The chemistry of pyrrolic compounds. VII. Synthesis of 5,5'-diformyldipyrryl-methanes

Chong, R.; Clezy, P. S.; Liepa, AJ; Nichol, A. W.

doi:10.1071/ch9690229

Cited by 130 publications

(58 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To a soln. of 7 (0.619 g, 1.69 mmol) and 8 [19] (0.247 g, 1.69 mmol) in dry CH,CI, (300 ml) was added CF,CO,H ( 5 drops). After stirring at r.t. for 18 h, o-chloranil (1.66 g, 6.76 mmol) was added and the mixture heated to reflux for 1 h. After adsorption on SiO, by evaporation, chromatography (SiO,, PhMe/AcOEt 9: 1) and recrystallization (CHCl,/MeOH) gave 9 1 H, (0.359 g, 43%).…”

Section: Diethyl44'-[(2-formyl-i3-phenylene)bis(oxy)]bis(butanoate)mentioning

confidence: 99%

“…For the synthesis of 6 * Zn (Scheme I), 2,6-dihydroxybenzaldehyde [18] was alkylated with ethyl 4-bromobutyrate (N,N-dimethylformamide (DMF)/ K,CO,) to give diester 7 in 65 YO yield. The meso-diarylporphyrin tetraester 9 -H, was constructed from 7 and di(pyrro1-2-y1)methane (8) [19] according to a protocol by Manka and Lawrence [20], and subsequent metal ion insertion yielded the Zn" porphyrin 9 * Zn. The longer-wavelength bands in the visible region of the electronic absorption spectra nicely reflected the successful insertion of the Zn" ion [Zl] [22] : whereas 9 * H, displayed in CH,Cl, four distinct bands at 502, 535, 578, and 633 nm, metallated 9 -Zn only exhibited three characteristic bands in this region at 501, 539, and 576 nm.…”

Section: R = Nhc(ch20ch2ch2c02ch3)3mentioning

confidence: 99%

See 1 more Smart Citation

Dendrimers with Porphyrin Cores: Synthetic models for globular heme proteins

Dandliker¹,

Diederich²,

Zingg³

et al. 1997

Helvetica Chimica Acta

124

View full text Add to dashboard Cite

Dendritic iron porphyrins were synthesized as functional mimics of globular electron-transfer heme proteins.The cascade molecules 1 * Zn-3 -Zn of first to third generation were obtained starting from the (meso-diarylporphyrin) zinc 6 * Zn which contains four carboxylate arms for attachment of the poly(ether-amide) dendritic branches by peptide-coupling methodology (Scheme I). Generation 3 compound 3 . Zn with 108 methyl-carboxylate end groups has a molecular weight of 19054 D, and computer modeling suggests that its structure is globular and densely-packed, measuring ea. 4 nm in diameter and, therefore, similar in dimensions to the electron-transfer protein cytochrome-c. Starting from the generation 1 poly(carboxy1ic acid) 11 * Zn and the generation 2 analog 12 * Zn the dendritic Zn" porphyrins 4 * Zn and 5 . Zn, respectively, were obtained by esterification with triethyleneglycol monomethyl ether (Schemes 3 and 4). Demetallation followed by insertion of Fe" and in situ oxidation afforded the water-soluble dendritic iron porphyrins 4 * FeCl and 5 * FeCl. The electrochemical behavior of esters 1 * Zn -3 . Zn in organic solvents changed smoothly with increasing dendritic generation (Table f).Progressing from 1 * Zn to 3 . Zn in THF, the first porphyrin-centered oxidation and reduction potentials become more negative by 320 and 210 mV, respectively. These changes were attributed to strong microenvironmental effects imposed on the electroactive core by the densely packed dendritic surroundings. The electrochemical properties of 4 * FeCI and 5 -FeCl were investigated by cyclic voltammetry in both CH,CI, and H,O (Tables 2 and 3). Progressing from 4 . FeCl to 5 * FeCl in CH,CI,, the redox potential of the biologically relevant Fe"'/Fe" couple remained virtually unchanged, whereas in aqueous solution, 5 * FeCl exhibited a potential 420 mV more positive than did 4 . FeCI. The large difference between these potentials in H,O was attributed to differences in solvation of the core electrophore. Whereas the relatively open dendritic branches in 4 -FeCl do not impede access of bulk solvent to the central core, the densely packed dendritic superstructure of 5 * FeCl significantly reduces contact between the heme and external solvent. As a result, the more charged Fe"' state is destabilized relative to Fe", and the redox potential is strongly shifted to a more positive value.

show abstract

Section: Diethyl44'-[(2-formyl-i3-phenylene)bis(oxy)]bis(butanoate)mentioning

confidence: 99%

Section: R = Nhc(ch20ch2ch2c02ch3)3mentioning

confidence: 99%

Dendrimers with Porphyrin Cores: Synthetic models for globular heme proteins

Dandliker¹,

Diederich²,

Zingg³

et al. 1997

Helvetica Chimica Acta

124

View full text Add to dashboard Cite

show abstract

“…Condensation of 4 with di(2-pyrryl)methane [18] gave a porphyrinogen [19] that was oxidized with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to afford 5 (44%). Metalation of 5 with Zn(OAc) 2´2 H 2 O in refluxing CHCl 3 /MeOH yielded 5´Zn in 92% yield.…”

mentioning

confidence: 99%

Porphyrin-[(E)-1,2-Diethynylethene] Scaffolding: Synthesis and Optical and Electrochemical Properties of Multinanometer-Sized Porphyrin Arrays

Wytko

Berl

McLaughlin

et al. 1998

HCA

View full text Add to dashboard Cite

“…Symmetrical octaalkylsubstituted 5,15 diphenylpor phyrins 3 (trans) have been rather long known, while their β unsubstituted analogs were described only recently when unsubstituted dipyrrolylmethane 29 (see Refs 26,83,131,132) and meso phenyldipyrrolylmethanes 14 (see Ref. 87,131,133) had become available.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of meso-phenyl-substituted porphyrins as starting compounds for the preparation of porphyrin-containing polymers

et al. 2007

View full text Add to dashboard Cite

show abstract

The chemistry of pyrrolic compounds. VII. Synthesis of 5,5'-diformyldipyrryl-methanes

Abstract: The preparation of a number of 5,5?-diformyldipyrrylmethanes is described using benzoyl chloride-N,N-dimethylformamide as the formylating mixture.

Cited by 130 publications

References 0 publications

Dendrimers with Porphyrin Cores: Synthetic models for globular heme proteins

Dendrimers with Porphyrin Cores: Synthetic models for globular heme proteins

Porphyrin-[(E)-1,2-Diethynylethene] Scaffolding: Synthesis and Optical and Electrochemical Properties of Multinanometer-Sized Porphyrin Arrays

Synthesis of meso-phenyl-substituted porphyrins as starting compounds for the preparation of porphyrin-containing polymers

Contact Info

Product

Resources

About