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Polysulfur- and Sulfur-Nitrogen Heterocycles

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 25719

Special Issue Editor

N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, 47 Leninsky Prospekt, 119991 Moscow, Russia
Interests: heterocyclic chemistry; sulfur-nitrogen heterocycles; selenium heterocycles; synthetic methods; biologically active compounds; organic sensitizers for DSSCs and OLEDs; 1,2,3-dithiazoles; 1,2,5-thiadiazoles; 1,2,5-oxadiazoles; disulfur dichloride
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Heterocyclic chemistry is a vast and important subject. Many different heterocyclic systems have now been explored. In the last century, a family of the structures at the borderline between organic and inorganic chemistry, which are characterized by an unusually high ratio of heteroatoms (sulfur and nitrogen) to carbon, was discovered. It turned out that these structures can be of practical interest as semiconductors, liquid crystals, and agrochemical, antimicrobial, antivirus, and similar objects. This Special Issue will focus on the advances in the synthesis, reactivity, and uses of polysulfur- and sulfur-nitrogen heterocycles.

Prof. Dr. Oleg A. Rakitin
Guest Editor

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Keywords

  • heterocycles
  • synthetic methods
  • medicinal, photovoltaic materials
  • reactivity
  • computational applications

Published Papers (10 papers)

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Research

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22 pages, 6470 KiB  
Article
Synthesis and Evaluation of Novel 1,2,6-Thiadiazinone Kinase Inhibitors as Potent Inhibitors of Solid Tumors
by Andreas S. Kalogirou, Michael P. East, Tuomo Laitinen, Chad D. Torrice, Kaitlyn A. Maffuid, David H. Drewry, Panayiotis A. Koutentis, Gary L. Johnson, Daniel J. Crona and Christopher R. M. Asquith
Molecules 2021, 26(19), 5911; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26195911 - 29 Sep 2021
Cited by 4 | Viewed by 2011
Abstract
A focused series of substituted 4H-1,2,6-thiadiazin-4-ones was designed and synthesized to probe the anti-cancer properties of this scaffold. Insights from previous kinase inhibitor programs were used to carefully select several different substitution patterns. Compounds were tested on bladder, prostate, pancreatic, breast, [...] Read more.
A focused series of substituted 4H-1,2,6-thiadiazin-4-ones was designed and synthesized to probe the anti-cancer properties of this scaffold. Insights from previous kinase inhibitor programs were used to carefully select several different substitution patterns. Compounds were tested on bladder, prostate, pancreatic, breast, chordoma, and lung cancer cell lines with an additional skin fibroblast cell line as a toxicity control. This resulted in the identification of several low single digit micro molar compounds with promising therapeutic windows, particularly for bladder and prostate cancer. A number of key structural features of the 4H-1,2,6-thiadiazin-4-one scaffold are discussed that show promising scope for future improvement. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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18 pages, 5941 KiB  
Article
Crystal Structure and Solid-State Packing of 4-Chloro-5H-1,2,3-dithiazol-5-one and 4-Chloro-5H-1,2,3-dithiazole-5-thione
by Christos P. Constantinides, Maria Koyioni, Fadwat Bazzi, Maria Manoli, Daniel B. Lawson and Panayiotis A. Koutentis
Molecules 2021, 26(19), 5875; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26195875 - 28 Sep 2021
Cited by 3 | Viewed by 1457
Abstract
The crystal structure and solid-state packing of 4-chloro-5H-1,2,3-dithiazol-5-one and two polymorphs of 4-chloro-5H-1,2,3-dithiazole-5-thione were analyzed and compared to structural data of similar systems. These five-membered S,N-rich heterocycles are planar with considerable bond localization. All three structures demonstrate tight solid-state [...] Read more.
The crystal structure and solid-state packing of 4-chloro-5H-1,2,3-dithiazol-5-one and two polymorphs of 4-chloro-5H-1,2,3-dithiazole-5-thione were analyzed and compared to structural data of similar systems. These five-membered S,N-rich heterocycles are planar with considerable bond localization. All three structures demonstrate tight solid-state packing without voids which is attributed to a rich network of short intermolecular electrostatic contacts. These include Sδ+…Nδ−, Sδ+…Oδ−, Sδ+…Clδ− and Sδ+…Sδ− interactions that are well within the sum of their van der Waals radii (∑VDW). B3LYP, BLYP, M06, mPW1PW, PBE and MP2 were employed to calculate their intramolecular geometrical parameters, the Fukui condensed functions to probe their reactivity, the bond order, Bird Index and NICS(1) to establish their aromaticity. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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14 pages, 3106 KiB  
Article
Efficient Regioselective Synthesis of Novel Condensed Sulfur–Nitrogen Heterocyclic Compounds Based on Annulation Reactions of 2-Quinolinesulfenyl Halides with Alkenes and Cycloalkenes
by Vladimir A. Potapov, Roman S. Ishigeev and Svetlana V. Amosova
Molecules 2021, 26(16), 4844; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26164844 - 10 Aug 2021
Cited by 2 | Viewed by 1523
Abstract
The preparation of novel reagents 2-quinolinesulfenyl chloride and bromide based on available 2-mercaptoquinoline has been described. This approach opens up opportunities for the introduction of 2-quinolinesulfenyl chloride and bromide into organic synthesis. Regioselective synthesis of novel 1,2-dihydro[1,3]thiazolo[3,2-a]quinolin-10-ium derivatives in high yields [...] Read more.
The preparation of novel reagents 2-quinolinesulfenyl chloride and bromide based on available 2-mercaptoquinoline has been described. This approach opens up opportunities for the introduction of 2-quinolinesulfenyl chloride and bromide into organic synthesis. Regioselective synthesis of novel 1,2-dihydro[1,3]thiazolo[3,2-a]quinolin-10-ium derivatives in high yields has been developed by annulation reactions of 2-quinolinesulfenyl chloride and bromide with alkenes. Condensed tetracyclic products have been obtained by the reactions of 2-quinolinesulfenyl chloride and bromide with cycloalkenes. The opposite regiochemistry in the reactions with styrene, isoeugenol and 1-alkenes was discussed. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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13 pages, 4330 KiB  
Article
Novel D-A-D Fluorescent Dyes Based on 9-(p-Tolyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole as a Donor Unit for Solution-Processed Organic Light-Emitting-Diodes
by Vladislav M. Korshunov, Maxim S. Mikhailov, Timofey N. Chmovzh, Andrey A. Vashchenko, Nikita S. Gudim, Lyudmila V. Mikhalchenko, Ilya V. Taydakov and Oleg A. Rakitin
Molecules 2021, 26(10), 2872; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26102872 - 12 May 2021
Cited by 9 | Viewed by 2324
Abstract
New fluorescent D-A-D dyes containing 9-(p-tolyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole as a donor unit and 2,1,3-benzochalcogenadiazoles as an electron-withdrawing group were synthesized. The photoluminescent and electroluminescent properties of novel dyes for fluorescent OLED application were investigated. It was demonstrated that the replacement of [...] Read more.
New fluorescent D-A-D dyes containing 9-(p-tolyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole as a donor unit and 2,1,3-benzochalcogenadiazoles as an electron-withdrawing group were synthesized. The photoluminescent and electroluminescent properties of novel dyes for fluorescent OLED application were investigated. It was demonstrated that the replacement of lightweight heteroatoms by heavier ones enables the fine tuning of the maximum emission without significantly reducing the luminescence quantum yield. The maximum quantum yield value of 62.6% for derivatives based on 2,1,3-benzoxadiazole (1a) in cyclohexane was achieved. Two devices with the architecture of glass/ITO/PEDOT-PSS/poly-TPD/EML/TPBi/LiF/Al (EML = emitting layer) were fabricated to check the suitability of the synthesized compounds as a single active emission layer in OLED. These OLEDs exhibited clear red electroluminescence of the dyes with the maximum current efficiency of 0.85 Cd/A. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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20 pages, 2394 KiB  
Article
The Fluoride Anion-Catalyzed Sulfurization of Thioketones with Elemental Sulfur Leading to Sulfur-Rich Heterocycles: First Sulfurization of Thiochalcones
by Grzegorz Mlostoń, Jakub Wręczycki, Katarzyna Urbaniak, Dariusz M. Bieliński and Heinz Heimgartner
Molecules 2021, 26(4), 822; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26040822 - 05 Feb 2021
Cited by 5 | Viewed by 2345
Abstract
Fluoride anion was demonstrated as a superior activator of elemental sulfur (S8) to perform sulfurization of thioketones leading to diverse sulfur-rich heterocycles. Due to solubility problems, reactions must be carried out either in THF using tetrabutylammonium fluoride (TBAF) or in DMF [...] Read more.
Fluoride anion was demonstrated as a superior activator of elemental sulfur (S8) to perform sulfurization of thioketones leading to diverse sulfur-rich heterocycles. Due to solubility problems, reactions must be carried out either in THF using tetrabutylammonium fluoride (TBAF) or in DMF using cesium fluoride (CsF), respectively. The reactive sulfurizing reagents are in situ generated, nucleophilic fluoropolysulfide anions FS(8−x), which react with the C=S bond according to the carbophilic addition mode. Dithiiranes formed thereby, existing in an equilibrium with the ring-opened form (diradicals/zwitterions) are key-intermediates, which undergo either a step-wise dimerization to afford 1,2,4,5-tetrathianes or an intramolecular insertion, leading in the case of thioxo derivatives of 2,2,4,4-tetramethylcyclobutane-1,3-dione to ring enlarged products. In reactions catalyzed by TBAF, water bounded to fluoride anion via H-bridges and forming thereby its stable hydrates is involved in secondary reactions leading, e.g., in the case of 2,2,4,4-tetramethyl-3-thioxocyclobutanone to the formation of some unexpected products such as the ring enlarged dithiolactone and ring-opened dithiocarboxylate. In contrast to thioketones, the fluoride anion catalyzed sulfurization of their α,β-unsaturated analogues, i.e., thiochalcones is slow and inefficient. However, an alternative protocol with triphenylphosphine (PPh3) applied as a catalyst, offers an attractive approach to the synthesis of 3H-1,2-dithioles via 1,5-dipolar electrocyclization of the in situ-generated α,β-unsaturated thiocabonyl S-sulfides. All reactions occur under mild conditions and can be considered as attractive methods for the preparation of sulfur rich heterocycles with diverse ring-size. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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12 pages, 1896 KiB  
Article
Synthesis and Physicochemical Properties of 2,7-Disubstituted Phenanthro[2,1-b:7,8-b’]dithiophenes
by Zhenfei Ji, Zeliang Cheng, Hiroki Mori and Yasushi Nishihara
Molecules 2020, 25(17), 3842; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25173842 - 24 Aug 2020
Cited by 1 | Viewed by 2019
Abstract
We report the design, synthesis, and physicochemical properties of an array of phenanthro[2,1-b:7,8-b’]dithiophene (PDT-2) derivatives by introducing five types of alkyl (CnH2n+1; n = 8, 10, 12, 13, and 14) or two types of decylthienyl [...] Read more.
We report the design, synthesis, and physicochemical properties of an array of phenanthro[2,1-b:7,8-b’]dithiophene (PDT-2) derivatives by introducing five types of alkyl (CnH2n+1; n = 8, 10, 12, 13, and 14) or two types of decylthienyl groups at 2,7-positions of the PDT-2 core. Systematic investigation revealed that the alkyl length and the type of side chains have a great effect on the physicochemical properties. For alkylated PDT-2, the solubility was gradually decreased as the chain length was increased. For instance, C8-PDT-2 exhibited the highest solubility (5.0 g/L) in chloroform. Additionally, substitution with 5-decylthienyl groups showed poor solubility in both chloroform and toluene, whereas PDT-2 with 4-decylthienyl groups resulted in higher solubility. Furthermore, UV-vis absorption of PDT-2 derivatives substituted by decylthienyl groups showed a redshift, indicating the extension of their π-conjugation length. This work reveals that modification of the conjugated core by alkyl or decylthienyl side chains may be an efficient strategy by which to change the physicochemical properties, which might lead to the development of high-performance organic semiconductors. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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16 pages, 4650 KiB  
Article
Synthesis of 2-((2-(Benzo[d]oxazol-2-yl)-2H-imidazol-4-yl)amino)-phenols from 2-((5H-1,2,3-Dithiazol-5-ylidene)amino)phenols through Unprecedented Formation of Imidazole Ring from Two Methanimino Groups
by Ilia V. Baranovsky, Lidia S. Konstantinova, Mikhail A. Tolmachev, Vadim V. Popov, Konstantin A. Lyssenko and Oleg A. Rakitin
Molecules 2020, 25(17), 3768; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25173768 - 19 Aug 2020
Cited by 1 | Viewed by 2219
Abstract
A new synthetic pathway to four substituted imidazoles from readily available 2-((4-aryl(thienyl)-5H-1,2,3-dithiazol-5-ylidene)amino)phenols has been developed. Benzo[d]oxazol-2-yl(aryl(thienyl))methanimines were proved as key intermediates in their synthesis. The formation of an imidazole ring from two methanimine derivatives likely includes the opening of [...] Read more.
A new synthetic pathway to four substituted imidazoles from readily available 2-((4-aryl(thienyl)-5H-1,2,3-dithiazol-5-ylidene)amino)phenols has been developed. Benzo[d]oxazol-2-yl(aryl(thienyl))methanimines were proved as key intermediates in their synthesis. The formation of an imidazole ring from two methanimine derivatives likely includes the opening of one benzoxazole ring followed by ring closure by intermolecular nucleophilic attack of the N-methanimine atom to a carbon atom of another methanimine. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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17 pages, 7406 KiB  
Article
Structural and Photophysical Properties of 2,1,3-Benzothiadiazole-Based Phosph(III)azane and Its Complexes
by Radmir Khisamov, Taisiya Sukhikh, Denis Bashirov, Alexey Ryadun and Sergey Konchenko
Molecules 2020, 25(10), 2428; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25102428 - 22 May 2020
Cited by 16 | Viewed by 2640
Abstract
Here we describe the synthesis of a novel N,N’-bis(2,1,3-benzothiadiazol-4-yl)-1-phenylphosphanediamine (H2L) and its zinc (II) and copper (I) coordination compounds [Zn2L2]·nC7H8 (1·nC7H8), [Zn2(H2L)2Cl [...] Read more.
Here we describe the synthesis of a novel N,N’-bis(2,1,3-benzothiadiazol-4-yl)-1-phenylphosphanediamine (H2L) and its zinc (II) and copper (I) coordination compounds [Zn2L2]·nC7H8 (1·nC7H8), [Zn2(H2L)2Cl4]·nC7H8 (2·nC7H8), and [Cu(H2L)Cl]n·nTHF (3·THF). According to single crystal X-ray diffraction analysis, H2L ligand and its deprotonated species exhibit different coordination modes. An interesting isomerism is observed for the complexes [Zn2(H2L)2Cl4] (2a and 2b) that differ by the arrangement of H2L. Both complexes possess internal cavities capable of incorporating toluene molecules. Upon toluene release, the geometry of 2b changes substantially, while that of 2a changes slightly. Due to the diverse structures, the compounds 13 reveal different photophysical properties. These results are discussed based on previously reported studies and DFT (density functional theory) calculations. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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15 pages, 1587 KiB  
Article
Natural Compounds and Their Structural Analogs in Regio- and Stereoselective Synthesis of New Families of Water-Soluble 2H,3H-[1,3]thia- and -Selenazolo[3,2-a]pyridin-4-ium Heterocycles by Annulation Reactions
by Vladimir A. Potapov, Roman S. Ishigeev, Irina V. Shkurchenko, Sergey V. Zinchenko and Svetlana V. Amosova
Molecules 2020, 25(2), 376; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25020376 - 16 Jan 2020
Cited by 16 | Viewed by 2790
Abstract
It has been found that both eugenol and isoeugenol derivatives reacted with 2-pyridinesulfenyl and 2-pyridineselenenyl halides in a regioselective mode affording products with opposite regiochemistry. Synthesis of new families of 2H,3H-[1,3]thia- and -selenazolo[3,2-a]pyridin-4-ium heterocycles has been developed [...] Read more.
It has been found that both eugenol and isoeugenol derivatives reacted with 2-pyridinesulfenyl and 2-pyridineselenenyl halides in a regioselective mode affording products with opposite regiochemistry. Synthesis of new families of 2H,3H-[1,3]thia- and -selenazolo[3,2-a]pyridin-4-ium heterocycles has been developed by annulation reactions of 2-pyridinechalcogenyl halides with natural compounds (eugenol, isoeugenol, methyl eugenol, methyl isoeugenol, acetyl eugenol, trans-anethole) and their structural analogs. The influence of the substrate structure and the nature of halogen on the product yields are studied. The 2-pyridinesulfenyl and 2-pyridineselenenyl chlorides are more efficient reagents compared to corresponding bromides. The obtained condensed heterocycles are novel water-soluble functionalized compounds with promising biological activity. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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Review

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43 pages, 19659 KiB  
Review
Synthesis and Reactivity of 3H-1,2-dithiole-3-thiones
by Oleg A. Rakitin
Molecules 2021, 26(12), 3595; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26123595 - 11 Jun 2021
Cited by 13 | Viewed by 4975
Abstract
3H-1,2-Dithiole-3-thiones are among the best studied classes of polysulfur-containing heterocycles due to the almost explosive recent interest in these compounds as sources of hydrogen sulfide as an endogenously produced gaseous signaling molecule. This review covers the recent developments in the synthesis [...] Read more.
3H-1,2-Dithiole-3-thiones are among the best studied classes of polysulfur-containing heterocycles due to the almost explosive recent interest in these compounds as sources of hydrogen sulfide as an endogenously produced gaseous signaling molecule. This review covers the recent developments in the synthesis of these heterocycles, including both well-known procedures and important novel transformations for building the 1,2-dithiole-3-thione ring. Diverse ring transformations of 3H-1,2-dithiole-3-thiones into various heterocyclic systems through 1,3-dipolar cycloaddition, replacement of one or two sulfur atoms to form carbon- and carbon-nitrogen containing moieties, and other unexpected reactions are considered. Full article
(This article belongs to the Special Issue Polysulfur- and Sulfur-Nitrogen Heterocycles)
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