Characterization of posticlure and the structure-related sex pheromone candidates prepared by epoxidation of (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes

trans-11,12-Epoxy-(6Z,9Z)-6,9-henicosadiene (posticlure) has been identified from a pheromone gland of the lymantriid species, Orgyia postica. Since the diversity of Lepidoptera suggests that some species utilize the structure-related epoxy compound as a sex pheromone component, epoxydienes and epoxytrienes derived from (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes with a C₁₉–C₂₁ chain were systematically synthesized and the chemical data were accumulated in order to contribute to a new pheromone research. Peracid oxidation of each triene and each tetraene produced, respectively, a mixture of three epoxydienes (cis-6,7-epoxy-9,11-diene; cis-9,10-epoxy-6,11-diene; and trans-11,12-epoxy-6,9-diene) and four epoxytrienes (cis-3,4-epoxy-6,9,11-triene; cis-6,7-epoxy-3,9,11-triene; cis-9,10-epoxy-3,6,11-triene; and trans-11,12-epoxy-3,6,9-triene). While the 9,10-epoxy compounds were unstable and, interestingly, converted into 9-ketone derivatives after chromatography over SiO₂, each positional isomer was isolated by HPLC equipped with an ODS column, and the chemical structure was determined by NMR analysis. On the GC-MS analysis with a DB-23 column, the positional isomers were also eluted separately and characteristic mass spectra were proposed. By comparing the spectral data of the epoxy compounds with a different carbon chain, diagnostic fragment ions reflecting the chemical structure were determined as follows: m/z 79, 109, 113, and M-114 for the 6,7-epoxydienes; m/z 69, 97, 111, 139, and M-111 for the 9,10-epoxydienes; m/z 57, 79, 109, 136, M-151, and M-111 for the 11,12-epoxydienes; m/z 79, 91, 105, and 119 for the 3,4-epoxytrienes; m/z 79, 124, M-124, M-96, and M-69 for the 6,7-epoxytrienes; m/z 79, 95, 109, 137, and M-108 for the 9,10-epoxytrienes; and m/z 79, 134, M-149, M-109, and M-95 for the 11,12-epoxytrienes.     

Decreased l-tryptophan concentration in distinctive brain regions of mice treated repeatedly with phencyclidine

It has been reported that repeated phencyclidine (PCP) treatment induces schizophrenia-like behavior in mice. l-Tryptophan (Trp) concentrations in brain tissues of control (n?=?8) and PCP-treated mice (10 mg/kg/day, s.c., 14 days, n?=?10) were determined using high-performance liquid chromatography (HPLC) with fluorescence detection. The HPLC method involved pre-column fluorescence derivatization with (R)-(?)-4-(N,N-dimethylaminosulfonyl)-7-(3-isothiocyanatopyrrolidin-1-yl)-2,1,3-benzoxadiazole (DBD-PyNCS). Eight different parts of the brain, namely, the frontal cortex, nucleus accumbens, striatum, hippocampus, amygdala, thalamus, hypothalamus, and cerebellum, of both groups were investigated. A significant decrease in the l-Trp concentration in the nucleus accumbens (p?=?0.024) and hippocampus (p?=?0.027) was observed in PCP-treated mice, suggesting that alteration of the l-Trp metabolism might occur in these brain parts.     

Modification effect of spherical zirconia with SiCl4 as a support of methylaluminoxane for heterogeneous single-site catalyst

Unmodified and SiCl₄-modified spherical zirconia-supported methylaluminoxane were used as cocatalyst for propylene polymerization as well as ethylene/1-hexene copolymerization in combined with Me₂Si(η³-C₁₃H₈)(η¹-N^tBu)TiMe₂ (1) at 0 °C. The modification with SiCl₄ improved the catalytic activity. The improvement was clearer in ethylene/1-hexene copolymerization than in propylene polymerization. The number average molecular weight (M_n) of polypropylenes increased linearly against the polymerization time regardless the cocatalyst used to give polymers with narrow molecular weight distribution (M_w/M_n < 1.32), indicating the living nature of the catalytic systems. Thus, propagation rate constant (k_p) and the number of active centers (C^*) were evaluated from M_n and the number of polymer-chains. When the zirconia was modified with SiCl₄, the k_p value decreased and the C^* increased. The latter effect was more significant to enhance the catalytic activity.     

Microwave-Accelerated Selective Acylation of (Hydroxyalkyl)phenols Using Acid Chlorides

Highly selective acylation of the alcoholic hydroxy group can be achieved with (hydroxyalkyl)phenols carrying both alcoholic and phenolic hydroxyls by the use of the most common acylating agents, acid chlorides, under microwave irradiation.     

A New Convenient Synthesis of α-Arylpropionic Acid Esters and α-Arylpropionitriles

Various types of α-arylpropionic acid esters were effectively obtained by the coupling reaction of aryl Grignard reagents and α-bromopropionic acid esters in the presence of nickel catalysts. α-Arylpropionitriles, precursors of α-arylpropionic acids, were also synthesized by the reaction of α-methanesulfonyloxypropionitrile and arylcopper reagents prepared from equimolar amount of arylmagnesium halides and copper(I) bromide.     

Time Courses and Time‐Resolved Spectra of Firefly Bioluminescence Initiated by Two Methods of ATP Injection and Photolysis of Caged ATP

The time‐dependent characteristics of firefly bioluminescence initiated by manual injection of adenosine triphosphate (ATP) into buffer solution containing luciferin (Ln), luciferase (Luc) and Mg²⁺ were measured with a resolution of 10 ms, and compared with those obtained by photolysis of caged ATP. The time course depends on pH; both rise and decay rates decrease when pH is lowered from 7.8 to 6.8. In contrast, the parameter λ in the kinetic formula related to diffusion of ATP is almost independent of pH. The pH dependence of the time course of bioluminescence can be explained by the same pH tendency as the rate of ATP binding at the active site of Luc. The time‐resolved spectra can be decomposed into two Gaussian components with maxima at 2.2 and 2.0 eV. At pH 7.8, the band at 2.2 eV is more intense than that at 2.0 eV for all three concentration conditions. At lower pH, the band at 2.2 eV becomes weaker than that at 2.0 eV. The intensity ratio of the 2.0 and 2.2 eV bands is constant for duration time of 600 s for both injection and photolysis experiments, and the above conclusions are unaffected by the concentration ratio [Ln]/[Luc].     

Mechanistic study of asymmetric Michael addition of malonates to enones catalyzed by a primary amino acid lithium salt

A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones.     

Synthesis of 2,3-dihydro-1H-isoindole-1-thiones via the bromine–lithium exchange between 1-bromo-2-(1-isothiocyanatoalkyl)benzenes and butyllithium

The reaction of 1-bromo-2-(1-isothiocyanatoalkyl)benzenes, which are easily derived from 2-bromophenyl ketones or (2-bromophenyl)methanamine, with butyllithium generates 1-(1-isothiocyanatoalkyl)-2-lithiobenzenes, which immediately underwent intramolecular cyclization to give rise to the corresponding 3-substituted and 3,3-disubstituted 2,3-dihydro-1H-isoindole-1-thiones in good yields.     

Improved synthesis of (R)-7-hydroxycarvone from (S)-α-pinene

A three-step synthesis of (R)-7-hydroxycarvone (1), which is anticipated to be a valuable building block for the versatile preparation of natural products, is described. Optimization of the reaction conditions for photooxygenation and migration of (S)-α-pinene 2, tetrapropylammonium perruthenate (TPAP) oxidation of the generated alcohol, and a subsequent ring-opening reaction in the presence of Cu(OTf)₂ led to the synthesis of 1 with good reproducibility. The desired product 1 was thus obtained in 46% yield over three steps.