Regioselective sulfonation of 2-porphyrinylthiophene under kinetic and thermodynamic control

Tetrahedron Letters

Volumn 49, Issue 40, 2008, Pages 5810-5812

  Arai, Yonbon ^a   Nakazaki, Jotaro ^a   Segawa, Hiroshi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

2 PORPHYRINYLTHIOPHENE; MESO TETRA(THIEN 2' YL)PORPHYRIN; PORPHYRIN DERIVATIVE; SULFURIC ACID;

ARTICLE; CHEMICAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE; REVERSED PHASE HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; SUBSTITUTION REACTION; SULFONATION; TEMPERATURE DEPENDENCE; THERMODYNAMICS;

TETRA;

EID: 49549121584     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2008.07.124     Document Type: Article

References (17)

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13. 3. The dried solid mixture was extracted with methanol for removing excess salts.
14. Reversed-phase liquid chromatography was performed using a Shimadzu Shim-pack PREP-ODS(H)Kit mounted on a Shimadzu LC-6AD HPLC system. All the experiments were conducted at room temperature. As a mobile phase, methanol/water (typically 54:46, v/v: the composition was changed depending on conditions such as concentration and reaction temperatures) with 0.01 M sodium phosphate buffer (pH 6.8) was used. The reaction mixtures dissolved in distilled water were injected into the sample loop (5 ml). Five fractions with similar absorption spectra were observed, and the area ratio of each fraction (monitored with UV-vis absorption) was found to change systematically depending on the sulfonation temperature. Collected fractions were purified out of salt mixture by utilizing the same HPLC system, where the first eluent of methanol/water (20:80, v/v) extracts majority of inorganic salts and the second eluent of methanol extracts remaining porphyrins. Compound 1 exited from the column first, and the retention time of other isomers became longer with the increasing number of 4-sulfothienyl group. The total yields of the tetrasodium salts of sulfonated meso-tetrakis(thien-2′-yl)porphyrin isomers at each reaction temperature were 54% (20 °C), 49% (50 °C), 50% (80 °C), 51% (110 °C) and 15% (130 °C).
15. max/nm (log ε) = 421 (5.55), 522 (4.17), 562 (3.79), 587 (3.84), 646 (3.31).
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17. a1 means that the electronic properties of 5- and 4-sulfothienyl groups differ in a considerable extent.