Synthesis of new soluble triphenodithiazines - donor properties, EPR/ENDOR investigation and crystalline radical ion salts

Kistenmacher, A.; Adam, Martin; Baumgarten, Martin; Pawlik, J.; Shen, Yongjia; Müllen, Kläus

doi:10.1016/0379-6779(93)90368-7

Cited by 3 publications

(3 citation statements)

References 11 publications

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“…As for the phenothiazine ring systems, it has been reported that the reductive ring closure of 1,1′‐diphenyl‐2‐nitrothioether provides phenothiazine 8. The cyclization reaction has been applied to the synthesis of triphenodithiazine 9. However, the corresponding ladder polymers or oligomers could not be obtained by this method because of the inherent low conversion.…”

Section: Resultsmentioning

confidence: 99%

“…Aromatic compounds containing phenothaizine ring systems attract attention because of their interesting aspects of electrophilic substitution14 and properties, such as redox and magnetic couplers 9. The rigid structures of the ladder polymers bearing phenothiazinium repeating units were typically reflected in their electric conductivity and thermal stability.…”

Section: Resultsmentioning

confidence: 99%

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Palladium-catalyzed synthesis of oligo(methylthio)aniline and conversion to polyacene-type electrolytes bearing phenothiazinium repeating units

Oyaizu

Mitsuhashi

Tsuchida

2002

Macromol. Chem. Phys.

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The synthetic routes to ladder polymers which consist of benzenetetrayl subunits with imino and methylsulfonio linkages are described. As the key intermediate, oligo‐ and polyaniline derivatives having pendant methylthio groups are prepared by the Pd‐catalyzed aryl amination from various monomers. The oxidation of the polymers with H2O2 in the presence of CH3COOH effects the high yielding conversion of methylthio to methylsulfinyl groups without the formation of the undesired methylsulfonyl groups. The superacid‐induced condensation of the resulting polymers under dilution conditions induced the polymer‐analogous intramolecular electrophilic ring closure reaction of the hydroxy(methyl)(phenyl)sulfonium cation onto the adjacent benzene ring to yield the required ladder polymers which have proved to be semiconductors with intrinsic electric conductivities of ca. 10−5 S · cm−1.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Palladium-catalyzed synthesis of oligo(methylthio)aniline and conversion to polyacene-type electrolytes bearing phenothiazinium repeating units

Oyaizu

Mitsuhashi

Tsuchida

2002

Macromol. Chem. Phys.

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“…The preparation of 2,8-bis(methoxycarbonylethylthio)-3,7-diamino-l0-dodecylphenothiazine (16) required five synthetic steps starting from N-dodecyl-33diaminophenothiazine (11) [16]. In the following synthetic step, the aminobenzothiazole ring in 14 was cleaved by refluxing a solution of 14 in aqueous KOH (60%) for 2-3 h. The thiolate solution formed was stabilized by addition to hydrochloric acid solution (20%), after which the air-insensitive hydrochloride salt of 3,7-diamino-l0dodecyl-2,8-phenothiazinodithiole (15) was isolated. The product, 3,7-bis(benzoylaminothiocarbonylamino)-lOdodecylphenothiazine (12), was obtained in a good yield (91%).…”

Section: Synthesismentioning

confidence: 99%

Polyphenothiazinobisthiazole: A novel polymer for third‐order nonlinear optics

et al. 1994

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+ Present address: BASF AG, D-67056 Ludwigshafen, FRGThe synthesis and the optical properties of the novel polymer polyphenothiazinobisthiazole (PPT) are described. The design of this polymer was planned taking into consideration several aspects that were anticipated to lead to a material with an enhanced nonlinear optical susceptibility Monomer 16 was prepared in a five-step synthesis starting from N-dodecyl-3,7-diaminophenothiazin (11). 16 was reacted with terephthaloyl chloride to yield the precursor polyamide 17.This precursor polyamide was subjected to a thermal cyclization at 300 OC under vacuum leading to the title polymer PPT (18).PPT shows UVIvis absorption maxima at 1 =282 nm,305 nm and 463 nm.The macroscopic nonlinear optical suscepti-bility~'~)(-3w; w, w, w ) of a thin film ofPPTwas determined with a third harmonic generation (THG) technique at a fundamental laser wavelength 1,. = 1064 nm. The results show that PPT exhibits nonlinear optical properties comparable to those of poly-p-phenylenevinylene (PPV).

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Alkylsulfonioarylene and Thioarylene Polymers Derived from Sulfonium Electrophiles

Tsuchida¹,

Oyaizu²

2003

Bulletin of the Chemical Society of Japan

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Superacidification of sulfoxides and sulfinates effects the electrophilic substitution reaction of the resulting hydroxysulfonium ions onto aromatic rings with the elimination of H2O at room temperature. The present account emphasizes the utility of the reaction for use as an elementary step in organic synthesis. The product, the alkyldiarylsulfonium ion, often quantitatively obtained, allows the synthesis of alkylsulfonio-bridged (λ4-alkylsulfanyliumdiyl) aromatic polymers. High molecular-weight poly(alkylsulfonioarylene) salts with a wide range of structural dimensionalities from linear to network architectures have been made accessible by the regioselective condensation of aryl sulfoxides. The polymers possess interesting properties such as good solubility in polar organic solvents and sometimes even in H2O, susceptibility to nucleophiles to provide thioarylene derivatives, photo-degradability, and electric semiconductivity, according to the dimensionality of the molecule. The synthetic chemistry of the alkylsulfonioarylene polymers as well as their possible applications in high molecular-weight poly(thioarylene) synthesis, photochemical recycling processes of an engineering plastic poly(thio-1,4-phenylene), and photo-resist technologies, are reviewed.

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Synthesis of new soluble triphenodithiazines - donor properties, EPR/ENDOR investigation and crystalline radical ion salts

Cited by 3 publications

References 11 publications

Palladium-catalyzed synthesis of oligo(methylthio)aniline and conversion to polyacene-type electrolytes bearing phenothiazinium repeating units

Palladium-catalyzed synthesis of oligo(methylthio)aniline and conversion to polyacene-type electrolytes bearing phenothiazinium repeating units

Polyphenothiazinobisthiazole: A novel polymer for third‐order nonlinear optics

Alkylsulfonioarylene and Thioarylene Polymers Derived from Sulfonium Electrophiles

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