Syntheses and X-ray Crystal Structures of Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene Derivatives

Finn, Terry; Moore, Adrian J.; Batsanov, Andrei S.; Howard, Judith A. K.

doi:10.1002/(sici)1099-0690(200001)2000:1<51::aid-ejoc51>3.0.co;2-k

Cited by 41 publications

(31 citation statements)

References 39 publications

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“…These dihedral angles are listed in Table 2. The ''saddles'' usually have an approximate C s symmetry, the mirror plane passing through the C(15), C(9), C(10), and C (20) atoms. Only in 5a is this symmetry somewhat distorted (see Figure 4) by a twist of (surprisingly) the symmetrically substituted dithiole ring: the S(3)ϪC (21)Ϫ C(22)ϪS(4) plane forms an angle of 82°(rather than 90°) with the C(15)ϪC (9)ϪC (10)ϪC (20) plane.…”

Section: Solution Electrochemical Studiesmentioning

confidence: 99%

“…Reduction of the methoxycarbonyl group of 3, [19,20] with lithium aluminium hydride afforded 4 (90% yield) (Scheme 1).…”

Section: Synthesismentioning

confidence: 99%

“…The only previous multi[9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene] derivatives are structurally very different from 6 and 7: they are dimers linked by an oxygen bridge between C(2) of the anthracene units, synthesized by Martín et al directly from the corresponding bis(anthraquinone) precursor. [9] By analogy with the preparation of 3 by monolithiation of compound 2 with lithium diisopropylamide (LDA), followed by in situ trapping with methylchloroformate, [19,20] we have explored the possibility of difunctionalising analogue 8 (which is readily available in ca. 1 g batches) [7] using Scheme 2.…”

Section: Scheme 1 Synthesis Of 4؊7mentioning

confidence: 99%

“…X-ray structural studies of 4, 5a, 5b·CH 2 Cl 2 , 10 and 11 have shown that each molecule adopts a normal [20,21] saddle-like conformation (Figures 3Ϫ7). The anthracenediylidene moiety is folded along the C(9)···C(10) vector by an angle ϕ; both dithiole rings tilt in the opposite direction and then fold inwards along the S(1)···S(2) and S(3)···S (4) vectors by δ 1 and δ 2 angles, so that the outlying planar S(1)ϪC (16)ϪC (17)ϪS(2) and S(3)ϪC (21)ϪC (22)ϪS(4) moieties of these rings form a (rather narrow) dihedral angle θ.…”

Section: Solution Electrochemical Studiesmentioning

confidence: 99%

“…In this context our attention is focussed on 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (1) [7] and derivatives (e.g. 2 and 3 [19,20] ) which undergo a single, quasi-reversible, two-electron oxidation wave to yield a thermodynamically stable dication at E ox ഠ ϩ0.3 to ϩ0.4 V (in MeCN vs. Ag/AgCl) in the cyclic voltammogram. X-ray crystal structures have shown that a major structural change accompanies oxidation to the dication: the central anthracenediylidene ring, which is boat shaped in the neutral molecule, becomes a planar and fully aromatic anthracene system, with the heteroaromatic 6π 1,3-dithiolium cations almost orthogonal to this plane.…”

Section: Introductionmentioning

confidence: 99%

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Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

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The synthesis of new derivatives of 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene is reported. 1 H NMR studies on compound 4 are consistent with two conformers of the saddle-shaped molecule which interconvert by a boat−boat flipping of the central ring at high temperature. The hydroxymethyl substituent of 4 is readily esterified to yield the benzoyl and 2-naphthaloyl ester derivatives 5a and 5b, respectively, and the dimer and the trimer structures 6 and 7, respectively, by reaction with benzoyl chloride, 2-naphthaloyl chloride, 1,4-benzenedicarbonyl chloride and 1,3,5-benzenetricarbonyl chloride. Deprotonation of 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)-10-(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (8) using lithium bis(trimethylsilyl) amide (LHMDS) followed by in situ quenching of the lithiated intermediate with methylchloroformate gave the diester derivative 10 (96% yield), whereas using LDA gave the monoester

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Section: Solution Electrochemical Studiesmentioning

confidence: 99%

“…Reduction of the methoxycarbonyl group of 3, [19,20] with lithium aluminium hydride afforded 4 (90% yield) (Scheme 1).…”

Section: Synthesismentioning

confidence: 99%

Section: Scheme 1 Synthesis Of 4؊7mentioning

confidence: 99%

Section: Solution Electrochemical Studiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

et al. 2001

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2,6-Dialkoxy-9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene Derivatives: Synthesis, Electrochemistry and X-ray Crystal Structures of Neutral and Dication Species

et al. 2000

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Keywords:The synthesis of 2,6-dialkoxy-9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene derivatives 15 and 16 is described. Solution electrochemistry shows that 15 and 16 display three redox waves, representing the sequential formation of the dication, radical trication and tetracation species in an E q E q E q process. The X-ray crystal structures of neutral compounds 15 and 16 and the charge transfer complex (15) 2+ (TCNQ -• ) 2 ⋅ 2MeCN are reported. The neutral molecules adopt a saddlelike conformation; the bis(1,3-dithiole)benzoquinone system [ ‡] Part 1: Ref. [3e] [a]

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Crown-Annelated 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene Derivatives as Cation Sensors: Synthesis, X-ray Crystal Structures, Voltammetric and Spectroscopic Monitoring of Metal Complexation

et al. 2001

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The synthesis of O 4 S 2 -crown annelated derivatives of 9,10bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene using the novel Horner−Wadsworth−Emmons reagent 7 is reported. The bis-and mono-crown systems 9 and 12 function as efficient ligands in the voltammetric and UV/Vis spectroscopic recognition of Na + and Ag + . Solution electrochemical studies reveal that metal complexation to the crown unit(s) leads to a significant positive shift in the potential of the first, twoelectron oxidation wave of 9 and 12 [maximum shift E 1 ox = 115 mV for 9 in the presence of Ag + (ca. 10 molar equivalents)]. Considerably smaller shifts (Ͻ 30 mV) were observed [ ‡] Molecular Saddles, 5. Ϫ Part 4: N. Godbert, A.

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Syntheses and X-ray Crystal Structures of Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene Derivatives

Cited by 41 publications

References 39 publications

Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

2,6-Dialkoxy-9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene Derivatives: Synthesis, Electrochemistry and X-ray Crystal Structures of Neutral and Dication Species

Crown-Annelated 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene Derivatives as Cation Sensors: Synthesis, X-ray Crystal Structures, Voltammetric and Spectroscopic Monitoring of Metal Complexation

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