Synthesis and properties of furo[4,3,2-de][1]benzopyran

A new heterocycle, furo[4,3,2-de][1]benzopyran ( 2 ), was synthesized. A key step in the sequence was the allylic bromination of 3,4-dihydrofuro[4,3,2-de][1]benzopyran ( 8 ) to give 3-bromo-3,4-dihydrofuro[4,3,2-de][1]-benzopyran ( 10 ) using N-bromosuccinimide under irradiation and high dilution conditions. Bromide 10 was dealt with 1,8-diazabicyclo[5.4.0]undec-7-ene to afford compound 2 . Several reactions of 2 were examined. Protonation of 2 in trifluoroacetic acid occurred at the 2-position to form a pyrylium ion 12 . Catalytic hydrogenation of 2 with palladium on charcoal proceeded smoothly to give 8 . Reduction of 2 by sodium and ethanol afforded 3-ethyl-4-hydroxybenzofuran ( 14 ). Electrophilic substitutions of 2 such as formylation, acetylation, and bromination, occurred easily at the 2-position. The above results show that compound 2 has both properties of benzofuran and 4-methylenepyran.     

Regioselective allylation reactions using crotyl Grignard reagent-CeCl3 systems

Regioselective allylation reactions using crotyl Grignard reagent-CeCl₃ systems are described. Regioselectivity depends on the lanthanide salts: α-product was predominantly produced with light rare earth elements such as La, Ce, Pr, Nd, whereas γ-product was formed when heavy rare earth elements were used.     

Dihydroboronium derivatives of (S,S)-1,2-bis(t-butylmethylphosphino)ethane as convenient chiral ligand precursors

Dihydroboronium derivatives of (S,S)-1,2-bis(t-butylmethylphosphino)ethane (t-Bu-BisP*) were prepared and used as chiral diphosphine ligand precursors in Rh-catalyzed asymmetric hydrogenation of methyl (Z)-acetamidocinnamate to afford the hydrogenation product in up to 94% enantioselectivity.     

Enhancement of electronic excitation energy transfer in the colloidal crystals of colloidal silica suspensions doped with fluorescent dyes

The efficiency of electronic excitation energy transfer from photo-excited rhodamine 110 (Rh110, energy donor) to rhodamine B (RhB, energy acceptor) in an exhaustively deionized colloidal silica suspension has been studied. This colloidal suspension shows Bragg reflection due to the formation of colloidal crystals and the Bragg-peak wavelength is controllable by the volume fraction of the silica spheres. When the Bragg-peak wavelength matches with the fluorescence band of Rh110, a depletion was observed in the Rh110 fluorescence spectrum. This means the fluorescence of Rh110 is partially trapped due to the Bragg reflection inside the crystal lattice. In the coexistence of RhB, the enhancement of RhB fluorescence intensity was observed. These facts clearly indicate the trapped photon energy of Rh110 is efficiently transferred to RhB within the colloidal crystals. The quantitative measurements showed that the enhancement of the transfer efficiency is 20% (or slightly more) in the present experimental conditions.     

Furan derivatives. Part 8 On substituent effects in the synthesis of 4,5-dihydro-3H-naphtho[1,8-bc]furans

4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 6 which have various substituents (R¹ and R²) have been synthesized from 8-oxo-5,6,7,8-tetrahydro-1-naphthyloxyacetic acids 1 and 3 or their ethyl esters 2 . The reaction of acids 1 and 3 with sodium acetate in acetic anhydride gave a mixture of furans 4 and 6 and lactones 5 and 7 . The ratios of the products were varied according to the types of substituents (R¹ and R²) in acids 1 and 3 . As the substituent R¹ (R² = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, production of furans 4 became more difficult. However, when a phenyl group was used as the substituent, furan 4 was obtained in good yield. Similarly, as the substituent R² (R¹ = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, furan formation was more difficult. In contrast, acids 3 which had electron-withdrawing substituents such as chlorine, bromine or a nitro group at the 4-position afforded furans 6 in good yield. 4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 4,5-dihydro-3H-naphtho[1,8-bc]furan-2-carbocylic acids 8 were synthesized from the reaction of esters 2 and potassium hydroxide in dioxane. When the substituents R¹ or R² in esters 2 were varied from hydrogen to a methyl, ethyl or isopropyl group the total yields of furans 4 and furancarboxylic acids 8 were reduced.     

Change of concentrations of trace elements and protein contents in the liver of zinc deficient mice

The concentrations of essential trace elements and proteins in cytosolic fraction of hepatic cells of mice fed with Zn-deficient diet (Zn-def, mice) and control were determined by ICP-MS and BCA protein assay method, respectively, after division into forty fractions by gel filtration chromatography. The concentrations of zinc and proteins decreased in the 14–17th fractions of Zn-def, mice, whereas cobalt concentrations increased in the 14, 17, and 18th fractions. However, no significant differences were found on the gel after SDS-PAGE for the 12–21st fractions, although the BCA protein assay date showed the decrease of protein amounts in 13–15th fractions of Zn-def. mice.     

First asymmetric total synthesis of (+)-steganacin determination of absolute stereochemistry

(+)-Steganacin was synthesized in a new and highly specific asymmetric pathway based on the novel application of chiral γ-lactone as a chiral synthon. By this synthesis the absolute stereochemistry of natural (?)-steganacin could be determined in unequivocal way.     

Solvent extraction of tetrachloronitridotechnetate(VI) ion with tetraphenylarsonium chloride

Radiochemical and spectrophotometric studies on the solvent extraction of tetrachloronitridotechnetate(VI) ion with tetraphenylarsonium chloride into chloroform have been reported. Analysis of the dependence of the distribution ratio for technetium species on the concentration of hydrogen ion (0.1–1.0M) revealed that an equilibrium between tetrachloronitridotechnetate(VI) ion and [(H₂OCl₃NTc–O–TcNCl₃(H₂O)]^2– is established in the aqueous phase. However, formation of di(-O) dimer was suggested, when the concentration of hydrochloric acid is less than 0.2M. The extraction constant for technetium and formation constant for -oxo technetium nitrido complex were evaluated.     

Synthesis and characterization of flavylium salts having three types color depending on recrystallization conditions

Three types of flavylium salts (FVs, yellow, green and red) have been synthesized and the colors depended on recrystallization conditions. The existence of these color states was confirmed by diffuse reflectance spectra. The spectra were almost the same as the absorption spectra in ethanol solution. The molecular state of FVs in crystals will be the same as that in solutions. The crystal colors of the FVs are controlled by the recrystallization conditions.     

Diaminothiazoles and diaminothiophenes

Several 2,4-diaminothiazoles and 2,4-diaminothiophenes could be easily obtained by metallation using LDA from aminomethylthiomethylenecyanamides $\text{2}$ and aminomethylthiomethylenemalononitrile, respectively.