3,6-diisopropyl-2-hydroxypyrazine and 3,6-diisopropyl-2-pyrazinethiol as carriers of some alkoxycarbonyl groups

Some derivatives of benzyloxycarbonylated 3,6-diisopropyl-2-hydroxypyrazine and 3,6-diisopropyl-2-pyrazinethiol were prepared and shown to be the versatile benzyloxycarbonylation reagents for amines and amino acids. It was also ascertained that 3,6-diisopropyl-2-hydroxypyrazine and 3,6-diisopropyl-2-pyrazine-thiol serve effectively as carriers of the β,β,β,-trichloroethoxycarbonyl group.     

Concise synthesis of polymethoxyflavone sudachitin and its derivatives,and biological evaluations

We accomplished a divergent synthesis of sudachitin (2), a polymethoxyflavone isolated from citrus fruits, and six derivatives from acetophenone 9, which was an intermediate in our previous synthesis of nobiletin (1). Compound 2 enhanced glucose-induced insulin secretion in INS-1D cells, but was less potent than 1. Compared with 1, compound 2 and two derivatives were more potent inhibitors of cAMP-specific phosphodiesterase.     

Application of indoline dyes attached with strongly electron-withdrawing carboxylated indan-1,3-dione analogues linked with a hexylthiophene ring to dye-sensitized solar cells

An indoline dye attached with a carboxylated indan-1,3-dione moiety linked with a hexylthiophene ring exhibited the highest conversion efficiency among six analogues and D205. This result comes from the bathochromic UV–vis absorption band, suitable energy levels, good stability for redox process, and sufficiently long excited-state lifetime.     

Determination of biotin following derivatization with 2-nitrophenylhydrazine by high-performance liquid chromatography with on-line UV detection and electrospray-ionization mass spectrometry

Currently, biotin is typically determined in Japan using a microbiological method. Such microbiological assays are sensitive, but they are not always highly specific and are also rather tedious and time-consuming. In the present study, RP-HPLC and LC-MS methods for the determination of biotin have been developed by derivatizing the carboxyl group with 2-nitrophenylhydrazine hydrochloride. 2-Nitrophenylhydrazine is used for the derivatization of carboxylic acids, and these derivatives are known to be applicable to LC-MS detection. Biotin in tablets were extracted by the addition of water and ultrasonic agitation. In order to clean up the sample solution, the filtrate was applied to an ODS cartridge and eluted with methanol. The conditions for preparing the 2-nitrophenylhydrazide derivatives were modified from a previous report for fatty acids. Good recovery rates of over 70% were obtained for the addition of 5-125 microg of biotin per formulation. The detection limit in HPLC at 400 nm was 0.6 ng per injection, with good linearity being obtained over the concentration range 0.001-0.2 microg per injection. Further, derivatives were determined by LC-MS with electrospray ionization, where the spectra indicated the molecular ions [M+H](+). The detection limit was 0.025 ng per injection in the selected ion monitoring analysis, and linearity was observed in the range of 0.6-6 ng per injection. The proposed method could be used to specifically determine the presence of biotin in relatively clean samples.     

Synthesis and properties of 2-(2-pyridyl)-1-azaazulene

The title azaazulene 3 was synthesized either by reaction of tropone with N-{(2-pyridyl)acetyl}pyridinium iodide in the presence of ammonium acetate or by palladium-catalyzed cross-coupling between 2-halo-1-azaazulene and 2-substituted pyridine. The compound shows relatively stronger basicity compared with 2,2′-bipyridyl. While 3 showed no emission from the S₁ state but from the S₂ state like azulene does, the protonated species of 3 exhibited emission from the S₁ state. Cationic metal-dependent absorption and emission relating to complexation were also studied.     

BaFeO3: a ferromagnetic iron oxide

Magnetic attraction: The cubic perovskite BaFeO(3) (see picture, Ba?blue, Fe?brown, O?white), which is obtained by a low-temperature reaction using ozone as an oxidant, exhibits ferromagnetism with a fairly large moment of 3.5?μ(B) per Fe ion above a small critical field of approximately 0.3?T. This specific ferromagnetism is attributed to the enhancement of O→Fe charge transfer that arises from deepening of the Fe(4+) d levels.     

High-resolution Fourier transform infrared absorption spectroscopy of the ν6 band of c-C3H2

The gas-phase high-resolution absorption spectrum of the ν(6) band of cyclopropenylidene (c-C(3)H(2)) has been observed using a Fourier transform infrared spectrometer for the first time. The molecule has been produced by microwave discharge in an allene (3.3 Pa) and Ar (4.0 Pa) mixture inside a side arm glass tube. The observed spectrum shows a pattern of c-type ro-vibrational transitions in which the Q-branch lines strongly and distinctly stand out in the spectrum. A combined least-squares analysis of the observed 216 ro-vibrational transitions together with 28 millimeter-wave rotational transitions from the previous study has resulted in an accurate determination of the molecular constants in the ν(6) state. The band center is found to be at 776.11622(13) cm(-1) with one standard deviation in parentheses, which is 2.3% lower than the matrix isolation value. The intensity ratio I(3)(ν(3))/I(6)(ν(6)) obtained from the observed ν(3) and ν(6) bands, 1.90(9), is somewhat lower than the ratio estimated from ab initio (2.4-2.6) and DFT (2.8) calculations.     

Studies in Cyciocopolymerization. XIII. A Study of Steric Effects in Cyciocopolymerization of Divinyl Ether with Substituted Electron-Acceptor Alkenes

The equilibrium constants for charge-transfer (CT) complex formation between divinyl ether (DVE) and several sub-stituted maleic anhydrides and 2-cyclopentene-l,4-dione were measured in CHC1₃ by use of UV spectroscopy. The copolymerizaticn of DVE with these acceptor monoolefins produced regular cyclocopolymers of constant 1:1 or 1:2 (DVE:monoolefin) composition regardless of the feed composition. Comparison of the CT complexation and the cyciocopolymerization leads to the following conclusions: 1) A strong CT complex gives regular cyclocopolymer of constant 1:1 composition having a copolymer backbone made up of only 1,4-diene units: 2) when a monoolefin is un-reactive (often sterically), the 1:1 cyclocopolymer is pro-duced: and 3) if CT complexation is weak and the monoolefin is reactive toward radicals (but not so reactive as to homo-polymerize easily), a 1:2 alternating cyclocopolymer is produced. A facile and quantitative elimination of hydrogen halides with dilute aqueous NaOH solution was found.     

Copolymerization of 2,3-Dihydropyran and Ethyl Vinyl Ether with Maleic Anhydride

2,3-Dihydropyran (DHP) and ethyl vinyl ether (EVE) were co-polymerized with maleic anhydride (MA) with benzoyl peroxide at 60°C, and 1:1 alternating copolymers were obtained. The rates were maximum at 1:1 monomer composition. Spontaneous copolymerization and solvent effect on the rate were observed in the copolymerization of DHP with MA, in which initial rates were slower in more polar solvents. Participation of charge transfer complex was considered. EVE copolymerized rapidly with MA, reaching the theoretical limiting conversion of 1:1 alternating copolymerization. Although DHP-MA comonomer pair and EVE-MA comonomer pair formed similar 1:1 charge transfer complexes, DHP copolymerized slowly with MA to produce a low molecular weight copolymer, and the limiting conversion was much lower than the theoretical one. To explain these, degradative chain transfer to DHP monomer is proposed as the initial rate of DHP-MA copolymerization is proportional to the initiator concentration to the power 1.1. Q and e values of DHP were calculated to be 0.013 and -0.93, respectively, from the monomer reactivity ratios of copolymerization of DHP with acrylonitrile [r₁ (DHP)=0.003 ± 0.006 and r₂ (AN)=3.6 ± 0.3].