New Synthesis of 3,6‐Dibromophthalonitrile and Phthalocyanine Having Eight Thienyl Substituents at Peripheral α‐Positions

Abstract

3,6‐Dibromophthalonitrile was successfully synthesized from 3,6‐dihydroxyphthalonitrile using triphenylphosphine dibromide as bromation reagent. Starting from 3,6‐dibromophthalonitrile, synthesis of 1,4,8,11,15,18,22,25‐octakis(4‐dodecylthiophen‐2‐yl)phthalocyaninatozinc(II) (ZnPc) was described. TGA demonstrated the perfect stability of ZnPc. The newly prepared ZnPc that was symmetrically substituted with thienyl substituents results in an intensively red‐shifted Q‐band. The HOMO and LUMO values of ZnPc were acquired by CV.

Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis, characterization, and investigation of their electrochemical, photochemical and computational properties

“…3.1. Synthesis and characterization 3,6-bis(3-hydroxypropylthio)phthalonitrile (3) was synthesized via a condensation reaction of 3,6-dibromophthalonitrile [22] with 3-mercapto propanol under very convenient conditions with a better yield than the first synthesis result (38%) (Scheme 1) [23]. This compound was prepared previously by the S N Ar reaction of 3,6-(4'-methylphenyl-sulfanyloxy) phthalonitrile with 3-mercapto-propanole.…”

The synthesis of symmetrical peripheral and non-peripheral octa-substituted metal-free phthalocyanines: simpler, better, faster, cheaper

“…The starting material for the non-peripheral alkyl substituted Pc's, 3,6dihalophthalonitrile (21b), is not commercially available and though the preparation of the 3,6-dibromo- 23 and 3,6-diiodophthalonitrile 24,25 have been documented, no reports for the application thereof in the preparation of 3,6-dialkylphthalonitriles (21) could be found. We therefore decided to apply the reliable Diels Alder strategy to the synthesis of 3,6-dialkylphthalonitriles (21).…”

“…36 The Diels-Alder reaction of thiophene 1,1-dioxide (24) with fumaronitrile is very sluggish, though. 23,28,30,31 A theoretical study by Jursic 36 indicated the HOMO energy of thiophene 1-oxide to be higher than that of thiophene 1,1-dioxide, thus confirming it to be more electron-rich than the latter. In this regard, Thiemann and co-workers [37][38][39] reported a one-pot oxidation-cycloaddition procedure wherein BF3.OEt2 by coordinating to the S-monoxide oxygen and decreasing the nucleophilicity of the sulphur atom, prevents over-oxidation to the dioxide in the presence of meta-chloroperbenzoic acid (mCPBA).…”

“…37,39 The Lewis acid may, in addition, decrease the energy of the dienophile LUMO. 37 By applying this concept in a novel oxidation -Diels-Alder reaction of substituted thiophene (23) with fumaronitrile, the crude 2,3-dicyano-1,4-dihexyl-7thiabicyclo[2.2.1]hept-5-ene S-oxide (26) could be obtained within 1 hour (as opposed to days reported for the S-dioxide method). The intermediate substituted S-oxide (26) could furthermore be converted into the desired 1,4-dialkylphthalonitrile (21) within an hour via a microwave irradiation process (Scheme 3c).…”

Ligation-Rolling Circle Amplification on Quantum Dot-Encoded Microbeads for Detection of Multiplex G-Quadruplex-Forming Sequences

“…The ligation-RCA produced long, randomly coiled DNA concatemers consisting of tandem repeats of target G4-forming sequence on the Qbead. The presence of a G4-specifc fluorescent label, zinc phthalocyanine (ZnPc), 49 induced the G4 formation, generating a "G4/ZnPc nanowireson-Qbead" superstructure. An array of the superstructures was readily subjected to flow cytometry, by which three targets were identified by the Qbead signals and quantified by the ZnPc signal.…”