Perfluoroalkylated bis(sulfilimine)s and bis(sulfoximine)s by a Ritter-type reaction

Article abstract of DOI:10.1002/ejoc.201301017

Our synthetic methodology, which was previously developed for the preparation of perfluoroalkyl sulfilimines by a reaction between fluorinated sulfoxides and nitriles, has been successfully extended to dinitriles. According to the reaction conditions, we can preferentially produce a cyano monosulfilimine or a bis(sulfilimine). New cyano thioethers have been synthesized through a rearrangement process. Mono- and bis(sulfilimine)s were also oxidized to afford the corresponding sulfoximines, which provide a direct route to potential new ligands for catalysis and new electrophilic perfluoroalkylating reagents. Our synthetic methodology, which was previously developed for the preparation of perfluoroalkyl sulfilimines through a reaction between fluorinated sulfoxides and nitriles, has been successfully extended to dinitriles. Copyright

Full text of DOI:10.1002/ejoc.201301017

FULL PAPER
DOI: 10.1002/ejoc.201301017
Perfluoroalkylated Bis(sulfilimine)s and Bis(sulfoximine)s by a Ritter-Type
Reaction
Bruce Pégot,[a] Céline Urban,[a] Patrick Diter,[a] and Emmanuel Magnier*[a]
Keywords: Synthetic methods / Sulfur / Fluorine / Cyanides / Ylides
Our synthetic methodology, which was previously developed
for the preparation of perfluoroalkyl sulfilimines by a reac-
tion between fluorinated sulfoxides and nitriles, has been
successfully extended to dinitriles. According to the reaction
conditions, we can preferentially produce a cyano monosulf-
ilimine or a bis(sulfilimine). New cyano thioethers have been
synthesized through a rearrangement process. Mono- and
bis(sulfilimine)s were also oxidized to afford the correspond-
ing sulfoximines, which provide a direct route to potential
new ligands for catalysis and new electrophilic perfluoroalk-
ylating reagents.
Beyond their inherent properties, sulfilimines are also of
great interest as they are precursors to another highly im-
Introduction
A sulfilimine contains a sulfur(IV) atom and belongs to portant class of sulfur(VI) compounds. They are easily oxi-
the family of sulfur–nitrogen ylides. Their fascinating and dized to give sulfoximines,[6] which are also a key functional
original skeleton makes them attractive compounds in or- group for various applications such as ligands for cataly-
ganic chemistry. Increasing research has been devoted to sis,[7] reagents,[8] or biologically active molecules.[9,10] Until
both their preparation and the study of their properties.[1] recently, the synthesis of the perfluoroalkylated derivatives
This functionality is indeed an emergent group in chemistry (i.e., the introduction of a halogenated group that is directly
because of its increasing applications to the life sciences,[2] attached to the sulfur) was relatively unknown for sulfil-
organic synthesis,[3] and catalysis as a coordination li- imines and quite cumbersome for sulfoximines. Our re-
gand.[4] Sulfilimines are usually obtained by the imination search group has described a flexible and versatile method-
of a thioether or sulfoxide with various elaborate reagents ology for the straightforward preparation of a wide range
and either assisted or not by a transition-metal catalyst.[5] of perfluoroalkyl sulfur(IV) and (VI) compounds. The main
Scheme 1. General synthesis of sulfilimines, sulfoximines, and ortho-substituted thioethers.
[a] Institut Lavoisier de Versailles (ILV), UMR CNRS 8180,
Université de Versailles,
results are summarized in the Scheme 1. Our divergent syn-
thetic pathway started with simple perfluoroalkyl sulfoxides
i. A Ritter-like reaction with nitriles as nucleophiles af-
forded bis(trifluoromethanesulfonate) ketal ii.[11] Structure
ii rapidly appeared as a common platform and key interme-
diate to routes that provide molecular diversity. Its hydroly-
St Quentin en Yvelines, 45 avenue des Etats-Unis,
78035 Versailles Cedex, France
E-mail: magnier@chimie.uvsq.fr
http://www.ilv.uvsq.fr/research/Echo/Fluor/fluor.html
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201301017.
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Eur. J. Org. Chem. 2013, 7800–7808

Perfluoroalkylated Bis(sulfilimine)s and Bis(sulfoximine)s
sis afforded acylsulfilimines iii, which were either isolated chain may increase the molecular diversity of the products
or smoothly oxidized by potassium permanganate to give with the possible formation of rearranged bis(thioether)
the corresponding sulfoximines iv (see Scheme 1, route a). skeleton 4b and also hybrid substrate 5b, which results from
The acyl function could then be easily removed by treat- a single transposition process from product 2b. Glutaro-
ment with acid.[12] These resulting NH-sulfoximines provide nitrile and adiponitrile have also been considered to com-
a direct path to both existing and new electrophilic per- plete our study.
fluoroalkylating reagents,[13] but also to new electron-with-
To decrease the number of compounds potentially
drawing groups.[14] Heating intermediate ii before hydrolysis formed and consequently simplify the reaction profile, we
led to the divergent synthetic pathway that allowed for the ran the first assay with phthalonitrile. The absence of a la-
isolation of perfluoroalkyl thioethers vi as the major prod- bile hydrogen atom would prevent any rearrangement pro-
uct (see Scheme 1, route b).[15] The formation of these sul- cess. According to our previously described conditions,
fur(II) compounds (i.e., vi) can been explained by a trans- phthalonitrile and phenyl trifluoromethyl sulfoxide were
position process. We assume that the pathway started with first treated with trifluoromethanesulfonic anhydride at
the elimination of trifluoromethanesulfonic acid to form in- –15 °C over two days (see Table 1). Even with 1 equiv. of
termediate vii, which could undergo a pericyclic reaction. sulfoxide, no trace amount of the monosulfilimine was de-
As a result, this transformation only occurred with nitriles tected. The only fluorinated product formed was the origi-
that contained hydrogen atoms at the α position.
nal bis(sulfilimine) 2g, albeit in low yield (see Table 1, En-
Our methodology is ecofriendly as it does not require a try 1). Increasing the amount of sulfoxide to 2 and 4 equiv.
metal or a solvent, it uses a nontoxic oxidizing agent and, led to the isolation of compound 2g along with sulfonium
furthermore, provides great structural flexibility. Variations 6 (see Table 1, Entries 2 and 3). This salt is formed by an
of the aromatic substituents (electron-donating and elec- autocondensation procedure of the trifluoromethyl sulfox-
tron-withdrawing groups), the nitrile (aromatic and ali- ide as previously described by both our group and Shreeve
phatic), and of the fluorinated chain (monofluoro- to per- and co-workers.[16] Finally, the yield for 2g was slightly im-
fluoroalkyl chains) are feasible and have been described
previously.
Table 1. Synthesis of sulfilimines with phthalonitrile.
Results and Discussion
As part of our program devoted to the development of
new sulfur derivatives for the aforementioned purposes, we
were intrigued by the extension of our methodology to em-
ploy dinitriles as nucleophiles. The presence of two reactive
sites would greatly enhance the achieved structural diver-
sity, providing that we could control the selectivity of our
transformations. The number of compounds formed would
be dependent not only on the reaction conditions but also
on the length of the tether between the two nitriles moieties.
Scheme 2 summarizes the great structural opportunities of-
fered by employing a dinitrile. Even the simplest member,
malonitrile, can lead to the formation of three molecules,
that is, monosulfilimine 1a, bis(sulfilimine) 2a, and the re-
arranged dinitrile 3a, which is derived from sulfur(IV) com-
pound 1a. The addition of one carbon atom to the linking
Entry Time Temperature
PhSOCF3
[equiv.]
% Yield
[h]
[°C]
2g
6
1
2
3
4
48
48
48
24
–15
–15
–15
r.t.
1
2
4
2
11
34
45
53
–
13
13
12
Scheme 2. Overview of thioethers, sulfilimines, and sulfoximines potentially obtained with dinitriles (Tf = trifluoromethanesulfonyl).
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B. Pégot, C. Urban, P. Diter, E. Magnier
FULL PAPER
proved to 53% through a change of the reaction tempera-
Neither the formation of bis(thioether) 4b nor sulfilimine
ture and a concomitant reduction of the equivalents of sulf- 5b was detected during this study. Steric hindrance seemed
oxide. be the most plausible explanation. To test this hypothesis,
These encouraging first results prompted us to study the we then turned out our attention to the reactivity of glut-
reactivity of aliphatic dinitriles. The first member of the aronitrile, which has one more carbon atom in the spacer
family, malonitrile, was tested unsuccessfully, despite a few between the two nitrile groups (n = 3). The results are re-
examples of Ritter-type reactions in literature.[17] Sulfonium ported in Table 3.
6 was the only product obtained. Fortunately, this lack of
reactivity disappeared with a spacer of two carbon atoms.
This supplementary methylene dramatically changed the
structural conformation of the molecule and increased the
distance between the two nitrile functions. This steric de-
compression may account for this clear-cut difference of re-
activity. The results for the synthesis of sulfilimines with
succinonitrile are reported in Table 2. Unlike the phthalo-
nitrile series, we were able to prepare the pure monosulf-
ilimine. With 1 equiv. of sulfoxide, a separable mixture of
monosulfilimine 1b and bis(sulfilimine) 2b was obtained
(see Table 2, Entry 1). The isolated yield of each new deriva-
tive 1b and 2b significantly increased by using 2 equiv. of
sulfoxide, but the ratio was still in favor of compound 1b
(see Table 2, Entry 2). The scale-up of the reaction resulted
in a slightly better overall yield along with a change of the
ratio to favor sulfilimine 2b (see Table 2, Entry 3). This
modification could be explained by the use of a vessel sys-
tem that allowed for better stirring and provided the tradi-
tional solidification of the reaction medium. This particular
iterative sequence could be a barrier to the second transfor-
mation. The employment of 4 equiv. of sulfoxide provided
for the isolation of bis(sulfilimine) 2b with some amount of
sulfonium 6 (see Table 2, Entry 4). Warming the reaction
mixture to room temperature was not deleterious to the
yield of sulfur(IV) compound 2b and also afforded thio-
ether 3b, which was formed by the rearrangement process
of compound 1b (see Table 2, Entry 5). Using only 1 equiv.
of the starting sulfoxide was detrimental to the yield of mo-
lecule 2b (see Table 2, Entry 6). Although isolated in a very
modest yield, the formation of this original sulfur com-
pound 3b is remarkable in the stimulating modern context
of the renewal of the chemistry of this perfluoroalkyl thio-
ether function.[18] We assume that we could improve the
yield of formation of trifluoromethyl thioether 3b with an
adaptation of the reaction conditions (e.g., temperature,
time, etc.), but this study is beyond the scope of this article.
Table 3. Synthesis of sulfilimines with glutaronitrile.
Entry Time Temperature PhSOCF3 % Yield
[h]
[°C]
[equiv.] 1c
2c
3c 4c 5c
6
1
48
48
48
48
24
–15
–15
–15
–15
r.t.
1
2
2
4
2
29
60
36
–
4
–
–
–
–
12
–
–
–
–
9
–
–
–
–
9
–
–
–
16
1
2
13
25
41
33
3[a]
4
5
5
[a] Scaleup conditions: Reaction conducted with 5.1 mmol of sulf-
oxide (instead of 0.51 mmol for other entries).
The first benefit of this additional carbon atom is the
greater overall yield of the reaction, in general, and the yield
of isolated monosulfilimine 1c, in particular, which reached
60% (see Table 3, Entry 2). As previously described, the
scale-up of the reaction as well as a greater number of
equivalents of sulfoxide favored the synthesis of 2c (see
Table 3, Entries 3 and 4). The second advantage was the
ability to prepare other new molecules as pure compounds.
At room temperature, not only monosulfilimine 1c and
bis(sulfilimine) 2c were formed but also thioethers 3c and
4c, which resulted from the transposition process of the
mono- and bis[sulfur(IV)] molecules, respectively (see
Table 3, Entry 5). A fifth compound 5c with an uncommon
structure that contains both a sulfilimine moiety and a thio-
ether function is formed during the same process. This skel-
eton is the result of either the reaction of the primary nitrile
of 3c with sulfoxide or a single rearrangement process start-
ing from 2c. This last hypothesis appears the most plausible
explanation to us.
Our best reaction conditions with glutaronitrile (see
Table 3, Entry 2) were then tested using other fluoroalkyl-
ated sulfoxides (see Scheme 3). Bromodifluoromethyl sulf-
oxide was then transformed with acceptable yield into a
Table 2. Synthesis of sulfilimines with succinonitrile.
Entry Time Temperature PhSOCF3
% Yield
2b 3b
[h]
[°C]
[equiv.]
1b
6
1
48
48
48
48
24
24
–15
–15
–15
–15
r.t.
1
2
2
4
2
1
15
38
29
–
–
3
8
–
–
–
–
17
19
–
–
–
12
–
–
2
17
30
57
50
19
3[a]
4
5
6
r.t.
[a] Scaleup conditions: Reaction conducted with 5.1 mmol of sulf-
oxide (instead of 0.51 mmol for other entries).
Scheme 3. Synthesis of dichlorofluoro- and bromodifluoromethyl
sulfilimines.
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Perfluoroalkylated Bis(sulfilimine)s and Bis(sulfoximine)s
separable mixture of monosulfilimine 1e as the major prod- nonsymmetrical bis[sulfur(IV)] molecules (see Scheme 4).
uct along with bis(sulfilimine) 2e. An equal distribution of The variation of the perfluoroalkylated chain was firstly re-
compounds 1f and 2f were produced by using the di- alized with 1b to afford compound 8 [see Scheme 4, Equa-
chlorofluoro sulfoxide substrate, albeit in lower and moder- tion (1)]. The variation of the aromatic moieties then deliv-
ate yield. The reduced reactivity of this sulfoxide is not so ered sulfilimines 10 and 12 [see Scheme 4, Equations (2) and
surprising and has already been noted in our previous stud- (3)]. Despite using a slight excess amount of the sulfur rea-
ies.[12]
gent and an increased reaction time, the conversions of the
The previous results were very similar to those obtained three transformations were rather low and, consequently,
with adiponitrile and allowed us to extrapolate upon our the isolated yields were quite poor. We did not carry out
methodology (see Table 4). Monosulfilimine 1d was ob- these reactions for a longer amount of time to avoid un-
tained as the major product with an acceptable yield by wanted side reactions. We preferred to give priority to the
using 2 equiv. of the substrate (see Table 4, Entry 2), recovery of starting materials 1b–1d.
whereas bis(sulfilimine) 2d was the unique sulfur(IV) deriv-
ative isolated when an excess amount of the substrate was
used (see Table 4, Entry 4). Once again, increasing the reac-
tion temperature afforded the new thioethers 3d and 4d as
well as the hybrid molecule 5d (see Table 4, Entry 5).
We then turned out our attention to the oxidation of the
sulfilimines. The reappraisal of our former protocol was
necessary to prevent the formation of a complex mixture
of the mono- and bis(sulfoximine)s along with the starting
material. The use of 10 equiv. of potassium permanganate
over 18 h provided for the isolation of the desired products
in good yields and as the sole fluorinated compounds. The
results are presented in Scheme 5. Four original bis(tri-
fluoromethyl sulfoximine)s 13b–13d and 13g were synthe-
sized with acceptable [for a long carbon spacer, see
Scheme 5, Equation (2)] to good yields [for a short carbon
spacer and an aromatic spacer, see Scheme 5, Equations (1)
and (2)]. Cyano sulfoximines 14b–14d were also prepared
with good to excellent yields [see Scheme 5, Equation (3)].
Bis(sulfilimine)s and bis(sulfoximine)s are already known
in the literature,[19] but the preparation of the perfluoroalk-
ylated versions of these sulfur(IV) and sulfur(VI) com-
pounds through traditional methods was not previously
possible. Our contribution now allows the complete synthe-
Table 4. Synthesis of sulfilimines with adiponitrile.
Entry Time Temperature PhSOCF3
% Yield
[h]
[°C]
[equiv.] 1d
2d
3d
4d 5d
6
1
48
48
48
48
24
–15
–15
–15
–15
r.t.
1
2
2
4
2
34
50
38
–
4
–
–
–
–
15
–
–
–
–
10
–
–
–
–
6
–
–
–
14
1
2
14
25
34
12
3[a]
4
5
15
[a] Scaleup conditions: reaction conducted with 5.1 mmol of sulfox-
ide (instead of 0.51 mmol for other entries).
The chemical potential of our original perfluoroalkylated ses of the whole series. We have provided access to the
sulfilimines was then explored according to two synthetic straightforward formation of new perfluoroalkylating rea-
directions. Monosulfilimines 1b–1d were first transformed gents as well as bidentate ligands for catalysis. An investiga-
into unsymmetrical bis(sulfilimine)s by engaging in a reac- tion into these topics is currently under development in our
tion with 2 equiv. of sulfoxide to afford the corresponding laboratory.
Scheme 4. Synthesis of dissymmetric sulfilimine.
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B. Pégot, C. Urban, P. Diter, E. Magnier
FULL PAPER
Scheme 5. Synthesis of mono- and bis(sulfoximine)s.
0.5 mmol, 2 equiv.) and succinonitrile (21 mg, 0.26 mmol, 1 equiv.).
The reaction mixture was stirred at –15 °C for 48 h. After the ad-
dition of CH2Cl2 (2 mL), the solution was then hydrolyzed with
Conclusions
We have demonstrated that we can access either mono-
or bis(sulfilimine)s through a modification of the experi- water (2 mL). The resulting mixture was extracted with CH2Cl2
(3ϫ 5 mL), and the combined extracts were dried with MgSO4 and
concentrated under reduced pressure. The residue was purified by
flash chromatography (diethyl ether) to give 1b (27 mg, 38% yield)
as a yellow viscous oil. 1H NMR (200 MHz, CDCl3): δ = 2.65–
2.73 (m, 2 H), 2.80–2.88 (m, 2 H), 7.59–7.75 (m, 3 H), 7.90 (d, J
= 7.4 Hz, 2 H) ppm. 19F NMR (188 MHz, CDCl3): δ = –64.8 (s, 3
F) ppm. 13C NMR (75 MHz, CDCl3): δ = 14.0, 32.8, 119.3, 123.9
(q, J = 322 Hz, CF3), 126.5, 128.8, 130.3, 134.7, 181.4 ppm. MS
(ESI+): m/z = 275 [M + H]+, 297 [M + Na]+, 571 [2M + Na]+.
HRMS (ESI): calcd. for C11H9F3N2OSNa [M + Na]+ 297.0285;
found 297.0271 (δ = –4.7 ppm).
mental conditions of a reaction between fluorinated sulfox-
ides and various dinitriles. Original thioethers that contain
a cyano group have been also prepared. We also proved that
structural diversity was possible by varying the perfluoro-
alkyl chain, the substituents of the aromatic ring, and of
the alkyl chain that links the two cyano functional groups.
Unsymmetrical bis(sulfilimine)s have been also synthesized.
Finally, various sulfoximines have been prepared using mild
oxidizing conditions. The full potential of these new com-
pounds will be evaluated and reported in due course.
N-(4-Cyanobutyryl) Phenyl Trifluoromethyl Sulfilimine (1c): Vis-
1
cous yellow oil (45 mg, 60% yield). H NMR (200 MHz, CDCl3):
Experimental Section
δ = 2.04 (quintuplet, J = 7.1 Hz, 2 H), 2.47 (t, J = 7.2 Hz, 2 H),
2.66 (t, J = 7.3 Hz, 2 H), 7.59–7.74 (m, 3 H), 7.89 (d, J = 7.3 Hz,
2 H) ppm. 19F NMR (188 MHz, CDCl3): δ = –64.8 (s, 3 F) ppm.
13C NMR (75 MHz, CDCl3): δ = 16.7, 22.1, 35.5, 119.5, 124.0 (q,
J = 324 Hz, CF3), 126.9, 128.7, 130.2, 134.5, 183.9 ppm. MS
1
General Methods: The H (200 or 300 MHz) and 13C NMR (50 or
75 MHz) spectroscopic data were recorded with 200 or 300 MHz
spectrometers, and the samples were dissolved in deuterated chloro-
form with the residual solvent peak as an internal standard. The
solvent peak of CFCl3 was the internal standard for the 19F NMR
(188 MHz) spectroscopic data. Chemical shifts (δ) are given in
parts per million, and coupling constants are given as absolute val-
ues expressed in Hertz. Reported coupling constants and chemicals
shifts were recorded on the basis of first-order analysis. Electro-
spray ionization mass spectra were collected with a Q-TOF instru-
ment. Thin-layer chromatography was carried out with aluminum
sheets precoated with silica gel 60 F254. Column chromatography
separations were performed with silica gel (0.040–0.060 mm).
(ESI+): m/z
= 311 [M +
Na]+. HRMS (ESI): calcd. for
C12H11F3N2OSNa [M + Na]+ 311.0442; found 311.0435 (δ =
–2.3 ppm).
N-(5-Cyanovaleryl) Phenyl Trifluoromethyl Sulfilimine (1d): Viscous
yellow oil (39 mg, 50% yield). 1H NMR (200 MHz, CDCl3): δ =
1.65–1.91 (m, 4 H), 2.36 (t, J = 6.8 Hz, 2 H), 2.53 (t, J = 6.8 Hz,
2 H), 7.57–7.76 (m, 3 H), 7.87 (d, J = 7.3 Hz, 2 H) ppm. 19F NMR
(188 MHz, CDCl3): δ = –64.7 (s, 3 F) ppm. 13C NMR (75 MHz,
CDCl3): δ = 16.7, 24.8, 25.0, 36.0, 119.4, 124.0 (q, J = 324 Hz,
CF3), 126.8, 128.4, 130.0 134.2, 184.8 ppm. MS (ESI+): m/z = 303
[M + H]+, 325 [M + Na]+. HRMS (ESI): calcd. for C13H14F3N2OS
[M + H]+ 303.0779; found 303.0780 (δ = 0.3 ppm).
General Procedure for the Preparation of Monosulfilimine Through
the Preparation of N-(3-Cyanopropionyl) Phenyl Trifluoromethyl
Sulfilimine (1b): Trifluoromethanesulfonic anhydride (160 μL,
0.78 mmol, 3 equiv.) was added under argon to a precooled
N-(4-Cyanobutyryl) Bromodifluoromethyl Phenyl Sulfilimine (1e):
(–15 °C) mixture of phenyl trifluoromethyl sulfoxide (97 mg, Viscous yellow oil (32 mg, 35% yield). 1H NMR (200 MHz,
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Perfluoroalkylated Bis(sulfilimine)s and Bis(sulfoximine)s
CDCl3): δ = 2.07 (quintuplet, J = 7.2 Hz, 2 H), 2.50 (t, J = 7.2 Hz, N,NЈ-Bis[bromodifluoromethyl(phenyl)-λ4-sulfanylidene]pentane-
2 H), 2.67 (td, J = 7.2 Hz, J = 3.5 Hz, 2 H), 7.63 (t, J = 7.7 Hz, 2
diamide (2e): Yellow waxy solid (33 mg, 21% yield; mixture of two
diastereomers, 1:1). 1H NMR (200 MHz, CDCl3): δ = 2.16 (d quin-
tuplet, J = 7.2 Hz, J = 2.1 Hz, 2 H), 2.61 (dt, J = 7.2 Hz, J =
H), 7.74 (t, J = 7.7 Hz, 1 H), 7.93 (d, J = 7.7 Hz, 2 H) ppm. 19F
NMR (188 MHz, CDCl3): δ = –45.7 and –46.9 (AB system, JA,B
=
135 Hz, 2 F) ppm. 13C NMR (75 MHz, CDCl3): δ = 16.7, 22.1, 2.1 Hz, 4 H), 7.60 (t, J = 7.7 Hz, 4 H), 7.71 (t, J = 7.7 Hz, 2 H),
36.2, 119.57, 123.8 (CF2Br), 127.9, 129.4, 129.7, 134.5, 183.7 ppm.
MS (ESI+): m/z = 348.98 [M + H]+. HRMS (ESI): calcd. for
C12H12F2BrN2OS [M + H]+ 348.9822; found 348.9823 (δ =
0.3 ppm).
7.93–7.97 (m, 4 H) ppm. 19F NMR (188 MHz, CDCl3): δ = –45.1
and –46.4 (AB system, JA,B = 136 Hz, 4 F), –45.2 and –46.5 (AB
system, JA,B = 136 Hz, 4 F) ppm. 13C NMR (75 MHz, CDCl3): δ
= 23.2, 23.3, 37.5, 37.6, 125.5 (CF2Br), 128.5, 129.4, 129.8, 134.2,
185.6 ppm. MS (ESI+): m/z = 603 [M + H]+. HRMS (ESI): calcd.
for C19H17F4Br2N2O2S2 [M + H]+ 602.9034; found 602.9030 (δ =
–0.7 ppm).
N-(4-Cyanobutyryl) Dichlorofluoromethyl Phenyl Sulfilimine (1f):
Viscous yellow oil (15 mg, 18% yield). 1H NMR (200 MHz,
CDCl3): δ = 2.04 (quintuplet, J = 7.2 Hz, 2 H), 2.47 (t, J = 7.2 Hz,
2 H), 2.66 (dt, J = 1.5 Hz, J = 7.2 Hz, 2 H), 7.63 (t, J = 7.7 Hz, 2
H), 7.70–7.76 (m, 1 H), 7.88 (d, J = 7.7 Hz, 2 H) ppm. 19F NMR
(188 MHz, CDCl3): δ = –64.7 (s, 3 F) ppm. 13C NMR (75 MHz,
CDCl3): δ = 16.7, 22.1, 35.5, 119.5, 124.1 (d, J = 324 Hz, CFCl2),
126.9, 128.7, 130.3, 134.6, 184.0 ppm. MS (ESI+): m/z = 321 [M +
H]+. HRMS (ESI): calcd. for C12H12FCl2N2OS [M + H]+ 321.0029;
found 321.0029 (δ = –0.6 ppm).
N,NЈ-Bis[dichlorofluoromethyl(phenyl)-λ4-sulfanylidene]pentane-
diamide (2f): Yellow waxy solid (12 mg, 8% yield; mixture of two
1
diastereomers, 1:1). H NMR (200 MHz, CDCl3): δ = 2.16 (q, J =
7.2 Hz, 2 H), 2.61 (t, J = 7.2 Hz, 4 H), 7.59 (t, J = 7.7 Hz, 4 H),
7.71 (t, J = 7.2 Hz, 2 H), 7.92 (dd, J = 8.2 Hz, J = 3.0 Hz, 4
H) ppm. 19F NMR (188 MHz, CDCl3): δ = –64.7 (s, 2 F), –64.6 (s,
2 F) ppm. 13C NMR (75 MHz, CDCl3): δ = 23.1, 23.2, 36.5, 36.7,
124.2 (d, J = 323 Hz, CFCl2), 124.3 (d, J = 322 Hz, CFCl2), 127.3,
127.4, 128.7, 130.1, 134.3, 185.7 ppm. MS (ESI+): m/z = 547 [M +
H]+. HRMS (ESI): calcd. for C19H17F2Cl4N2O2S2 [M + H]+
546.9454; found 546.9450 (δ = –0.7 ppm).
General Procedure for the Preparation of Bis(sulfilimine) Through
the Preparation of N,NЈ-Bis[trifluoromethyl(phenyl)-λ4-sulfanylid-
ene]butanediamide (2b): Trifluoromethanesulfonic anhydride
(160 μL, 0.78 mmol, 3 equiv.) was added under argon to a pre-
cooled (–15 °C) mixture of phenyl trifluoromethyl sulfoxide
(194 mg, 1 mmol, 4 equiv.) and succinonitrile (21 mg, 0.26 mmol,
1 equiv.). The reaction mixture was stirred at –15 °C for 48 h. After
the addition of CH2Cl2 (2 mL), the solution was then hydrolyzed
with water (2 mL). The resulting mixture was extracted with
CH2Cl2 (3ϫ 5 mL), and the combined extracts were dried with
MgSO4 and concentrated under reduced pressure. The residue was
purified by flash chromatography (diethyl ether) to give 2b (69 mg,
57% yield; mixture of two diastereomers, 1:1) as a yellow waxy
solid. 1H NMR (200 MHz, CDCl3): δ = 2.9 (s, 4 H), 7.53–7.68 (m,
6 H), 7.87 (d, J = 7.3 Hz, 4 H) ppm. 19F NMR (188 MHz, CDCl3):
δ = –64.9 (s, 6 F), –64.8 (s, 6 F) ppm. 13C NMR (75 MHz, CDCl3):
δ = 33.5, 33.6, 124.1 (q, J = 332 Hz, CF3), 127.2, 127.3, 128.6,
129.9, 130.0, 134.1, 134.2, 185.0 ppm. MS (ESI+): m/z = 469 [M +
H]+, 491 [M + Na]+, 959 [2M + Na]+. HRMS (ESI): calcd. for
C18H15F6N2O2S2 [M + H]+ 469.0479; found 469.0465 (δ =
–3.0 ppm).
N,NЈ-Bis[trifluoromethyl(phenyl)-λ4-sulfanylidene]phthalamide (2g):
Trifluoromethanesulfonic anhydride (160 μL, 0.78 mmol, 3 equiv.)
was added under argon to a mixture of phenyl trifluoromethyl sulf-
oxide (100 mg, 0.5 mmol, 2 equiv.) and phthalonitrile (32 mg,
0.25 mmol, 1 equiv.). The reaction mixture was stirred at room tem-
perature for 24 h. After the addition of CH2Cl2 (2 mL), the solution
was then hydrolyzed with water (2 mL). The resulting mixture was
extracted with CH2Cl2 (3ϫ 5 mL), and the combined extracts were
dried with MgSO4 and concentrated under reduced pressure. The
residue was purified by flash chromatography (diethyl ether) to give
2g (68 mg, 53% yield; mixture of two diastereomers, 1:1) as a yel-
low solid; m.p. 128 °C. 1H NMR (200 MHz, CDCl3): δ = 7.40–7.62
(m, 8 H), 7.79–7.92 (m, 6 H) ppm. 19F NMR (188 MHz, CDCl3):
δ = –64.8 (s, 6 F), –64.6 (s, 6 F) ppm. 13C NMR (75 MHz, CDCl3):
δ = 124.1 (q, J = 324 Hz, CF3), 124.2 (q, J = 324 Hz, CF3), 126.9,
127.1, 128.6, 128.7, 128.8, 129.5, 129.8, 133.9, 134.0, 136.3, 136.4,
180.0 ppm. MS (ESI+): m/z = 517 [M + H]+, 539 [M + Na]+.
HRMS (ESI): calcd. for C22H15F6N2O2S2 [M + H]+ 517.0479;
found 517.0477 (δ = –0.4 ppm).
N,NЈ-Bis[trifluoromethyl(phenyl)-λ4-sulfanylidene]pentanediamide
(2c): Yellow waxy solid (51 mg, 41% yield; mixture of two dia-
General Procedure for the Preparation of Unsymmetrical Bis(sulf-
ilimine) Through the Preparation of N-[Trifluoromethyl(phenyl)-λ4-
sulfanylidene]-NЈ-[nonafluorobutyl(phenyl)-λ4-sulfanylidene]butane-
diamide (8): Trifluoromethanesulfonic anhydride (55 μL, 0.4 mmol,
2 equiv.) was added under argon to a precooled (–15 °C) mixture
of phenyl nonafluorobutyl sulfoxide (137 mg, 0.4 mmol, 2 equiv.)
and 1b (55 mg, 0.2 mmol, 1 equiv.). The reaction mixture was
stirred at –15 °C for 48 h. After the addition of CH2Cl2 (2 mL),
the solution was then hydrolyzed with water (2 mL). The resulting
mixture was extracted with CH2Cl2 (3ϫ 5 mL), and the combined
extracts were dried with MgSO4 and concentrated under reduced
pressure. The residue was purified by flash chromatography (diethyl
1
stereomers, 1:1). H NMR (200 MHz, CDCl3): δ = 2.05–2.16 (m,
2 H), 2.52–2.61 (m, 4 H), 7.56–7.87 (m, 6 H), 7.93 (t, J = 4.6 Hz,
4 H) ppm. 19F NMR (188 MHz, CDCl3): δ = –64.7 (s, 6 F), –64.6
(s, 6 F) ppm. 13C NMR (75 MHz, CDCl3): δ = 23.0, 23.2, 36.4,
36.6, 124.0 (q, J = 322 Hz, CF3), 124.1 (q, J = 322 Hz, CF3), 127.3,
127.4, 128.6, 128.7, 130.6, 130.7, 134.2, 185.8 ppm. MS (ESI+): m/z
= 483 [M + H]+, 505 [M + Na]+, 987 [2M + Na]+. HRMS (ESI):
calcd. for C19H16F6N2O2S2Na [M + Na]+ 505.0455; found
505.0450 (δ = –1.0 ppm).
N,NЈ-Bis[trifluoromethyl(phenyl)-λ4-sulfanylidene]hexanediamide
(2d): Yellow solid (44 mg, 34% yield; mixture of two diastereomers,
1:1); m.p. 107–108 °C. 1H NMR (200 MHz, CDCl3): δ = 1.73–1.80
ether) to give 8 (39 mg, 32% yield; mixture of two diastereomers,
1
(m,4 H), 2.50–2.56 (m, 4 H), 7.56–7.73 (m, 6 H), 7.87 (d, J = 1:1) as a yellow waxy solid. H NMR (200 MHz, CDCl3): δ = 2.89
7.2 Hz, 4 H) ppm. 19F NMR (188 MHz, CDCl3): δ = –64.7 (s, 6
(s, 4 H), 7.55–7.69 (m, 6 H), 7.89 (t, J = 6.5 Hz, 4 H) ppm. 19F
NMR (188 MHz, CDCl3): δ = –64.8 (s, 3 F), –64.9 (s, 3 F), –81.1
F) ppm. 13C NMR (75 MHz, CDCl3): δ = 26.1, 37.0, 124.2 (q, J =
322 Hz, CF3), 127.3, 128.5, 130.0, 134.2, 186.1 ppm. MS (ESI+): (m, 3 F), –104.4 and –109.4 (AB system, JA,B = 234 Hz, 2 F),
m/z = 497 [M + H]+, 519 [M + Na]+. HRMS (ESI): calcd. for
C20H18F6N2O2S2Na [M + Na]+ 519.0612; found 519.0597 (δ =
–2.9 ppm).
–119.8 (m, 2 H), –125.2 and –127.1 (AB system, JA,B = 291 Hz, 2
F) ppm. 13C NMR (75 MHz, CDCl3): δ = 29.7, 30.3, 34.6, 34.7,
34.0, 34.1, 124.2 (q, J = 324 Hz, CF3), 124.1 (q, J = 324 Hz, CF3),
Eur. J. Org. Chem. 2013, 7800–7808
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7805

B. Pégot, C. Urban, P. Diter, E. Magnier
FULL PAPER
126.4, 126.5, 127.3, 127.4, 128.6, 129.7, 129.9, 130.0, 134.1, 134.4,
184.7, 185.1 ppm. MS (ESI+): m/z = 619 [M + H]+, 641 [M +
Na]+. HRMS (ESI): calcd. for C21H15F12N2O2S2 [M + H]+
619.0383; found 619.0386 (δ = 0.5 ppm).
2.79 (m, 1 H), 4.64 (t, J = 7.7 Hz, 2 H), 7.27 (td, J = 7.7 Hz, J =
1.5 Hz, 2 H), 7.63–7.74 (m, 4 H), 7.80 (d, J = 7.7 Hz, 2 H) ppm.
19F NMR (188 MHz, CDCl3): δ = –42.2 (s, 6 F) ppm. 13C NMR
(75 MHz, CDCl3): δ = 31.3, 39.1, 117.7, 122.5, 127.7 (q, J =
308 Hz, CF3), 128.3, 129.3, 131.9, 138.1, 138.3 ppm. MS (ESI+):
m/z = 447 [M + H]+. HRMS (ESI): calcd. for C19H13F6N2S2 [M +
H]+ 447.0424; found 447.0435 (δ = 2.5 ppm).
N-[Trifluoromethyl(phenyl)-λ4-sulfanylidene]-NЈ-[trifluoromethyl(p-
tolyl)-λ4-sulfanylidene]pentanediamide (10): Yellow waxy solid
(20 mg, 20% yield; mixture of two diastereomers, 1:1). 1H NMR
(200 MHz, CDCl3): δ = 2.03–2.15 (m, 2 H), 2.27 (s, 3 H), 2.56 (q,
2,5-Bis[2-(trifluoromethylsulfanyl)phenyl]hexanedinitrile (4d): Vis-
J = 6.8 Hz, 4 H), 7.41 (d, J = 8.2 Hz, 2 H), 7.59–7.96 (m, 7 H) ppm. cous yellow oil (11 mg, 9% yield; mixture of two diastereomers,
1
19F NMR (188 MHz, CDCl3): δ = –64.1 (s, 3 F), –64.2 (s, 3 F),
1:1). H NMR (200 MHz, CDCl3): δ = 2.00–2.26 (m, 4 H), 4.63–
–64.5 (s, 3 F), –64.6 (s, 3 F) ppm. 13C NMR (75 MHz, CDCl3): δ 4.70 (m, 2 H), 7.46 (td, J = 7.8 Hz, J = 1.8 Hz, 2 H), 7.63 (m, 4
= 21.7, 23.1, 23.2, 36.5, 36.8, 124.3 (q, J = 324 Hz, CF3), 124.4 (q,
J = 322 Hz, CF3), 124.0, 124.1, 128.7, 130.1, 130.8, 134.2, 145.5,
185.8, 185.9 ppm. MS (ESI+): m/z = 497 [M + H]+. HRMS (ESI):
calcd. for C20H19F6N2O2S2 [M + H]+ 497.0792; found 497.0792 (δ
= 0 ppm).
H), 7.78 (d, J = 7.7 Hz, 2 H) ppm. 19F NMR (188 MHz, CDCl3):
δ = –42.8 (s, 6 F), –42.7 (s, 6 F) ppm. 13C NMR (75 MHz, CDCl3):
δ = 32.9, 33.0, 34.5, 34.6, 119.5, 124.8 (q, J = 310 Hz, CF3), 128.9,
129.8, 130.9, 132.7, 132.8, 139.3, 140.5, 140.5 ppm. MS (ESI+): m/z
= 483 [M + Na]+. HRMS (ESI): calcd. for C20H15F6N2S2
[M + H]+ 461.0581; found 461.0599 (δ = 3.9 ppm).
N-[Trifluoromethyl(phenyl)-λ4-sulfanylidene]-NЈ-[trifluoromethyl-
(p-chlorophenyl)-λ4-sulfanylidene]hexanediamide (12): Yellow waxy
solid (20 mg, 19% yield; mixture of two diastereomers, 1:1). 1H
NMR (200 MHz, CDCl3): δ = 1.71–1.80 (m, 4 H), 2.49–2.54 (m, 4
H), 7.56–7.71 (m, 5 H), 7.80–7.90 (m, 4 H) ppm. 19F NMR
(188 MHz, CDCl3): δ = –64.7 (s, 6 F), –64.6 (s, 6 F) ppm. 13C NMR
(75 MHz, CDCl3): δ = 26.1, 29.7, 30.3, 36.9, 37.0, 124.1 (q, J =
324 Hz, CF3), 124.2 (q, J = 322 Hz, CF3), 127.3, 127.4, 128.6,
129.8, 130.1, 130.5, 134.2, 141.1 186.1, 186.2 ppm. MS (ESI+): m/z
= 531 [M + H]+, 553 [M + Na]+. HRMS (ESI): calcd. for
4-Cyano-N-[phenyl(trifluoromethyl)-λ4-sulfanylidene]-4-{[2-(tri-
fluoromethyl)thio]phenyl}butanamide (5c): Viscous yellow oil
(11 mg, 9% yield; mixture of two diastereomers, 1:1). 1H NMR
(200 MHz, CDCl3): δ = 2.18–2.33 (m, 2 H), 2.67–2.75 (m, 2 H),
4.75–4.87 (m, 1 H), 7.41 (td, J = 7.5 Hz, J = 1.7 Hz, 1 H), 7.55–
7.77 (m, 6 H), 7.89 (d, J = 7.5 Hz, 2 H) ppm. 19F NMR (188 MHz,
CDCl3): δ = –64.2 (s, 3 F), –42.4 (s, 3 F) ppm. 13C NMR (75 MHz,
CDCl3): δ = 31.7, 34.3, 34.5, 120.4, 124.2 (q, J = 315 Hz, CF3),
124.9 (q, J = 310 Hz, CF3), 127.0, 128.7, 129.0, 129.3, 130.2, 131.0,
132.5, 134.5, 138.9, 141.6, 184.9 ppm. MS (ESI+): m/z = 465 [M +
H]+. HRMS (ESI): calcd. for C19H15F6ON2S2 [M + H]+ 465.0530;
found 465.0531 (δ = 0.2 ppm).
C
20H18F6N2O2S2Cl [M + H]+ 531.0402 found; 531.0406 (δ =
0.8 ppm).
2-{2-[(Trifluoromethyl)thio]phenyl}butanedinitrile (3b): Viscous yel-
5-Cyano-N-[phenyl(trifluoromethyl)-λ4-sulfanylidene]-4-[2-(tri-
fluoromethylsulfanyl)phenyl]pentanamide (5d): Viscous yellow oil
(8 mg, 6 % yield; mixture of two diastereomers, 1:1). 1H NMR
(200 MHz, CDCl3): δ = 1.86–2.00 (m, 4 H), 2.52–2.60 (m, 2 H),
4.60–4.66 (m, 1 H), 7.40 (td, J = 7.5 Hz, J = 1.8 Hz, 1 H), 7.53–
7.77 (m, 6 H), 7.87 (d, J = 7.3 Hz, 2 H) ppm. 19F NMR (188 MHz,
CDCl3): δ = –64.7 (s, 3 F), –64.6 (s, 3 F), –42.8 (s, 3 F), –42.9 (s, 3
F) ppm. 13C NMR (75 MHz, CDCl3): δ = 23.9, 35.0, 35.2, 36.4,
123.0, 123.5 (q, J = 335 Hz, CF3), 124.0 (q, J = 324 Hz, CF3),
126.8, 127.3, 128.7, 129.2, 129.3, 130.2, 132.5, 134.5, 138.9, 141.3,
183.5 ppm. MS (ESI+): m/z = 479 [M + H]+. HRMS (ESI): calcd.
for C20H17F6N2OS2 [M + H]+ 479.0687; found 479.0690 (δ =
0.6 ppm).
1
low oil (13 mg, 19% yield). H NMR (200 MHz, CDCl3): δ = 2.94
(dd, J = 6.4 Hz, J = 13.5 Hz, 1 H), 3.06 (dd, J = 6.4 Hz, J =
13.5 Hz, 1 H), 5.04 (t, J = 6.4 Hz, 1 H), 7.55 (td, J = 7.4 Hz, J =
1.5 Hz, 1 H), 7.70 (td, J = 7.8 Hz, J = 1.3 Hz, 1 H), 7.84 (dd, J =
7.8 Hz, J = 1.3 Hz, 1 H) ppm. 19F NMR (188 MHz, CDCl3): δ =
–42.7 (s, 3 F) ppm. 13C NMR (75 MHz, CDCl3): δ = 23.9, 31.5,
114.6, 117.4, 122.9, 128.8 (q, J = 309 Hz, CF3), 129.3, 130.8, 133.1,
137.7, 139.5 ppm. MS (ESI–): m/z = 255 [M – H]–. HRMS (ESI):
calcd. for C11H6F3N2S [M – H]– 255.0204; found 255.0211 (δ =
2.7 ppm).
2-{[2-(Trifluoromethyl)thio]phenyl}pentanedinitrile (3c): Viscous yel-
1
low oil (9 mg, 12% yield). H NMR (200 MHz, CDCl3): δ = 2.22–
2.30 (m, 2 H), 2.59–2.64 (m, 2 H), 4.78 (t, J = 8.0 Hz, 1 H), 7.49
(td, J = 7.7 Hz, J = 1.5 Hz, 1 H), 7.62–7.70 (m, 2 H), 7.81 (d, J =
7.7 Hz, 1 H) ppm. 19F NMR (188 MHz, CDCl3): δ = –42.1 (s, 3
F) ppm. 13C NMR (75 MHz, CDCl3): δ = 15.3, 31.0, 34.2, 117.3,
118.7, 123.0, 128.8 (q, J = 309 Hz, CF3), 129.0, 130.8, 132.9,
139.4 ppm. MS (ESI+): m/z = 271 [M + H]+. HRMS (ESI): calcd.
for C12H10F3N2S [M + H]+ 271.0517; found 271.0522 (δ =
1.8 ppm).
General Procedure for the Oxidation of Sulfilimine Compounds
Through the Preparation of N,NЈ-Bis[oxo-phenyl-(trifluoromethyl)-
λ6-sulfanylidene]butanediamide (13b): A mixture of N,NЈ-bis(tri-
fluoromethylphenyl-λ4-sulfanylidene) butanediamide (2b, 100 mg,
0.21 mmol) and potassium permanganate (332 mg, 2.1 mmol,
10 equiv.) in water (1 mL) was stirred at room temperature over-
night. The mixture became colorless by the addition of a solution
of 10% Na2S2O4, and the product was extracted with CH2Cl2 (3ϫ
5 mL). The combined organic layers were dried with MgSO4 and
concentrated under reduced pressure. The residue was purified by
preparative TLC (diethyl ether) to give 13b (76 mg, 72% yield; mix-
ture of two diastereomers, 1:1) as a white solid; m.p. 122 °C. 1H
NMR (200 MHz, CDCl3): δ = 2.74–3.01 (m, 4 H), 7.52–7.82 (m, 6
H), 8.05 (t, J = 7.3 Hz, 4 H) ppm. 19F NMR (188 MHz, CDCl3):
δ = –75.8 (s, 6 F), –75.0 (s, 6 F) ppm. 13C NMR (75 MHz, CDCl3):
δ = 34.3, 34.4, 120.0 (q, J = 325 Hz, CF3), 120.1 (q, J = 326 Hz,
CF3), 129.9, 130.0, 130.1, 130.2, 130.3, 136.0, 136.1, 179.8,
179.9 ppm. MS (ESI+): m/z = 501 [M + H]+, 523 [M + Na]+.
HRMS (ESI): calcd. for C18H15F6N2O4S2 [M + H]+ 501.0377;
2-{[2-(Trifluoromethyl)thio]phenyl}hexanedinitrile (3d): Viscous yel-
1
low oil (9 mg, 12% yield). H NMR (200 MHz, CDCl3): δ = 1.75–
2.11 (m, 4 H), 2.43–2.49 (m, 2 H), 4.62–4.70 (m, 1 H), 7.45 (td, J
= 7.4 Hz, J = 1.6 Hz, 1 H), 7.58–7.80 (m, 3 H) ppm. 19F NMR
(188 MHz, CDCl3): δ = –42.7 (s, 3 F) ppm. 13C NMR (75 MHz,
CDCl3): δ = 16.7, 23.0, 34.2, 34.5, 118.4, 119.6, 124.6 (q, J =
315 Hz, CF3), 128.9, 129.7, 130.9, 132.7,139.2, 140.6 ppm. MS
(ESI+): m/z = 285 [M + H]+. HRMS (ESI): calcd. for C13H12F3N2S
[M + H]+ 285.0673; found 285.0681 (δ = 2.8 ppm).
2,4-Bis[2-(trifluoromethylsulfanyl)phenyl]pentanedinitrile (4c): Vis-
cous yellow oil (10 mg, 9% yield; mixture of two diastereomers,
1
1:1). H NMR (200 MHz, CDCl3): δ = 2.39–2.49 (m, 1 H), 2.69– found 501.0381, (δ = 0.8 ppm).
7806
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 7800–7808

Perfluoroalkylated Bis(sulfilimine)s and Bis(sulfoximine)s
N,NЈ-Bis[oxo-phenyl-(trifluoromethyl)-λ6-sulfanylidene]pentane- 341 [M + Na]+. HRMS (ESI): calcd. for C13H14F3N2O2S
diamide (13c): White solid (58 mg, 54% yield; mixture of two dia-
stereomers, 1:1); m.p. 81 °C. 1H NMR (300 MHz, CDCl3): δ = 1.97
(quintuplet, J = 7.3 Hz, 2 H), 2.54 (t, J = 7.3 Hz, 4 H), 7.59 (t, J
= 7.3 Hz, 4 H), 7.81 (td, J = 7.3 Hz, J = 1.2 Hz, 2 H), 7.97 (d, J
= 7.7 Hz, 4 H) ppm. 19F NMR (188 MHz, CDCl3): δ = –74.2 (s, 6
F), –74.3 (s, 6 F) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.6, 20.7,
38.4, 38.5, 120.1 (q, J = 327 Hz, CF3), 129.4, 130.0, 130.1, 130.2,
136.1, 180.5 ppm. MS (ESI+): m/z = 515 [M + H]+, 537 [M +
Na]+. HRMS (ESI): calcd. for C19H17F6N2O4S2 [M + H]+
515.0534; found 515.0530 (δ = –0.8 ppm).
[M + H]+ 319.0728; found 319.0724 (δ = –1.3 ppm).
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the NMR spectra of all the compounds.
Acknowledgments
C. C.-U. thanks the French Ministry of Research for the Ph.D.
grant. François Metz (Rhodia-Solvay company) is gratefully
acknowledged for the gift of fluorinated reagents, and Jean-Claude
Blazejewski is acknowledged for the helpful discussions. We also
warmly acknowledge F. Bourdreux and E. Galmiche-Loire for the
NMR and ESI-MS analyses and Lucy Cooper for the linguistic
improvement of the manuscript.
N,NЈ-Bis[oxo-phenyl-(trifluoromethyl)-λ6-sulfanylidene]hexanedi-
amide (13d): Slight yellow viscous oil (61 mg, 55% yield; mixture
of two diastereomers, 1:1). 1H NMR (300 MHz, CDCl3): δ = 1.66–
1.71 (m, 4 H), 2.41–2.52 (m, 4 H), 7.60 (td, J = 7.7 Hz, J = 1.9 Hz,
4 H), 7.74 (td, J = 7.7 Hz, J = 1.9 Hz, 2 H), 8.05 (d, J = 7.7 Hz, 4
H) ppm. 19F NMR (188 MHz, CDCl3): δ = –74.2 (s, 6 F), –74.1 (s,
6 F) ppm. 13C NMR (75 MHz, CDCl3): δ = 24.6, 39.3, 120.2 (q, J
= 328 Hz, CF3), 130.0, 130.1, 130.4, 136.0, 180.9 ppm. MS (ESI+):
m/z = 529 [M + H]+, 551 [M + Na]+. HRMS (ESI): calcd. for
C20H19F6N2O4S2 [M + H]+ 529.0690; found 529.0691 (δ =
0.2 ppm).
[1] a) T. L. Gilchrist, C. J. Moody, Chem. Rev. 1977, 77, 409–435;
b) P. C. Taylor, Sulfur Rep. 1999, 21, 241–280.
[2] a) P. D. L. Raleigh, D. T. M. Cary, J. L. P. Apex, M. T. P. Cary,
T.-T. Wu, C. Hill, U.S. Patent US 6,136,983, 2000; b) K. K.
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[3] a) J. L. G. Ruano, C. Alemparte, F. R. Clemente, L. G. Gutiér-
rez, R. Gordillo, A. M. Martin Castro, J. H. Rodriguez Ramos,
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Wang, J. Org. Chem. 2005, 70, 8538–8549; c) J. P. Marino, N.
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tafa, Tetrahedron Lett. 2008, 49, 3216–3220.
N,NЈ-Bis[oxo-phenyl-(trifluoromethyl)-λ6-sulfanylidene]phthalimide
(13g): White gum solid (92 mg, 84 % yield; mixture of two dia-
stereomers, 1:1). 1H NMR (200 MHz, CDCl3): δ = 7.51–7.87 (m, 10
H), 8.16 (d, J = 7.6 Hz, 4 H) ppm. 19F NMR (188 MHz, CDCl3): δ
= –75.3 (s, 6 F), –74.4 (s, 6 F) ppm. 13C NMR (75 MHz, CDCl3):
δ = 115.3, 115.7, 120.1 (q, J = 326 Hz, CF3), 120.2 (q, J = 327 Hz,
CF3), 129.1, 129.2, 129.8, 129.9, 130.0, 130.3, 130.4, 130.7, 130.8,
133.2, 133.5, 136.0, 136.1, 136.2, 136.3, 174.2, 174.3 ppm. MS
(ESI+): m/z = 549 [M + H]+ . HRMS (ESI): calcd. for
C22H15F6N2O4S2 [M + H]+ 549.0377; found 549.0385 (δ =
1.5 ppm).
[4] V. V. Thakur, N. S. C. Ramesh Kumar, A. Sudalai, Tetrahedron
Lett. 2004, 45, 2915–2918.
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3-Cyano-N-[oxo-phenyl-(trifluoromethyl)-λ6-sulfanylidene]propane-
amide (14b): Slight yellow viscous oil (43 mg, 70% yield). 1H NMR
(200 MHz, CDCl3): δ = 2.60 (t, J = 7.2 Hz, 2 H), 2.81 (t, J =
6.7 Hz, 2 H), 7.64 (t, J = 7.2 Hz, 2 H), 7.79 (t, J = 7.7 Hz, 1 H),
8.01 (d, J = 7.7 Hz, 2 H) ppm. 19F NMR (188 MHz, CDCl3): δ =
–74.9 (s, 3 F) ppm. 13C NMR (75 MHz, CDCl3): δ = 13.2, 34.8,
118.8, 120.2 (q, J = 328 Hz, CF3), 129.8, 130.1, 130.2, 136.5,
176.9 ppm. MS (ESI+): m/z = 291 [M + H]+, 313 [M + Na]+.
HRMS (ESI): calcd. for C11H10F3N2O2S [M + H]+ 291.0415;
found 291.0416 (δ = 0.3 ppm).
[6] A. Pandey, C. Bolm, Synthesis 2010, 17, 2922–2925, and refer-
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4-Cyano-N-[oxo-phenyl-(trifluoromethyl)-λ6-sulfanylidene]butane-
amide (14c): Yellow viscous oil (58 mg, 91 % yield). 1H NMR
(200 MHz, CDCl3): δ = 1.93 (q, J = 7.2 Hz, 2 H), 2.41 (t, J =
7.2 Hz, 2 H), 2.66 (t, J = 6.7 Hz, 2 H), 7.63 (t, J = 7.2 Hz, 2 H),
7.78 (t, J = 7.7 Hz, 1 H), 7.98 (d, J = 7.7 Hz, 2 H) ppm. 19F NMR
(188 MHz, CDCl3): δ = –74.6 (s, 3 F) ppm. 13C NMR (75 MHz,
CDCl3): δ = 16.4, 20.8, 37.4, 113.8, 119.3, 120.3 (q, J = 328 Hz,
CF3), 130.1, 130.2, 136.3, 179.4 ppm. MS (ESI+): m/z = 305 [M +
H]+, 327 [M + Na]+. HRMS (ESI): calcd. for C12H12F3N2O2S [M
+ H]+ 305.0572; found 305.0570 (δ = –0.7 ppm).
5-Cyano-N-[oxo-phenyl-(trifluoromethyl)-λ6-sulfanylidene]pentane-
amide (14d): Yellow viscous oil (55 mg, 81 % yield). 1H NMR
(200 MHz, CDCl3): δ = 1.66–1.91 (m, 4 H), 2.38 (t, J = 6.8 Hz, 2
H), 2.58 (t, J = 6.8 Hz, 2 H), 7.67 (t, J = 7.8 Hz, 2 H), 7.78 (t, J =
7.8 Hz, 1 H), 8.05 (d, J = 7.5 Hz, 2 H) ppm. 19F NMR (188 MHz,
CDCl3): δ = –74.5 (s, 3 F) ppm. 13C NMR (75 MHz, CDCl3): δ =
17.0, 24.1, 24.8, 38.5, 119.4, 120.3 (q, J = 324 Hz, CF3),130.0,
130.1, 130.3, 136.2, 180.2 ppm. MS (ESI+): m/z = 319 [M + H]+,
Eur. J. Org. Chem. 2013, 7800–7808
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7807

B. Pégot, C. Urban, P. Diter, E. Magnier
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Received: July 9, 2013
Published Online: October 9, 2013
7808
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 7800–7808