(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• demonstrated that 1,1,1,4,4,4-hexafluorobut-2-ene reacts with dithietane, sulfur and KF with the formation of the corresponding 1,3-dithiole [16]. Also, a recent patent presents a method for the preparation of 5,6-bis(trifluoromethyl)-1,2,4-triazine-3-carboxylic acid ethyl ester starting from 1,1,1,4,4,4

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

• Christina Schøttler,
• Kasper Lund-Rasmussen,
• Line Broløs,
• Philip Vinterberg,
• Ema Bazikova,
• Viktor B. R. Pedersen and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2024, 20, 59–73, doi:10.3762/bjoc.20.8

• to literature procedures [14][19][20], as were the 1,3-dithiole-2-thiones 2 and 3 [21]. Fluorenone 5 is commercially available. The new building blocks 7 and 8 were prepared according to related literature procedures [21], as described in Supporting Information File 1. Our first objective was to

• explore further annellation of dihydropyrrole and pyrrole units at the DTF moiety of an IF-DTF. A phosphite-mediated coupling of either 1,3-dithiole-2-thione 2, 7, or 8 with IF dione 1 afforded IF-DTFs 9–11, as shown in Scheme 1. Compound 11 was also obtained from building block 4 via the pyrrolo

• smaller fluorene PAH. These compounds were prepared by a Lawesson’s reagent-promoted coupling between fluorenone 5 and the Ts-protected 1,3-dithiole-2-thione building blocks 2 and 3, respectively, shown in Scheme 3 (albeit in modest yields). Fluorene-based DTF compounds have previously been explored in

Introducing a new 7-ring fused diindenone-dithieno[3,2-b:2',3'-d]thiophene unit as a promising component for organic semiconductor materials

• Valentin H. K. Fell,
• Joseph Cameron,
• Alexander L. Kanibolotsky,
• Eman J. Hussien and
• Peter J. Skabara

Beilstein J. Org. Chem. 2022, 18, 944–955, doi:10.3762/bjoc.18.94

• further functionalised with (triisopropylsilyl)ethynyl [24] (6) or with 1,3-dithiole units [25] (7) by other research groups. The (triisopropylsilyl)ethynyl (TIPSE) groups are introduced to improve the solubility and solid-state order, fostering intermolecular π-orbital interactions [26]. Moreover

Annulation of a 1,3-dithiole ring to a sterically hindered o-quinone core. Novel ditopic redox-active ligands

• Sergey V. Norkov,
• Anton V. Cherkasov,
• Andrey S. Shavyrin,
• Maxim V. Arsenyev,
• Viacheslav A. Kuropatov and
• Vladimir K. Cherkasov

Beilstein J. Org. Chem. 2021, 17, 273–282, doi:10.3762/bjoc.17.26

• State University, 23 Gagarin Ave, 603950, Nizhny Novgorod, Russia 10.3762/bjoc.17.26 Abstract The fused 1,3-dithiole spacer seems to be very suitable for the functionalization of sterically hindered o-quinones with additional groups capable of coordination of metal ions and/or possessing a redox

• ligand; 1,3-dithiole; ditopic ligand; o-quinone; thiete; Introduction There are a number of methods which may be used for the synthesis of new o-quinones in order to vary their redox properties and coordination abilities. The key features of o-quinones are redox activity as well as chelating

• annulation of sterically hindered o-quinones with a 2-substituted 1,3-dithiole cycle seems to be a promising tool for the preparation of redox-active dioxolene species bearing additional functionalities. The previously described o-quinones with an annulated 1,3-dithiole fragment display a remarkable

Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

• Aya Yoshimura,
• Hitoshi Kimura,
• Kohei Kagawa,
• Mayuka Yoshioka,
• Toshiki Itou,
• Dhananjayan Vasu,
• Takashi Shirahata,
• Hideki Yorimitsu and
• Yohji Misaki

Beilstein J. Org. Chem. 2020, 16, 974–981, doi:10.3762/bjoc.16.86

• (FETs), and positive electrode materials for rechargeable batteries because the TTF moiety has strong electron-donating properties attributed to the formation of stable aromatic 1,3-dithiol-2-ylidenes (1,3-dithiole rings) by one- and two-electron oxidation [1][2][3][4][5][6][7][8][9][10][11][12][13][14

• of 1,3-dithiole rings to aromatic rings appears very appealing since these allow to produce novel multistage redox systems. However, such molecules could formerly not be synthesized by conventional approaches. In 2011, a breakthrough synthesis of arylated TTF derivatives by a palladium-catalyzed

• direct C–H arylation was reported, and the structural and electrochemical properties of the products were clarified [30]. This motivated us to synthesize novel multistage redox-TTFs bearing 1,3-dithiole rings on aromatic rings, 1–3 (Figure 1). In addition, we focused on cross-conjugated systems with 1,3

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• alkylation of 1,3-dithiole-2-thiones C and E and the corresponding TTF molecules derived from them often in very good yields. An additional strategy to obtain non-symmetrically substituted TTF derivatives is the stepwise reaction of TTF tetrathiolate with different electrophiles [48]. Another important

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

• Alexander L. Kanibolotsky,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1749–1766, doi:10.3762/bjoc.11.191

• ) and BHJSCs. So far, various electroactive units have been anchored aside the polythiophene backbone, including ferrocene [8], porphyrin [9], 2-carboxyanthraquinone [10], 1,3-dithiole-2-ylidenefluorene [11][12], dithiinoquinoxaline [13][14] and fullerene C60 [15][16]. The incorporation of acceptor

• precursor. The retrosynthetic scheme for these monomers with direct fusion of the TTF unit to a thiophene 14a–c is shown in Scheme 5, with the key building block thieno[3,4-d][1,3]dithiole-2-one 15a–c. Where there is no substitution at the α-position of the thiophene monomer, e.g., 14a, triethylphosphite

• mediated heterocoupling of 15a with 4,5-bis(hexylthio)-1,3-dithiole-2-thione (16) proceeds in low yield (20–30%) [54]. However, the same procedure for the synthesis of dibromo derivative 14b turned out to be more effective, with the monomer 14b being isolated in 70% yield [55]. The starting compound

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

• Shintaro Iwamoto,
• Yuu Inatomi,
• Daisuke Ogi,
• Satoshi Shibayama,
• Yukiko Murakami,
• Minami Kato,
• Kazuyuki Takahashi,
• Kazuyoshi Tanaka,
• Nobuhiko Hojo and
• Yohji Misaki

Beilstein J. Org. Chem. 2015, 11, 1136–1147, doi:10.3762/bjoc.11.128

• and 8c) as a positive electrode material. Results and Discussion Synthesis The synthesis of new donors was carried out according to Scheme 1. A trimethylphosphite-mediate cross coupling between a 1,3-dithiole-2-thione (10) [21] and 1,3-dithiol-2-one (11) [22][23][24] gave a TTF derivative with two

• ethoxyphosphoryl groups (12) in 63% yield. We adopted the cross-coupling reaction between the 1,3-dithiole-2-thione and the 1,3-dithiol-2-one derivatives for the following reasons. The homo-coupling reaction of 10 afforded 12 in low yields, and purification by column chromatography was difficult because of

• the molecules induces significantly large on-site coulomb repulsion. The E5 and E6 of 7d are lower by 0.12–0.14 V than those of 5d, suggesting that 7d6+ is more stabilized than 5d6+. The thiophene spacers inserted between two cationic 1,3-dithiole rings might reduce the intramolecular coulomb

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

• Luke J. O’Driscoll,
• Sissel S. Andersen,
• Marta V. Solano,
• Dan Bendixen,
• Morten Jensen,
• Troels Duedal,
• Jess Lycoops,
• Cornelia van der Pol,
• Rebecca E. Sørensen,
• Karina R. Larsen,
• Kenneth Myntman,
• Christian Henriksen,
• Stinne W. Hansen and
• Jan O. Jeppesen

Beilstein J. Org. Chem. 2015, 11, 1112–1122, doi:10.3762/bjoc.11.125

• prepare BPTTFs using homocoupling reactions and functionalised MPTTFs using cross-coupling reactions with a variety of 1,3-dithiole-2-thiones (19). Subsequently, the incorporation of more complex functionality is discussed. We show how the 2-cyanoethyl protecting group can be used to afford MPTTFs

• published scale [25]. The equivalent reaction can be conducted using 7 to give BPTTF 5b with a similar yield of 79% [36], a modest improvement on the reported yield of 73% for the Boc-protected analogue [35]. The synthesis of MPTTFs can be achieved using cross-coupling reactions between 6 and 1,3-dithiole-2

• -dithiole-2-thiones) with 1,3-dithiole-2-ones than with excess 1,3-dithiole-2-thiones [39]. Table 1 lists a selection of N-tosylated MPTTFs 4a–f prepared from 6 and 19a–f, respectively, with yields ranging from 70–87% despite the concomitant formation of homocoupled byproducts. Compound 7 (and related

Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones

• Flavia Pop and
• Narcis Avarvari

Beilstein J. Org. Chem. 2015, 11, 1105–1111, doi:10.3762/bjoc.11.124

• 4 [33] and 5 [10] have been prepared as described in the literature. Syntheses (S,S)-3: A mixture of (S,S)-5 (0.56 g, 2.21 mmol) and 3,3'-((2-oxo-1,3-dithiole-4,5-diyl)bis(sulfanediyl))dipropanenitrile (4, 1.23 g, 4.36 mmol, 2 equiv) in 10 mL of freshly distilled trimethylphosphite was heated under

Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F₄TCNQ

• Raúl García,
• M. Ángeles Herranz,
• Edmund Leary,
• M. Teresa González,
• Gabino Rubio Bollinger,
• Marius Bürkle,
• Linda A. Zotti,
• Yoshihiro Asai,
• Fabian Pauly,
• Juan Carlos Cuevas,
• Nicolás Agraït and
• Nazario Martín

Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120

• end [15][16]. Furthermore, extended TTF cruciform molecules, formed by two orthogonally placed, π-conjugated moieties bearing the 1,3-dithiole rings at the ends, have also been used for single-molecule measurements [17]. A singular TTF analogue is the so-called π-extended TTF (exTTF, (9,10-bis(1,3

• symmetry resulting in relatively simple spectra, which confirms the proposed structures. In particular, compound 5 exhibits the methyl groups as a singlet at 2.45 ppm, and the protons corresponding to the 1,3-dithiole rings appear as a singlet at 6.37 ppm. In the 13C NMR of the target molecule 5, the

• ) in the (a) neutral form and (b) in the oxidized (2+) state. In the oxidized state the two positive charges reside on the two 1,3-dithiole rings. Cyclic voltammograms of compound 5 and pristine exTTF (at concentrations of approximately 0.2 mM) using THF as a solvent and TBAPF6 (0.1 M) as a supporting

A hybrid electron donor comprising cyclopentadithiophene and dithiafulvenyl for dye-sensitized solar cells

• Gleb Sorohhov,
• Chenyi Yi,
• Michael Grätzel,
• Silvio Decurtins and
• Shi-Xia Liu

Beilstein J. Org. Chem. 2015, 11, 1052–1059, doi:10.3762/bjoc.11.118

• [20] of 4,5-bis(hexylthio)-1,3-dithiole-2-thione with the dialdehyde CPDT 3 [21] was successfully applied. The preparation of the latter was accomplished in 57% yield through the reaction of 4,4-dihexyl-4H-cyclopenta[2,1-b:3,4-b’]dithiophene [22] with oxalyl chloride in the presence of DMF. However

• , the synthesis of the key intermediate 7 involves the protection of one aldehyde group as an acetal using pinacol prior to HWE reaction of 5 with 4,5-bis(hexylthio)-1,3-dithiole-2-thione, followed by deprotection under acidic conditions. Aldehyde 5 was readily obtained by palladium-catalyzed Suzuki

• –1.87 (m, 4H), 1.21–1.10 (m, 12H), 0.96–0.78 (m, 10H) ppm; 13C NMR (75 MHz, CDCl3) δ 183.0, 161.5, 146.8, 145.2, 129.6, 37.7, 31.7, 29.8, 29.7, 24.8, 22.7, 14.1 ppm; ESIMS (m/z): [M + H]+ calcd for C23H31O2S2, 403.18; found, 403.18. Synthesis of 4: A solution of 4,5-bis(hexylthio)-1,3-dithiole-2-thione

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• (bromomethyl)-2-thioxo-1,3-dithiole (6) [21]. In order to determine the optimized experimental procedure to carry out the urea N-alkylation of compound 5, we took advantage from literature of previous works realized on glycoluril for such reaction using a 2,3-bis(halogenomethyl)aryl derivative. Reported

• procedures were using KOH [22][23], t-BuOK [24][25][26] or NaH [27] as the base with DMSO as an aprotic polar solvent. Different experimental conditions were tested for the reaction between diphenylglycoluril 5 and 4,5-bis(bromomethyl)-2-thioxo-1,3-dithiole (6) as the electrophilic reagent (Scheme 2) by

• silica gel chromatography. We should note that an increase of temperature resulted in the degradation of starting material 6. This first strategy to reach clips 1 and 2 was considering the trimethylphosphite-mediated cross-coupling reaction involving 2-oxo-1,3-dithiole moiety 8 [28] as an efficient route

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

• Sandrina Oliveira,
• Dulce Belo,
• Isabel C. Santos,
• Sandra Rabaça and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

• -tetrathiafulvalene (CNB-EDT-TTF), was obtained in high yield, by a cross-coupling reaction with triethyl phosphite between 2-thioxobenzo[d][1,3]dithiole-5-carbonitrile and 5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-one. This new donor was characterized namely by single crystal X-ray diffraction, cyclic

• route to prepare non-symmetrically substituted TTF derivatives by cross coupling of two different 1,3-dichalcogenole-2-chalconegones [14][15], involving the coupling between 2-thioxobenzo[d][1,3]dithiole-5-carbonitrile (1) [16] and 5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiin-2-one (2) in 1:1.1 ratio in

• anisotropic thermal parameters whereas H-atoms were placed in idealised positions and allowed to refine riding on the parent C atom. Molecular graphics were prepared using MERCURY 1.4.2 [29]. General procedure for the synthesis of 3 In freshly destilled triethyl phosphite (10 mL), 2-thioxobenzo[d][1,3

Tuning of tetrathiafulvalene properties: versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions

• Vladimir A. Azov,
• Diana Janott,
• Dirk Schlüter and
• Matthias Zeller

Beilstein J. Org. Chem. 2015, 11, 860–868, doi:10.3762/bjoc.11.96

• approaches for the preparation of N-arylated MPTTF derivatives 4 have been reported (Scheme 1). In the first procedure [14][15][16], the aryl substituent is incorporated during the initial synthetic steps to form a N-aryl-1,3-dithiolo[4,5-c]pyrrole-2-thione 5, which is then coupled to 1,3-dithiole-2-thione 6

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• -withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated from a combination of structural, electrochemical, spectrochemical and theoretical investigations

• MeOH gives the corresponding primary amide 7 in 63% yield. Its dehydration with POCl3 in sulfolane gives 2ac in 60% yield. A similar phosphite-based cross-coupling reaction between the bis(trifluoromethyl)-1,3-dithiole-2-one derivative 9cc and the diester derivative 10bb gave the TTF 3bc in 15% yield

• C10H4F3NS6: C, 30.99; H, 1.04; N, 3.61; found: C, 30.82; H, 1.01; N, 3.49; MS m/z: calcd, 386.86, found, 386.69. Preparation of o-TTF(CO2Me)2(CF3)2 (3bc): A solution of bis(trifluoromethyl)-1,3-dithiole-2-thione (9cc) (2 g, 7 mmol) and bis(carbomethoxy)-1,3-dithiole-2-thione (10bb) (6 g, 24 mmol) in P(OMe)3

TTFs nonsymmetrically fused with alkylthiophenic moieties

• Rafaela A. L. Silva,
• Bruno J. C. Vieira,
• Marta M. Andrade,
• Isabel C. Santos,
• Sandra Rabaça,
• Dulce Belo and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

• , Portugal 10.3762/bjoc.11.71 Abstract Two new dithiolene ligand precursors, containing fused TTF and alkyl thiophenic moieties 3,3'-{[2-(5-(tert-butyl)thieno[2,3-d][1,3]dithiol-2-ylidene)-1,3-dithiole-4,5-diyl]bis[sulfanediyl]}dipropanenitrile (α-tbtdt, 1), and 3,3'-{[2-(5-methylthieno[2,3-d][1,3]dithiol-2

• -ylidene)-1,3-dithiole-4,5-diyl]bis[sulfanediyl]}dipropanenitrile (α-mtdt, 2), were synthesized and characterized. The electrochemical properties of these electronic donors were studied by cyclic voltammetry (CV) in dichloromethane. Both compounds show two quasi-reversible oxidation processes, versus Ag

• '-{[2-(5-(tert-butyl)thieno[2,3-d][1,3]dithiol-2-ylidene)-1,3-dithiole-4,5-diyl]bis[sulfanediyl]}dipropanenitrile (α-tbtdt, 1), and 3,3'-{[2-(5-methylthieno[2,3-d][1,3]dithiol-2-ylidene)-1,3-dithiole-4,5-diyl]bis[sulfanediyl]}dipropanenitrile (α-mtdt, 2) (Scheme 1). These new TTF-type donors can also be

Sexithiophenes as efficient luminescence quenchers of quantum dots

• Christopher R. Mason,
• Yang Li,
• Paul O’Brien,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2011, 7, 1722–1731, doi:10.3762/bjoc.7.202

• -(hydroxythiophene-2-yl-methyl)-[1,3]dithiole-2-thione (A) [29] A solution of 1,3-dithiole-2-thione (4.00 g, 29.8 mmol) in dry tetrahydrofuran (250 mL) was cooled to −78 °C under dry nitrogen. Lithium diisopropylamide mono(tetrahydrofuran) (1.5 M in cyclohexanes, 21.9 mL, 32.9 mmol) was added and the mixture was

• ), manganese dioxide (10× excess w/w, ~101 g) was added portionwise and the mixture was stirred for approximately 2 min. The mixture was filtered through a silica plug (eluted with dichloromethane) and the solvent removed under reduced pressure to afford B as a yellow solid (9.50 g, 90% from 1,3-dithiole-2

• -thione 3); mp 91–92 °C (lit. [29] mp 92 °C); 1H NMR (CDCl3) δ 7.76 (dd, J = 1.1 and 4.9, 2H), 7.72 (dd, J = 1.1 and 4.0, 2H), 7.14 (t, J = 4.4, 2H); MS (EI) m/z: 354 (M+, 75%), 278 (12%), 250 (13%); MS (CI) m/z: 372 (M + NH4+, 100%), 355 (M + H+, 58%), 281 (21%). 4,5-Bis(thiophene-2-carbonyl)[1,3

Redox-active tetrathiafulvalene and dithiolene compounds derived from allylic 1,4-diol rearrangement products of disubstituted 1,3-dithiole derivatives

• Filipe Vilela,
• Peter J. Skabara,
• Christopher R. Mason,
• Thomas D. J. Westgate,
• Asun Luquin,
• Simon J. Coles and
• Michael B. Hursthouse

Beilstein J. Org. Chem. 2010, 6, 1002–1014, doi:10.3762/bjoc.6.113

• series of compounds by exploiting the unusual 1,4-aryl shift observed for electron-rich 1,3-dithiole-2-thione and tetrathiafulvalene (TTF) derivatives in the presence of perchloric acid. The mechanistic features of this rearrangement are discussed since this synthetic strategy provides an alternative

• to extensive investigations of the chemistry of 1,3-dithiole-2-thione (1, Figure 1) [1][2], since this heterocycle and its derivatives are frequently used as convenient precursors to TTF compounds through phosphite-mediated coupling [3]. Our efforts to prepare triaryl derivatives of compound 1 led to

• the discovery of an unexpected rearrangement of 4,5-bis(2-arylhydroxymethyl)-1,3-dithiole-2-thiones (2) in the presence of acid catalysts [4]. As well as the expected dihydrofuran, formed by a nucleophilic ring-closing reaction, other compounds were also produced depending on the nature of the aryl

Synthesis and redox behavior of new ferrocene- π-extended- dithiafulvalenes: An approach for anticipated organic conductors

• Abdelwareth A. O. Sarhan,
• Omar F. Mohammed and
• Taeko Izumi

Beilstein J. Org. Chem. 2009, 5, No. 6, doi:10.3762/bjoc.5.6

• the modified Wittig–Horner cross-coupling reaction using n-BuLi/THF at temperature varies from −78 °C to 0 °C. These new classes of bis(1,3-dithiafulvalene)ferrocenes have the 1,3-dithiole ring system separated by ferrocene as conjugated spacer. The ferrocene-dithiafulvalenes derivatives 9 and 12 were

• ) skeleton 1 in the search of new molecular-based organic metals [12][13][14][15][16]. Furthermore, the extension of conjugation between the two 1,3-dithiole units of TTF and their conducting salts has been prepared studied [17][18][19][20][21][22][23]. The first compound belonging to the class of 1,1′-bis

• oxidation peak was observed as irreversible at a more positive potential value (Ep3 = 1043 mV), Table 3 and Figure 2. The aforementioned electrochemical results of compounds 7a, 7b, 8, 10 and 11, where ferrocene is a spacer between the two 1,3-dithiole units, indicate that the interaction of ferrocene