Deuteroporphyrin dimethyl ester

The Vilsmeier formylation of copper deuteroporphyrin dimethyl ester (6) in which unsubstituted /3-positions are present yields a complex mixture of mono- and disubstituted formylation products which can be partially separated by chromatography on neutral alumina.106... 

A similar rcgioselccti vity is observed in the Friedel-C rafts acylation of copper deuteroporphyrin dimethyl ester (6) which gives a mixture of two /Fmonoacylated products 9 when the reaction time and temperature are carefully controlled or diacylated products 10 on prolonged reaction time.85b-100 106 As with the four / -monoformylated deuteroporphyrin derivatives 7a. the acylated products can be separated by chromatography.100106... 

Single isobacteriochlorin stereoisomers even in enantiomcrically pure form can be obtained230 when the Claisen rearrangement is performed with the pure hematoporphyrin stereoisomers23d which can be prepared by stereogenic enantioselective reduction from diacetyl deuteroporphyrin dimethyl ester. 

R1 = R2 = Et, mesoporphyrin dimethyl ester, H2MPDME R1 = R2 = H, deuteroporphyrin dimethyl ester, H2DPDME R1 = R2 = CH=CH2, protoporphyrin IX dimethyl ester, H2PPDME R1 = R2 = CH(OH)Me, hematoporphyrin dimethyl ester, H2HPDME... 

Scheme 13. Preparation of benzoporphyrin derivatives from isomerically pure mono-acetyl-mono-vinyl deuteroporphyrin dimethyl esters.

Table 5 Basicity of Substituted Deuteroporphyrin-IX Dimethyl Esters...

Mossbauer data for 2,4 diacetyl deuteroporphyrin IX dimethyl ester and Fe(II) protoporphyrin IX obtained at 77 °K show isomer shifts... 

Not only has binding of imidazoles and pyridines to Fe protoporphyrin IX been studied, as discussed in Section 4.1.2, but also photodissociation of axial ligands such as pyridines, imidazoles, or piperidines from six-coordinate, low-spin Fe porphyrins, in which the porphyrin is derived from protoporphyrin IX, or proto- or deuteroporphyrin IX dimethyl ester, has been investigated in nonaqueous solvents using picosecond transient absorption spectroscopy (see Photochemistry of Transition Metal Complexes). It has been shown that photodissociation leads to the formation of five-coordinate complexes, that is, only one ligand appears to be released upon excitation of the six-coordinate complex. ... 

Janson, T. R., Katz, J. J. (1972). An Examination of the 220 MHz NMR Spectra of Meso-porphyrin IX Dimethyl Ester, Deuteroporphyrin IX Dimethyl Ester, and Protoporphyrin IX Dimethyl Ester, J. Magn. Resonance, 6 209. 

Table I. Spectroscopic Properties of Deuteroporphyrin IX Dimethyl Ester Iron (III) Compounds...

Figure 2. Absorption spectra for deuteroporphyrin IX dimethyl ester iron-fill) derivatives in chloroform ligands correspond to X of Figure I...

Figure 5. Proton magnetic resonance spectra at 60 MHz of 2,4-dipropionyU deuteroporphyrin IX dimethyl ester at different concentrations in CDCl at 35°C. Arrows indicate ester methyls.

Other derivatives containing glycosidic and thioglycosidic moieties have also been prepared from protoporphyrin-IX [51]. Esterification of protopor-phyrin-IX 21 was performed with methanol containing 5% sulfuric acid [90]. The obtained dimethyl ester 22 was directly converted into isohemato-porphyrin dimethyl ester 27B (Scheme 1) treatment of protoporphyrin-IX dimethyl ester 22 with thaUium(III) nitrate in methanol gave the bis(2 -dimethoxyethyl)deuteroporphyrin which was then reacted with formic acid. 

Figure 6-5 lists most of the pyrrole-, thiophene-, amino- and hydroxy-substituted porphyrins employed for electropolymerization and the references. Monomers 49a - k [136-147] are based on synthetic porphyrins and 50a, b on deuteroporphyrin [148-150]. Surprisingly, the electrooxidation of metal complexes of protoporphyrin-DC dimethyl ester, possibly via the vinyl groups, leads to the deposition of electroactive porphyrin films on the electrode surface [151-153],... 

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