<b>Thiacyanocarbons. I. Tetracyano-1,4-dithiin, Tetracyanothiophene and Tricyano-1,4-dithiino [c]isothiazole</b>

Simmons, Howard E.; Vest, Robert D.; Blomstrom, Dale C.; Roland, John R.; Cairns, T. L.

doi:10.1021/ja00883a028

Cited by 98 publications

(31 citation statements)

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“…The UV-Vis spectrum of monomer 3 in DMSO showed the absorption maxim band at 320, 435 and 580 nm, in accordance with Draber [17]. The TGA measurement of monomer 3 showed a maximum decomposition temperature at 442 • C. The weight loss was 26% and the rate of weight loss at the maximum decomposition temperature was 0.98%/ • C. This can, probably, be ascribed to the extrusion of one atom of sulfur by the heating at its melting temperature, in accordance with Simmons et al [20] (Scheme 1). The IR spectrum of the resulted compound by heating of monomer 3 at 450 • C for 30 min (compound 4) does not present major modifications, except the appearance of the strong absorption band at 1385-1400 cm −1 corresponding to the C N Cbending maleimide ring (Fig.…”

Section: Monomer Synthesissupporting

confidence: 86%

Polyethers and polythioethers containing 1,4-dithiin-2,3;5,6-tetrayl diimide

Găină¹,

Gaina²

2005

Designed Monomers and Polymers

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New polythioethers containing a 1,4-dithiin-2,3;5,6-tetrayl diimide structure were synthesized by condensation of N-(p-chlorophenyl)-2,3-dichloromaleimide (2) with anhydrous sodium sulfide in molar ratio 2:3 or by condensation of bis(N,N -p-chlorophenyl)-1,4-dithiin-2,3:5,6-tetrayl diimide (3) with various bisphenols. The polyethers were prepared by condensation of 3 with various bisphenols. The monomer 3 was synthesized by nucleophilic substitution of 2 with nonahydrate sodium sulfide. IR and UV spectroscopy, as well as elemental analysis confirmed the structures. The polymers were characterized by viscosimetric measurements, softening points and thermogravimetric data. They showed good solubility in aprotic solvents and high thermal stability.

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Section: Monomer Synthesissupporting

confidence: 86%

Polyethers and polythioethers containing 1,4-dithiin-2,3;5,6-tetrayl diimide

Găină¹,

Gaina²

2005

Designed Monomers and Polymers

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“…Yield 18 g (96%), mp 177oC. IR spectrum, n, cm !1 : 3096 (C Ar 3H), 3032 (C Alk 3H), 2,3-Di(methylsulfanyl)-2-butenodinitrile II and 2,3-dihydro-1,4-dithiin-5,6-dicarbonitrile III were prepared and purified as described in [13,14]. [6,7;11,12;16,17-(3,6-dipentoxy)benzo]tetraazaporphine V. A mixture of 1 g of dinitrile I and 0.57 g of 2,3-di(methylsulfanyl)-2-butenedinitrile II was added to a system 1-pentanol3 magnesium pentylate prepared by dissolving 0.5 g of Mg in 30 ml of 1-pentanol.…”

Section: 6-dipentoxyphthalonitrile Imentioning

confidence: 99%

Unsymmetrical Pentoxy-Substituted Porphyrazines

et al. 2005

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The reactions of 3,6-dipentoxyphthalonitrile (A) in the 1-pentanol3magnesium pentylate medium with phthalonitrile, 2,3-di(methylsulfanyl)-2-butenedinitrile, and 2,3-dihydro-1,4-dithiin-5,6-dicarbonitrile (B) were performed. Unsymmetrically substituted porphyrazines A 3 B were prepared and studied. The influence of the structure of fragment B on the spectral characteristics of the porphyrazines was examined.Much attention is given today to unsymmetrically substituted porphyrazines, which are very promising for various branches of science and engineering [13 4]. The main route to unsymmetrically substituted porphyrazines is random condensation of two o-dinitriles or 1,3-diiminoisoindolines in various molar ratios. The reaction in all cases yields a mixture of all the possible porphyrazines, which are usually separated chromatographically. The product separation is often the most difficulty step; therefore, active efforts are made to develop procedures for selective synthesis of unsymmetrically substituted porphyrazines [537].We reported previously [8] that 3,6-didecyloxyphthalonitrile can be used for selective synthesis of ABAB-type phthalocyanines. 3,6-Dipentoxyphthalonitrile I does not form the corresponding symmetrical octasubstituted phthalocyanine in the reaction with magnesium pentylate in 1-pentanol. At the same time, in the presence of another dinitrile containing no bulky substituents, e.g., 2,3-di(methylsulfanyl)-2-butenodinitrile, a mixture of unsymmetrically substituted porphyrazines is formed.To find the causes of such a behavior of I, it was heated in 1-pentanol in the presence of magnesium pentylate; after removing the solvent, the precipitate was treated with acetic acid and purified by column chromatography (Al 2 O 3 , eluent benzene). We recovered the starting 3,6-dipentoxyphthalonitrile I, as judged from the IR data and comparison of the melting points of I before and after the attempted reaction (cf.[9]). Thus, dinitrile I does not undergo closure of the isoindole ring with the formation of the corresponding alkoxy derivatives. Apparently, for the porphyrazine ring to be formed, the magnesium ion should coordinate four dinitrile molecules. With I, such a coordination is apparently impossible because of steric interactions between bulky substituents in positions 3 and 6. On adding another dinitrile containing no bulky substituents, the formation of fairly stable 1 : 4 complexes becomes possible, and the porphyrazine ring is formed around the metal cation.The absence of octasubstituted phthalocyanines in the reaction products considerably simplifies the chromatographic separation of the product mixture, because the A 3 B products are in all cases the most mobile. The synthesis was performed in accordance with the scheme shown below under the conditions excluding formation of octapentoxyphthaloxyanine.We were able to isolate pure only the compound A 3 B. Chromatographic separation of A 2 B 2 isomers was difficult because of their similar polarity and solubility. Porphyrazines AB 3 were not isolated...

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“…Silylation also provides a method of assessing the Lewis basicity of the C 5 (CN) 5 2 anion using a ranking for weakly coordinating anions based on downfield 29 Si NMR shifts in i-Pr 3 Si(Anion) compounds. 2 The C 5 (CN) 5 2 anion was prepared in multigram quantities as a trimethylammonium salt from tetracyano-1,4-dithiin 10 5 ] which was characterized by elemental analysis, IR, 1 H and 13 C NMR, and X-ray crystallography. ‡ Reaction of this trityl salt with trialkylsilanes in toluene solution is fast and stoichiometric, giving silyl species, R 3 Si(C 5 (CN) 5 ).…”

mentioning

confidence: 99%

Exploration of the pentacyano-cyclo-pentadienide ion, C₅(CN)₅⁻, as a weakly coordinating anion and potential superacid conjugate base. Silylation and protonation

Richardson

Reed

2004

Chem. Commun.

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Thiacyanocarbons. I. Tetracyano-1,4-dithiin, Tetracyanothiophene and Tricyano-1,4-dithiino [c]isothiazole

Cited by 98 publications

References 0 publications

Polyethers and polythioethers containing 1,4-dithiin-2,3;5,6-tetrayl diimide

Polyethers and polythioethers containing 1,4-dithiin-2,3;5,6-tetrayl diimide

Unsymmetrical Pentoxy-Substituted Porphyrazines

Exploration of the pentacyano-cyclo-pentadienide ion, C₅(CN)₅⁻, as a weakly coordinating anion and potential superacid conjugate base. Silylation and protonation

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Thiacyanocarbons. I. Tetracyano-1,4-dithiin, Tetracyanothiophene and Tricyano-1,4-dithiino [c]isothiazole

Cited by 98 publications

References 0 publications

Polyethers and polythioethers containing 1,4-dithiin-2,3;5,6-tetrayl diimide

Polyethers and polythioethers containing 1,4-dithiin-2,3;5,6-tetrayl diimide

Unsymmetrical Pentoxy-Substituted Porphyrazines

Exploration of the pentacyano-cyclo-pentadienide ion, C5(CN)5−, as a weakly coordinating anion and potential superacid conjugate base. Silylation and protonation

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Exploration of the pentacyano-cyclo-pentadienide ion, C₅(CN)₅⁻, as a weakly coordinating anion and potential superacid conjugate base. Silylation and protonation