Toshiharu Namauo

Triacylated peonidin 3-sophoroside-5-glucosides from the purple flowers of Moricandia ramburii Webb.

Triacylated peonidin 3-sophoroside-5-glucosides were isolated from the purple flowers of Moricandia ramburii Webb. (Family: Brassicaceae), and determined to be peonidin 3-O-[2-O-(2-O-(trans-feruloyl)-glucosyl)-6-O-(trans-p-coumaroyl)-glucoside]-5-O-[6-O-(malonyl)-glucoside] (1), peonidin 3-O-[2-O-(2-O-(trans-feruloyl)-glucosyl)-6-O-(cis-p-coumaroyl)-glucoside]-5-O-[6-O-(malonyl)-glucoside] (2) and peonidin 3-O-[2-O-(2-O-(trans-sinapoyl)-glucosyl)-6-O-(trans-p-coumaroyl)-glucoside]-5-O-[6-O-(malonyl)-glucoside] (3), respectively, by chemical and spectroscopic methods. In addition, one known acylated cyanidin glycoside, cyanidin 3-O-[2-O-(2-O-(trans-feruloyl)-glucosyl)-6-O-(trans-p-coumaroyl)-glucoside]-5-O-[6-O-(malonyl)-glucoside] (4), was also identified in the flowers. Peonidin glycosides have not been reported hitherto in floral tissues in to Brassicaceae.

Preparation and electrochemical and optical properties of α-octaalkylphthalocyanines with four fused TTF units

3,6-Dialkylphthalonitriles (6a) and (6b) with a fused TTF unit at 4,5-positions were prepared from dialkyltetrabromobenzenes via five step reactions (alkyl: butyl and octyl). Compounds 6a and 6b were treated with lithium in n-hexanol at 120 °C for 3 h to produce α-octaalkyltetrakis(tetrathiafulvaleno)phthalocyanines (8a) and (8b), respectively. The structure of the products was determined by 1H NMR, FAB MS, and MALDI TOF MS. The 1H NMR measurement was performed in chloroform-d at around 55 °C because of their higher aggregative property. Electrochemical and optical properties of 8a and 8b were examined by cyclic voltammetry and UV-vis and MCD spectroscopy. Molecular orbital calculations succeeded in reproducing the observed absorption spectrum of tetrakis(tetrathiafulvaleno)phthalocyanine.

Preparation of unsymmetric phthalocyanines with benzylchalcogeno and butoxy groups

A mixture of 4,5-dibenzylchalcogeno-3,6-diethylphthalonitrile and 4,5-dibutoxyphthalonitrile was treated with lithium in n-pentanol at 110 °C to give unsymmetric phthalocyanines. Optical and electrochemical properties of them were examined by UV-vis spectroscopy and cyclic voltammetry.

Photolytic preparation of tetrabromothianthrene and its transformation to dinuclear phthalocyanines

Photolysis of dibromobenzotrithiole (1) and tetrabromodibenzotetrathiocin (4) in CH 2 Cl 2 produced tetrabromothianthrene (2). Compound (2) was treated with CuCN in DMF at 150 °C to give tetracyanothianthrene (5). Dinuclear phthalocyanine (9) was constructed by treatment of a mixture of 5 and dioctoxyphthalonitrile (6) with lithium in n-pentanol.

Preparation and electrochemical and optical properties of tetrakis(dithiaselenolo)phthalocyanine

- Four o-xylylene groups of phthalocyanine (2) were removed by Birch reduction and the generated octathiolate anions were then reacted with Se to give tetrakis(dithiaselenolo)phthalocyanine (3). The dication generated from 3 in CHCl 3 /TFA was determined with UV-vis and NMR spectroscopy.

Preparation of pentathiepinoquinoline via ipso-substitution reactions of phenylsulfinyl and iso-propylsulfinyl groups with sulfur anions in liquid ammonia

3-Phenylsulfinyl-4-isopropylsulfinylquinolines (5a,b) were prepared from 3-bromoquinoline via four-step reactions. Compounds (5a,b) were treated with elemental sulfur in liquid ammonia at 120 °C for 12 h. The reaction mixture was cooled and dropped into dichloromethane and stirred for 24 h. After purification of the product, pentathiepinoquinoline (6) was obtained in low yield.

Preparation of Phthalocyaninato and Porphyrinato Titanium (IV) Benzenedichalcogenolates

Abstract The reaction of octabutoxyphthalocyaninato titanium (IV) oxide (4) and tetraphenylporphyrinato titanium (IV) oxide (6) with diethylbenzenedithiol (3a) or diethylbenzenediselenol (3b) produced the corresponding titanium (IV) complexes (5) and (7a,b) with titanium–sulfur or titanium–selenium bonds. Optical and electrochemical properties of the products were determined by ultraviolet-visible (UV-Vis) spectroscopy and cyclic voltammetry.

Preparation of Octakis (methylthio)octaethylphthalocyaninato Titanium (IV) Benzenedichalcogenolates

Octakis(methylthio)octaethylphthalocyaninato titanium (IV) oxide (PcSMeTiO) was prepared from octakis(methylthio)octaethylphthalocyanine (PcSMe) upon treatment with titanium (IV) tetrabutoxide in DMF at 130°C. The reaction of PcSMeTiO with benzenedithiol or benzenediselenol produced octakis(methylthio)octaethylphthalocyaninato titanium (IV) benzenedichalcogenolates (4a,b) bearing titanium–sulfur or titanium–selenium bonds.