287. A synthesis of coproporphyrin III

Bullock, E.; Johnson, A. W.; Markham, E.; Shaw, K. B.

doi:10.1039/jr9580001430

Cited by 73 publications

(22 citation statements)

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“…The target bis-porphyrin conjugates 2Hbipy2H and 2Hphen2H were obtained as follows: 2 was treated with 3,3'-diethyl-4,4'-dimethyl-2,2'-dipyrrylmethane (4; [26,27] 10 equiv), 3,5-di-tert-butylbenzaldehyde (3; [9] 8 equiv), and five drops of trifluoroacetic acid at room temperature in CH 2 Cl 2 for 17 h, following a procedure described by Lindsey et al…”

Section: Resultsmentioning

confidence: 99%

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Intramolecular Energy Transfer in Bis-porphyrins Containing Diimine Chelates of Variable Geometry as Spacers

et al. 1999

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Free-base porphyrin dimers bridged by either 6,6'-diphenyl-2,2'-bipyridine or 2,9-diphenyl-1,10-phenanthroline spacers were synthesized and characterized. Metallation of one of the porphyrins with Zn II allowed us to study intramolecular energy-transfer processes between the Zn II -porphyrin photoreceptor and the freebase porphyrin energy acceptor by time-correlated single-photon counting. The rate of energy transfer was shown to depend strongly on the nature of the bridge, being enhanced by a factor of nearly 6 when comparing the (cis) phenanthroline bridge with the trans-bipyridine bridge. A detailed analysis of the fluorescence decays suggests the presence of two slowly interconverting conformers for the 6,6'-diphenyl-2,2'-bipyridine spacer.

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Section: Resultsmentioning

confidence: 99%

“…Synthesis: Dialdehyde 1, [9] 3,5-di-tert-butylbenzaldehyde (3), [9] 3,3'-diethyl-4,4'-dimethyl-2,2'-dipyrrylmethane (4), [26,27] and p-bromophenyl-1,3-dioxolane (6) were prepared according to the literature procedures. All other chemicals were of the best commercially available grade and were used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular Energy Transfer in Bis-porphyrins Containing Diimine Chelates of Variable Geometry as Spacers

et al. 1999

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“…Kryptopyrrole 3 was commercially available; the pyrroles 1, 2, and 4 were obtained by adapting reported procedures for the hydrolysis and decarboxylation of diethyl 3,5-dimethylpyrrole-2,4-dicarboxylate 5 [30,311 and ethyl 3,4,5-trimethylpyrrole-2-carboxylate 6 [32,33] and the thermolysis of tert-butyl 3,5-dimethyl-4-carboethoxypyrrole-2- [34]. In reactions with appropriate acyl chlorides pyrroles 1-4 afforded the unstable intermediate pyrromethene derivatives 9b-f.…”

Section: Results and Discussion Synthesismentioning

confidence: 99%

“…The following compounds were prepared according to the directions cited: ethyl 2,4-dimethylpyrrole-3-carboxylate 4 [34]; diethyl 3,5-dimethylpyrrole-2,4-dicarboxylate 5 [30, 3 11; ethyl 3,4,5-trimethylpyrrole-2-carboxylate 6 [32]; tevt-butyl 3 5 dimethyl-4-carboethoxypyrrole-2-carboxylate 7 [34]; 2-formyl-3,5-dimethylpyrrole 8 [ 121; 3,5,3',5'-tetramethylpyrromethene 9a (modified for isolation as its hydrochloride salt) [ 141; 1,3,5,7-tetramethylpyrromethene-BFz complex 10a (modified procedure) [ 141; and 4,4'-dicarboethoxy-6-ethyl-3,5,3',5'-tetramethylpyrromethene 9g (modified for isolation as the hydrochloride derivative, mp 227-232°C (dec), EI-MS (relative abundance): 373 (100, M C -Cl)) [341.…”

Section: Wayelexgth (Iim)mentioning

confidence: 99%

Pyrromethene–BF₂ complexes as laser dyes:1.

Shah

Thangaraj

Soong

et al. 1990

Heteroatom Chemistry

244

172

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Condensations between 3‐X‐2,4‐dimethylpyrroles (X = H, CH3, C2H5, and CO2C2H5) and acyl chlorides gave derivatives of 3,5,3′,5′‐tetramethylpyrromethene (isolated as their hydrochloride salts): 6‐methyl, 6‐ethyl, 4,4′,6‐trimethyl, 4,4′‐diethyl‐6‐methyl, and 4,4′‐dicarboethoxy‐6‐ethyl derivatives for conversion on treatment with boron trifluoride to 1,3,5,7‐tetramethylpyrromethene–BF2 complex (TMP–BF2) and its 8‐methyl (PMP–BF2), 8‐ethyl, 2,6,8‐trimethyl (HMP–BF2),2,6,‐diethyl‐8‐methyl (PMDEP–BF2), and 2,6‐dicarboethoxy‐8‐ethyl derivatives. Chlorosulfonation converted, 1,3,5,7,8‐pentamethylpyrromethene–BF2 complex to its 2,6‐disulfonic acid isolated as the lithium, sodium (PMPDS–BF2), potassium, rubidium, cesium, ammonium, and tetramethylammonium disulfonate salts and the methyl disulfonate ester. Sodium 1,3,5,7‐tetramethyl‐8‐ethylpyrromethene‐2,6‐disulfonate–BF2 complex was obtained from the 8‐ethyl derivative of TMP–BF2. Nitration and bromination converted PMP–BF2 to its 2,6‐dinitro‐(PMDNP–BF2) and 2,6‐dibromo‐ derivatives. The time required for loss of fluorescence by irradiation from a sunlamp showed the following order for P–BF2 compounds (10−3 to 10−4 M) in ethanol: PMPDS–BF2, 7 weeks; PMP–BF2, 5 days; PMDNP–BF2, 72 h; HMP–BF2, 70 h; and PMDEP–BF2, 65 h. Under similar irradiation PMPDS–BF2 in water lost fluorescence after 55 h. The dibromo derivative was inactive, but each of the other pyrromethene–BF2 complexes under flashlamp excitation showed broadband laser activity in the region λ 530–580 nm. In methanol PMPDS–BF2 was six times more resistant to degradation by flashlamp pulses than was observed for Rhodamine‐6G (R‐6G). An improvement (up to 66%) in the laser power efficiency of PMPDS–BF2 (10−4 M in methanol) in the presence of caffeine (a filter for light <300 nm) was dependent on flashlamp pulse width (2.0 to 7.0 μsec).

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“…(2): 3-Ethyl-5-formyl-4-methylpyrrol-2-carbons~ure-ethylester (1, 8.36 g, 40 mmol)[61 wird rnit Toluol (100 ml), Ethylenglykol (25 ml) und p-Toluolsulfonsaure (0.5 g) 5 h am Wasserabscheider unter Ruckflu0 erhitzt. Nach dem Abkuhlen wird zuerst mit IOproz.…”

Section: Experimenteller Teilunclassified

Tripyrrylmethane als Bausteine zur Synthese funktioneller Porphyrine

Berlin

Breitmaier

1993

Liebigs Ann. Chem.

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Tripyrrylmethanes as Building Blocks for the Preparation of Functionalized PorphyrinsTripyrrylmethanetricarbaldehyde 4 is prepared in three steps from the tripyrrylmethanetricarboxylate 2. The mono-mesopyrrylporphyrines 6a and b a r e obtained in moderate yields by MacDonald condensation of 4 with the di-2-pyrrylmetha n e s 5a a n d b.Werden 5-Formylpyrrol-2-carbonsaure-ethylester 1 rnit Ethylenglykol in Toluol oder Benzol in Gegenwart einer Saure am Wasserabscheider erhitzt, so entsteht nicht das erwartete cyclische Acetal, sondern der symmetrische Tripyrrylmethantricarbonsaure-triethylester 21'1. Dagegen fuhrt die Reaktion des 1 entsprechenden Benzylesters rnit Ethylenglykol unter sonst gleichen Bedingungen zum erwarteten Acetal. Fur dieses Verhalten konnte ein n-Stacking der beiden aromatischen Systeme und der daraus resultierende sterische Anspruch verantwortlich sein.Obgleich diese einfache Synthese von Tripyrrylmethantricarbonsaureestern schon lange bekannt istll], wurden bisher keine Versuche beschrieben, diese analog zu den Di-2-pyrrylmethandicarbonsaureestern nach Derivatisierung zur Synthese funktionalisierter Porphyrine einzusetzen.Wir beschreiben hier die Uberfuhrung des Tripyrrylmethantricarbonsaureesters 2 in das entsprechende in den 5-Stellungen unsubstituierte Tripyrrylmethan 3, das sich rnit Phosphorylchlorid und Dimethylformamid nach Vilsmeier zu dem Tripyrrylmethantricarbaldehyd 4 formylieren IaBt. Dieser reagiert rnit den Dipyrrylmethanen 5a und b[2-51 zu den auf anderem Wege kaum darstellbaren Mono-meso-pyrrylporphyrinen 6a und b, deren verbleibende Aldehydfunktion fur weitere Reaktionen zur Verfugung steht. Experimenteller TeilSchmelzpunkte: Buchi SMP-20 (nicht korrigiert). T~is[S-(eiho~~-).carbonyl)-4-ethyl-3-meil1ylp~~rrol-2-yl]riieil1un (2):3-Ethyl-5-formyl-4-methylpyrrol-2-carbons~ure-ethylester (1, 8.36 g, 40 mmol)[61 wird rnit Toluol (100 ml), Ethylenglykol (25 ml) und p-Toluolsulfonsaure (0.5 g) 5 h am Wasserabscheider unter Ruckflu0 erhitzt. Nach dem Abkuhlen wird zuerst mit IOproz. Natronlauge, dann zweimal mit Wasser Ge 100 ml) gewaschen und rnit Magnesiumsulfat getrocknet. Das Losungsmittel wird abdestilliert, der blakosafarbene kristalline Ruckstand unter Erwiirmen in moglichst wenig Chloroform gelost und mit Diethylether (75 ml) ver-

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287. A synthesis of coproporphyrin III

Cited by 73 publications

References 0 publications

Intramolecular Energy Transfer in Bis-porphyrins Containing Diimine Chelates of Variable Geometry as Spacers

Intramolecular Energy Transfer in Bis-porphyrins Containing Diimine Chelates of Variable Geometry as Spacers

Pyrromethene–BF₂ complexes as laser dyes:1.

Tripyrrylmethane als Bausteine zur Synthese funktioneller Porphyrine

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287. A synthesis of coproporphyrin III

Cited by 73 publications

References 0 publications

Intramolecular Energy Transfer in Bis-porphyrins Containing Diimine Chelates of Variable Geometry as Spacers

Intramolecular Energy Transfer in Bis-porphyrins Containing Diimine Chelates of Variable Geometry as Spacers

Pyrromethene–BF2 complexes as laser dyes:1.

Tripyrrylmethane als Bausteine zur Synthese funktioneller Porphyrine

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Pyrromethene–BF₂ complexes as laser dyes:1.