Pentafluorosulfanyl (SF5) in dyes: C3-Regioselective synthesis of α-mono-substituted subphthalocyanine with SF5-phenyl group

Iida, Norihito; Tokunaga, Etsuko; Saito, Nozomu; Shibata, Norio

doi:10.1016/j.jfluchem.2014.08.016

Cited by 17 publications

(5 citation statements)

References 42 publications

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“…3) was reported. 35 The selectivity observed in the cyclotrimerization reaction of the corresponding phthalonitrile was attributed by the authors to the steric hindrance of the SF 5 group. Interestingly, the preparation of the trifluoromethylphenyl-substituted analogue lead to the obtention of a mixture of both the C 3 and C 1 regioisomers.…”

Section: Subphthalocyaninesmentioning

confidence: 99%

“…As a matter of fact, in the presence of both electron-donor (see for example ref. 16, 19, 20, 23, 35, 46, 47, 50, 51, 55, 105 and 118) and electron-withdrawing (see for example ref. 29, 32, 50, 52, 80, 114 and 122) peripheral substituents able to slightly extend the π-conjugation of the macrocycle, the Q band is commonly shifted to higher wavelengths with respect to the perhydrogenated SubPc derivative.…”

Section: Subphthalocyaninesmentioning

confidence: 99%

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Recent advances in subphthalocyanines and related subporphyrinoids

et al. 2022

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Section: Subphthalocyaninesmentioning

confidence: 99%

Section: Subphthalocyaninesmentioning

confidence: 99%

Recent advances in subphthalocyanines and related subporphyrinoids

et al. 2022

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“…However, SF 5 ‐phthalonitriles 4 b and 4 c failed to be cyclized under these conditions. This is presumably due to the steric hindrance and strong electronegativity of the SF 5 group on the neighboring cyano moiety. Finally, desired α‐SF 5 ‐substituted Pc 3 b and α,β‐SF 5 ‐substituted 3 c were obtained under harsh conditions, that is, without solvent at higher reaction temperatures (180–200 °C), in 28 % and 7.8 % yield, respectively, as a mixture of regioisomers.…”

Section: Figurementioning

confidence: 99%

Synthesis of Phthalocyanines with a Pentafluorosulfanyl Substituent at Peripheral Positions

et al. 2015

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The pentafluorosulfanyl (SF5) group is more electronegative, lipophilic and sterically bulky relative to the well‐explored trifluoromethyl (CF3) group. As such, the SF5 group could offer access to pharmaceuticals, agrochemicals and optoelectronic materials with novel properties. Here, the first synthesis of phthalocyanines (Pcs), a class of compounds used as dyes and with potential as photodynamic therapeutics, with a SF5 group directly attached on their peripheral positions is disclosed. The key for this work is the preparation of a series of SF5‐containing phthalonitriles, which was beautifully regio‐controlled by a stepwise cyanation via ortho‐lithiation/iodination from commercially available pentafluorosulfanyl arenes. The macrocyclization of the SF5‐containing phthalonitriles to SF5‐substituted Pcs required harsh conditions with the exception of the synthesis of β‐SF5‐substituted Pc. The regiospecificity of the newly developed SF5‐substituted Pcs observed by UV/Vis spectra and fluorescence quantum yields depend on the peripheral positon of the SF5 group.

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“…The incorporation of fluorinated groups, with the CF 3 being the prevalent one, in relevant molecules has a significant impact on their physical, chemical and biological properties due to the electronic characteristics and the relatively small size of the fluorine atom . Out of the emerging fluorinated groups, the pentafluorosulfanyl (SF 5 ) group, has become a promising substituent in pharmaceutical, agrochemical and material sciences . This is mostly because of its unique chemical and metabolic stability, lipophilicity and electron‐withdrawing nature combined with a large dipole moment , .…”

Section: Introductionmentioning

confidence: 99%