769-86-8Relevant articles and documents
Synthesis of internally alkylated azuliporphyrins
Moriones, Julian S. D.,Latham, Alissa N.,Lash, Timothy D.
, p. 817 - 829 (2020/01/21)
Examples of internally alkylated azuliporphyrins were prepared by MacDonald-type 3 + 1 condensations. 2-Methyl- and 2-ethylazulene reacted with an acetoxymethylpyrrole in the presence of an acid catalyst to give azulitripyrranes. Following cleavage of the terminal protective groups, condensation with a diformylpyrrole in the presence of hydrochloric acid and oxidation with ferric chloride afforded 21-alkylazuliporphyrins. An azulene dialdehyde similarly reacted with an N-methyltripyrrane to generate a 23-methylazuliporphyrin. The products could only be isolated in protonated form and the free-base internally alkylated azuliporphyrins proved to be unstable. Nevertheless, the dications are highly diatropic and the internal alkyl group resonances were shifted upfield to beyond -3 ppm. Reaction of a 23-methylazuliporphyrin with palladium(II) acetate primarily afforded a palladium(II) complex with loss of the internal methyl substituent. However, two palladium(II) benzocarbaporphyrins were also identified that were formed by sequential oxidative ring contraction and methyl group migration. Internally alkylated azuliporphyrins provide new insights into the reactivity of the system and the results show that the introduction of alkyl substituents within porphyrinoid cavities greatly modifies the properties of these structures.
Transition metal compounds
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, (2008/06/13)
The present invention relates to a catalyst for polymerization of α-olefin, which comprises: an essential component (A) of a transition metal compound, an essential component (B) of an ion exchangeable layer compound except for silicate, or an inorganic silicate, and an optional component (C) of an organoaluminum compound, said component (A) being represented by the general formula (I):
Synthesis and Properties of Fluoroazulenes. II. Electrophilic Fluorination of Azulenes with N-Fluoro Reagents
Ueno, Tetsuya,Toda, Haruhiko,Yasunami, Masafumi,Yoshifuji, Masaaki
, p. 1645 - 1656 (2007/10/03)
1-Fluoro- and 1,3-difluoroazulenes were synthesized for the first time by the electrophilic fluorination of azulenes with N-fluoro reagents. Selective preparation of 1-fluoroazulenes were performed by the fluorination of methyl azulene-1-carboxylates, followed by demethoxycarbonylation in 100% H3PO4 2-Substituted azulenes were fluorinated in higher yields. In the 1HNMR of 1-fluoroazulene, long-range .JFH values were not observed at H-2 and H-8, in contrast to those for 1-fluoronaphthalene. The 1-fluorine atom causes significant bathochromic shifts in the visible absorption of azulene, due to the so-called +Iπ effect.