Imination of sulfur-containing compounds: XXXVI. A new method of synthesis and oxidative arylsulfonylimination of sulfenamides

Article abstract of DOI:10.1007/s11178-005-0174-2

Sulfenylation of ammonia, amines, and arenesulfonamide sodium salts with N-(arylsulfenyl)-N,N′-bis(arylsulfonyl)sulfinimidamides afforded unsubstituted and N-substituted arenesulfenamides. Oxidation of the latter with N-chloro sulfonamide sodium salts gav

Full text of DOI:10.1007/s11178-005-0174-2

Russian Journal of Organic Chemistry, Vol. 41, No. 3, 2005, pp. 386–389. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 3, 2005,
pp. 396–399.
Original Russian Text Copyright © 2005 by Koval’.
Imination of Sulfur-Containing Compounds:
XXXVI.* A New Method of Synthesis and Oxidative
Arylsulfonylimination of Sulfenamides
I. V. Koval’
Ukrainian State University of Chemical Technology, pr. Gagarina 8, Dnepropetrovsk, 49005 Ukraine
Received July 8, 2003
Abstract—Sulfenylation of ammonia, amines, and arenesulfonamide sodium salts with N-(arylsulfenyl)-N,N'-
bis(arylsulfonyl)sulfinimidamides afforded unsubstituted and N-substituted arenesulfenamides. Oxidation of
the latter with N-chloro sulfonamide sodium salts gave the corresponding sulfinimidamides.
ing agents effective toward N–H or N–M compounds
is important from both preparative and theoretical
viewpoints. In the preceding communication [1] it was
shown that previously unknown N-arylsulfenyl-N,N'-
bis(phenylsulfonyl)sulfinimidamides are effective sul-
fenylating agents with respect to thiols and that these
compounds can be used for the preparation of both
symmetric and asymmetric disulfides. Proceeding with
studies in this line, in the present work we examined
reactions of N-arylsulfenyl-N,N'-bis(phenylsulfonyl)-
sulfinimidamides Ia and Ib with compounds having
N–H or N–M bonds. As the latter we used ammonia,
primary and secondary amines, and arenesulfonamide
sodium salts.
Sulfenylation reactions are important from the
preparative viewpoint and are widely used for the syn-
thesis of sulfides [2], disulfides [3], sulfenamides [4],
and other valuable products, as well as for introduction
of protecting groups in peptide syntheses and syn-
theses of natural compounds [5]. Until recently,
sulfenyl chlorides were mainly used as sulfenylating
agents [6]. However, these reagents are not always
convenient because of their low stability and relatively
poor accessibility. In addition, their high reactivity
often gives rise to various undesirable side processes.
Therefore, a number of new sulfenylating agents have
been proposed in the recent years. According to the
data of [7], sulfenamides and sulfenyl acetates activat-
ed by SO3 and AlBr3, respectively, can be successfully
used for sulfenylation of aromatic hydrocarbons to
obtain sulfides. Sulfenamides activated by POCl3
were proposed as sulfenylating agents with respect
to alkenes [8, 9], alkynes [10], and aromatic hydro-
carbons having strong electron-donor groups in the
aromatic ring [11].
We have found that compounds Ia and Ib vigor-
ously react with ammonia and primary and secondary
amines in anhydrous inert organic solvents to give,
respectively, unsubstituted and N-mono- and N,N-di-
substituted arenesulfenamides IIa–IIc (Scheme 1). The
Scheme 1.
SO2Ph
Apart from sulfenyl chlorides, thiols [12], disul-
fides activated by metal salts [3, 4], thiosulfonic acid
S-esters, and sulfenyl thiocyanates [4, 5] were some-
times used as sulfenylating agents in the synthesis of
sulfenamides. However, these reactions are not gen-
eral, and they have not found wide application. At
present, the only preparative method for the synthesis
of sulfenamides is based on reactions of sulfenyl
chlorides with compounds containing N–H or N–M
bonds (M = Na, K, Li, Ag). Search for new sulfenylat-
ArS
N
+
2RR'NH
NSO2Ph
S
NSO2Ph
Ar
Ia, Ib
ArSNRR'
+
Ar
S
RR'NH2
NSO2Ph
IIa–IIc
IIIa–IIIc
I, Ar = Ph (a), 4-MeC6H4 (b); II, III, Ar = Ph, R = R' = H (a);
R = R' = Et (b); R = H, R' = Ph (c).
* For communication XXXV, see [1].
1070-4280/05/4103-0386 © 2005 Pleiades Publishing, Inc.

IMINATION OF SULFUR-CONTAINING COMPOUNDS: XXXVI.
387
corresponding N,N'-bis(phenylsulfonyl)arenesulfin-
imidamide ammonium salts IIIa–IIIc were also
formed as by-products; they were identified via trans-
formation into sulfinimidamides by acidification.
interesting to study oxidative imination of sulfen-
amides IIa and IIb with N-chloro-arenesulfonamide
sodium salts.
We have found that sulfenamides IIa and IIb
relatively readily undergo imination with N-chloro-
arenesulfonamide sodium salts in acetone to afford
the corresponding sulfinimidamides VIa and VIb
(Scheme 4).
By reaction of compounds Ia and Ib with arene-
sulfonamide sodium salts in anhydrous acetone we
obtained N-(arylsulfonyl)arenesulfenamides IVa and
IVb and N,N'-bis(arylsulfonyl)arenesulfinimidamide
sodium salts Va and Vb (Scheme 2).
Scheme 4.
Scheme 2.
NRR'
IIa, IIb
+
ArSO2NClNa
Ph
S
Ia, Ib
+
PhSO2NHNa
–NaCl
NSO2Ar
VIa, VIb
NSO2Ph
NSO2Ph
ArSNHSO2Ph
+
Ar
S
Na+
VI, R = R' = H, Ar = Ph (a); R = R' = Et, Ar = 4-MeC6H4 (b).
IVa, IVb
Va, Vb
Imination of sulfenamides IVa and IVb can also be
effected using N-chloro sulfonamide sodium salts in
acetone [15]; however, the imination of the corre-
sponding sodium salts occurs more smoothly due to
enhanced nucleophilicity of the sulfur atom in the
sulfenamide N-anion [22] (Scheme 5).
IV, V, Ar = Ph (a), 4-MeC6H4 (b).
Sulfenamides IIa–IIc, IVa, and IVb were reported
previously [13–15]; they were identified by the
melting points (by mixing with authentic samples) or
refractive indices (for liquid substances). N-(Aryl-
sulfenyl)-N,N'-bis(phenylsulfonyl)sulfinimidamides Ia
and Ib were prepared by the procedure developed by
us previously [16, 17], namely by oxidative imination
of sodium benzenethiolates with N,N-dichlorobenzene-
sulfonamide in carbon tetrachloride (Scheme 3).
Scheme 5.
ArSN(Na)SO2Ph
+
PhSO2NClNa
NSO2Ph
NHSO2Ph
NSO2Ph
H+
Ar
S
Na+
Ar
S
–NaCl
NSO2Ph
Va, Vb
Scheme 3.
VIc, VId
4RSNa
+
2PhSO2NCl2
Ia, Ib
–RSSR, –4NaCl
VI, Ar = Ph (c), 4-MeC6H4 (d).
It is known that N-(arylsulfenyl)-N,N'-bis(aryl-
sulfonyl)sulfinimidamides react with an equimolar
amount of sodium thiolate to give 1 equiv of the cor-
responding disulfide and 1 equiv of N,N'-bis(phenyl-
sulfonyl)sulfinimidamide. Presumably, the latter are
formed as intermediate products in reactions of sodium
thiolates with N,N-dichloro sulfonamides at a ratio of
5:2; these reactions underlie a number of preparative
procedures for the synthesis of N,N'-disubstituted sul-
finimidamides [18]. Another equally important reac-
tion leading to sulfinimidamides is oxidative imination
of sulfenamides with N-halo derivatives [4, 5]. Here,
the ability of sulfenamides to undergo imination with
N-halo compounds is determined by the structure of
the initial sulfenamide [19], nucleophilicity of the
sulfur atom therein [20, 21], acidity of the substrate
[22], strength of the C–S bond [23], solvent nature
[13, 24], and other factors which should be taken into
account in each particular case. Therefore, it was
The reaction of sulfenamide IIc with N-chloro-
benzenesulfonamide sodium salt in acetone was not
selective. It resulted in formation of a mixture of
several products, from which only N,N'-bis(phenyl-
sulfonyl)sulfinimidamide and diphenyl disulfide were
isolated and identified. The observed reaction pattern
may be rationalized in terms of insufficient nucleo-
philicity of the sulfur atom in sulfenamide IIc, on the
one hand, and weakness of the S–N bond therein, on
the other. Cleavage of that bond during the process
gives rise to subsequent imination of the PhS frag-
ment, as was observed previously in the imination
of bis(arylsulfenyl)imides [23]. According to [23],
anomalous imination with cleavage of the S–N bond
occurs as a rule with N-substituted sulfenamides; the
force constant for stretching vibrations of that bond
does not exceed 1920.5×10–17 J mol–1 m2. In the IR
spectrum of sulfenamide IIc, stretching vibration fre-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005

KOVAL’
388
quency of the S–N bond is 743 cm–1; using the formula
given in [25], the corresponding force constant was
estimated at 1910×10–17 J mol–1 m2.
40 min. The solvent was evaporated in air, the residue
was treated with 100 ml of water, and the precipitate
was filtered off, dried, and recrystallized from approp-
riate solvent to obtain sulfenamide IVa or VIb. The
aqueous filtrate was acidified to isolate sulfinimid-
amide Va or Vb which was identified by comparing
with an authentic sample [15].
Arenesulfinimidamides VIa–VId were reported
previously [1, 13, 15, 26]; they were identified by the
melting points (by mixing with authentic samples)
and IR and mass spectra. The IR spectrum of VIa
contains two strong absorption bands in the region
3250–3350 cm–1, which belong to stretching vibrations
of the free NH2 group. Absorption bands due to
stretching vibrations of the sulfonyl group appear at
about 1160 cm–1. In the IR spectra of VIc and VId,
absorption bands corresponding to symmetric and anti-
symmetric stretching vibrations of the sulfonyl group
(1150–1160 and 1310–1320 cm–1, respectively) and
stretching vibrations of the N–H bond (3050–
3100 cm–1) were present.
Oxidative arylsulfonylimination of sulfenamides
IIa and IIb. N-Chlorobenzenesulfonamide sodium
salt, 0.001 mol, was added to a solution of 0.001 mol
of sulfenamide IIa in 10 ml of acetone, and the
mixture was stirred until complete disappearance of
active chlorine. The mixture was filtered, the filtrate
was evaporated in air, and the residue was recrys-
tallized from benzene to obtain 0.26 g (92%) of
N-phenylsulfonylbenzenesulfinimidamide (VIa) which
was identified by comparing with an authentic sample
[13] and by IR spectroscopy. The reaction with
sulfenamide IIb was performed in a similar way to
isolate 0.22 g (62%) of N-p-tolylsulfonyl-N,N'-diethyl-
benzenesulfinimidamide (VIb) which was identified
by the melting point [26].
Like N-aroyl-N'-arylsulfonyltrichloromethanesul-
finimidamides [19], compounds VIc and VId showed
no molecular ion peak in the mass spectra. Presumably,
their molecular ions are unstable because of the large
size. The most abundant were fragment ions corre-
sponding to the aryl and arylsulfonyl residues.
Oxidative phenylsulfonylimination of sulfen-
amide IVa and IVb sodium salts. Sulfenamide IVa or
IVb, 0.001 mol, was added to a solution of 0.001 mol
of sodium methoxide in 10 ml of methanol. The
solvent was distilled off under reduced pressure, the
residue was dissolved in 15 ml of anhydrous acetone,
and 0.001 mol of N-chlorobenzenesulfonamide sodium
salt was added to the solution. The mixture sponta-
neously warmed up, and finely dispersed sodium
chloride precipitated. The mixture was shaken for
15 min until complete disappearance of active chlorine
and filtered, the filtrate was evaporated in air, and
the residue was dissolved in 50 ml of water. The solu-
tion was filtered, and the filtrate was acidifed with
5% hydrochloric acid to isolate N,N'-bis(phenylsul-
fonyl)benzenesulfinimidamide (VIc) or N,N'-bis-
(phenylsulfonyl)-p-toluenesulfinimidamide (VId)
(yield quantitative) which were identified by com-
paring with authentic samples [15] and by the IR and
mass spectra.
EXPERIMENTAL
The IR spectra were recorded on a UR-20 spec-
trometer. The mass spectra were obtained on an CB-
9000 instrument with direct sample admission into the
ion source.
Sulfenamides IIa–IIc. Compound Ia, 0.01 mol,
was dissolved in 100 ml of anhydrous benzene, and
0.02 mol of the corresponding amine was added or (in
the synthesis of IIa) dry gaseous ammonia was passed
through the solution. A tarry material precipitated, the
mixture was stirred for 15–30 min, and the solution
was separated from the tarry residue by decanting. The
solvent was evaporated in air, and the residue was
crystallized from appropriate solvent or distilled under
reduced pressure (for liquid products) to obtain sul-
fenamides IIa–IIc. The tarry material was dissolved in
100 ml of water, the solution was filtered, and the
filtrate was acidified to isolate N,N'-bis(phenylsul-
fonyl)benzenesulfinimidamide which was identified by
comparing with an authentic sample [15].
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