Meso -Tetraphenylporphine

Stereospecific ene reaction. Singlet oxygen (meso-tetraphenylporphine) reacts with anhydrotetracycline (1) to give the hydroperoxide 2 in 97% yield. Hydrogenation of 2 provides the antibiotic tetracycline (3).2... 

A number of acyl silanes have been isolated from the photosensitized oxygenation of silyl diazo compounds using meso-tetraphenylporphine (TPP) as the sensitizer (Scheme 15)15. This synthesis is most useful for aromatic acyl silanes and the yellow u-carboxyacyl silanes, but it is not of general applicability, isolation difficulties commonly being encountered in the synthesis of aliphatic and other acyl silanes, resulting in poor overall yields. 

Suitable light sources for exciting the sensitizer include halogen or mercury lamps equipped with a 400 nm cut-off filter to transmit visible light. The sensitizers methylene blue (MB), meso-tetraphenylporphine (TPP), sulfonated aluminum phtha-locyanine, and Rose Bengal (RB) are widely used in homogeneous solutions. The main appeal of heterogeneous sensitizers is that they are easy to separate from... 

Treatment of the cobalt porphyrins [Co(TPP)X] (X = Cl, Br, or I) and [Co(OEP)Br] (TPP = meso-tetraphenylporphine and OEP = octaethylpor-phine) with diazomethane gives the corresponding halomethyl cobalt(II) porphyrins [Co(TPP)CH2X] (X = Cl, Br, or I) and [Co(OEP)CH2Br], respectively. These reactions are proposed to proceed via the insertion of the carbene moity into a Co—N bond, and only subsequent nucleophilic attack by the halide results in the formation of the CH2X group (95). 

Cobalt meso-tetraphenylporphine (CoTPP, 1). The cobalt salt is prepared as maroon crystals by reaction of TPP with Co(OAc)2 in CHC13-HOAc. The salt is soluble in benzene, chloroform, and pyridine.1... 

Rearrangement of 1,4-endoperoxides.1 CoTPP catalyzes the rearrangement of 1,4-endoperoxides to syn-1,2 3,4-diepoxides at -78°. Neither meso-tetraphenylporphine nor zinc meso-tetraphenylporphine catalyzes this rearrangement. N,N,N, N -Tetramethyl-ethylenediamine catalyzes the reaction, but only very slowly. The yields from the catalyzed reaction are much higher than those obtained by thermolysis. 

GLyfl-Enones.1 Photooxygenation (meso-tetraphenylporphine) of cycloalkenes followed by in situ acetylation of the resulting hydroperoxide produces cycloalkenones directly. The method is also applicable to acyclic alkenes. 

Berg, K., Madslien, K., Bommer, J.C., Oftebro, R., Winkelman, J.W., and Moan, J. (1991) Light induced relocalization of sulfonated meso-tetraphenylporphines in NHIK 3025 cells and effects of dose fractionation, Photochem. Photobiol., 53 203-210. 

The consumption of rubrene (Eastman, recrystallized from benzene-methanol) in solution was followed by the decrease in optical density at 492.5 nm. The photosensitizers, dibenzanthrone (K K Laboratories) and meso-tetraphenylporphine (Strem Chemicals), were used as received. The olefins were pure (> 98%) commercial samples and were passed through a short column of aluminum before use. 

Figure 7. Arrhenius plots for the H-exchange in meso-tetraphenylporphine. Dashed line normal (H) isotopomer. Solid line bideuterated molecule. The Y-axis represents the decimal logarithm of the rate constant in s ...

K. Berg, J. Moan, J.C. Bommer, J.W. Winkelman (1990). Cellular inhibition of microtubule assembly by photoactivated sulphonated meso-tetraphenylporphines. Int. J. Radiat. Biol, 58, 475 87. 

Re2(CO)io reacts with meso-tetraphenylporphine in decalin under reflux to afford (meso-tetraphenylporphinato)bis tricarbonylrhenium(i) which has been shown by X-ray crystallography to involve the basic structural unit (92). Each Re atom is 142 pm out of the macrocyclic plane. The metal-metal separation of 312.6 pm is rather long for any direct interaction. Similar complexes containing two Re(CO)3 groups or one Re(CO)3 and one Tc(CO)3 group have been prepared with mesoporphyrin IX dimethyl ester. 

Tetramethylthiourca, 359 meso-Tetraphenylporphin, 267 Tetraselenofulvalene, 200 Tetrathiafulvalenes, 387 Thallium(lll) acetate, 360-361 Thallium(l) acetate-iodine, 359-360 Thalliiim(l) bromide, 361 ThalUum(I) ethoxide, 362 Thallium(lll) nitrate, 362-365 Thallium(Ill) perchlorate, 365 Thallium(IIl) trifluoroacetate, 365 Thiepins, 5... 

Chart 8.7 Sensitizers employed in the photochemotherapy of cancer cells. TPP meso-tetraphenylporphine, TMPyP meso-tetra 4-/V-methylpyridyl)porphine, MB methylene blue,... 

The kinetics of the hydrogen migration between the degenerate tautomers of meso-tetraphenylporphine (TPP-H2) and of the deuterated species (TPP-D2)... 

Cft6H2eKFeN6 2 C3H6O, Potassium dicyano(meso-tetraphenylporphin-ato)-iron(111) bis(acetone), 46B, 504 Cft 6H3,N Nb03 C2H 02, Acetato-oxo(5,10,15,20-tetraphenyl-porphyrinato)niobium(V) acetic acid solvate, 45B, 537 CftsHsijMgNg, Di (pyridine )magnesium( 11) octaethylporphyrinate, 43B,... 

Cft9H32NsORu 1.5 C7H8, (Tetraphenylporphinato)(carbonyl)(pyridine)-rutheniumdl) - 1.5-toluene, 39B, 372 Cft 9H35Cl3FeN70, Nitrosyl-a, j3,7, 6-tetraphenylporphinato( 1-methylimidazole) irondl) chloroform solvate, 40B, 471 42B, 380 Cft9H35Cl3NftNi02, Nickeldl) meso-tetraphenylporphine ethoxycarbonyl-... 

---