Novel Cu-and Co-phthalocyanines (7a-e, 8a, b) possessing intramolecular crown ether bridges between their different aromatic rings were successfully synthesized from the reaction of the corresponding bisphthalonitriles (6a-e) bearing polyethyleneoxy chains in the presence of CuCl and CoCl 2 , respectively. As 1,8-diazabicyclo [5.4.0]-7-undecene (DBU) was used as a base in n-pentanol at reflux temperature for 30 h under N 2 atmosphere, these new phthalocyanines were found to be characteristic of satisfactory solubility in some of organic solvents, and showed strong absorption bands in ultraviolet and visible wave length region (l max Z719-739 nm). Extraction experiment of metal chlorides (NaCl, KCl, MgCl 2 , CaCl 2 , CeCl 3 , ZnCl 2 , FeCl 3 ) in chloroform was carried out by using Cu-phthalocyanine (7b) bearing two intramolecular bridges with tri(ethyleneoxy) chains. Among these metal salts, 7b formed a complex (9b) with only FeCl 3 , which showed a dark-red amorphous solid. Spectroscopic analysis of the complex (9b) indicated that original strong absorption bands near 738 nm characteristic for phthalocyanines completely disappeared, and new two strong bands appeared near 799-853 nm. FAB-MASS spectrum of the complex (9b) showed that new strong peaks came out in the region centered at m/zZ1879 and 1881 besides original peaks in the region centered at 1488, which corresponded to molecular peak of the starting phthalocyanine (7b). These facts indicated that the complex (9b) included two molecules of FeCl 3 into the protonated crown ether bridges of the phthalocyanine skeleton. Furthermore, it was found that the complex (9b) was transformed to the original phthalocyanine (7b) quantitatively by treatment with triethylamine. q

Electroreduction of benzoic anhydride derivatives in the presence of aliphatic acid anhydrides gave the corresponding C- and O-diacylated products or 1,2-diacetoxy olefins depending upon the reaction conditions. Particularly, nucleophilic acylation of carbonyl carbon atoms may be an interesting reaction in organic synthesis. C- and O-diacylated products are useful as starting materials of sympathomimetic drugs such as epinephrine and ephedrine derivatives.

Treatment of anthracene or benzyl acrylate with magnesium turnings for Grignard reaction in the presence of various acid chlorides in N,N-dimethylformamide at room temperature brought about one-pot reductive double C-acylation or tandem intermolecular cycloaddition to give the corresponding C-diacylated products in satisfactory yields.

A novel one-pot double C-acylation of anthracene or benzyl acrylates is achieved by electron transfer from Mg-metal to obtain 9,10-diacylated 9,10-dihydroanthracenes or keto esters of type (X) and (XI), respectively. -(MATSUNAMI, M.; SAKAI, N.; MORIMOTO, T.; MAEKAWA, H.; NISHIGUCHI*, I.; Synlett 2007, 5, 769-774; Dep. Chem., Nagaoka Univ. Technol., Nagaoka, Niigata 940-21, Japan; Eng.) -Mais 30-071