N-sulfinyl-substituted arylhydrazines from N- sulfinyltrifluoromethansulfonamide

Article abstract of DOI:10.1134/S1070428009020043

Arylhydrazines react with N-sulfinyltrifluoromethanesulfonamide CF ₃SO₂NSO providing N-sulfinylarylhydrazines and trifluoromethanesulfonamide. The discovered reaction is a first example of a transfer of a sulfinyl group from N-sulfin

Full text of DOI:10.1134/S1070428009020043

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 2, pp. 178−181. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.V. Bel’skikh, L.L. Tolstikova, B.A. Shainyan, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 2,
pp. 191−193.
N-Sulfinyl-SubstitutedArylhydrazines
from N-Sulfinyltrifluoromethansulfonamide
A. V. Bel’skikh, L. L. Tolstikova, and B. A. Shainyan
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
Irkutsk, 664033 Russia
e-mail: bagrat@irioch.irk.ru
Received March 17, 2008
Abstract—Arylhydrazines react with N-sulfinyltrifluoromethanesulfonamide CF3SO2NSO providing N-sulfinyl-
arylhydrazines and trifluoromethanesulfonamide. The discovered reaction is a first example of a transfer of
a sulfinyl group from N-sulfinylsulfonamides to hydrazines. The reasons of different hydrolytic stability of
CF3SO2NSO andArNHNSO are discussed.
DOI: 10.1134/S1070428009020043
hydrazines and thionyl chloride in the cold with 70–80%
yields [20], but the later study failed to reproduce these
yields [21]. The preparation of N-sulfinylphenylhydrazine
by the treatment of phenylhydrazine with thionyl chloride
is complicated by further reaction of the product with
SOCl2 giving phenyldiazonium chloride that with the initial
phenylhydrazine formed phenyl azide and diphenylamine
[21]. Besides carrying out the reaction by procedure [21]
we were unable to totally separate from the reaction
product the side compound trifluoromethanesulfonamide.
N-Sulfinylamides of aromatic sulfonic acids
ArSO2NSO are fairly reactive compounds whose
formation and chemical reactions were investigated in
detail in nineteen sixties [1–4]. N-Sulfinylamides of
perfluoroalkanesulfonic acids RfSO2NSO are still more
active [5], among them also the simplest representative,
N-sulfinyltrifluoromethanesulfonamide CF3SO2NSO (I)
[6]. It reacts with fluorine, phosgene, DMSO [7], forms
cyclic compounds with versatile silicon-, tin-, lead-,
phosphorus-, and arsenic-containing electrophiles [8–10],
adds (trifluoromethyl)trimethylsilane in the presence of
alkali metal fluorides [11], undergoes condensation with
aldehydes [12–14], ketones, sulfoxides and phosphorus
oxychloride [12], alcohols [15, 16], carboxylic acids [17,
18], and oxiranes [19]. However no information exists
on the reaction between perfluoroalkanesulfonic acids
N-sulfinylamides RfSO2NSO or arylsulfonic acids
N-sulfinylamidesArSO2NSO and hydrazines.
The reactions of N-sulfinyltrifluoromethanesulfon-
amide (I) with phenyl-, p-nitrophenyl-, 2,4-dinitrophenyl-
hydrazines IIa–IIc, and 3-hydrazinobenzoic acid (IId)
were carried out in CH2Cl2 at room temperature or in
the cold. In contrast to the reactions with compounds
containing active proton, carbonyl, and some other groups,
CF3SO2NSO reacted with the phenylhydrazine and its
derivatives without SO2 liberation.
3-Hydrazinobenzoic acid unlike the other carboxylic
acids reacts with amide I not at the carboxy but at the
hydrazine group yielding 3-(N-sulfinylhydrazino)benzoic
acid [18]. In order to establish the general character of
this reaction we studied in this work the reactions of
N-sulfinyltrifluoromethanesulfonamide CF3SO2NSO (I)
with some arylhydrazines.
CF3SO2N
S
O + ArNHNH2
I
II
ArNHN
S
O + CF3SO2NH2
III
IV
Ar = Ph (a), 4-(NO2)C6H4 (b), 2,4-(NO2)2C6H3 (c),
3-COOHC6H4 (d) [18].
N-Sulfinylphenylhydrazine, [2-(phenyl)hydrazono]-
4
(oxo)-λ -sulfane and some its N-substituted derivatives
The structure of compounds IIIa–IIId was proved
by H, C, and mass spectra. The replacement of the
1
13
PhN(R)N=S=O were prepared from the corresponding
178

N-SULFINYL-SUBSTITUTED ARYLHYDRAZINES
179
Bond lengths (l), bond angle NSO (α), atomic charges (q, a.e.u.), energy of the lowest unoccupied molecular orbital (ΕLUMO),
contribution of the atomic orbital of sulfur into LUMO (CS), and heats of reaction for RN=S=O + H2O → RNHSOOH (ΔE) as
calculated by MP2/6-311+G* procedure
Compound no. lS=O, Å lN=S, Å α,
α
d
,
e
d
g
eg
qS
qN
qO
qNSO
Ε
LUMO, eV CS, % ΔE, kcal mol−1
I
1.4815 1.5575
1.4965 1.6005
120.5
111.6
+0.835
+0.558
–0.570 –0.400 –0.135 –0.0490
–0.203 –0.584 –0.229 +0.0217
42.2
3.8
–7.8
IIIa
+13.9
elimination giving triflamide and phenylhydrazine
respectively.
amino group in arylhydrazines by electron-acceptor
heterocumulene moiety N=S=O led to a sharp decrease
in the donor properties of NH group, as seen from the
considerable shift of some signals in the NMR spectra.
The calculations were performed by MP2/6-311+G*
method with the complete geometry optimization applying
software package GAUSSIAN03 [22]. The geometrical
and electronic parameters characterizing the N=S=O
fragment and also the heat of reaction for the first stage
of hydrolysis are presented in the table.
1
For instance, the H NMR spectra of N-sulfinylaryl-
hydrazines III compared to the spectra of initial aryl-
hydrazines II lacked the signal of NH2 group at ~4 ppm,
and the signal of NH group suffered a considerable
downfield shift from 6.9–9.9 (II) to ~13 ppm (III). The
most characteristic feature of the 13C NMR spectra of
compounds III consists in a large upfield shift of the signal
C–NH compared to the corresponding signal in the spectra
of initial arylhydrazines II (by ~8–10 ppm) resulting from
the appearance of an electron-acceptor S=O group
(analogous to the shift of the C–NH signal by ~8 ppm in
acetanilide with respect to aniline). In the mass spectra
of compounds IIIb and IIIc molecular ions were present
with m/z 244 and 199 following a common fractionation
scheme with a successive elimination of HSO. radical
and a nitrogen molecule.
Evidently the heterocumulene fragments N=S=O are
quite different in molecules I and IIIa. The analysis of
the geometrical parameters indicates that both multiple
bonds N=S and S=O in molecule I are to a greater extent
regular double bond; therewith the configuration of the
sulfur atom in molecule I is materially trigonal whereas
in molecule IIIa it is close to tetrahedral. The positive
charge on the electrophilic center (sulfur atom) in
molecule I is significantly larger, and the electron density
on the total heterocymulene fragment N=S=O is
considerably smaller than in IIIa molecule. The LUMO
of molecule I is situated essentially lower, and its
localization on the AO of the sulfur atom is much higher
than in molecule (LUMO in the latter by >90% is
localized on the phenyl group). Consequently, molecule I
is much more active electrophile both in the charge-
controlled and in the orbital-controlled reactions. As
a result the first stage of hydrolysis of amide I is
exothermal, whereas for hydrazine IIIa is endothermal
in complete agreement with the experimental findings.
N-Sulfinylarylhydrazines III are sufficiently stable and
are not hydrolyzed even at recrystallization from boiling
aqueous ethanol. Yet heterocumulene I is fast hydrolyzed
even in open air. We formerly suggested [18] that this
strong difference in the reactivity originated from the fact
that in compound I the fragment N=S=O was connected
to the electron-acceptor group CF3SO2 sharply increasing
the capability to the hydrolysis whereas in compounds
III this fragment was bound to the π-donor group NH.
To elucidate in detail the reason of the difference in the
reactivity of compounds I and III we carried out the
calculation of molecules I and IIIa and also of heat of
reaction for the first stage of water molecule addition to
the N=S bond in these compounds leading to the formation
of N-trifluoromethylsulfonylamido- and N'-phenyl-
hydrazidosulfurous acids that further decomposed by SO2
Hence by an example of the reactions of N-sulfinyl-
trifluoromethanesulfonamide CF3SO2NSO with aryl-
hydrazines we discovered for the first time the transfer
of a sulfinyl group from N-sulfinylsulfonamides to
hydrazines.
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer
Specord 75IR from mulls in mineral oil and KBr pellets.
NMR spectra were registered from solutions in DMSO-
d6 on a spectrometer Bruker DPX-400 [400 (1H), 100
RNHSOOH
RNH2
RN
S
O + H2O
R = CF3SO2, PhNH
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 2 2009
_SO2

BEL’SKIKH et al.
180
(13C), and 376 MHz (19F)], chemical shifts were reported
with respect to TMS (1H, 13C) and CCl3F (19F). Mass
spectra taken in electron impact mode (70 eV) were
measured on instruments GC-MS Shimadzu QP5050A
with direct sample admission into the ion source (IIIc)
or Thermo Trace DSQ II (IIId) from an emulsion of the
sample in DMSO.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant no.
07-03-00425).
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4
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4
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