Microwave-assisted reactions of α-diazoketones with hetaryl and ferrocenyl thioketones*

Article abstract of DOI:10.1080/17415993.2017.1363206

Differently substituted hetaryl thioketones react with less reactive diazoketones under microwave (MW) irradiation in toluene solution. After only 2 min, the reactions were complete and, depending on the type of the used diazoketone, α,β-unsaturated keton

Full text of DOI:10.1080/17415993.2017.1363206

Journal of Sulfur Chemistry
ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: http://www.tandfonline.com/loi/gsrp20
Microwave-assisted reactions of α-diazoketones
with hetaryl and ferrocenyl thioketones
Grzegorz Mlostoń, Róża Hamera-Fałdyga, Małgorzata Jeske, Magdalena
Godziszewska, Katarzyna Urbaniak & Heinz Heimgartner
To cite this article: Grzegorz Mlostoń, Róża Hamera-Fałdyga, Małgorzata Jeske, Magdalena
Godziszewska, Katarzyna Urbaniak & Heinz Heimgartner (2017): Microwave-assisted reactions
of α-diazoketones with hetaryl and ferrocenyl thioketones, Journal of Sulfur Chemistry, DOI:
10.1080/17415993.2017.1363206
To link to this article: http://dx.doi.org/10.1080/17415993.2017.1363206
Published online: 13 Aug 2017.
Submit your article to this journal
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=gsrp20
Download by: [Wilfrid Laurier University]
Date: 14 August 2017, At: 04:06

JOURNAL OF SULFUR CHEMISTRY, 2017
https://doi.org/10.1080/17415993.2017.1363206
Microwave-assisted reactions of α-diazoketones with hetaryl
and ferrocenyl thioketones∗
Grzegorz Mlostońa, Róża Hamera-Fałdygaa, Małgorzata Jeskea,
Magdalena Godziszewskaa, Katarzyna Urbaniaka and Heinz Heimgartnerb
aDepartment of Organic and Applied Chemistry, University of Łódź, Łódź, Poland; bDepartment of Chemistry,
University of Zurich, Zurich, Switzerland
ABSTRACT
ARTICLE HISTORY
Received 1 July 2017
Accepted 28 July 2017
Differently substituted hetaryl thioketones react with less reactive
diazoketones under microwave (MW) irradiation in toluene solution.
After only 2 min, the reactions were complete and, depending on the
type of the used diazoketone, α,β-unsaturated ketones, acyl substi-
tuted thiiranes or 1,3-oxathioles were obtained as final products. In
the case of azibenzil and di(thiophen-2-yl) thioketone, a new type of
1,5-dipolar electrocyclization of the intermediate thiocarbonyl ylide
involving a thiophene ring led to a fused sulfur heterocycle. In con-
trast to hetaryl thioketones, the ferrocenyl analogues decompose
under MW irradiation. Alternatively, they react with diazopropanone
and 2-diazo-1-phenylethanone in boiling THF in the presence of
LiClO4 to give α,β-unsaturated ketones as sole products. In these
cases, the reactions require long reaction times.
KEYWORDS
Diazo compounds;
thioketones; microwave
irradiation; thiocarbonyl
ylides; sulfur heterocycles
1. Introduction
Reactions of diazomethane with ‘superdipolarophilic’ thioketones have extensively been
studied, and it is well established that both cycloaliphatic and aromatic thioketones yield
1,3,4-thiadiazolines regioselectively even at low temperature. These [3+2]-cycloadducts
extrude N2 upon warming and reactive thiocarbonyl S-methanides are generated thereby
CONTACT Grzegorz Mlostoń
gmloston@uni.lodz.pl
Department of Organic and Applied Chemistry, University
of Łódź, Tamka 12, Łódź, PL 91-403, Poland
*Dedicated to Professor Zbigniew Kudzin (University of Łódź) on the occasion of his 70th birthday.
© 2017 Informa UK Limited, trading as Taylor & Francis Group

2
G. MLOSTOŃ ET AL.
Scheme 1. In situ generation of α-acyl-substituted thiocarbonyl ylides 3 and their DEC.
[1–3]. In recent publications, we demonstrated that hetaryl thioketones react with dia-
zomethane with immediate evolution of N2 already below −70°C [4,5]. In these reactions,
delocalized diradicals were postulated as intermediates, which either undergo dimerization
or trap the starting thioketone to give 4,4,5,5-tetrasubstituted 1,3-dithiolanes in a regios-
elective manner. An analogous behavior of hetaryl thioketones was observed in reactions
with alkyl- and trimethylsilyl-substituted diazomethanes. On the other hand, diphenyldia-
zomethane reacts with hetaryl thioketones only at ca. 0°C, and after spontaneous evolution
of N2 the corresponding tetra-substituted thiiranes or ethenes were obtained [6].
α-Diazoketones form an important class of propargyl-allenyl-type 1,3-dipoles [7,8],
which are widely explored in the [3+2]-cycloaddition chemistry. Moreover, they are
known as important precursors of carbenes and carbenoids generated photolytically or
by treatment with metal salts, for example, rhodium(II) acetate [9]. The presence of
an electron-withdrawing acyl group reduces the 1,3-dipolar reactivity and their [3+2]-
cycloadditions require harsher reaction conditions, or Lewis acids are applied as catalyst
[10]. In recent years, microwave (MW)-supported reactions have extensively been elabo-
rated, and in many cases drastic reduction of reaction times and improvement of yields of
products were reported also for [3+2]-cycloadditions performed with diverse 1,3-dipoles
[11,12].
In our earlier studies, we described the reactions of some diazoketones 1 with
cycloaliphatic and aromatic thioketones 2 (Scheme 1). In general, they were performed
at enhanced temperature and, in some cases, LiClO4 was used as an efficient catalyst.
Depending on the substitution pattern, 1,3-oxathioles 4 or thiiranes 5 formed from the
intermediate thiocarbonyl ylides 3 via 1,5- and 1,3-dipolar electrocyclization (DEC),
respectively, were obtained [13–16]. Reactions leading to five membered heterocycles via
=
1,5-dipolar electrocyclizations of thiocarbonyl S-methanides bearing a C X group at the
α-position have been summarized in a recent review [17].
=
The reactivity of α-diazoketones 1 in [3+2]-cycloadditions with C S dipolarophiles
depends strongly on their structures and acyclic α-diazoketones were shown to be more
reactive than cyclic analogues [10,18]. Due to our continuing interest in the chemistry of

JOURNAL OF SULFUR CHEMISTRY
3
Figure 1. α-Diazoketones 1 selected for the reactions with hetaryl and ferrocenyl thioketones.
hetaryl and ferrocenyl thioketones as useful building blocks in the organic chemistry of
sulfur [19], their reactions with diverse α-diazoketones 1 as representatives of diazo 1,3-
dipoles should be compared with aromatic analogues. For this study, differently substituted
α-diazoketones 1a–e, presented in Figure 1, were selected in order to compare the influence
of Me and Ph groups on the course of the investigated reactions.
2. Results and discussion
In an earlier publication, the reaction of thiobenzophenone (2a, R3 = R4 = Ph) with
2-diazo-1,2-diphenylethanone (azibenzil, 1a) was reported to occur in Et2O at room tem-
perature within 96 h to give 2-benzoyl-2,3,3-triphenylthiirane (5a, R1 – R4 = Ph) in only
5% yield [16]. On the other hand, in THF in the presence of LiClO4, the reaction was
complete after 15 h, and the 1,3-oxathiole 4a (R1 – R4 = Ph) was obtained in 51% yield
[13]. The same reaction conditions were applied in a test experiment with 1a and phenyl
(thiophen-2-yl) thioketone (2b). Unexpectedly, no reaction was observed after 24 h. More-
over, even after 7 d, the main part of 1a remained unchanged, whereas 2b underwent
slow decomposition. Similarly, the attempted reaction in boiling THF in the presence of
LiClO4 was unsuccessful. For that reason, the reaction conditions were changed, and the
reaction was carried out in toluene under MW irradiation (200 W, 150°C). In that case,
the characteristic green color of 2b disappeared already after 2 min. After evaporation of
1
the solvent, the H NMR spectrum of the crude mixture suggested the presence of two
products, which were separated and identified as 2,4,5-triphenyl-2-(thiophen-2-yl)-1,3-
oxathiole (4b) and 3,3,4-triphenyl-4-(thiophen-2-yl)thietan-2-one (6a) (Scheme 2); the
latter is a known compound [20]. In the case of 4b, the structure was established based
on 13C NMR and IR data as well as the elemental analysis. In the 13C NMR spectrum, the
most characteristic signal of C(2) appeared at 96.2 ppm. Importantly, in the registered IR
=
spectrum, no C O absorption was observed.
Scheme 2. Reaction of hetaryl thioketone 2b with azibenzil (1a) under MW irradiation.

4
G. MLOSTOŃ ET AL.
Scheme 3. Formation of α,β-unsaturated ketones 7 in reactions of diazopropanone (1b) with hetaryl
and ferrocenyl thioketones 2 (Fc = ferrocenyl, Sel = selenophen-2-yl, Thi = thiophen-2-yl).
The formation of 4b results from the 1,5-DEC of the in situ generated thiocarbonyl
S-methanide 3b (R1 – R3 = Ph, R4 = thiophen-2-yl) according to the mechanistic expla-
nation presented in Scheme 1. Very likely, the intermediate 3b is formed via addition
=
of the initially formed benzoyl(phenyl)carbene onto the C S group of 2b [3]. The
reactive benzoyl(phenyl)carbene undergoes a competitive Wolff rearrangement to give
diphenylketene, which is known to trap thioketones yielding thietan-2-ones, for example,
6a, in a regioselective manner [20].
Prompted by these results, we decided to study reactions of the α-diazoketones 1a–e
with hetaryl and ferrocenyl thioketones 2 systematically. The first series of experiments
comprises reactions of diazopropanone (1b) with thioketones 2c–f (Scheme 3). In the
experiment with 2c under MW irradiation, the only product isolated after chromato-
graphic workup was the α,β-unsaturated ketone 7a. Remarkably, only one stereoisomer
was obtained. The collected spectroscopic data did not allow determining the configu-
ration of the product. In contrast, the attempted MW-assisted reactions with ferrocenyl
thioketones 2d–f were unsuccessful and only decomposition of the thioketones was
observed. For that reason, the reactions of 1b with 2d–f were repeated in boiling THF in
the presence of LiClO4. After 16 h, the conversions were complete and the α,β-unsaturated
ketones 7b–d were obtained as single stereoisomers with unknown configuration in fair
yields (Scheme 3).
The mechanistic explanation of the pathway leading to products 7 is based on the
assumption that the intermediate thiocarbonyl ylides of type 3 bearing hetaryl or/and fer-
rocenyl groups undergo 1,3-DEC to give thiiranes of type 5, which under the reaction
conditions extrude sulfur immediately. The reaction sequence 1 + 2 → 7 corresponds
formally with the ‘two-fold extrusion reaction’ [21], which belongs to the most useful
olefinition reactions. These results point out that the presence of hetaryl or ferrocenyl sub-
stituents promotes the extrusion of sulfur from the initially formed thiiranes in analogy to
results obtained in reactions with N-protected diazoproline performed in boiling THF in
the presence of LiClO4 [22]. In the present study, N-benzoyldiazoproline was reacted with
di(thiophen-2-yl)- and di(selenophen-2-yl)thioketone (2g,h) under MW irradiation, and
the corresponding α,β-unsaturated ketones 7e,f were obtained in high yields (Figure 2).
The MW-assisted reactions of diazoacetophenone (1c) and 3-diazobutan-2-one (1d)
with diverse hetaryl thioketones 2 led, in most cases, to the corresponding α,β-unsaturated
ketones of type 7 (Scheme 4). However, the initially formed thiiranes 5b,c could be isolated
in the reactions of 1d with 2b and 2i, respectively.

JOURNAL OF SULFUR CHEMISTRY
5
Figure 2. α,β-Unsaturated ketones obtained from N-benzoyldiazoproline and dihetaryl thioketones 2g
and 2h.
Scheme 4. Reactions of α-diazoketones 1c and 1d with hetaryl and ferrocenyl thioketones.
In analogy to the experiments performed with 1b, the attempted reactions of 1c
with ferrocenyl thioketones 2d–f led to α,β-unsaturated ketones 7k–m only in boiling
THF/LiClO4.
The next diazocompound used was 2-diazo-1-phenylpropan-1-one (1e). The MW-
assisted reactions carried out with hetaryl thioketones 2b,g–i gave 1,3-oxathiole derivatives
4, which in most cases were obtained side by side with the corresponding α,β-unsaturated
ketones 7 (Scheme 5). Apparently, the presence of the benzoyl group in the intermediate
thiocarbonyl ylide 3 enhances its ability to undergo the 1,5-DEC leading to 1,3-oxathioles 4
as major products. The competitive 1,3-DEC results in the formation of the corresponding
benzoyl-substituted thiiranes, which subsequently extrude sulfur to give alkenes 7.

6
G. MLOSTOŃ ET AL.
Scheme 5. Formation of 1,3-oxathioles 4 and α,β-unsaturated ketones 7 in the reactions of 2-diazo-1-
phenylpropan-1-one (1e) with hetaryl thioketones 2.
Figure 3. Products of the reaction of azibenzil (1a) with aryl hetaryl thioketones 2 (Fur = furan-2-yl).
In extension of the study presented in Scheme 2, azibenzil (1a) was used for reactions
with hetaryl thioketones 2c,g,i, and 2j (Ar1 = Ph, Ar2 = Fur). In this series, neither thi-
iranes 5 nor α,β-unsaturated ketones 7 were formed, and only 1,3-oxathioles 4 as well as
thietan-2-ones 6 were isolated from the reaction mixtures. The reaction course is presented
in Scheme 2, and the obtained products are depicted in Figure 3.
An unexpected result was obtained in the reaction of 1a with 2g. The chromato-
graphic separation gave two products, and one of them was identified as the known
3,3-diphenyl-4,4-di(thiophen-2-yl)thietan-2-one 6d [20]. The second product 8, isolated
in a comparable amount as a solid material, showed in the 13C NMR spectrum the char-
acteristic absorption of a keto group at 203.5 ppm. The corresponding IR absorption was
found at 1682 cm−1. In addition, the 1H NMR spectrum revealed the presence of a singlet
for a CH group at 5.60 ppm, which correlated with the signal of a sp3-C atom in the 13
C
NMR spectrum (42.2 ppm). Moreover, the presence of five signals for Carom indicated that
one of the former CH atoms of a thiophene ring was involved in the formation of a new σ-
bond. Based on these data, the structure 8 was attributed to the new product isomeric with
the expected thiirane or 1,3-dithiole (Scheme 6). An additional argument was found in the
1H NMR spectrum, in which two doublets with J = 5.2 Hz localized at 6.22 and 7.09 ppm
corresponded with two H-atoms in α- and β-positions of the fused thiophene ring.
The reaction pathway leading to 8 is presented in Scheme 6. The intermediate thiocar-
bonyl ylide 3a undergoes a formal 1,5-DEC involving a thiophene ring. The resulting fused
sulfur heterocycle 9 stabilizes via 1,3-H-shift to give 8 as the final product. This is the first
example of a benzoyl-substituted thiocarbonyl ylide, which forms neither a 1,3-oxathiole
nor a thiirane as products of dipolar electrocyclization.

JOURNAL OF SULFUR CHEMISTRY
7
Scheme 6. Reaction of azibenzil (1a) with di(thiophen-2-yl) thioketone (2g) leading to thieno[3,4-
b]thiophene derivative 8.
Scheme 7. Synthesis of α,β-unsaturated ketones 7q,r from hetaryl thioketones 2c,g.
In two additional experiments, 2-diazo-1-(thiophen-2-yl)ethanone (1f) and 2-
diazoacenaphthen-1-one (1g) were reacted with thioketones 2c and 2g, respectively.
In both cases, the corresponding α,β-unsaturated ketones 7q and r, respectively, were
obtained as the sole product (Scheme 7). Analogous to previously described examples
(Scheme 3), only one stereoisomer of 7q was formed.
3. Conclusions
The presented results show that the less reactive diazoketones can be used efficiently
for reactions with hetaryl thioketones under MW irradiation. Under these conditions,
the reaction time was reduced to 2 min in all cases. Depending on the type of sub-
stituents in the starting diazoketones, α,β-unsaturated ketones, acyl-substituted thiiranes

8
G. MLOSTOŃ ET AL.
or 1,3-oxathioles were obtained as final products. Remarkably, the reaction of azibenzil
and di(thiophen-2-yl) thioketone gave a fused sulfur heterocycle (thieno[3,4-b]thiophene
skeleton) upon involvement of a thiophene ring in the electrocyclization process (1,5-
dipolar electrocyclization). The presented method supplements the very few methods
reported for the synthesis of thieno[3,4-b]thiophene derivatives, which are of current inter-
est for materials chemistry [23]. Ferrocenyl thioketones are not suitable substrates for
MW-supported reactions, but in the studied cases, α,β-unsaturated ketones were formed
as sole products when the reactions with diazoketones 1b and 1c were carried out in boil-
ing THF in the presence of LiClO4. The mechanistic explanation for all these reactions is
based on the assumption that acyl-substituted thiocarbonyl ylides are formed as reactive
intermediates, which subsequently undergo DEC processes. The course of the latter reac-
tions depends on the type of substituents in the diazoketone used. In contrast to known
analogous reactions of aromatic and cycloaliphatic thioketones with diazomethanes, which
proceed via initial [3+2]-cycloaddition, the generation of the thiocarbonyl ylides under
MW-irradiation occur, very likely, via decomposition of the starting diazoketones. The
carbene formed thereby adds to the thiocarbonyl group of the thioketone. A piece of evi-
dence for this reaction sequence is the observed formation of diphenylketene in reactions
performed with azibenzil, which led to the corresponding thietan-2-ones.
4. Experimental design
4.1. General
All solvents were dried over appropriate drying agents and distilled before use. The 1H and
13C NMR spectra were measured on a Bruker Avance III instrument (600 and 150 MHz,
respectively), using the solvent (CDCl3/residual CHCl3) signal as reference. The IR spectra
(KBr pellets) were recorded on a Nexus FT-IR spectrophotometer. The elemental analyses
were determined on a Vario Micro Cube. Flash column chromatography (FCC) was carried
out using Silica gel 60 (Sigma-Aldrich, 230–400 mesh). Melting points were determined
in a capillary using a StewartꢀR SMP30. MW experiments were carried out with CEM-
focused Microwave-type Discover SPD at 150 W. The notation Fc represents in this study
‘ferrocenyl’.
4.2. Starting materials
The applied α-diazoketones 1 were obtained by known methods either via oxidation of
the corresponding hydrazone [24] or by treatment of an acid chloride with excess dia-
zomethane or diazoethane (Arndt-Eistert reaction) [25]. Aryl and hetaryl thioketones
2a–c,g–j [4,26] as well as ferrocenyl-substituted thioketones 2d–f [27] were prepared from
parent ketones via thionation using Lawesson’s reagent.
4.3. Reactions of α-diazoketones 1 with thioketones 2 under
MW irradiation – general procedure
A solution of a diazocompound 1 (1 mmol) and a thioketone 2 (1 mmol) in anhydrous
toluene (3 mL) was subjected to MW irradiation at 150°C for ca. 2 min. The reactions were

JOURNAL OF SULFUR CHEMISTRY
9
performed until the color of thioketone 2 disappeared. If necessary, additional portions of
1 were added to achieve full consumption of thioketone 2. After complete reaction, the
solvent was evaporated and the crude mixtures were purified chromatographically (SiO2)
using as eluent petroleum ether or hexane with increasing amounts of CH2Cl2. Analytically
pure samples were obtained after crystallization from petroleum ether or hexane with small
amounts of CH2Cl2.
4.3.1. 2,4,5-Triphenyl-2-(thiophen-2-yl)-1,3-oxathiole (4b)
Red crystals; m.p. 127.4–129.8°C; yield: 100 mg (25%). 1H NMR: 6.98 (dd, JH,H = 5.0 Hz,
JH,H = 3.7 Hz, 1CHarom); 7.12 (dd, JH,H = 3.7 Hz, JH,H = 1.3 Hz, 1CHarom); 7.24–7.34
(m, 8CHarom); 7.37–7.48 (m, 6CHarom); 7.73–7.76 (m, 2CHarom). 13C NMR: 96.2, 111.9
(CThi, C(4)); 126.1, 126.5, 127.0, 127.5, 127.7, 127.9, 128.1, 128.2, 128.3, 128.5, 128.7, 129.2
(18CHarom); 130.7, 132.2, 141.2, 143.4 (4Carom); 148.9 (C(5)). IR (KBr): 3082m, 3050m,
3015m, 1609s, 1496s, 1445s, 1223s, 1150m, 1065s, 965m, 954m, 831m, 748vs, 691vs. Anal.
calcd for C25H18OS2 (398.54): C 75.34, H 4.55, S 16.09; found: C 75.44, H 4.73, S 15.98.
4.3.2. 4-Methyl-2,5-diphenyl-2-(thiophen-2-yl)-1,3-oxathiole (4c)
Brown-orange crystals; m.p. 84–86°C; yield: 315 mg (94%). 1H NMR: 2.14 (s, CH3); 6.95
(dd, JH,H = 5.0 Hz, JH,H = 3.6 Hz, 1CHarom); 7.06 (dd, JH,H = 3.6 Hz, JH,H = 1.4 Hz,
1CHarom); 7.30–7.41 (m, 7CHarom); 7.57–7.59 (m, 2CHarom); 7.66–7.69 (m, 2CHarom). 13
C
NMR: 12.9 (CH3); 95.8, 107.1 (CThi, C(4)); 126.0, 126.4, 126.8, 127.2, 127.3, 127.8, 128.0,
128.3, 128.4 (13CHarom); 130.8, 141.3, 143.7 (3Carom); 149.3 (C(5)). IR (KBr): 3098m,
2911m, 1635m, 1489m, 1442m, 1429m, 1233s, 1147s, 1071m, 1011s, 831m, 767m, 745m,
707vs, 694v. Anal. calcd for C20H16OS2 (336.47): C 71.39, H 4.79, S 19.06; found: C 71.44,
H 4.90, S 19.12.
4.3.3. 4-Methyl-2,5-diphenyl-2- (selenophen-2-yl)-1,3-oxathiole (4d)
1
Beige crystals; m.p. 90–92°C; yield: 210 mg (55%). H NMR: 2.14 (s, CH3); 7.20 (d,
JH,H = 3.4 Hz, 2CHarom); 7.31–7.42 (m, 6CHarom); 7.59 (d, JH,H = 7.6 Hz, 2CHarom);
7.71 (d, JH,H = 7.8 Hz, 2CHarom); 8.05 (dd, JH,H = 6.0 Hz, JH,H = 3.4 Hz, 1CHarom).
13C NMR: 12.9 (CH3); 97.4, 107.2 (CSel, C(4)); 126.0, 127.3, 127.8, 128.0, 128.2, 128.3,
129.0, 129.1, 132.3 (13CHarom); 130.9, 141.2, 143.7 (3Carom); 156.5 (C(5)). IR (KBr): 3056s,
2914m, 2851m, 1632m, 1492s, 1445s, 1382m, 1233s, 1144s, 1078m, 1011s, 834m, 767m,
736s, 694vs, 675m. Anal. calcd. for C20H16OSSe (383.37): C 62.66, H 4.21, S 8.36; found C
62.65, H 4.40, S 8.56.
4.3.4. 4-Methyl-5-phenyl-2,2-di(thiophen-2-yl)-1,3-oxathiole (4e)
1
Beige crystals; m.p. 74.2–75.3°C; yield: 170 mg (50%). H NMR: 2.15 (s, CH3); 6.99
(dd, JH,H = 5.0 Hz, JH,H = 3.6 Hz, 2CHarom); 7.20 (dd, JH,H = 3.6 Hz, JH,H = 1.1 Hz,
2CHarom); 7.30–7.33 (m, 2CHarom); 7.36–7.41 (m, 3CHarom); 7.56–7.60 (m, 2CHarom).
13C NMR: 12.9 (CH3); 93.0, 107.4 (CThi, C(4)); 126.0, 126.5, 127.0, 127.4, 127.9, 128.2
(11CHarom); 130.6, 141.2 (3Carom); 148.3 (C(5)). IR (KBr): 3088m, 1622m, 1594m, 1492s,
1429m, 1350m, 1233s, 1138s, 1071m, 1036s, 1005s, 843m, 827m, 777m, 764s, 707vs, 691vs.
Anal. calcd for C18H14OS3 (342.50): C 63.12, H 4.12, S 28.09; found: C 63.17, H 4.64,
S 28.05.

10
G. MLOSTOŃ ET AL.
4.3.5. 4-Methyl-5-phenyl-2,2-di(selenophen-2-yl)-1,3-oxathiole (4f)
Beige crystals; m.p. 87–89°C; yield: 150 mg (35%). 1H NMR: 2.15 (s, CH3); 7.23
(dd, JH,H = 5.6 Hz, JH,H = 3.8 Hz, 2CHarom); 7.30–7.33 (m, 1CHarom); 7.37–7.41 (m,
4CHarom); 7.54–7.58 (m, 2CHarom); 8.06 (dd, JH,H = 5.6 Hz, JH,H = 1.0 Hz, 2CHarom).
13C NMR: 12.9 (CH3); 96.2, 107.6 (CSel, C(4)); 127.4, 127.9, 128.2, 128.9, 129.0, 132.2
(11CHarom); 130.6, 141.0 (3Carom); 155.2 (C(5)). IR (KBr): 3098m, 3060m, 1625m, 1492m,
1442s, 1236s, 1230s, 1144s, 1125s, 1074m, 1027m, 1002m, 843m, 834m, 764s, 732s, 694vs,
618m. Anal. calcd for C18H14OSSe2 (436.29): C 49.55, H 3.23, S 7.35; found: C 49.62,
H 3.41, S 7.59.
4.3.6. 2-(4-Chlorophenyl)-4,5-diphenyl-2-(selenophen-2-yl)-1,3-oxathiole (4g)
Brown crystals; m.p. 128–130°C; yield: 150 mg (31%). 1H NMR: 7.21–7.33 (m, 12CHarom);
7.37–7.40 (m, 2CHarom); 7.42–7.44 (m, 2CHarom); 7.68–7.71 (m, 2CHarom); 8.01 (dd,
JH,H = 5.1 Hz, JH,H = 1.8 Hz, 1CHarom). 13C NMR: 97.3, 112.1 (CSel, C(4)); 127.6, 127.9,
128.2, 128.3, 128.4, 128.7, 129.1, 129.2, 129.6, 132.9 (17CHarom); 130.5, 132.0, 134.5, 141.2,
142.1 (5Carom); 155.2 (C(5)). IR (KBr): 3053m, 3033m, 1616s, 1570m, 1486s, 1439m,
1391m, 1230s, 1214m, 1087s, 1052m, 983m, 954m, 812m, 758vs, 691vs. Anal. calcd for
C25H17ClOSSe (479.88): C 62.57, H 3.57, S 6.68; found: C 62.62, H 3.62, S 6.82.
4.3.7. 2,4,5-Triphenyl-2-(selenophen-2-yl)-1,3-oxathiole (4h)
Green-brown crystals; m.p. 141–143°C; yield: 50 mg (11%). H NMR: 7.21–7.32 (m,
1
9CHarom); 7.36–7.46 (m, 6CHarom); 7.74–7.76 (m, 2CHarom); 8.08 (dd, JH,H = 5.6 Hz,
JH,H = 1.0 Hz, 1CHarom). 13C NMR: 97.8, 112.0 (CSel, C(4)); 126.1, 127.6, 127.8, 128.1,
128.2, 128.3, 128.5, 128.6, 129.1, 129.2, 129.4, 132.5 (18CHarom); 130.7, 132.2, 141.1, 143.5
(4Carom); 156.2 (C(5)). IR (KBr): 3085m, 3047m, 3018m, 3000s, 2958s, 1613m, 1489m,
1445s, 1264s, 1217m, 1144m, 1062s, 1027s, 967m, 808m, 755s, 698vs. Anal. calcd for
C25H18OSSe (445.43): C 67.41, H 4.07, S 7.20; found: C 67.36, H 4.22, S 7.21.
4.3.8. 2-(Furan-2-yl)-2,4,5-triphenyl-1,3-oxathiole (4i)
Pale-brown viscous oil; yield: 100 mg (26%). 1H NMR: 6.39–6.40 (m, 1CHarom); 6.49 (d,
JH,H = 3.3 Hz, 1CHarom); 7.17–7.22 (m, 1CHarom); 7.24–7.34 (m, 6CHarom); 7.38–7.47
(m, 6CHarom); 7.52–7.54 (m, 1CHarom); 7.69–7.72 (m, 2CHarom). 13C NMR: 93.6, 111.4
(CFur, C(4)); 110.2, 110.5, 126.2, 127.7, 127.9, 128.2, 128.3, 128.4, 128.5, 128.6, 129.1, 129.3
(18CHarom); 131.7, 132.2, 141.3, 141.7 (4Carom); 154.9 (C(5)). IR (KBr): 3061m, 3024m,
2956m, 1676m, 1627m, 1599m, 1491s, 1448s, 1223s, 1153s, 1063s, 1017m, 882m, 851m,
746vs, 700vs, 592m. Anal. calcd for C25H18O2S (382.47): C 78.51, H 4.74, S 8.38; found:
C 78.38, H 4.82, S 8.38.
4.3.9. 1-[2-Methyl-3-phenyl-3-(thiophen-2-yl)thiiran-2-yl]ethanone (5b)
Pale-orange crystals; m.p. 38.8–40.2°C; yield: 180 mg (66%). 1H NMR: 1.69, 1.72 (2CH3);
6.89–6.91 (m, 1CHarom); 6.99–7.01 (m, 1CHarom); 7.18–7.22 (m, 1CHarom); 7.27–7.34 (m,
3CHarom); 7.49–7.51 (m, 2CHarom). 13C NMR: 21.1, 28.8 (2CH3); 58.5, 60.7 (C(2),C(3));
=
126.2, 126.9, 127.9, 128.0, 128.4, 129.3 (8CHarom); 140.3, 145.2 (2Carom); 207.2 (C O).
IR (KBr): 3075m, 3063m, 2933m, 1685vs (C O), 1442s 1359s, 1347s, 1261s, 1233s, 1097m,
=
850m, 726s, 720s, 694s. Anal. calcd for C15H14OS2 (342.50): C 65.66, H 5.14, S 23.37; found:
C 65.54, H 5.58, S 23.41.

JOURNAL OF SULFUR CHEMISTRY
11
4.3.10. 1-[2-Methyl-3-phenyl-3-(selenophen-2-yl)thiiran-2-yl]ethanone (5c)
1
Pale-brown crystals; m.p. 42–44°C; yield: 160 mg (50%). H NMR: 1.70, 1.78 (2CH3);
7.14–7.16 (m, 2CHarom); 7.24–7.34 (m, 3CHarom); 7.48–7.50 (m, 2CHarom); 7.90 (dd,
JH,H = 5.1 Hz, JH,H = 2.0 Hz, 1CHarom). 13C NMR: 21.0, 28.8 (2CH3); 60.6, 60.8 (C(2),
C(3)); 128.1, 128.5, 129.2, 129.5, 130.0, 132.3 (8CHarom); 140.7, 152.4 (2Carom); 207.3
=
=
(C O). IR (KBr): 3060m, 3003m, 2920m, 1685vs (C O), 1492m, 1445m, 1356s, 1236s,
1097m, 1055m, 979m, 777m, 736s, 704s, 688s. Anal. calcd for C15H14OSSe (321.30):
C 56.07, H 4.39, S 9.98; found: C 56.30, H 4.73, S 9.98.
4.3.11. 3,3,4-Triphenyl-4-(thiophen-2-yl)thietan-2-one (6a)
Pale-yellow crystals; m.p. 145°C (dec) ([20]: 146°C (dec)); yield: 240 mg (60%). 1H NMR:
6.59 (dd, JH,H = 3.8 Hz, JH,H = 1.2 Hz, 1CHarom); 6.67 (dd, JH,H = 5.0 Hz, JH,H = 3.8 Hz,
1CHarom); 7.04–7.10 (m, 6CHarom); 7.21–7.28 (m, 8CHarom); 7.43–7.46 (m, 2CHarom). 13
C
NMR: 62.4, 94.2 (C(3),C(4)); 126.3, 126.9, 127.2, 127.6, 127.7, 127.9, 128.6, 129.2, 130.0,
=
130.2 (18 CHarom); 137.2, 138.5, 140.1, 150.8 (4 Carom); 193.5 (C O).
4.3.12. 3,3,4-Triphenyl-4-(selenophen-2-yl)thietan-2-one (6b)
Pale-yellow solid; m.p. 162°C (dec) ([20]: 163°C (dec)); yield: 250 mg (56%). 1H NMR: 6.75
(d, JH,H = 3.7 Hz, 1CHarom); 6.91 (dd, JH,H = 5.6 Hz, JH,H = 4.0 Hz, 1CHarom); 7.03–7.11
(m, 5CHarom); 7.21–7.29 (m, 8CHarom); 7.49–7.50 (m, 2CHarom); 7.79 (d, JH,H = 5.6 Hz,
1CHarom). 13C NMR: 64.3, 94.3 (C(3),C(4)); 127.2, 127.3, 127.6, 127.7, 127.8, 127.9 128.9,
129.0, 129.2, 130.0, 132.0, 133.1 (18CHarom); 137.2, 138.6, 140.7, 159.1 (4Carom); 193.6
=
(C O).
4.3.13. 4-(Furan-2-yl)-3,3,4-triphenylthietan-2-one (6c)
Pale-brown crystals; m.p. 146°C (dec); yield: 240 mg (63%). 1H NMR: 5.85 (d,
JH,H = 3.2 Hz, 1CHarom); 6.12 (dd, JH,H = 3.2 Hz, JH,H = 1.9 Hz, 1CHarom); 7.02–7.11
(m, 5CHarom); 7.19–7.22 (m, 3CHarom); 7.25–7.29 (m, 6CHarom); 7.46–7.48 (m, 2CHarom).
13C NMR: 60.0, 92.5 (C(3),C(4)); 110.2, 112.6, 127.0, 127.3, 127.4, 127.5, 127.6, 127.7,
=
127.9, 129.0, 130.2, 143.1 (18CHarom); 137.8, 138.2, 138.4, 154.8 (4Carom); 193.4 (C O). IR
(KBr): 3060m, 3025m, 1746vs (C O), 1609s, 1597m, 1486s, 1439s, 1198m, 1144m, 1049s,
=
1021m, 831s, 818s, 732vs, 691vs, 650m, 631m. Anal. calcd for C25H18O2S (382.47): C 78.51,
H 4.74, S 8.38; found: C 78.48, H 4.73 S 8.30.
4.3.14. 4-(4-Chlorophenyl)-4-(selenophen-2-yl)but-3-en-2-one (7a)
Beige crystals: m.p. 62–64°C: yield: 120 mg (39%). 1H NMR: 1.97 (CH3); 6.61 (s, 1CH); 7.06
(dd, JH,H = 3.9 Hz, JH,H = 1.0 Hz, 1CH); 7.24–7.29 (m, 3CH); 7.43–7.45 (m, 2CH); 8.09
(dd, JH,H = 5.5 Hz, JH,H = 1.2 Hz, 1CH). 13C NMR: 30.8 (CH3); 125.4, 128.7, 130.3, 130.8,
=
=
133.0, 134.1 (7CHarom, CH ); 134.9, 136.8, 148.2, 151.0 (3Carom, C ); 197.9 (C=O). IR
=
(KBr): 3104m, 2990m, 1679s (C O), 1594s, 1572s, 1486s, 1429m, 1375m, 1350m, 1214m,
1176s, 1090m, 1014s, 970m, 840s, 777s, 717s, 574s. Anal. calcd for C14H11ClOSe (309.65):
C 54.30, H 3.58; found: C 54.43, H 3.66.
4.3.15. (S)-1-(1-Benzoylpyrrolidin-2-yl)-3,3-di(thiophen-2-yl)prop-2-en-1-one (7e)
Yellow viscous oil; yield: 330 mg (85%); mixture of two rotamers in the ratio ca. 80:20;
according to ref. [22]. 1H NMR (major rotamer): 1.84–2.25 (m, CH2CH2); 3.52–3.85 (m,

12
G. MLOSTOŃ ET AL.
CH2N); 4.85–4.92 (m, CHN); 6.87 (s, CH ); 7.04–7.59 (m, 11CHarom). 13C NMR: 25.3
(CH2); 28.7 (CH2); 50.2 (CH2N); 65.3 (CHN); 121.7 (CH ); 126.8, 127.3, 127.7, 127.8,
=
=
=
128.2, 128.4, 130.0, 130.2, 130.4 (11CHarom); 136.4, 138.1, 141.1, 145.4 (3Carom; C ); 169.5
=
=
(C O); 196.9 (C O).
4.3.16. (S)-(1-Benzoylpyrrolidin-2-yl)-3,3-di(selenophen-2-yl)prop-2-en-1-one (7f)
Yellow viscous oil; yield: 380 mg (78%); mixture of two rotamers in the ratio ca. 80:20;
according to ref. [22]. 1H NMR (major rotamer): 1.81–2.20 (m, CH2CH2); 3.46–3.80 (m,
CH2); 4.81–4.85 (m, CHN); 6.78 (s, CH ); 7.06–8.20 (m, 11CHarom). 13C NMR: 25.3
(CH2); 29.9 (CH2); 49.8 (CH2N); 65.3 (CHN); 121.6 (CH ); 127.9, 128.6, 129.2, 129.0,
=
=
=
130.5, 132.4, 132.7, 133.9, 134.0 (11CHarom); 136.6, 144.2, 145.3, 151.7 (3Carom; C ); 169.5
=
=
(C O), 197.0 (C O).
4.3.17. 3-(4-Chlorophenyl)-1-phenyl-3-(selenophen-2-yl)prop-2-en-1-one (7g)
Brown-orange crystals; m.p. 142–144°; yield: 165 mg (44%). 1H NMR: 7.19–7.22 (m, 2CH);
7.30–7.34 (m, 1CH); 7.35–7.40 (m, 4CH); 7.55–7.64 (m, 5CH); 8.09 (dd, JH,H = 5.2 Hz,
JH,H = 1.6 Hz, 1CH). 13C NMR: 121.3, 128.3, 128.4, 128.5, 130.4, 130.8, 132.7, 132.8, 133.8
=
=
=
(12CHarom, CH ); 134.5, 137.1, 138.6, 149.6, 151.4 (4Carom, C ); 190.4 (C O). IR (KBr):
3101m, 3053m, 1647s (C O), 1568s, 1555s, 1486s, 1426m, 1385m, 1264m, 1220s, 1173m,
=
1087m, 1021s, 1011s, 907m, 780s, 723s, 691s, 631s. Anal. calcd for C19H13ClOSe (371.72):
C 61.39, H 3.53; found: C 61.37, H 3.56.
4.3.18. 1-Phenyl-3,3-di(thiophen-2-yl)prop-2-en-1-one (7h)
1
Yellow crystals; m.p. 82–84°C; yield: 230 mg (78%). H NMR: 6.98 (dd, JH,H = 5.0 Hz,
JH,H = 3.6 Hz, 1CH); 7.09 (dd, JH,H = 5.1 Hz, JH,H = 3.8 Hz, 1CH); 7.13 (s, 1CH); 7.16
(d, JH,H = 3.5 Hz, JH,H = 1.1 Hz, 1CH); 7.23 (d, JH,H = 3.8 Hz, JH,H = 1.1 Hz, 1CH);
7.35 (d, JH,H = 5.0 Hz, JH,H = 1.1 Hz, 1CH); 7.39–7.45 (m, 3CH); 7.45–7.51 (m, 1CH);
7.91 (d, JH,H = 1.2 Hz, 1CH); 7.93 (d, JH,H = 1.2 Hz, 1CH). 13C NMR: 122.8, 126.8, 127.8,
=
127.9, 128.0, 128.4, 128.6, 129.8, 130.2, 132.6 (11CHarom, CH ); 138.3, 138.8, 139.8, 145.0
=
=
=
(3Carom, C ); 191.9 (C O). IR (KBr): 3117m, 3094m, 3063m, 2920m, 1635s (C O); 1568s,
1524m, 1445m, 1432m, 1315m, 1268s, 1242m, 1109m, 1059m, 1021m, 853m, 831m, 777m,
729s, 707s. Anal. calcd for C17H12OS2 (296.41): C 68.89, H 4.08, S 21.64; found: C 68.89,
H 4.20, S 21.49.
4.3.19. 3-Methyl-4,4-di(thiophen-2-yl)but-3-en-2-one (7i)
1
Pale viscous oil; yield: 130 mg (52%). H NMR: 1.84, 2.09 (2CH3); 6.90, 6.98 (2d,
JH,H = 3.2 Hz, 2CHarom); 7.31 (m, CHarom). 13C NMR: 19.1, 29.3 (2CH3); 126.8, 127.1,
=
127.4, 128.3, 129.3, 130.0 (6CHarom); 129.6, 139.7, 142.5, 143.1 (2Carom, 2C ); 206.9
=
=
(C O). IR (KBr): 2952m, 2920m, 1673vs (C O), 1439s 1347m, 1277m, 1239m, 1179m,
1100m, 1033m, 983m, 856m, 840m, 770m, 685s. Anal. calcd for C13H12OS2 (248.36):
C 62.87, H 4.87, S 25.82; found: C 62.90, H 5.09, S 25.84.
4.3.20. 3-Methyl-4,4-di(selenophen-2-yl)but-3-en-2-one (7j)
Brown-orange crystals; m.p. 36.7–38.3°C; yield: 160 mg (47%). H NMR: 2.00, 2.14
1
(2CH3); 7.17–7.18 (m, 1CHarom); 6.21–7.23 (m, 1CHarom); 7.28–7.29 (m, 1CHarom);
7.30–7.32 (m, 1CHarom); 8.14 (dt, JH,H = 5.5 Hz, JH,H = 0.8 Hz, 2CHarom). 13C NMR:

JOURNAL OF SULFUR CHEMISTRY
13
19.2, 29.3 (2CH3); 129.2, 129.3, 131.1, 132.1, 133.3, 134.3 (6CHarom); 133.8, 138.4, 149.0,
=
=
=
149.9 (2Carom, 2C ); 207.2 (C O). IR (KBr): 3107m, 2958m, 2914m, 1676vs (C O),
1616m, 1578m, 1515m, 1420s 1353s, 1280m, 1239m, 1223m, 1100m, 1046m, 983m, 853m,
827m, 707s. Anal. calcd for C13H12OSe2 (342.15): C 45.63, H 3.54; found: C 45.44, H 3.65.
4.3.21. (Z,E)-2-Methyl-1,3-diphenyl-3-(selenophen-2-yl)prop-2-en-1-one (7n)
1
Beige solid; m.p. 116°C (dec.); yield: 130 mg (37%). H NMR: 2.06, 2.30 (2CH3); 6.94
(dd, JH,H = 5.6 Hz, JH,H = 3.8 Hz, CHarom); 6.99 (dd, JH,H = 3.8 Hz, JH,H = 0.7 Hz,
CHarom); 7.06–7.08 (m, CHarom); 7.12–7.15 (m, CHarom); 7.24–7.27 (m, CHarom); 7.34 (dd,
JH,H = 5.6 Hz, JH,H = 3.8 Hz, CHarom); 7.37–7.50 (m, CHarom); 7.73 (dd, JH,H = 5.6 Hz,
JH,H = 1.1 Hz, CHarom); 7.80 (dd, JH,H = 5.6 Hz, JH,H = 1.1 Hz, CHarom); 7.85–7.87
(m, CHarom); 7.92 (dd, JH,H = 5.6 Hz, JH,H = 0.7 Hz, CHarom); 8.22 (dd, JH,H = 5.6 Hz,
JH,H = 0.7 Hz, CHarom). 13C NMR: 19.8 (CH3); 20.2 (CH3); 127.7, 127.9, 128.1, 128.2,
128.4, 128.5, 129.0, 129.1, 129.2, 129.4, 130.1, 131.2, 131.4, 132.5, 133.0, 133.1 (26CHarom);
=
134.2, 134.8, 135.9, 137.0, 137.7, 138.5, 141.1, 141.4, 149.1, 150.0 (6Carom, 4C ); 200.6,
=
=
201.0 (2C O). IR (KBr): 3091m, 3053m, 2939m, 2914m, 1651s (C O), 1594m, 1578m,
1448m, 1309m, 1245m, 1217m, 1157m, 1005m, 948m, 783m, 701vs, 641m. Anal. calcd. for
C20H16OSe (351.30): C 68.38, H 4.59; found C 68.06, H 4.57.
4.3.22. 2-Methyl-1-phenyl-3,3-di(thiophen-2-yl)prop-2-en-1-one (7o)
1
Beige crystals; m.p. 115–117°C; yield: 240 mg (77%). H NMR: 2.32 (s, CH3); 6.71
(dd, JH,H = 5.4 Hz, JH,H = 3.6 Hz, 1CHarom); 6.88 (dd, JH,H = 3.6 Hz, JH,H = 1.0 Hz,
1CHarom); 7.11–7.14 (m, 2CHarom); 7.18 (dd, JH,H = 3.5 Hz, JH,H = 1.1 Hz, 1CHarom);
7.34–7.37 (m, 2CHarom); 7.44–7.47 (m, 2CHarom); 7.83–7.85 (m, 2CHarom)
13C NMR: 20.2
(CH3); 126.5, 126.8, 126.9, 127.5, 128.3, 129.0, 129.1, 129.7, 132.8 (11CHarom); 132.8, 136.2,
=
=
137.0, 142.1, 143.0 (3Carom, 2C ); 200.2 (C O). IR (KBr): 3069m, 2946m, 2914m, 1651s
(C O), 1597m, 1575m, 1445m, 1366m, 1312s, 1249s, 1176m, 989s, 840m, 827m, 732s, 723s,
=
704vs, 647s. Anal. calcd for C18H14OS2 (310.43): C 69.64, H 4.55, S 20.66; found: C 69.62,
H 4.63, S 20.58.
4.3.23. 2-Methyl-1-phenyl-3,3-di(selenophen-2-yl)prop-2-en-1-one (7p)
Pale-brown crystals; m.p. 112–114°C; yield: 140 mg (35%). 1H NMR: 2.27 (s, CH3); 6.94
(dd, JH,H = 5.6 Hz, JH,H = 3.8 Hz, 1CHarom); 7.06 (dd, JH,H = 3.8 Hz, JH,H = 1.0 Hz,
1CHarom); 7.34–7.39 (m, 4CHarom); 7.46–7.48 (m, 1CHarom); 7.83–7.85 (m, 3CHarom);
8.16 (dd, JH,H = 5.6 Hz, JH,H = 1.0 Hz, 1CHarom). 13C NMR: 20.3 (CH3); 128.4, 128.9,
129.0, 129.3, 130.8, 131.8, 132.8, 132.9, 133.5 (11CHarom); 133.1, 135.6, 136.1, 148.6, 149.8,
=
=
=
(3Carom, 2C ); 200.4 (C O). IR (KBr): 3091m, 3075m, 3056m, 1647vs (C O), 1591m,
1578m, 1448m, 1435m, 1312m, 1280s, 1242m, 1169m, 983s, 846m, 834m, 774m, 704vs,
653m. Anal. calcd for C18H14OSe2 (404.22): C 53.48, H 3.49; found: C 53.06, H 3.70.
4.3.24. 3-(4-Chlorophenyl)-3-(selenophen-2-yl)-1-(thiophen-2-yl)prop-2-en-1-one
(7q)
Brown crystals; m.p. 169°C (dec.); yield: 210 mg (56%). 1H NMR: 7.16 (dd, JH,H = 5.0 Hz,
JH,H = 3.9 Hz, 1CH); 7.20 (dd, JH,H = 3.9 Hz, JH,H = 1.0 Hz, 1CH); 7.28–7.31 (m,
4CH); 7.38–7.41 (m, 2CH); 7.64 (dd, JH,H = 5.0 Hz, JH,H = 1.0 Hz, 1CH); 7.78 (dd,
JH,H = 3.9 Hz, JH,H = 1.0 Hz, 1CH); 8.14 (dd, JH,H = 5.6 Hz, JH,H = 1.0 Hz, 1CH). 13
C

14
G. MLOSTOŃ ET AL.
=
NMR: 119.7, 128.2, 128.4, 130.3, 130.9, 131.5, 133.0, 133.7, 134.2 (9CHarom, CH ); 134.5,
=
=
=
137.0, 146.5, 150.1, 151.4 (4Carom, C ); 181.5 (C O). IR (KBr): 3094m, 1628s (C O),
1556s, 1483s, 1426m, 1413s, 1353m, 1350m, 1271m, 1226s, 1204m, 1055m, 986m, 891m,
853m, 834m, 720s, 634s. Anal. calcd for C17H11ClOSSe (377.75): C 54.05, H 2.94, S 8.49;
found: C 54.08, H 3.12, S 8.53.
4.3.25. 2-[Di(thiophen-2-yl)methylene]acenaphthylen-1-one (7r)
1
Orange crystals; m.p. 80–82°C; yield: 300 mg (87%). H NMR: 6.62 (d, JH,H = 7.3 Hz,
1CH); 7.15 (dd, JH,H = 5.0 Hz, JH,H = 3.8 Hz, 1CH); 7.22 (dd, JH,H = 5.1 Hz,
JH,H = 3.7 Hz, 1CH); 7.30 (dd, JH,H = 3.4 Hz, JH,H = 1.0 Hz, 1CH); 7.39 (t, JH,H = 7.4 Hz,
1CH); 7.59 (dd, JH,H = 5.2 Hz, JH,H = 0.7 Hz, 1CH); 7.61–7.63 (m, 2CH); 7.73 (t,
JH,H = 7.2 Hz, 1CH); 7.78 (d, JH,H = 8.3 Hz, 1CH); 8.03 (d, JH,H = 7.0 Hz, 1CH); 8.07
(d, JH,H = 8.2 Hz, 1CH). 13C NMR: 120.7, 121.4, 125.0, 127.0, 127.4, 127.8, 128.2, 128.6,
129.7, 130.6, 131.0, 133.5 (12CHarom); 130.0, 131.7, 133.3, 135.6, 136.2, 138.5, 142.0, 143.1
=
=
=
(6Carom, 2C ); 190.8 (C O). IR (KBr): 3078m, 3047m, 1687s (C O), 1622m, 1599m,
1547s, 1516s, 1489s 1457m, 1409s, 1359s, 1338s, 1270s, 1254s, 1222s, 1156m, 1135m,
1092m, 1024vs, 914s, 850s, 828s, 796s, 777s, 717s, 706s, 647m, 624m. Anal. calcd for
C21H12OS2 (344.45): C 73.23, H 3.51, S 18.62; found: C 73.35, H 3.52, S 18.58.
4.3.26. Phenyl-[4-phenyl-6-(thiophen-2-yl)-4,6-dihydrothieno[3,4-b]thiophen-4-
yl]methanone (8)
1
Pink crystals; m.p. 152°C (dec.); yield: 195 mg (48%). H NMR: 5.60 (s, 1CH); 6.22 (d,
JH,H = 5.2 Hz, 1CH); 6.87–6.88 (m, 2CH); 7.00 (dd, JH,H = 5.1 Hz, JH,H = 3.7 Hz, 1CH);
7.09 (d, JH,H = 5.2 Hz, 1CH); 7.11–7.13 (m, 2CH); 7.16 (d, JH,H = 3.3 Hz, 1CH); 7.27–7.29
(m, 3CH); 7.36 (d, JH,H = 5.1 Hz, 1CH); 7.40–7.43 (m, 3CH). 13C NMR: 42.2 (CH);
70.2 (Cq–Ph); 123.3, 126.8, 126.9, 127.4, 127.8, 128.3, 128.5, 128.9, 130.0, 130.1, 130.8
=
(15CHarom); 137.2, 139.4, 139.5, 141.3, 142.8 (5Carom); 203.5 (C O). IR (KBr): 3063m,
3022m, 2923m, 1682s (C O), 1594m, 1496m, 1445m, 1233m, 1040m, 995m, 834m, 742m,
=
726m, 694s, 634m. Anal. calcd for C23H16OS3 (404.57): C 68.28, H 3.99, S 23.78; found:
C 68.26, H 4.11, S 23.55.
4.4. Reactions of α-diazoketones 1b,c with ferrocenyl-substituted thioketones
2d–f – general procedure
To the solution of a thioketone 2 (1 mmol) in THF (10 mL), the corresponding α-
diazoketone 1 (1 mmol) and a catalytic amount of LiClO4 were added. The mixture was
heated at reflux overnight. Then, the solvent was evaporated and the crude product was
purified by FCC (petroleum ether/CH2Cl2 2:8).
4.4.1. 4-Ferrocenyl-4-phenylbut-3-en-2-one (7b)
Red crystals; m.p. 78.8–80.7°C; yield: 185 mg (56%). H NMR: 1.73 (s, CH3); 4.19 (s,
1
=
5CH(Fc)); 4.33 (brs, 2CH(Fc)); 4.43 (brs, 2CH(Fc)); 6.54 (brs, CH ); 7.28–7.31 (m,
2CHarom); 7.41–7.48 (m, 3CHarom). 13C NMR: 30.2 (CH3); 68.5, 70.9 (4CH(Fc)); 69.9
=
(5CH(Fc)); 83.9 (C(Fc)); 124.2, 128.1, 128.4 (6CHarom); 138.9, 156.7 (Carom, C ); 199.0
=
(C O). IR (KBr): 3098m, 3088m, 1635vs, 1578vs, 1489m, 1435m, 1378m, 1356s, 1271vs,

JOURNAL OF SULFUR CHEMISTRY
15
1204m, 1154m, 1106m, 1055m, 998m, 941m, 843m, 821s, 720s, 704s, 603w, 489s. Anal.
calcd for C20H18FeO (330.20): C 72.75, H 5.49; found: C 72.56, H 5.48.
4.4.2. 4-Ferrocenyl-4-(thiophen-2-yl)but-3-en-2-one (7c)
1
Red crystals; m.p. 106.2–108.7°C; yield: 218 mg (65%). H NMR: 1.88 (s, CH3); 4.23 (s,
=
5CH(Fc)); 4.41–4.42 (m, 2CH(Fc)); 4.43–4.44 (m, 2CH(Fc)); 6.56 (brs, CH ); 7.03–7.05
(m, 1CHarom); 7.10 (dd, JH,H = 3.6 Hz, JH,H = 4.8 Hz, 1CHarom); 7.47 (d, JH,H = 5.4 Hz,
1CHarom). 13C NMR: 29.5 (CH3); 68.5, 70.9 (4CH(Fc)); 70.2 (5CH(Fc)); 84.1 (C(Fc));
=
=
=
126.4, 126.8, 126.9, 128.7 (3CHarom, CH ); 138.3, 148.2 (Carom, C ); 199.2 (C O). IR
(KBr): 3077w, 3066w, 1628vs, 1584s, 1521m, 1451w, 1451w, 1363m, 1271vs, 1204w, 1103w,
1002w, 929w, 840w, 818m, 707m, 501m. Anal. calcd for C18H16FeOS (336.23): C 64.30,
H 4.80, S 9.54; found: C 64.28, H 4. 85, S 9.51.
4.4.3. 4-Ferrocenyl-4-(selenophen-2-yl)but-3-en-2-one (7d)
1
Red crystals; m.p. 107.9–111.0°C; yield: 241 mg (63%). H NMR: 1.96 (s, CH3); 4.34 (s,
=
5CH(Fc)); 4.51–4.64 (m, 4CH(Fc)); 6.51 (brs, 1CH ); 7.15 (brs, 1CHarom); 7.31 (brs,
1CHarom); 8.15 (d, JH,H = 4.8 Hz, 1CHarom). 13C NMR: 29.7 (CH3); 68.6, 70.8 (4CH(Fc));
=
70.1 (5CH(Fc)); 84.1 (C(Fc)); 125.6, 129.1, 131.0, 132.9 (3CHarom, CH ); 144.1, 150.4
=
=
(Carom, C ); 199.4 (C O). IR (KBr): 3104m, 3091m, 1638vs, 1591s, 1534m, 1464m, 1416m,
1366m, 1271vs, 1220m, 1201m, 1106m, 1002m, 843m, 824m, 793m, 704s. Anal. calcd for
C18H16FeOSe (383.12): C 56.43, H 4.21; found: C 56.24, H 4.23.
4.4.4. 3-Ferrocenyl-1,3-diphenylprop-2-en-1-one (7k)
1
Red crystals; m.p. 99.0–101.5°C; yield: 192 mg (49%). H NMR: 4.23 (s, 5CH(Fc));
=
4.43–4.46 (m, 4CH(Fc)); 7.23 (brs, CH ); 7.29–7.36 (m, 5CHarom); 7.37–7.41 (m,
2CHarom); 7.46–7.50 (m, 1CHarom); 7.86–7.88 (m, 2CHarom). 13C NMR: 68.6, 70.8
(4CH(Fc)); 70.0 (5CH(Fc)); 84.2 (C(Fc)); 118.6, 127.6, 127.7, 128.2, 128.3, 128.4, 132.1
=
=
=
(10CHarom, CH ); 139.1, 139.3, 157.7 (2Carom, C ); 190.7 (C O). IR (KBr): 3055w,
3033w, 3011w, 1638m, 1591m, 1578s, 1562vs, 1489m, 1445s, 1391m, 1277m, 1220s, 1100m,
1030m, 1014s, 964m, 818m, 767m, 717m, 694s, 631s, 476s. Anal. calcd for C25H20FeO
(392.27): C 76.55, H 5.14; found: C 76.44, H 5.16.
4.4.5. 3-Ferrocenyl-1-phenyl-3-(thiophen-2-yl)prop-2-en-1-one (7l)
Red crystals; m.p. 114.2–116.9°C; yield: 192 mg (61%). 1H NMR: 4.33 (s, 5CH(Fc)); 4.50
=
(brs, 2CH(Fc)); 4.59 (brs, 2CH(Fc)); 6.90 (brs, CH ); 7.00 (brs, 1CHarom); 7.07 (brs,
1CHarom); 7.28–7.48 (m, 4CHarom); 7.84 (d, JH,H = 6.6 Hz, 2CHarom). 13C NMR: 68.5,
70.7 (4CH(Fc)); 70.2 (5CH(Fc)); 84.4 (C(Fc)); 121.5, 126.4, 126.5, 128.1, 128.4, 128.7,
=
=
=
132.1 (8CHarom, CH ); 138.8, 148.1 (Carom, C ); 192.1 (C O). IR (KBr): 1635vs, 1575m,
1524w, 1445w, 1315w, 1274m, 1103w, 1062w, 1033w, 998w, 824m, 710m, 495m. Anal. calcd
for C23H18FeOS (398.30): C 69.36, H 4.56, S 8.05; found: C 69.34, H 4.55, S 8.26.
4.4.6. 3-Ferrocenyl-1-phenyl-3-(selenophen-2-yl)prop-2-en-1-one (7m)
Red crystals; m.p. 95.6–98.7°C; yield: 235 mg (53%). 1H NMR: 4.30 (s, 5CH(Fc)); 4.47 (brs,
=
2CH(Fc)); 4.60 (brs, 2CH(Fc)); 7.11 (brs, CH ); 7.15 (dd, JH,H = 3.6 Hz, JH,H = 5.4 Hz,
1CHarom); 7.17–7.19 (m, 1CHarom); 7.35–7.40 (m, 2CHarom); 7.44–7.48 (m, 1CHarom);
7.87 (d, JH,H = 7.2 Hz, 2CHarom); 8.02 (d, JH,H = 5.4 Hz, 1CHarom). 13C NMR: 68.8, 70.5

16
G. MLOSTOŃ ET AL.
(4CH(Fc)); 70.1 (5CH(Fc)); 84.7 (C(Fc)); 120.8, 128.2, 128.4, 128.8, 131.2, 132.1, 132.5
=
=
=
(8CHarom, CH ); 138.9, 144.7, 150.3 (2Carom, C ); 192.1 (C O). IR (KBr): 3082w, 3053w,
3025w, 1632vs, 1594m, 1568s, 1530m, 1442m, 1315m, 1274s, 1223m, 1176w, 1103m,
1062m, 1033m, 998m, 859s, 821s, 767s, 704vs, 660w, 599w, 501s, 482m. Anal. calcd for
C23H18FeOSe (445.19): C 62.05, H 4.08; found: C 61.96, H 4.06.
Acknowledgements
Skillful performance of elemental analysis of all new compounds by Ms Agnieszka Cieślińska and
Ms Hanna Jatczak (University of Łódź) is gratefully acknowledged. The authors thank also Ms
Małgorzata Celeda for her help in preparation of diverse starting materials explored in this study.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
The authors thank the National Science Center (Cracow, Poland) for generous financial support
(Grant Maestro-3 (Dec-2012/06/A/ST5/00219)).
References
[1] Huisgen R, Fluka C, Kalwinsch I, et al. Recent developments of the chemistry of thiocarbonyl
ylides. Bull Soc Chim Belg. 1984;93:511–532.
[2] Mlostoń G, Heimgartner H. Generation and typical reactions of thiocarbonyl ylides. Pol J
Chem. 2000;74:1503–1532.
[3] Mlostoń G, Heimgartner H. In: Padwa A, Pearson WH, editors. 1,3-Dipolar cycloaddition
chemistry towards heterocycles and natural products. New York (NY): Wiley; 2002. p. 315–360.
[4] Mlostoń G, Urbaniak K, Linden A, et al. Selenophen-2-yl-substituted thiocarbonyl ylides – at
the borderline of dipolar and biradical reactivity. Helv Chim Acta. 2015;98:453–461.
[5] McKee ML, Mlostoń G, Urbaniak K, et al. Dimerization reactions of aryl selenophen-2-yl-
substituted thiocarbonyl S-methanides as diradical processes: a computational study. Beilstein
J Org Chem. 2017;13:410–416.
[6] Mlostoń G, Urbaniak K, Pawlak A, et al. New applications of hetaryl thioketones for
the synthesis of hetaryl-substituted ethenes via ‘two-fold extrusion reaction’. Heterocycles.
2016;93:127–139.
[7] Huisgen R. 1,3-Dipolar cycloaddition. Past and future. Angew Chem Int Ed Engl.
1963;2:565–598.
[8] Sustmann R. Rolf Huisgen’s contribution to organic chemistry, emphasizing 1,3-dipolar
cycloadditions. Heterocycles. 1995;40:1–18.
[9] Padwa A, Hornbuckle S. Ylide formation from the reaction of carbenes and carbenoids with
heteroatom lone pairs. Chem Rev. 1991;91:263–309.
[10] Mereshchenko AS, Ivanov AV, Baranovski VI, et al. On the strong difference in reactivity of
acyclic and cyclic diazoketones with thioketones: experimental results and quantum-chemical
interpretation. Beilstein J Org Chem. 2015;11:504–513.
[11] Appukkuttan P, Mehta VP, Van der Eycken EV. Microwave-assisted cycloaddition reactions.
Chem Soc Rev. 2010;39:1467–1477.
[12] Bougrin K, Benhida R. In: de la Hoz A, Loupy A, editors. Micowaves in organic synthesis. 3rd
ed. Vol. 2. Weinheim: Wiley VCH; 2013, p. 737–810.
[13] Kägi M, Linden A, Mlostoń G, et al. 1,3-Oxathiole and thiirane derivatives from the reac-
tions of azibenzil and α-diazo amides with thiocarbonyl compounds. Helv Chim Acta.
1998;81:285–302.

JOURNAL OF SULFUR CHEMISTRY
17
[14] Nikolaev VA, Ivanov AV, Shakhim AA, et al. The first examples of cycloadditions of 2-diazo-
1,3-dicarbonyl compounds to aromatic thioketones. Tetrahedron Lett. 2012;53:3095–3099.
[15] Nikolaev VA, Ivanov AV, Rodina LL, et al. Less reactive dipoles of diazocarbonyl compounds
in reaction with cycloaliphatic thioketones - first evidence for the 1,3-oxathiole–thiocarbonyl
ylide interconversion. Beilstein J Org Chem. 2013;9:2751–2761.
[16] Villalgordo JM, Enderli A, Linden A, et al. Diazo-transfer reaction with diphenyl phosphorazi-
date. Helv Chim Acta. 1995;78:1983–1998.
[17] Mlostoń G, Heimgartner H. Synthesis of five-membered sulfur-heterocycles via 1,5-
dipolar electrocyclization of thiocarbonyl ylides and related processes. Curr Org Chem.
2011;15:675–693.
[18] Kelmendi B, Mlostoń G, Heimgartner H. Reactions of α-diazocycloalkanones with thiocar-
bonyl compounds. Heterocycles. 2000;52:475–482.
[19] Mlostoń G, Grzelak P, Hamera-Fałdyga R, et al. Aryl, hetaryl, and ferrocenyl thioketones as
versatile building blocks for exploration in the organic chemistry of sulfur. Phosphorus Sulfur
Silicon Relat Elem. 2017;192:204–211.
[20] Mlostoń G, Urbaniak K, Szychowska A, et al. Thermal [2+2]-cycloadditions of diphenylketene
with aryl- and hetaryl-substituted thioketones. Heterocycles. 2015;90:529–539.
[21] Guziec FS, Sanfilippo LY. Synthetically useful extrusion reactions of organic sulfur, selenium
and tellurium compounds. Tetrahedron. 1988;44:6241–6285.
[22] Mlostoń G, Pipiak P, Linden A, et al. 1,3-Dipolar cycloadditions of α-diazo ketones derived
from N-protected (S)-proline with aromatic and cycloaliphatic thioketones. Helv Chim Acta.
2015;98:190–200.
[23] Zhang C, Zhu X. Thieno[3,4-b]thiophene-based novel small-molecule optoelectronic materi-
als. Acc Chem Res. 2017;50:1342–1350.
[24] Staudinger H, Gaule A. Vergleich der Stickstoff-Abspaltung bei verschiedenen aliphatischen
Diazoverbindungen. Ber Deutsch Chem Ges. 1916;49:1897–1918.
[25] Haiss P, Zeller K-P. Teilweise Sauerstoff-Wanderung in der photochemischen Wolff-
Umlagerung – α-Oxocarben–Oxiren-Isomerisierung oder intermolekularer Mechanismus? Z
Naturforsch B. 2003;58b:595–605.
[26] Mlostoń G, Urbaniak K, Gębicki K, et al. Hetaryl thioketones: synthesis and selected reactions.
Heteroatom Chem. 2014;25:548–555.
[27] Mlostoń G, Hamera R, Heimgartner H. Synthesis of ferrocenyl thioketones and their reactions
with diphenyldiazomethane. Phosphorus Sulfur Silicon Relat Elem. 2015;190:2125–2133.