Abstract:Macrocyclic bis-dienes and a diendienophile were prepared in Diels-Alder reactions starting from the bis-dienophilic (hemiporphyrazinato)nickel complex 1. 1 was reacted either with the tetraene 2 or with tetraphenylcyclopentadienone (4). By combination of macrocyclic bisdienes and bis-dienophiles, ladder-type oligomers were synthesized. They are precursors to the corresponding conjugated molecules, which are of interest as potential organic conductors. Monofunctional and bifunctional dienophilic macrocycles we… Show more
“…In the next synthetic step, we therefore envisaged the addition of four molecules of 1,2,3,4-tetraphenylcyclopen-The completeness of the tetracyclone addition is clearly demonstrated by the integration values obtained from the tadienone (tetracyclone, 5) to the tetrafunctional PcNi 4a (Scheme 3). [9] This was accomplished in a single reaction 1 H-NMR spectrum of 6 which are in excellent agreement with the expected values. Moreover, in the DEPT-135 specby stirring 4a with a fourfold excess of 5 in toluene at 75°C over 48 h. Chromatographic workup (silica gel; n-hexane/ trum of 6, no signal is found downfield from δ ϭ 131.…”
The octasubstituted (phthalocyanine)nickel complexes 4a,b, soluble in common organic solvents, bearing four dienophilic functionalities were synthesized from the corresponding phthalodinitriles 3a,b and nickel(II) acetate. Reaction of 4a with tetracyclone 5 led to the phthalocyanine–tetracyclone adduct 6 which is a precursor for an intermediate phthalocyanine 7 containing four isobenzofuran moieties. The capability of 7 to react as tetrakis(diene) was demonstrated by its reaction with naphthoquinone. Furthermore, the unsymmetrical phthalocyanines 13 and 16a,b,c containing one dienophilic functionality were synthesized using a statistical approach. Their tetracyclone adducts 17, 18a,b,c can be used for the synthesis of ladder‐type phthalocyanine dimers. The dimer 22 was synthesized from 18c and p‐benzoquinone via the isobenzofuran intermediate 19 and the benzoquinone adduct 21. For dehydration experiments the naphthoquinone monoadduct 23 was synthesized from 18c. Dehydration of 22 and 23 was carried out successfully with p‐toluenesulfonic acid. The Diels–Alder reactions are discussed with respect to the occurring exo/endo ratio.
“…In the next synthetic step, we therefore envisaged the addition of four molecules of 1,2,3,4-tetraphenylcyclopen-The completeness of the tetracyclone addition is clearly demonstrated by the integration values obtained from the tadienone (tetracyclone, 5) to the tetrafunctional PcNi 4a (Scheme 3). [9] This was accomplished in a single reaction 1 H-NMR spectrum of 6 which are in excellent agreement with the expected values. Moreover, in the DEPT-135 specby stirring 4a with a fourfold excess of 5 in toluene at 75°C over 48 h. Chromatographic workup (silica gel; n-hexane/ trum of 6, no signal is found downfield from δ ϭ 131.…”
The octasubstituted (phthalocyanine)nickel complexes 4a,b, soluble in common organic solvents, bearing four dienophilic functionalities were synthesized from the corresponding phthalodinitriles 3a,b and nickel(II) acetate. Reaction of 4a with tetracyclone 5 led to the phthalocyanine–tetracyclone adduct 6 which is a precursor for an intermediate phthalocyanine 7 containing four isobenzofuran moieties. The capability of 7 to react as tetrakis(diene) was demonstrated by its reaction with naphthoquinone. Furthermore, the unsymmetrical phthalocyanines 13 and 16a,b,c containing one dienophilic functionality were synthesized using a statistical approach. Their tetracyclone adducts 17, 18a,b,c can be used for the synthesis of ladder‐type phthalocyanine dimers. The dimer 22 was synthesized from 18c and p‐benzoquinone via the isobenzofuran intermediate 19 and the benzoquinone adduct 21. For dehydration experiments the naphthoquinone monoadduct 23 was synthesized from 18c. Dehydration of 22 and 23 was carried out successfully with p‐toluenesulfonic acid. The Diels–Alder reactions are discussed with respect to the occurring exo/endo ratio.
“…The second route takes advantage of a thermal decomposition reaction of the precursor molecule 26 . It was synthesized by addition of two units of 1,2,3,4-tetraphenylcyclopentadienone ( 25 ) to 18 . Heat treatment of the precursor 26 (e.g., boiling toluene) led to the bis-diene 27 , whereby loss of CO and 1,2,3,4-tetraphenylbenzene occurred.…”
Section: Synthesismentioning
confidence: 99%
“…AB-monomers such as 35 and 36 can be prepared by following the above-described routes if the relative amounts of 23 or 25 are chosen appropriately (0.4−1 equiv). 27b, …”
ContentsI. Introduction 563 II. Synthesis 564 A. Hemiporphyrazines 564 B. Triazolehemiporphyrazines 569 C. Other Hemiporphyrazines 570 III. Molecular Organization of Hemiporphyrazines in Condensed Phases 571 IV. Hemiporphyrazines as Units for Molecular Organic Materials 573 V. Concluding Remarks 574 VI. Acknowledgments 574 VII. References 574
“…The syntheses of 2a and 2b are described in ref. 8. The ladder-type compounds 3a and 5a show good solubility in CHC13 or THF, while the trimer 5b is almost insoluble in common organic solvents.…”
Ladder oligomers with two or three nickel hemiporphyrazine units are synthesized via Diels-Alder reaction, using intermediates with isobenzofuran moieties as diene components.
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