reacted with 1-phenylpyrazolidin-3-one
and 4-methyl-1-phenylpyrazolidin-3-one to give 1-phenyl-1,2-dihydro-3H-pyrazol-3-ones. A probable oxida-
tion mechanism was proposed.
DOI: 10.1134/S107042801704025X
Trifluoro-N-(oxo-λ4-sulfanylidene)methanesulfon-
amide CF3SO2N=S=O (1), as well as its perfluoroalkyl
analogs, is known to react with aromatic and hetero-
cyclic aldehydes and cyclopentanone to give the corre-
sponding N-ylidene derivatives [1, 2] (Scheme 1).
used, so that they precipitated as the reaction prog-
ressed; the products can also be precipitated with
acetonitrile and separated from trifluoromethanesul-
fonamide by washing with water. The formation of
CF3SO2NH2 was confirmed by the 19F NMR spectra
which contained a signal at δF –79 ppm (cf. δF –78 to
–77 ppm for Ht=NSO2CF3). The melting points and
1H and 13C NMR spectra of 4 and 5 coincided with
those reported in [3–6]. The IR spectra of 4 and 5
displayed strong absorption bands at 1600 and
1550 cm–1 typical of stretching vibrations of C=C bond
and bending vibrations of NH group, respectively.
Scheme 1.
XCHO
CF3SO2N=CHX
CF3SO2N=S=O
–SO2
O
1
NSO2CF3
Scheme 2.
X = Ar, Ht.
R
With the goal of extending the series of ylidene
derivatives of trifluoromethanesulfonamide and eluci-
dating general character of the above condensation,
compound 1 was brought into reaction with 1-phenyl-
pyrazolidin-3-ones 2 and 3 possessing a pharmaco-
phoric pyrazolone fragment. The reactions were
carried out at room temperature or on cooling (–30 to
–20°C) in methylene chloride, chloroform, or benzene
in the absence of a catalyst. However, instead of ex-
pected N-(pyrazolidin-3-ylidene) derivatives, we iso-
lated oxidation products, 1-phenyl-1,2-dihydro-3H-pyr-
azol-3-ones 4 and 5 in high yields (>80%; Scheme 2).
CF3SO2N=S=O
+
N
Ph
O
+
N
H
1
2, 3
R
+
CF3SO2NH2
[S=O]
N
Ph
O
N
H
4, 5
S + SO2
2, 4, R = H; 3, 5, R = Me.
Unlike pyrazolidinones 2 and 3, compound 1 failed
to react with 1-methylpyrrolidin-2-one, pyrrolidine-
2,5-dione, 2,4-dihydro-3H-1,2,4-triazol-3-one, and
5,5-diethylhexahydropyrimidine-2,4,6-trione, regard-
less of the solvent nature (CH2Cl2, benzene, or no
Upon addition of sulfonamide 1 to a solution of 2
or 3, the mixture instantaneously turned violet, but it
became colorless after stirring for 5 h. Oxidation
products 4 and 5 are poorly soluble in the solvents
632

REACTION OF TRIFLUORO-N-(OXO-λ4-SULFANYLIDENE)METHANESULFONAMIDE
633
solvent), catalyst [SOCl2, Y(OTf)3, AlCl3], and tem- (1 mmol) of 4-methyl-1-phenylpyrazolidin-3-one (3)
perature (from –30°C to the boiling point).
in 1 mL of methylene chloride and 0.19 g (1.01 mmol)
of 1 in 1 mL of methylene chloride at room tempera-
ture. Yield 0.15 g (88%), yellow powder, mp 209°C
Compounds 4 and 5 and their enol tautomers were
obtained previously by oxidation of pyrazolidinones
with Fe(III), MnO2, sulfur, or benzoquinone [7–9]. We
have found no examples of using N-(oxo-λ4-sulfanyli-
dene)sulfonamides as oxidants in any reactions. Pre-
sumably, the oxidation mechanism involves addition of
the enol tautomer of 2 or 3 to the N=S bond of 1, fol-
lowed by rearrangement with elimination of trifluoro-
methanesulfonamide molecule and sulfur(II) oxide
which undergoes disproportionation to sulfur(IV)
oxide and elemental sulfur [10] (Scheme 3).
1
[5, 6]. H NMR spectrum, δ, ppm: 1.90 s (3H, CH3),
7.12 t (1H, p-H, J = 7.3 Hz), 7.38 t (2H, m-H, J =
8.1 Hz), 7.60 d (2H, o-H, J = 7.8 Hz), 8.01 s (1H,
=CH), 10.14 (1H, NH). 13C NMR spectrum, δC, ppm:
7.0, 103.3, 116.2, 123.9, 126.5, 129.3, 139.9, 161.4.
The spectral parameters of 5 coincided with those
given in [5, 6].
The IR spectra (400–4000 cm–1) were recorded in
1
KBr on a Varian 3100 spectrometer. The H and 13C
NMR spectra were recorded on a Bruker DPX-400
spectrometer at 400.13 and 100.62 MHz, respectively,
using DMSO-d6 as solvent and reference.
Scheme 3.
O
O
R
S
R
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 17-03-00213) using the facilities of the Baikal
Joint Analytical Center (Siberian Branch, Russian
Academy of Sciences).
CF3SO2N=S=O +
NH
NHTf
N
N
Ph
OH
N
H
H
Ph
1
O
R
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+
CF3SO2NH2
NH
–[S=O]
N
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 4 2017