You are on page 1of 10

molecules

Article
Fused 1,2,3-Dithiazoles: Convenient Synthesis,
Structural Characterization, and
Electrochemical Properties
Lidia S. Konstantinova 1,2 , Ilia V. Baranovsky 1 , Irina G. Irtegova 3 , Irina Y. Bagryanskaya 3,4 ,
Leonid A. Shundrin 3,4 , Andrey V. Zibarev 3,5 and Oleg A. Rakitin 1,2, *
1 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia;
konstantinova_ls@mail.ru (L.S.K.); ilay679@rambler.ru (I.V.B.)
2 Nanotechnology Education and Research Center, South Ural State University, 454080 Chelyabinsk, Russia
3 N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
630090 Novosibirsk, Russia; irteg@nioch.nsc.ru (I.G.I.); bagryan@nioch.nsc.ru (I.Y.B.);
shundrin@nioch.nsc.ru (L.A.S.); zibarev@nioch.nsc.ru (A.V.Z.)
4 Department of Natural Sciences, National Research University–Novosibirsk State University,
630090 Novosibirsk, Russia
5 Department of Chemistry, National Research University–Tomsk State University, 634050 Tomsk, Russia
* Correspondence: orakitin@ioc.ac.ru; Tel.: +7-499-135-53-27; Fax: +7-499-135-53-28

Academic Editors: Panayiotis A. Koutentis and Andreas S. Kalogirou


Received: 28 March 2016; Accepted: 29 April 2016; Published: 6 May 2016

Abstract: A new general protocol for synthesis of fused 1,2,3-dithiazoles by the reaction of cyclic
oximes with S2 Cl2 and pyridine in acetonitrile has been developed. The target 1,2,3-dithiazoles fused
with various carbocycles, such as indene, naphthalenone, cyclohexadienone, cyclopentadiene, and
benzoannulene, were selectively obtained in low to high yields. In most cases, the hetero ring-closure
was accompanied by chlorination of the carbocyclic moieties. With naphthalenone derivatives,
a novel dithiazole rearrangement (15Ñ13) featuring unexpected movement of the dithiazole
ring from α- to β-position, with respect to keto group, was discovered. Molecular structure of
4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one 13 was confirmed by single-crystal X-ray diffraction.
Electrochemical properties of 13 were studied by cyclic voltammetry and a complex behavior was
observed, most likely including hydrodechlorination at a low potential.

Keywords: fused 1,2,3-dithiazoles; synthesis; sulfur monochloride; X-ray diffraction;


cyclic voltammetry

1. Introduction
1,2,3-Dithiazoles, the five membered sulfur-nitrogen heterocycles, are promising for science and
technology because of their biological activity, unusual chemical transformations and interesting
physical properties [1–3]. In particular it has been shown that the 1,2,3-dithiazole scaffold can be
effectively used in the design and synthesis of stable neutral and negatively charged radicals (i.e.,
radical anions)—actual or potential building blocks for molecule-based conductive and/or magnetic
functional materials [4–7]. One can imagine that continued exploration of the 1,2,3-dithiazole chemistry
is guaranteed to yield new compounds of fundamental and/or applied significance.
Normally, monocyclic 1,2,3-dithiazoles are prepared from 4,5-dichloro-1,2,3-dithiazolium chloride
(the Appel salt) as the key synthon [8,9]. Benzo-fused 1,2,3-dithiazolium chlorides (the Herz salts)
can be easily prepared by the Herz reaction from aromatic amines and sulfur monochloride S2 Cl2 .
Although this reaction has been known for about one hundred years, it is still used nowadays as
well [10,11].

Molecules 2016, 21, 596; doi:10.3390/molecules21050596 www.mdpi.com/journal/molecules


Molecules 2016, 21, 596 2 of 10
Molecules 2016, 21, 596 2 of 10
Molecules 2016, 21, 596 2 of 10

Other synthetic
Other synthetic
Other precursors
syntheticprecursors
precursors of
of fused
of fused fused 1,2,3-dithiazoles
1,2,3-dithiazoles
1,2,3-dithiazoles are cyclic
are oximes
are cyclic cyclic usedoximes
oximes used
used in
in reactions reactions
inwith
reactions
S2 Cl2
with
with
in S 2Cl2 in the presence of organic bases such as N-ethyldiisopropylamine (Hünig’s base) and
the Spresence
2Cl2 in the presence
of organic such as N-ethyldiisopropylamine
of organic
bases bases such as N-ethyldiisopropylamine
(Hünig’s base) and (Hünig’s base) and
triisobutylamine.
triisobutylamine.
disadvantageThe
triisobutylamine.
The The disadvantage
disadvantage
of this of
of this
method is that no method
this general is
method is that
that no
procedureno general
general procedure
procedure
is established andisisinestablished
established and
and in
all cases arduous in
all cases arduous
all cases arduous
purification purification
purification
of products of products
of products
by column by column chromatography
by columnischromatography
chromatography is required
required [12–15].is required [12–15]. [12–15].
During our
During ourongoing
our ongoingwork
ongoing work
work with
with
withSS22Cl
ClS222we
Cl2 have
we have found
we have that
that the
foundfound reaction
thethat
reaction conditions
conditions
the reaction and
and nature
nature
conditions andof
of
the organic
the organic
nature of thebase
base have a
have base
organic crucial
a crucial role
haverole influencing
influencing
a crucial the yields of
the yields ofthe
role influencing the target
theyields sulfur-nitrogen
targetofsulfur-nitrogen heterocycles
heterocycles
the target sulfur-nitrogen
[16–19].
[16–19]. It
heterocyclesIt was
was shown
shown
[16–19]. that many
many nitrogen
that shown
It was nitrogen
that many organic
organic
nitrogen bases,
bases, such
suchbases,
organic as
as tertiary
such asamines,
tertiary tertiaryfor
amines, for example
example
amines, for
1,4-diazabicyclooctane
1,4-diazabicyclooctane
example (DABCO),
1,4-diazabicyclooctane interact
(DABCO),(DABCO),
interact with with S 2Cl2 forming ionic complexes in some cases [17].
S2Cl2with
interact forming
S2 Cl2ionic
formingcomplexes in some cases
ionic complexes [17].
in some
However,
[17]. to
However,
cases to the
the best
However, of
bestto our
ofthe knowledge,
ourbest
knowledge, possible
possible interaction/complexation
of our knowledge, interaction/complexation
possible interaction/complexation between
between SS22between
Cl
Cl22 and
and such
S2 Cla2a
such
strong
strong
and suchnitrogen
nitrogen
a strongorganic
organic
nitrogenbase
base such
such as
organic as pyridine
basepyridine
such as has
has not
not been
pyridine beenhasinvestigated.
investigated.
not been investigated.
In this
In this paper
this paper we
paperwe report
wereport
reporta study
a study
a studyof a
of aof reaction
reaction between
between
a reaction cyclic oximes
cyclic cyclic
between oximesoximesand
and SS22Cl
Cl
and2/pyridine covering
2/pyridine covering
S2 Cl2 /pyridine
selective
covering synthesis
selective selective
synthesis of fused
of fused
synthesis 1,2,3-dithiazoles
1,2,3-dithiazoles
of fused 1,2,3-dithiazoles together
together with
withwith
together their
their
theirstructural
structural characterization
characterization by
structuralcharacterization by
single-crystal X-ray
single-crystal X-ray diffraction
diffraction (XRD)
(XRD) and and investigation
investigation of of their
their electrochemical
electrochemical properties
properties by by cyclic
by cyclic
cyclic
voltammetry
voltammetry (CV).
voltammetry (CV).
(CV).

2.
2. Results
2. Resultsand
Results andDiscussion
and Discussion
Discussion

2.1. Syntheses
2.1. Syntheses
In
In anan effort
an effort
efforttoto improve
toimprove
improvethe the synthesis
synthesisofof
thesynthesis fused
offused 1,2,3-dithiazoles,
fused1,2,3-dithiazoles,
1,2,3-dithiazoles, wewe
we re-investigated
re-investigated
re-investigated thethe reaction
reaction
the reactionof
of
of 1-indanone
1-indanone
1-indanone oximeoxime 11 with
1 with
oxime S2 Cl2SS.22Cl
with Cl22.. Treatment
Treatment
Treatment of
of 11 Swith
of 1 with 2 Cl2 in
with SS22Cl 2 in dimethylformamide
dimethylformamide
Cl (DMF),(DMF),
2 in dimethylformamide (DMF), i.e., a
i.e., a
i.e., a solvent
solvent
which iswhich is
frequently frequently
used in used
S Cl in S Cl
reactions
2 2 reactions
[16,19], [16,19],
in the in the temperature
temperature range range
from from
´25 to −25
20 ˝to
C 20 °C
gave
solvent which is frequently used 2 2in S2Cl2 reactions [16,19], in the temperature range from −25 to 20 °C
gave 8-chloroindeno[1,2-d]-1,2,3-dithiazole
8-chloroindeno[1,2-d]-1,2,3-dithiazole 2 in 2
lowin low
yields.yields.
Note, Note,
that that
in in
this this
case
gave 8-chloroindeno[1,2-d]-1,2,3-dithiazole 2 in low yields. Note, that in this case the hetero ring-closure case
the the
heterohetero ring-closure
ring-closure was
was
was accompanied
accompanied
accompanied by
by chlorination.
by chlorination.
chlorination. The
The type
The type of base
type of
of base
usedused
base was
was important
was important
used for the
important for the
the success
forsuccess of
of reactions
of reactions
success with
reactions
Swith
Cl Sin
2 Cl in
other
2 other solvents,
solvents, such such
as as chloroform
chloroform or or acetonitrile
acetonitrile (MeCN). (MeCN).
Reaction
2 2 S2Cl2 in other solvents, such as chloroform or acetonitrile (MeCN). Reaction of 1 with a two-fold
with Reaction
of 1 of
with 1
a with a
two-fold two-fold
excess
excess
of S2 Clof
excess SS22Cl
2 and
of 2 and DABCO
ClDABCO in chloroform
in chloroform at ´5 ˝atC−5 led°Ctoled to complex
complex mixtures
mixtures containing
containing
2 and DABCO in chloroform at −5 °C led to complex mixtures containing 2 in the yield of
2 inyield
2 in the the yield
of 35%.of
35%.
The The
best best
results results
were were
achievedachievedby by treating
treating 1 with1 with
a a three-fold
three-fold excess
excess of
35%. The best results were achieved by treating 1 with a three-fold excess of S2Cl2 or a four-fold excess S2of
Cl S22Cl
or2aor a four-fold
four-fold excess
excess of
of
of pyridine
pyridine
pyridine in in MeCN
MeCN
in MeCN 5 ˝55C°C
at at
at forfor
°C for1h 11 h
h which
which
which gave
gave target
target2 22selectively
gavetarget selectively
selectivelyinin 81%
in81%
81%yieldyield (Scheme
yield(Scheme
(Scheme1). 1). The
1). The main
The main
main
feature this
this and
and other
other SS22Cl2 2/pyridine
/pyridine reactions
reactions is
is that
that the
the reaction
feature of this and other S2Cl2/pyridine reactions is that the reaction mixtures are not tarry, and the
of reaction mixtures
mixtures are
are not
not tarry,
tarry, and the
product
product isolations
product isolations
isolations do do not
do not require
not require chromatography
require chromatography
chromatographyin in contrast
incontrast
contrastwith with
withthethe literature
theliterature procedures
literatureprocedures
procedures[12–15].[12–15].
[12–15].

Scheme1.1.Reaction
Reaction ofoxime
oxime 1 withSS22Cl
Cl2/pyridine to
togive
givedithiazole
dithiazole 2.
Scheme 1. Reactionof
Scheme of oxime11with
with S2Cl22/pyridine
/pyridine to give dithiazole 2.
2.

Under the
Under the same
same conditions,
same conditions, 3-phenylindanone
conditions, 3-phenylindanone oxime 33 gave
3-phenylindanone oxime gave the
gave the corresponding
the corresponding 1,2,3-dithiazole
corresponding 1,2,3-dithiazole
1,2,3-dithiazole
4 even in
even in
4 even a higher
in aa higher yield,
higher yield, meanwhile
yield, meanwhile chlorination
meanwhile chlorination was
chlorination was not
was not observed
not observed (Scheme
observed (Scheme 2).
(Scheme2).
2).

Scheme 2. Reaction of oxime 3 with S2Cl2/pyridine to give dithiazole 4.


Scheme2.2.Reaction
Scheme Reactionof
ofoxime
oxime33with
withSS22Cl
Cl22/pyridine
/pyridine to
to give
give dithiazole
dithiazole 4.
4.
Molecules 2016, 21, 596
596 3 of 10

Molecules 2016,2016,
Molecules 21, 596
21, 596 3 of 103 of 10
Treatment of the archetypal cyclopentanone oxime 5a with an excess of S2Cl2 (6 equiv) and
Treatment
pyridine (8 equiv)of the
in archetypal
boiling MeCN cyclopentanone oxime 5a with an excess of S2 Cl26a(6inequiv)
gave 4,5,6-trichlorocyclopenta-1,2,3-dithiazole and
moderate
Treatment
Treatmentof the archetypal
of the archetypal cyclopentanone
cyclopentanone oxime5a5awith
oxime withanan excess
excess of Sof
2ClS22Cl (6 equiv)
(6 2equiv) and and
pyridine
yield. (8
Using equiv)
lesser in boiling
amounts MeCN
ofMeCN gave
Cl2 or/and
S2MeCN 4,5,6-trichlorocyclopenta-1,2,3-dithiazole
pyridine in an attempt to obtain less chlorinated 6a in moderate
product
pyridine
pyridine (8 equiv)
(8 equiv) in boiling
in boiling gave 4,5,6-trichlorocyclopenta-1,2,3-dithiazole
gave 4,5,6-trichlorocyclopenta-1,2,3-dithiazole 6a in6amoderate
in moderate
yield.
failed Using
since lesser
only amounts
6aamounts
was of S
isolated 2 Cl 2
in2Cl or/and pyridine in an attempt to obtain less chlorinated product
yield.yield.
UsingUsing lesser
lesser amounts ofof
S2SCl 2lower
or/and yields.
2 or/and With
pyridine
pyridine inaan
in similar
an attempt
attempt procedure,
toto
obtain
obtain 4-carbethoxy
less chlorinated
less chlorinated substituted
productproduct
failed since
failed
derivative 5bonly
since
was 6a
only was
6a
convertedisolated
was isolated
into in inlower
lower yields.
yields. With
With
dichlorocyclopentadithiazole a
a similar
similar procedure,
procedure,
6b in a 4-carbethoxy
4-carbethoxy
good yield substituted
substituted
(Scheme 3). In both
failed since only 6a was isolated in lower yields. With a similar procedure, 4-carbethoxy substituted
derivative
cases, the 5b was
derivative
yields converted
5bofwas converted
dithiazoles into
6intodichlorocyclopentadithiazole
were dichlorocyclopentadithiazole
slightly higher than those 6binin a good
6breported
a good in yield
yield
the (Scheme
(Scheme
literature In3).
3).[12,15].
bothIn both
derivative 5b was converted into dichlorocyclopentadithiazole 6b in a good yield (Scheme 3). In both
cases,cases,
the yields of dithiazoles
the yields of dithiazoles6 6were
wereslightly higherthan
slightly higher than those
those reported
reported inliterature
in the the literature
[12,15].[12,15].
cases, the yields of dithiazoles 6 were slightly higher than those reported in the literature [12,15].

Scheme 3. Reaction of oximes55with


with S2Cl2/pyridine to to
give dithiazoles 6. 6.
Scheme3.3. Reaction
Scheme Reactionof
ofoximes
oximes 5 withSS22Cl /pyridine
Cl22/pyridine give
to give dithiazoles
dithiazoles 6.
Scheme
In the previous 3. Reaction
study of oximes 5oximes,
on six-membered with S2Cl 2/pyridine to give
p-benzoquinone dithiazoles
monooxime 6. a complex
7 gave
In the previous
mixture of products study on six-membered
on reaction with S2Cl2 and oximes, p-benzoquinone
the desired fused dithiazolemonooxime 7 gave
was obtained in aa complex
low
mixture
In of[13].
the
yield products
previous
We have onfound
studyreaction
onthat with SS22Cl22 and
six-membered
the treatment and of the
the
oximes,
7 with desired
desired fused
fused dithiazole
p-benzoquinone
S2Cl2/pyridine MeCN was
dithiazole
inmonooxime leadsobtained
was obtained
7selectively intoa low
gave a complex
yield [13].
dichloro
mixture We
We have
have
dithiazole
of products found
found that
that
on8 reaction the
the
or to trichlorotreatment
treatment
with dithiazole of
S2Cl2 and9theof7 7 with
with
depending SS
desired2 Cl
Cl
2 on
2 /pyridine
/pyridine
2 the molar
fused in MeCN
in MeCN
excesswas
dithiazole leads
of the leadsselectively to
selectively
reagents.inIna low
obtained
dichloro
to dichloro
yield dithiazole
boiling
[13]. WeMeCN,
dithiazole 8 or
havereaction
found to trichloro
8 orwith athe
to trichloro
that dithiazole
larger excess (Sof
dithiazole
treatment 9
2Cl7 depending
2, 9
6with
equiv;
depending
S2Cl on
pyridine, the molar
on 8the
2/pyridine equiv)
molar excess
gave
in MeCN of
9, leads
excess the
whereas reagents.
with
of selectively
the a In
reagents.
to
In smaller
boiling MeCN,
boiling
dichloro excess
MeCN,
dithiazole (S8
reaction2Cl2, with
reactionor 3toequiv;
with apyridine,
a larger
larger
trichloro 4 equiv)
excess
excess
dithiazole(S(S 928,
2Cl Cl, in both
62 ,equiv; cases,
6 equiv;
2depending however,
pyridine,
pyridine,
on 8in
the molar low
8 equiv)
equiv) yields
gave
excessgaveof9,(Scheme
whereas
9,
thewhereas 4).with
reagents. a
with
In
asmaller
smaller excess
excess (S(S
boiling MeCN, reaction
2 ClCl , 3, equiv;
3 equiv;pyridine,
pyridine, 4 equiv)
4 equiv) 8, in
8, both
in both cases,
cases, however,
however,
2 2 with a larger excess (S2Cl2, 6 equiv; pyridine, 8 equiv) gave 9, whereas with a
2 in low
in low yields
yields (Scheme
(Scheme 4).
4).
smaller excess (S2Cl2, 3 equiv; pyridine, 4 equiv) 8, in both cases, however, in low yields (Scheme 4).

Scheme 4. Reaction of oxime 7 with S2Cl2/pyridine to give dithiazoles 8 and 9.

Treatment of benzosuberone
Scheme ofoxime
oxime10 with
withSSS222Cl
Cl222/pyridine gave selectively 4,5,6-trichlorobenzo[6,7]
Scheme 4.4. Reaction
Reactionof oxime 77with Cl /pyridine
/pyridinetotogive
givedithiazoles
dithiazoles88andand9.9.
cyclohepta[1,2-d][1,2,3]dithiazole 11 independent of the quantities of reagents; the best yield of 11
Scheme 4. Reaction of oxime 7 with S2Cl2/pyridine to give dithiazoles 8 and 9.
(61%) was obtained
Treatment when 6 equiv
of benzosuberone of S2Cl
oxime 102 and
with8 Sequiv of pyridine were employed (Scheme 5).
2Cl2/pyridine gave selectively 4,5,6-trichlorobenzo[6,7]
Treatment of benzosuberone oxime 10 with S2 Cl2 /pyridine gave selectively
cyclohepta[1,2-d][1,2,3]dithiazole 11 independent
Treatment of benzosuberone oxime of2/pyridine
10 with S2Cl the quantities
4,5,6-trichlorobenzo[6,7]cyclohepta[1,2-d][1,2,3]dithiazole 11gave of reagents;
selectively
independent ofthethebest yield of 11
4,5,6-trichlorobenzo[6,7]
quantities of
(61%) was obtained when 6 equiv
cyclohepta[1,2-d][1,2,3]dithiazole of
11 S2Cl2 and 8 equiv
independent of of
the pyridine were
quantities of employed
reagents; (Scheme
the best 5).
yield
reagents; the best yield of 11 (61%) was obtained when 6 equiv of S2 Cl2 and 8 equiv of pyridine were of 11
(61%) was (Scheme
employed when 6 equiv of S2Cl2 and 8 equiv of pyridine were employed (Scheme 5).
obtained 5).

Scheme 5. Reaction of oxime 10 with S2Cl2/pyridine to give dithiazole 11.

1,4-Naphthoquinone oxime 12 treated with 3 equiv of S2Cl2 and 4 equiv of pyridine gave
4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one 13 in 74% yield (Scheme 6). The structure of 13 was
confirmed by Scheme 5. Reaction
single-crystal of oxime
XRD (Figure 1).10 with S2Cl2/pyridine to give dithiazole 11.
Scheme5.5.Reaction
Scheme Reactionof
ofoxime
oxime10
10with
withSS22Cl
Cl22/pyridine
/pyridine to
to give
give dithiazole
dithiazole 11.
11.
1,4-Naphthoquinone oxime 12 treated with 3 equiv of S2Cl2 and 4 equiv of pyridine gave
4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one
1,4-Naphthoquinone oxime with1333inequiv
74% yield
of SS2(Scheme
Cl2 and 6). The structure of 13gave
was
1,4-Naphthoquinone oxime 12 treated with
12 treated equiv of 4 equiv of pyridine
2 Cl2 and 4 equiv of pyridine gave
confirmed by single-crystal XRD (Figure 1).
4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one 13
13 in
in 74%
74% yield
yield (Scheme
(Scheme 6).
6). The
The structure
structure of
of 13
13 was
was
4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one
confirmed by single-crystal XRD (Figure 1).
confirmed by single-crystal XRD (Figure 1).
Molecules 2016, 21, 596 4 of 10
Molecules 2016, 21, 596 4 of 10
Molecules 2016, 21, 596 4 of 10

Molecules 2016, 21, 596 4 of 10

Scheme 6. Reaction of oxime 12 with S2Cl2/pyridine to give dithiazole 13.


Scheme 6. Reaction
Scheme 6. Reaction of
of oxime 12 with
oxime 12 with SS22Cl /pyridineto
Cl22/pyridine togive
givedithiazole
dithiazole13.
13.

Scheme 6. Reaction of oxime 12 with S2Cl2/pyridine to give dithiazole 13.

Figure 1. XRD molecular structure of dithiazole 13 (displacement ellipsoids at 50%, atoms H are
shown as cycles). Selected bond distances (Å) and angles (o) (crystallographic numbering): C3-S1
1.7264(5), S1-S2 2.0774(5), S2-N1 1.6297(13), N1-C4 1.3054(19), C4-C3 1.456(2), C1-O1 1.2301(19),
C2-Cl1 1.7259(16); C3-S1-S2 92.18(5), S1-S2-N1 98.13(5), S2-N1-C4 117.09(11), N1-C4-C3 118.65(13),
C4-C3-S1 113.94(10).
Figure 1. XRD molecular structure of dithiazole 13 (displacement ellipsoids at 50%, atoms H are
Figure 1. XRD molecular structure of dithiazole 13 (displacement ellipsoids at 50%, atoms H are shown
shown as The
as cycles). cycles).
SelectedSelected bond planar
molecule is perfectly
bond distances distances (Å)bond
and the
(Å) and angles and(o )angles
o) (crystallographic
distances (and
(crystallographic numbering):numbering):
angles correspond to the statisticalC3-S1
C3-S1 1.7264(5),
means
1.7264(5), [20]. 2.0774(5),
S1-S2 The crystalS2-N1
packing reveals shortened
1.6297(13), N1-C4 contacts S···O
1.3054(19), together
C4-C3 with π-π
1.456(2), C1-O1 and Cl-π
S1-S2Figure
2.0774(5), S2-N1
1. XRD 1.6297(13),
molecular N1-C4
structure of1.3054(19),
dithiazole C4-C3 1.456(2),
13 (displacement C1-O1 1.2301(19),
ellipsoids atoms 1.2301(19),
at 50%, C2-Cl1 H1.7259(16);
are
interactions [21].
C2-Cl1 1.7259(16);
shown as C3-S1-S2
cycles).
C3-S1-S2 92.18(5), Selected
S1-S2-N1 92.18(5),
bond S1-S2-N1
distances (Å) 98.13(5),
and anglesS2-N1-C4
( 117.09(11),
o) (crystallographic N1-C4-C3
numbering): 118.65(13),
C3-S1
An unexpected result98.13(5), S2-N1-C4
was obtained 117.09(11), N1-C4-C3
with naphthoquinone oxime 14, an118.65(13), C4-C3-S1
isomer of oxime 113.94(10).
12. Treatment
C4-C3-S1
of 14113.94(10).
1.7264(5),
withS1-S2 2.0774(5),
S2Cl2/pyridine S2-N1 gave
in MeCN 1.6297(13), N1-C4
a mixture of two1.3054(19), C4-C3 1.456(2), C1-O1 1.2301(19),
isomeric chloronaphthodithiazolones 13 and 15
C2-Cl1 1.7259(16); C3-S1-S2 92.18(5), S1-S2-N1 98.13(5), S2-N1-C4 117.09(11), N1-C4-C3 118.65(13),
in comparable yields (Scheme 7). First of all,
The molecule is perfectly planar and theit bond
was shown that 14 was
distances andanangles
individual compound with
correspond to theno statistical
The molecule
C4-C3-S1 itsisisomer
perfectly
traces of 113.94(10). planar
12. Special and the on
experiments bond distances
individual 13 andand anglesthat
15 showed correspond
15 convertsto into the
13 statistical
means [20]. when
The crystal
treated with
packing
S
reveals shortened contacts S¨ ¨ ¨ O together with π-π and Cl-π
2Cl2/pyridine, whereas 13 remains unchanged. Effectively, the dithiazole ring
means [20]. The crystal packing reveals shortened contacts S···O together with π-π and Cl-π
interactionsThe [21].
movedmolecule
from α- is to
perfectly
β-position,planar
withand the bond
respect to the distances
keto group, and andangles correspond
the reaction undertodiscussion
the statistical
interactions [21].
An
means unexpected
represents
[20]. Thea novel result
crystal was obtained
rearrangement.
packing Earlier,
reveals with processes
similar
shortened naphthoquinone
contacts were S···O discoveredoxime
together by us
with 14, for an
π-π andisomer
fused Cl-π of
An unexpected result was[22–24].
1,2,3,4,5-pentathiepines obtained with naphthoquinone
Apparently, the mechanism of oxime
this 14, an isomer
rearrangement of oxime
includes 12. Treatment
dithiazole
oxime interactions
12. Treatment[21]. of 14 with S2 Cl2 /pyridine in MeCN gave a mixture of two isomeric
of 14 withAnSring-opening
2Cl2/pyridine
unexpectedinresult 15inbyMeCN gave
the action
was of a
obtained
mixture
the of two
chlorinating isomeric
agent (i.e., S2Clchloronaphthodithiazolones
2) followed by the ring-closure to 13 and 15
chloronaphthodithiazolones
afford 13 (Scheme
and
13 scope
7). The
15 inwith
ofofthis
naphthoquinone
comparable
rearrangement
yields
is under
oxime
(Scheme 14, an7).
consideration.
isomer
Firstofofoxime
all, it12.
was Treatment
shown that
in comparable
of 14 with Syields (Scheme 7). First all, it was shown that 14 was
2Cl2/pyridine in MeCN gave a mixture of two isomeric chloronaphthodithiazolones 13 and 15
an individual compound with no
14 was an individual compound with no traces of its isomer 12. Special experiments on individual
tracesinof its isomeryields
comparable 12. Special
(Schemeexperiments
7). First of all, itonwas individual
shown that1314and was15 an showed
individualthat 15 converts
compound with nointo 13
13 and 15 showed that 15 converts into 13 when treated with S2 Cl2 /pyridine, whereas 13 remains
whentraces
treated
of itswith
isomer S2Cl 12.2/pyridine, whereas on
Special experiments 13 individual
remains unchanged.
13 and 15 showed Effectively, the dithiazole
that 15 converts into 13 ring
unchanged. Effectively, the dithiazole ring moved from α- to β-position, with respect to the keto
moved whenfromtreated
α- towith S2Cl2/pyridine,
β-position, with whereas
respect to 13 the
remains
ketounchanged.
group, and Effectively,
the reactionthe dithiazole ring
under discussion
group, and the
moved from reaction
α- to under discussion
β-position, with represents
respect to the a novel
keto rearrangement.
group, and the Earlier,
reaction under similar processes
discussion
represents a novel rearrangement. Earlier, similar processes were discovered by us for fused
were represents
discovereda by novelus for fused 1,2,3,4,5-pentathiepines
rearrangement. Earlier, [22–24]. Apparently,
discoveredthe mechanism of this
1,2,3,4,5-pentathiepines [22–24]. Apparently, thesimilar processes
mechanism of thiswere rearrangement byincludes
us for fused
dithiazole
rearrangement includes dithiazole
1,2,3,4,5-pentathiepines ring-opening
[22–24]. Apparently, in 15 by of
the mechanism thethisaction of the chlorinating
rearrangement agent (i.e.,
includes dithiazole
ring-opening in 15 by the action of the chlorinating agent (i.e., S2Cl 2) followed by the ring-closure to
S2 Cl2ring-opening
) followed by in 15 the byring-closure
the action of the to chlorinating
afford 13 (Schemeagent (i.e., 7).S2ClThe scope of
2) followed by this rearrangement
the ring-closure to is
afford 13 (Scheme 7). The scope of this rearrangement is under consideration.
underafford 13 (SchemeScheme
consideration. 7). The7.scope
Reactionofofthis rearrangement
oxime is under
14 with S2Cl2/pyridine consideration.
to give dithiazoles 15 and 13.

Scheme 7. Reaction of oxime 14 with S2Cl2/pyridine to give dithiazoles 15 and 13.


Scheme 7. Reaction
Scheme 7. Reaction of
of oxime 14 with
oxime 14 with SS22Cl2/pyridine
/pyridineto
togive
givedithiazoles
dithiazoles15 and13.
15and 13.
Molecules 2016, 21, 596 5 of 10

Molecules 2016, 21, 596 5 of 10


2.2.Molecules
Electrochemical
2016, 21, 596
Reduction and Oxidation of Dithiazole 13 5 of 10
2.2. Electrochemical Reduction and Oxidation of Dithiazole 13
Recently, it was shown that benzo-fused 1,2,3-dithiazoles are able to form persistent radical-anions
2.2. Electrochemical Reduction andthat
Oxidation of Dithiazole 13
(RAs) Recently,
under conditionsit was shown
of electrochemical benzo-fused 1,2,3-dithiazoles
and chemical reduction and are one
ableoftotheform
RAs persistent
was isolated
radical-anions
Recently, (RAs)
it wasunder conditions
shown that of electrochemical
benzo-fused and chemical
1,2,3-dithiazoles reduction
are able to and one persistent
form of the RAs
in the form of thermally-stable paramagnetic salts [6,7]. Amongst compounds synthesized in this
was isolated in
radical-anions the under
(RAs) form conditions
of thermally-stable paramagnetic salts reduction
[6,7]. Amongst onecompounds
work napthoquinone-fused derivatives of 13electrochemical and chemical
and 15 are especially interesting and
in the contextofof
theRAs
RAssince
synthesized in this work napthoquinone-fused derivatives 13 and 15 are especially interesting in the
onewas
mayisolated
expect some in theconcentration
form of thermally-stable
of a negativeparamagnetic
charge on thesalts C=O [6,7]. Amongst
moieties compounds
(ultimately leading to
context of RAs since one may expect some concentration of a negative charge on the C=O moieties
thesynthesized
C–O´ bonding in thissituation)
work napthoquinone-fused
enlarging derivatives
their ability 13 and 15metal
to coordinate are especially interesting
cations. This mightinbethea new
(ultimately
context of RAsleading sinceto one
the C–O − bonding situation) enlarging their ability to coordinate metal cations.
may expect some concentration of a negative charge on the C=O moieties
approach
This
to
might be
the design
a newto
and
approach
synthesis of sulfur-nitrogen π-heterocyclic RA salts as potential building
(ultimately leading the C–O−tobonding
the design and synthesis
situation) enlarging oftheir
sulfur-nitrogen π-heterocyclic
ability to coordinate RA salts
metal cations.
blocks
asThis of magnetic
potential functional materials [25–29].
might building
be a new blocks
approach of magnetic
to the design functional materials
and synthesis [25–29].
of sulfur-nitrogen π-heterocyclic RA salts
The
Theelectrochemical
electrochemical behavior
behavior ofof1313was studied
was studiedandandfound to be
found to abe
very complex
a very complexmultistep process.
multistep
as potential building blocks of magnetic functional materials [25–29].
Thus, the
process. CV
TheThus,
of 13 in MeCN
the CV of 13
electrochemical
(0 > E
in MeCN
behavior
> ´2.0
of (0
V)
13>was
contains
E > −2.0 six irreversible
V) contains
studied and foundsix to peaks
irreversible in the
be a verypeaks
cathodic
complexin the cathodic of
branch
multistep
the voltammogram.
branch
process. ofThus, the CVTheofadditional
the voltammogram. Thequasi-reversible
13 in MeCN additional V)peaks 1c’´1a’
(0 > E > −2.0quasi-reversible
contains and 2c’´2a’
peaks 1c’−1a’
six irreversible were
peaksand observed
in 2c’−2a’
the in the
were
cathodic
second cycle at lower potentials than E 1C (Figure 2). 1C
observed
branch of in the second cycle at lower
voltammogram. The additionalpotentials
p than E (Figure
quasi-reversible
p 2).
peaks 1c’−1a’ and 2c’−2a’ were
1C
observed in the second cycle at lower potentials than Ep (Figure 2).
I / μA

I / μA
6C
-20 4C
6C
-20 1C 3C4C 5C
2C 5C
1C 3C
-10 2C

-10
2c'
1c'
0 2c'
1c'
0
1a' 2a'
2a'
0.0 1a' -0.5 -1.0 -1.5 -2.0
E/V
0.0 -0.5 -1.0 -1.5 -2.0
E/V
Figure2.2.CV
Figure CVofof13 13in inMeCN
MeCN (black
(black curve:
curve: first
first cycle;
cycle;red
redcurve:
curve:second
second cycle). The
cycle). potential
The sweep
potential sweep
Figure
range
range was2. 0CV
was of
0>> EE >>13´2.0
in MeCN
−2.0 and(black
VVand the curve: first
thepotential
potentialsweep cycle;
sweep rate red
100curve:
rate mV·s
100 second
–1
mV¨ . Peak cycle). The (−E
potentials
s–1 . Peak potential
potentials
ij
p [30],
(´E sweep
ij 1C,
V):[30], V):
p
range was 0 >3C,
E >1.37;
−2.04C,
V and the potential sweep rate0.24;
100 1a’,
mV·s –1. Peak potentials (−Eij [30], V): 1C,
0.80; 2C, 0.93; 1.47; 5C, 1.68, 6C, 1.76; 1c’, 0.19; 2c’, 0.62; 2a’, 0.56.
1C, 0.80; 2C, 0.93; 3C, 1.37; 4C, 1.47; 5C, 1.68, 6C, 1.76; 1c’, 0.24; 1a’, 0.19; 2c’, 0.62; 2a’, 0.56. p

0.80; 2C, 0.93; 3C, 1.37; 4C, 1.47; 5C, 1.68, 6C, 1.76; 1c’, 0.24; 1a’, 0.19; 2c’, 0.62; 2a’, 0.56.
With a limited potential sweep covering only reduction peaks 1C and 2C (0 > E > −1.2 V), peaks
With a limited
limitedpotential sweep covering only reductionpeakspeaks 1Cand and2C2C (0 (0 E−1.2
> E>>potential
> ´1.2 V), peaks
1c’–1a’With
anda2c’–2a’ potential
did sweep(Figure
not vanish covering only
3a). reduction
Moreover, further 1C
decrease in the V), peaks
sweep
1c’–1a’ andand
1c’–1a’ 2c’–2a’ diddid not vanish (Figure 3a).3a).
Moreover, further decrease in the potential sweep down
down to the 2c’–2a’
range 0 > Enot vanish
> −0.88 (Figure
V embracing Moreover,
only the firstfurther decrease
irreversible stepinofthe
thepotential
reduction sweep
of 13
to the range
down to 0 > E > ´0.88 V embracing only the first irreversible step of the reduction of 13 (Figure
13 3b)
(Figure 3b)thedidrange
not 0cause
> E >any
−0.88qualitative
V embracing onlyin
change thethe
first irreversibleCV.
compound’s stepWeof the reduction
conclude thatofboth
did not cause
(Figure
electrode 3b) any
did qualitative
processes not1c’–1a’ change
cause any
and in the
qualitative
2c’–2a’ compound’s
change
belong to the CV. We conclude
in product(s)
the compound’s CV.that
Weboth
of transformation electrode
conclude
of that
13 at processes
theboth
first
step of its reduction, and their currents are kinetically controlled by the reactions at the peak 1C.first and
electrode
1c’–1a’ and processes
2c’–2a’ 1c’–1a’
belong to and
the 2c’–2a’ belong
product(s) of to the product(s)
transformation of of
13 transformation
at the first step of 13
its at the
reduction,
step
their of its reduction,
currents and their
are kinetically currents by
controlled arethe
kinetically
reactions controlled by the
at the peak 1C.reactions at the peak 1C.
I / μA I / μA
-40I / μA 2C I / μA
-40 1C
-40 1C 2C -40 1C
-30 1C
-30
-30
-30
-20 2c'
-20 2c' -20
1c' -20
-10 2c'
1c'
-10 2c'
-10 1c'
0 -10 1c'
0
10 0
10 0
20 2a' 2a'
2a' 10 2a'
20 10
1a' 1a'
30 1a' 1a'
30
0.0 -0.5 -1.0 0.0 -0.5 -1.0
0.0 -0.5E / V -1.0 0.0 -0.5
E/V -1.0
E/V E/V
(a)
(a) (b)
(b)
Figure 3. CVs of 13 in MeCN with potential sweep ranges 0 > E > −1.2 (a) and 0 > E > −0.88; (b) V.
Figure 3. CVs of 13 in MeCN with potential sweep ranges 0 > E > −1.2 (a) and 0 > E > −0.88; (b) V.
Figure CVs of 13 in
3. sweep
Potential MeCN(first
with potential sweep250,
ranges E > 1050,
0 > 850, (a) and
´1.2 and > Ecycles,
0(2–7 > ´0.88;
Potential sweeprates
rates were
were 50
50 (first cycle,
cycle, red
red curve),
curve), 250, 450, 650.
450, 650. 850, 1050, 1250(2–7
and 1250 cycles,
(b) V. Potential mV·s
black sweep–1 rates were 50 (first cycle, red curve), 250, 450, 650. 850, 1050, and 1250 (2–7 cycles,
blackcurves)
curves) mV·s–1. .
black curves) mV¨ s–1 .
Molecules 2016, 21, 596 6 of 10
Molecules 2016, 21, 596 6 of 10

The
Theelectrochemical
electrochemicalreduction
reductionofof1313couldcouldbe beaccompanied
accompaniedby byits
itsrapid
rapidirreversible
irreversibledechlorination
dechlorination
initiated
initiatedbybyelectron
electrontransfer
transfer(cf. (cf.[31]).
[31]).Additionally,
Additionally,the thebond
bondC=N C=Nofofthe the1,2,3-dithiazole
1,2,3-dithiazolering
ringcan
can
undergo
undergoirreversible
irreversiblereduction
reductionininthe theRA
RAstate
stateofofaamolecule,
molecule,ororthe
thering
ringcan
canbebeopened
openedby bythe
thecleavage
cleavage
ofofS-S
S-Sor/and
or/and S-NS-Nbonds
bonds (cf.(cf.
[32]). However,
[32]). However,it itis isimpossible
impossibletotoassign,
assign,unambiguously,
unambiguously,these theseprocesses
processes
totothe
thepeaks
peaks1C 1Coror2C.
2C. NoNo long-lived
long-livedparamagnetic
paramagneticproductsproductswere wereobserved
observedby byconventional
conventionalEPR EPR
spectroscopy
spectroscopyunder understationary
stationaryelectrolysis
electrolysisofof13 13ininthe
therange
rangeofofpotentials
potentials−0.8´0.8> >E E> >−1.8 V. V.
´1.8
CV
CVofof1313ininoxidative
oxidative areaareaof of
potentials is characterized
potentials is characterized by the onlyonly
by the irreversible
irreversiblepeakpeak
1A (Ox) at theat
1A (Ox)
1A(Ox) 1A(Ox) 2A(Ox) 2A(Ox)
potential E
the potential
p =
Ep1.53 V (Figure 4). An additional irreversible peak
= 1.53 V (Figure 4). An additional irreversible peak 2C (Ox) (E = 0.85
p 2C (Ox) (Ep V) corresponding
= 0.85 V)
tocorresponding
the reduction to of the
oxidation
reduction products of 13 isproducts
of oxidation observedofin13 the
is cathode
observedbranch
in the of the CV.
cathode branch of the CV.

I / μA
30

1A(Ox)
20

10

2C(Ox)
-10
0.0 0.5 1.0 1.5 2.0
E/V

Figure
Figure4.4.CV
CVofof1313in
in MeCN
MeCN in the range
range of
ofpotential
potentialsweep
sweep0 0< <EE< <2.0
2.0V.V.
TheThe potential
potential sweep
sweep raterate
was
was
100100 s´1 .–1.
mV¨mV·s

Overall, the electrochemical behavior of 13 is characterized by a large number of multistage


Overall, the electrochemical behavior of 13 is characterized by a large number of multistage
irreversible processes and their interpretation is a real challenge. Due to this complexity, at the
irreversible processes and their interpretation is a real challenge. Due to this complexity, at the
current state of research only a qualitative description of the electrochemical behavior of 13 is
current state of research only a qualitative description of the electrochemical behavior of 13 is possible.
possible. For further work preparative electrochemical reduction of 13 at controlled potentials is
For further work preparative electrochemical reduction of 13 at controlled potentials is planned
planned to obtain samples of reduction products enable their conventional characterization, together
to obtain samples of reduction products enable their conventional characterization, together with
with generation of RAs from chlorine-less 1,2,3-dithiazoles such as 4 and related derivatives.
generation of RAs from chlorine-less 1,2,3-dithiazoles such as 4 and related derivatives.

3.3.Experimental Section
Experimental Section

3.1.
3.1.General
GeneralInformation
Information
Elemental
Elementalanalyses
analysesforforC,C,H,
H,and
andNNwere wereperformed
performedwithwithPerkin
PerkinElmer
Elmer2400
2400Elemental
ElementalAnalyser
Analyser
(Perkin
(Perkin Elmer, Waltham,MA,
Elmer, Waltham, MA, USA).
USA). Melting
Melting points
points were were determined
determined on a hot-stage
on a Boetius Boetius hot-stage
apparatus
apparatus and are uncorrected.
and are uncorrected.
1H1H(300.1
(300.1MHz)
MHz)and and1313
CC(75.5
(75.5MHz)
MHz)NMR NMRspectra
spectrawere
weretaken
takenfor
forCDCl
CDCl solutions
33 solutionswith
witha aBruker
Bruker
AM-300
AM-300(Bruker
(BrukerAXSAXSHandheld
HandheldInc., Inc.,Kennewick,
Kennewick,WA, WA,USA).
USA).
MSMSspectra
spectra(EI,
(EI,7070eV)
eV)were
wereobtained
obtainedwith witha aFinnigan
FinniganMATMATINCOS
INCOS5050(Hazlet,
(Hazlet,NJ,
NJ,USA),
USA),andand
high-resolution
high-resolutionMS MSspectra
spectrawith
witha aBruker
BrukermicrOTOF
micrOTOFIIII(Bruker
(BrukerDaltonik
DaltonikGmbh,
Gmbh,Bremen,
Bremen,Germany)
Germany)
instruments
instrumentsusing
usingelectrospray
electrosprayionization.
ionization.The Themeasurements
measurementswere wereoperated
operatedinina apositive
positiveion
ionmode
mode
(interface
(interfacecapillary
capillaryvoltage
voltage−4500
´4500V)V)ororinina anegative
negativeion
ionmode
mode(3200
(3200V);
V);mass
massrange
rangewaswasfrom
fromm/zm/z5050toto
m/z
m/z3000 Da;
3000 external
Da; externalor or
internal
internalcalibration
calibration was done
was with
done Electrospray
with ElectrosprayCalibrant Solution
Calibrant (Fluka).
Solution A
(Fluka).
A syringe injection was used for solutions in MeCN, methanol, or water (flow rate 3 µL¨ min 1 ).
syringe injection was used for solutions in MeCN, methanol, or water (flow rate 3 µL·min ´
−1). Nitrogen

was applied
Nitrogen as applied
was a dryingasgas; interface
a drying gas;temperature was 180 °C.was 180 ˝ C.
interface temperature
IRIRspectra
spectrawere
weremeasured
measuredwith withaaSpecord
SpecordM-80
M-80instrument
instrument(Carl
(CarlZeiss,
Zeiss,Jena,
Jena,Germany)
Germany)inin
KBr
KBrpellets.
pellets.
Oximes
Oximes33[33],
[33],77[34],
[34],12
12[35]
[35]and
and14 14[36]
[36]were
wereprepared
preparedaccording
accordingto tothe
thepublished
publishedprocedures.
procedures.
Molecules 2016, 21, 596 7 of 10

3.2. General Procedure for the Reaction of Cyclic Oximes with S2 Cl2 and Pyridine in Acetonitrile
At ´25 ˝ C and under argon, S2 Cl2 (0.24 mL, 3.0 mmol; or 0.48 mL, 6.0 mmol) was added dropwise
to a stirred solution of oxime (1.0 mmol) and pyridine (0.32 mL, 4.0 mmol; or 0.64 mL, 8.0 mmol) in dry
MeCN (10 mL). The mixture was stirred for 0.5 h at ´5–0 ˝ C, for 24 h at ambient temperature, refluxed
for 1 h, filtered and the solvent was distilled off under reduced pressure. The residue was dissolved in
EtOH (20 mL), diluted by H2 O (20 mL) and extracted with ether (3 ˆ 20 mL). Combined extracts were
washed with H2 O (20 mL), dried, and solvent was evaporated.
8-Chloroindeno[1,2-d]-1,2,3-dithiazole 2. Red solid, mp 108–110 ˝ C (107–109 ˝ C [12]). IR and MS spectra
are similar to the literature data [12].
8-Phenylindeno[1,2-d]-1,2,3-dithiazole 4. Yellow solid, mp 111–112 ˝ C (111–113 ˝ C [12]). IR and MS
spectra are similar to the literature data [12].
4,5,6-Trichlorocyclopenta[d][1,2,3]dithiazole 6a. Deep purple solid, mp 122–124 ˝ C (125–127 ˝ C [12]).
IR and MS spectra are similar to the literature data [12].
Ethyl 5,6-dichlorocyclopenta[d][1,2,3]dithiazole-4-carboxylate 6b. Yellow solid, mp 80–82 ˝ C (83–84 ˝ C [15]).
IR and MS spectra are similar to the literature data [15].
5,7-Dichloro-6H-1,2,3-benzodithiazol-6-one 8. Red solid, mp 259–261 ˝ C (257–258 ˝ C [13]). IR and MS
spectra are similar to the literature data [13].
4,5,7-Trichloro-6H-1,2,3-benzodithiazol-6-one 9. Red solid, mp 214–215 ˝ C (216–217 ˝ C [13]). IR and MS
spectra are similar to the literature data [13].
4,5,6-Trichlorobenzo[6,7]cyclohepta[1,2-d][1,2,3]dithiazole 11. Red solid, mp 119–121 ˝ C (121–122 ˝ C [12]).
IR and MS spectra are similar to the literature data [12].
4-Chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one 13. Red solid, mp 230–233 ˝ C (234–235 ˝ C [13]). IR and
MS spectra are similar to the literature data [13].
9-Chloro-4H-naphtho[2,3-d][1,2,3]dithiazol-4-one 15. Blue solid, mp 192–195 ˝ C (195–196 ˝ C [13]). IR and
MS spectra are similar to the literature data [13].
All compounds synthesized had correct elemental analyses and NMR spectra.

3.3. Behavior of 1,2,3-Dithiazoles 13 and 15 in the S2 Cl2 /Pyridine System


At ´25 ˝ C and under argon, S2 Cl2 (0.048 mL, 0.6 mmol) was added dropwise to a stirred solution
of 15 (25 mg, 0.1 mmol) and pyridine (0.064 mL, 8.0 mmol) in dry MeCN (3 mL). The mixture was
refluxed for 2 h, filtered and the solvent was distilled off under reduced pressure. The residue was
dissolved in CH2 Cl2 (7 mL), washed with H2 O (3 ˆ 2 mL), dried over MgSO4 , and the residue was
separated by flash chromatography (silica gel Merck 60, hexane to hexane/CH2 Cl2 mixtures) to give
13 (10 mg, 39%) and 15 (11 mg, 43%).
In the experiment with 13 under the same reaction conditions it was quantitatively recovered.

3.4. X-ray Diffraction


XRD data of 13 were obtained with a Bruker Kappa Apex II CCD diffractometer (Bruker
AXS Gmbh, Karlsruhe, Germany) using ϕ, ω scans of narrow (0.5˝ ) frames with Mo Kα radiation
(λ = 0.71073 Å) and a graphite monochromator. The structure of 13 was solved by direct methods
and refined by full-matrix least-squares method against all F2 in anisotropic approximation using
the SHELX-97 (Bruker AXS, Madison, WI, USA) programs set [37]. The H atoms positions were
calculated with the riding model. Absorption corrections were applied empirically using SADABS
programs [38]. Shortened intermolecular contacts were analyzed using the PLATON [39] and
MERCURY [40] programs.
Molecules 2016, 21, 596 8 of 10

Compound 13 is orthorhombic, space group Pca21 , a = 16.6153(6), b = 3.8775(1), c = 15.4168(6) Å,


V = 993.24(6) Å3 , Z = 4, C10 H4 ClNOS2 , Dcalc = 1.697 g¨ cm–3 , µ = 0.770 mm–1 , F(000) = 512, crystal
size 0.80 ˆ 0.20 ˆ 0.07 mm3 , independent reflections 2254 (Rint. = 0.0404), wR2 = 0.0512, S = 1.09
for all reflections (R = 0.0196 for 2202 F > 4σ). Tables listing detailed crystallographic data, atomic
positional parameters, and bond lengths and angles are available as CCDC 1468963 from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

3.5. Cyclic Voltammetry


The CV measurements on compound 13 (~1.2 mM solutions in MeCN) were performed with a
PG 310 USB potentiostat (HEKA Elektronik, Germany) at 293 K in an argon atmosphere at a stationary
Pt spherical electrode (S = 0.08 cm2 ) with 0.1 M Et4 NClO4 as a supporting electrolyte. A standard
electrochemical cell (solution volume was 5 mL) connected to the potentiostat with three-electrode
scheme was used. Peak potentials were quoted with reference to a saturated calomel electrode (sce).

4. Conclusions
In this work, a new general procedure for the selective synthesis of carbocycle-fused
1,2,3-dithiazoles based on the reaction of cyclic oximes with S2 Cl2 and pyridine in MeCN was
established. With naphthalenone derivatives, a novel dithiazole rearrangement was discovered, i.e.,
isomerization of 15 into 13. The structure of 1,2,3-dithiazole 13 was confirmed by single-crystal XRD.
In most cases the hetero ring-closure was accompanied by chlorination. The presence of chlorine
atoms in the 1,2,3-dithiazoles synthesized most likely causes instability of their reduced forms.
Particularly, under the CV conditions and with compound 13, we speculate that hydrodechlorination
occurs at a low potential. In any case, no long-lived paramagnetic products were observed
by conventional EPR spectroscopy under stationary electrolysis of 13 in the potential range
´0.8 > E > ´1.8 V. In further syntheses of carbocycle-fused 1,2,3-dithiazoles as potential precursors
of persistent RAs (cf. [6,7]) using the established procedure the chlorination must be prevented by
appropriate substitution in starting oximes.
The effectiveness of the S2 Cl2 /pyridine system in the chemistry described in this work motivates
a special investigation of possible interaction/complexation between its components.

Acknowledgments: The authors are grateful to the Russian Science Foundation (grant no. 15-13-10022), the
Leverhulme Trust (project IN-2012-094), and the Ministry of Education and Science of the Russian Federation
(project of joint laboratories of Siberian Branch of the Russian Academy of Sciences and National Research
Universities) for financial support of various aspects of this work.
Author Contributions: OAR and AVZ suggested research upon fused 1,2,3-dithiazoles towards their use in
materials science; LSK and IVB performed synthetic work; LSK and OAR analyzed synthetic data; IYB obtained
and analized XRD data; IGI and LAS obtained and analyse CV data; and OAR and AVZ wrote the paper.
All authors read and approved the final manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

References and Notes


1. Khmelnitsky, L.I.; Rakitin, O.A. 1,2-Oxa-3-azoles and 1,2-thia-3-azoles. In Comprehensive Heterocyclic
Chemistry II; Storr, R.C., Ed.; Pergamon: Oxford, UK, 1996; pp. 433–452.
2. Rakitin, O.A. 1,2-Oxa/thia-3-azoles. In Comprehensive Heterocyclic Chemistry III; Katritzky, A.R.,
Ramsden, C.A., Scriven, E.F.V., Taylor, R.J.K., Eds.; Elsevier: Oxford, UK, 2008; pp. 1–36.
3. Konstantinova, L.S.; Rakitin, O.A. Synthesis and properties of 1,2,3-dithiazoles. Russ. Chem. Rev. 2008, 77,
521–546. [CrossRef]
4. Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds; Hicks, R.G., Ed.; Wiley:
Chichester, UK, 2010.
5. Rakitin, O.A. Stable heterocyclic radicals. Russ. Chem. Rev. 2011, 80, 647–659. [CrossRef]
Molecules 2016, 21, 596 9 of 10

6. Makarov, A.Y.; Chulanova, E.A.; Semenov, N.A.; Pushkarevsky, N.A.; Lonchakov, A.V.; Bogomyakov, A.S.;
Irtegova, I.G.; Vasilieva, N.V.; Lork, E.; Gritsan, N.P.; et al. A novel sulfur-nitrogen π-heterocyclic radical
anion, (6H-1,2,3-benzothiadiazole-6-ylidene)malononitrilidyl, and its homo- and heterospin salts. Polyhedron
2014, 72, 43–49. [CrossRef]
7. Chulanova, E.A.; Irtegova, I.G.; Vasilieva, N.V.; Bagryanskaya, I.Y.; Gritsan, N.P.; Zibarev, A.V.
Novel long-lived π-heterocyclic radical anion: A hybrid of 1,2,5-thiadiazo- and 1,2,3-dithiazolidyls.
Mendeleev Commun. 2015, 25, 336–338. [CrossRef]
8. Appel, R.; Janssen, H.; Siray, M.; Knoch, F. Synthese und reaktionen des 4,5-dichlor-1,2,3-dithiazolium
chlorids. Chem. Ber. 1985, 118, 1632–1643. [CrossRef]
9. Kim, K. Synthesis and reactions of 1,2,3-dithiazoles. Sulfur Rep. 1998, 21, 147–207. [CrossRef]
10. Oakley, R.T.; Reed, R.W.; Robertson, C.M.; Richardson, J.F. Naphthalene-1,2,3-dithiazolyl and its
selenium-containing variants. Inorg. Chem. 2005, 44, 1837–1845. [CrossRef] [PubMed]
11. Neo, A.G; Carrillo, R.M.; Marcos, C.F. A straightforward synthesis of 2-aminobenzothiazoles from Herz
compounds. Org. Biomol. Chem. 2011, 9, 4850–4855. [CrossRef] [PubMed]
12. Plater, M.J.; Rees, C.W.; Roe, D.G.; Torroba, T. Cyclopenta-1,2,3-dithiazoles and related compounds. J. Chem.
Soc. Perkin Trans. 1 1993. [CrossRef]
13. Polo, C.; Ramos, V.; Torroba, T.; Rakitin, O.A.; Rees, C. W. One-pot synthesis of 1,2,3-benzodithiazol-6-ones.
Tetrahedron 1998, 54, 223–232. [CrossRef]
14. Macho, S.; Rodriguez, T.; Torroba, T.; Rees, C.W. A novel oxime to pentathiepin cascade reaction. J. Chem.
Soc. Chem. Commun. 2001. [CrossRef]
15. Macho, S.; Miguel, D.; Gomez, T.; Rodriguez, T.; Torroba, T. From cyclopentanone oximes
to bis[1,2,3]dithiazolo-s-indacenes, cyclopenta[c][1,2]thiazine, pentathiepino-, tetrathiino-, and
thienocyclopenta[1,2,3]dithiazoles as a rich source of new materials. J. Org. Chem. 2005, 70, 9314–9325.
[CrossRef] [PubMed]
16. Rakitin, O.A.; Konstantinova, L.S. Sulfur monochloride in the synthesis of heterocyclic compounds.
Adv. Heterocycl. Chem. 2008, 96, 175–229.
17. Rakitin, O.A. One-pot synthesis of sulfur heterocycles from simple organic substrates. Arkivoc 2009, 1,
129–149.
18. Rakitin, O.A.; Konstantinova, L.S. Design of sulfur heterocycles with sulfur monochloride: Retrosynthetic
analysis and prospects. Mendeleev Commun. 2009, 19, 55–61.
19. Rakitin, O.A.; Konstantinova, L.S. Sulfur monochloride in organic synthesis. Russ. Chem. Rev. 2014, 83,
225–250.
20. Allen, F.H.; Kenard, O.; Watson, D.G.; Bramer, L.; Orpen, A.G.; Taylor, R. Tables of bond lengths determined
by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds. J. Chem. Soc. Perkin
Trans. II 1987. [CrossRef]
21. In the crystal of 13, the intermolecular contacts S...O are shortened to 2.84–2.91 Å and form an infinite chains
of molecules along the crystallographic axis c (normal contact S¨ ¨ ¨ O is 3.32 Å: Rowland, R.S.; Taylor, R.
Intermolecular nonbonded contact distances in organic crystal structures: Comparison with distances
expected from van der Waals radii. J. Phys. Chem. 1996, 100, 7384–7391). These chains form infinite
stacks along the axis b through the arene-arene π¨ ¨ ¨ π interactions (centroid-to-centroid distance is 3.64 Å,
interplanar separation 3.51 Å). Additionally to the π . . . π interactions, the Cl¨ ¨ ¨ π interactions are observed,
the atom-to-plane distance is 3.53 Å.
22. Konstantinova, L.S.; Rakitin, O.A.; Rees, C.W. One-pot synthesis of fused pentathiepins. Chem. Commun.
2002, 2009, 1204–1205.
23. Amelichev, S.A.; Konstantinova, L.S.; Lyssenko, K.A.; Rakitin, O.A.; Rees, C.W. Direct synthesis of fused
1,2,3,4,5-pentathiepins. Org. Biomol. Chem. 2005, 3, 3496–3501. [CrossRef] [PubMed]
24. Konstantinova, L.S.; Amelichev, S.A.; Rakitin, O.A. Regioselective synthesis of pentathiepins fused with
pyrroles, thiophene and indoles. Russ. Chem. Bull. 2006, 55, 2081–2084. [CrossRef]
25. Lonchakov, A.V.; Rakitin, O.A.; Gritsan, N.P.; Zibarev, A.V. Breathing some new life into an old topic:
Chalcogen-nitrogen π-heterocycles as electron acceptors. Molecules 2013, 18, 9850–9900. [CrossRef] [PubMed]
Molecules 2016, 21, 596 10 of 10

26. Pushkarevsky, N.A.; Semenov, N.A.; Dmitriev, A.A.; Kuratieva, N.V.; Bogomyakov, A.S.; Irtegova, I.G.;
Vasilieva, N.V.; Bode, B.E.; Gritsan, N.P.; Konstantinova, L.S.; et al. Synthesis and properties of the heterospin
(S1 = S2 = 1/2) radical-ion salt bis(mesitylene)molibdenium(I) [1,2,5][thiadiazolo[3,4-c][1,2,5]thiadiazolidyl.
Inorg. Chem. 2015, 54, 7007–7013. [CrossRef] [PubMed]
27. Semenov, N.A.; Pushkarevsky, N.A.; Suturina, E.A.; Chulanova, E.A.; Kuratieva, N.V.; Bogomyakov, A.S.;
Irtegova, I.G.; Vasilieva, N.V.; Konstantinova, L.S.; Gritsan, N.P.; et al. Bis(toluene)chromium(I)
[1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl and [1,2,5]thiadiazolo[3,4-b]pyrazinidyl: New heterospin
(S1 = S2 = 1/2) radical-ion salts. Inorg. Chem. 2013, 52, 6654–6663. [CrossRef] [PubMed]
28. Semenov, N.A.; Pushkarevsky, N.A; Lonchakov, A.V.; Bogomyakov, A.S.; Pritchina, E.A.; Suturina, E.A.;
Gritsan, N.P.; Konchenko, S.N.; Mews, R.; Ovcharenko, V.I.; et al. Heterospin π-heterocyclic
radical-anion salt: Synthesis, structure and magnetic properties of decamethylchromocenium
[1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl. Inorg. Chem. 2010, 49, 7558–7564. [CrossRef] [PubMed]
29. Gritsan, N.P.; Zibarev, A.V. Chalcogen-nitrogen π-heterocyclic radical-anion salts: The synthesis and
properties. Russ. Chem. Bull. 2011, 60, 2131–2140. [CrossRef]
ij
30. In the potential Ep designation, i is a number of peak, j = A or C indicates the anode or cathode branch of
the CV curve, respectively. An additional symbol Ox is related to CV in the area of oxidative potentials.
The designation of corresponding currents is the same.
31. Vasilieva, N.V.; Irtegova, I.V.; Gritsan, N.P.; Lonchakov, A.V.; Makarov, A.Y.; Shundrin, L.A.; Zibarev, A.V.
Redox properties and radical anions of fluorinated 2,1,3-benzothia(selena)diazoles and related compounds.
J. Phys. Org. Chem. 2010, 23, 536–543. [CrossRef]
32. Konstantinova, L.S.; Knyazeva, E.A.; Obruchnikova, N.V.; Vasilieva, N.V.; Irtegova, I.G.; Nelyubina, Y.V.;
Bagryanskaya, I.Y.; Shundrin, L.A.; Sosnovskaya, Z.Y.; Zibarev, A.V.; et al. 1,2,5-Thiadiazole 2-oxides,
their benzo-fused derivatives and parent compounds: Selective synthesis, structural characterization and
electrochemical properties. Tetrahedron 2014, 70, 5558–5568. [CrossRef]
33. Banzi, V.; Gila, L.; Santi, R.; Biagini, P.; Borsotti, G. Process for Preparing Elastomeric ep(d)m Copolymers.
EP 0806436, 12 November 1997.
34. Kim, S.-H.; Kwon, J.-H.; Yoon, S.-H. An improved synthesis of 41 -hydroxydiclofenac. Bull. Korean Chem. Soc.
2010, 31, 3007–3009. [CrossRef]
35. Meyer, K.H.; Lenhardt, S. Die Reaktionsweise der Enole und der Phenole; ein Beitrag zur Kenntnis der
ungesättigten Verbindungen. Liebigs Ann. Chem. 1913, 398, 66–82. [CrossRef]
36. Henriques, R.; Ilinski, M. Zur darstellung der nitrosonaphtole. Chem. Ber. 1885, 18, 704–706. [CrossRef]
37. Sheldrick, G.M. Crystal structure refinement with SHELXL. Acta Crystallogr. C 2015, 71, 3–8. [CrossRef]
[PubMed]
38. SADABS. Version 2008-1; Bruker AXS: Madison, WI, USA, 2008.
39. Spek, A.L. PLATON, A Multipurpose Crystallographic Tool (Version 10M); Utrecht University: Utrecht,
The Netherlands, 2003.
40. Macrae, C.F.; Edgington, P.R.; McCabe, P.; Pidcock, E.; Shields, G.P.; Taylor, R.; Towler, M.; van de Stree, J.
Mercury: Visualization and analysis of crystal structures. J. Appl. Crystallogr. 2006, 39, 453–457. [CrossRef]

Sample Availability: Samples of all compounds are available from the authors.

© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC-BY) license (http://creativecommons.org/licenses/by/4.0/).