Distribution analysis of epoxy groups in polymers by derivatization-electron probe X-ray microanalysis.

An analytical method, referred to as "derivatization-electron probe X-ray micro-analysis (XMA)", has been developed to determine the distribution of a small amount of the functional groups in a polymer. The suitable conditions for the derivatization reaction with epoxy groups, which contribute to the hardening reactions of polymers, were investigated. It was found that epoxy groups in polymers were derivatized selectively using gas-phase esterification with hydrochloric acid (HCI). The most suitable amount of HCl in a 50 ml vial was 300 microl. After setting a sample in the vessel without directly contacting the reagent, by reacting the reagent and the sample at 25 degrees C for 1 h, the highest reaction yield and selectivity were obtained. By derivatization-XMA using this reaction condition, the measurement of the distribution of epoxy groups in the polymer became feasible. Actual applications to a depth analysis of epoxy groups in the hardened acrylic coating and epoxy resin proved that this method is useful for the characterization of polymers and for the study of the hardening reaction of polymers.     

Studies on the syntheses of heterocyclic and natural compounds. Part 939: An efficient and stereoselective synthesis of des-a-ring steroids—potential intermediates to estradiol,cortisone and progesterone

A stereoselective synthesis of des-A-ring steroids $\text{9}$ and $\text{17}$ has been achieved by an intramolecular cycloaddition of 3-isopropenyl-5-(4-methoxybenzocyclobutenyl) pentan-2-one-2-ethylene ketal $\text{7}$ and 1-(4-methoxy-benzocyclobutenyl)-4-methylpent-4-en-3-ol $\text{16}$, respectively.     

Studies on the syntheses of heterocyclic compounds—DCXCIII: A total synthesis of atheroline by photolysis

Atheroline (3) an oxoaporphine alkaloid, has been synthesised by photolysis of 8 bromo 1-(3-hydroxy-4-methoxybenzoyl)-6,7-dimethoxyisoquinoline (13) in the presence of sodium hydroxide.     

Syntheses of Polycyclic Natural Products Employing the Intramolecular Double Michael Reaction

The one-pot intramolecular double Michael reaction of compounds having two different α, β-unsaturated carbonyl groups to form polycyclic compounds can be carried out by three different methods: in the first the substrate is treated with lithium hexamethyldisilazide, in the second with chlorotrimethylsilane, triethylamine, and zinc chloride at an elevated temperature, and in the third with tert-butyldimethylsilyl trifluoromethanesulfonate and triethylamine. The reaction proceeds with complete regioselectivity and high stereoselectivity following a stepwise mechanism. Spiro-fused bicyclo[2.2.2]octane derivatives can be constructed with high stereoselectivity by the intromolecular double Michael reaction by using the first method. Enantiomerically pure atisine and the enantiomer of atisirene were synthesized stereoselectively by application of this methodology. The syntheses of steroids and angular triquinane-type sesquiterpenoids were possible with the second method. Heterocyclic compounds with a bridgehead nitrogen atom were obtained by the reaction of α, β-unsaturated amides following the second and third methods. The asymmetric synthesis of tylophorine with diastereofacial control was achieved by the intramolecular reaction according to the third method. The sulfur-mediated intramolecular double Michael reaction utilizing the third method produced trans-hydroindane derivatives. Furthermore, the intramolecular Michael-aldol reaction can be employed in synthesizing polycyclic systems with cyclobutane units by treatment with tert-butyldimethylsilyl trifluoromethanesulfonate in the presence of triethylamine. The intermolecular double Michael reaction and related reactions will also be described.     

A modified synthesis of codamine under eschweiler-clarke conditions

Codamine (1) was obtained in 88.4% yield by Eschweiler-Clarke reaction of X with formalin and formic acid, whereas it formed in 46.2% yield in case of Mannich reaction of X with formalin and hydrochloric acid.     

Stereoselective Construction of Copaborneol and Longiborneol Frameworks by Intramolecular Double Michael Reaction

Stereoselective syntheses of tricyclo[5.3.0.0(3,8)]decane 22 and tricyclo[6.3.0.0(3,9)]undecane 26, the basic skeletons of copaborneol and longiborneol, were achieved by the intramolecular double Michael reactions of 2-cyclopenten-1-ones 15-17. The substrates were prepared starting with tricyclo[5.2.1.0(2,6)]deca-4,8-dien-3-one (6). The intramolecular double Michael reactions were carried out under three different conditions: TMSCl-Et(3)N-ZnCl(2), TMSI-(TMS)(2)NH, and Bu(2)BOTf-(TMS)(2)NH. The framework 26 of longiborneol was constructed in good yields using the latter two reagent systems.     

Intramolecular double Michael reaction. Part II. Synthesis of isoatisirene type compound

Intramolecular double Michael reaction of the α,β-unsaturated enone ester (16), prepared from the dienone (5), stereoselectively gave the tetracyclic product (17), which was converted into the isoatisirene type compound (20).     

Stereoselective olefinic cyclization assisted by the selenyl group — biogenetic-type synthesis of caparrapi oxide

The acid catalysed cyclization of β-hydroxy selenide ($\text{4}$), which was prepared from nerolidol ($\text{1}$) $\text{via}$ the epoxide ($\text{3}$), was carried out to give bicyclic ether ($\text{5}$) directly which was further transformed into caparrapl oxide ($\text{6}$).     

Superoxide anion-scavenging effect of 2-amino-1,3-selenazoles

We investigated the superoxide anion scavenging effects of thirteen 2-amino-1,3-selenazoles using a highly sensitive quantitative chemiluminescence method. At 166 microM, the 2-amino-1,3-selenazoles scavenged in the range of 14.3 to 96.7% of O2-. 2-Piperidino-1,3-selenazole and 4-phenyl-2-piperidino-1,3-selenazole exhibited the strongest superoxide anion-scavenging activity among the 2-amino-1,3-selenazoles. The 50% inhibitory concentrations (IC50) of 2-piperidino-1,3-selenazole and 4-phenyl-2-piperidino-1,3-selenazole were determined to be 4.03 microM and 92.6 microM, respectively. Thus, these compounds acted in vitro as effective O2- scavengers.