Synthesis of photoreactive polyimide having indan structure

Polyimide containing an indan unit and alkyl moiety with a high molecular weight was prepared from 5,7‐diamino‐1,1,4,6‐tetramethylindan and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride. This polyimide was amorphous and soluble in common organic solvents, such as tetrahydrofuran, chloroform, and cyclopentanone. Thermogravimetry of the polyimide showed good thermal stability, indicating that a 10% weight loss of the polyimide was observed at 500 °C in nitrogen. The glass‐transition temperature of the polyimide was not observed by DSC measurement between room temperature and 400 °C at a heating rate of 10 °C/min (Apparatus: DSC3100 MAC Science Co., Ltd.). Transparency of the polyimide at 365 nm was 80%. The polyimide acted as a photosensitive resist of negative type by UV radiation. The resist had a sensitivity of 31 mJ/cm² and a contrast of 2.3 when it was developed with cyclopentanone at room temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 423–428, 2002     

Separation behaviors of xylenol isomers by gas chromatography with helps of hydrogen bonding

Summary Xylenol isomers can be resolved on most polyols (sugars or sugar alcohols) and polyethers (polyethylene glycol or polypropylene glycol) with hydrogen-bonding interaction. They are separated on vinical polyols which have more hydroxy hydrogen than tetrol, and even on vicinal triol when its hydroxy hydrogen is acidic (stronger proton donor). The stronger is the hydrogen bonding interaction between xylenols and the liquid phase, the better is the separation of 2,4- and 2,5-xylenol, and the poorer the separation of 2,4-and 2,3-xylenol.     

Application of negative chemical ionization mass spectrometry to the structure elucidation of perfluorochemicals and related compounds

The negative chemical ionization mass spectra of representative perfluorinated alkanes, cycloalkanes, ethers and tertiary amines have been examined, using Ar at about 0.5 torr as the reagent gas. The compounds chosen are typical of those under study as components of fluorochemical emulsion blood substitutes. Many such PFC's, particularly those with cyclic or branched structures, give intense molecular ions; most give simple spectra with a few major fragment ions at high mass, in marked contrast to the EI spectra which are dominated by m/e 69 (CF₃+) and 131 (C₃F₅+) of no value for structure elucidation. NCI-GC/MS is more sensitive than conventional EI-GC/MS and promises to be more generally useful for structure determination. Specific examples from the various classes will be presented, and their NCI and EI mass spectra compared.     

Efficient synthesis of 2-modified 1alpha,25-dihydroxy-19-norvitamin D3 with Julia olefination: high potency in induction of differentiation on HL-60 cells

Six novel 2-substituted analogues of 1alpha,25-dihydroxy-19-norvitamin D(3), 6a,b-8a,b, were efficiently synthesized utilizing (-)-quinic acid as the A-ring precursor. The C2-modified A-rings were prepared as 4-alkylated (3R,5R)-3,5-dihydroxycyclohexanones 12-15 from (-)-quinic acid based on radical allylation at the C4 position of methyl (-)-quinicate. The new type of the CD-ring coupling partner 23 was synthesized from 25-hydroxy Grundmann's ketone 19 to apply to the modified Julia olefination to construct a diene unit between the A-ring and the CD-ring. The coupling yields, including a deprotection step, were 47-62%. After the separation of the diastereomers based on C2 stereochemistry, the structure (2alpha or 2beta) was determined by (1)H NMR experiments and compared to DeLuca's 2-methyl- and 2-ethyl-1alpha,25-dihydroxy-19-norvitamin D(3). Thus, the synthesized 2alpha-(3-hydroxypropyl)-1alpha,25-dihydroxy-19-norvitamin D(3) (8a) showed almost the same potency in binding to the bovine thymus vitamin D receptor (VDR) as the natural hormone 1, while its beta-isomer 8b had only a 3% affinity. Both 2alpha-allyl- and 2alpha-propyl-1alpha,25-dihydroxy-19-norvitamin D(3) (6a and 7a) and their 2beta-analogues (6b and 7b) possessed a weak affinity for the VDR. The strong VDR ligand 8a was ca. 36-fold more potent in induction of HL-60 cell differentiation than 1, and interestingly, even the weaker ligand 8b showed a 6.7-fold higher potency in the cell differentiation activity than that of 1.     

Determination of trace moisture in hydrogen chloride gas by Karl Fischer titration

Moisture of several ppm in hydrogen chloride gas has been accurately determined by a new method using the Karl Fischer reagent, which hitherto had a limitation in accuracy because of a partial reaction with hydrogen chloride when direct titration was employed.The moisture in the sample gas was collected in a cold trap kept at about ?80 °C while the hydrogen chloride gas passed through and the frozen moisture was dissolved by pyridine-methanol (1:1) solvent. a KF Reagent of factoe: 0.35 mg H₂O/ml.Titration by the Karl Fischer reagent having the equivalency factor of, e.g., 0.5 mg H₂O/ml was carried out and the concentration of the moisture was calculated from the sample volume used.     

Synthesis of block copolymer with polystyrene and nylon units

Bis-ε-aminocaproylaminocaproylhexamethylenediamine ( I ) was synthesized as an analog of 6-nylon pentamer diamine, and its incorporation into block copolymers was studied with the use of α,ω-dihydroxyl, α,ω-bisdimethylchlorosilyl, and α,ω-diepoxy polystyrene. In the course of the experiments, the stability and the reactivity of 4,4′-diphenylmethane diisocyanate and tetramethylene diisocyanate in aprotic dipolar solvents were examined by infrared spectroscopy. The only usable solvent, N-methylpyrrolidone, was found still inadequate for the synthesis involving I, diisocyanate, and α,ω-dihydroxyl polystyrene. A block copolymer having M _n = 18,000 was obtained by the reaction of I and α,ω-diepoxy polystyrene. All T_g values of the block copolymers were above 90°C, higher than for polystyrenes with corresponding molecular weight.     

Reaction of tetraazathiapentalene and thiadiazolopyrimidine derivatives with heterocumulenes: Cycloaddition and elimination reactions via hypervalent sulfur intermediates

Tetraazathiapentalene derivative 1 reacts with heterocumulenes such as diphenylketene (2) and 2‐pyridylisothiocyanate (5) to give heterocycles 3, 6 and 7 with elimination of methylisothiocyanate. The reactions of thiadiazolopyrimidine derivatives 8a‐b with ethoxycarbonyl isothiocyanate (9) and carbon disulfide (11) gives heterocycles 10 and 12 via thermal decomposition of 1:1 cycloadducts C and D which have a hypervalent sulfur. The mechanistic and reactivity features of these reactions are described.     

A new synthetic method: Direct replacement of the nitro group by hydrogen or deuterium

The nitro group in tertiary or secondary aliphatic nitro compounds is replaced by hydrogen or deuterium on treatment with tributyltin hydride or tributyltin deuteride, respectively.     

Preparation and properties of molybdenum and tungsten dinitrogen complexes : `XVI. Electrochemical properties of tungsten and molybdenum diazoalkane complexes

Diazoalkane complexes of type [MF(NNCRR′)(dpe)₂][BF₄] (M = Mo or W; dpe = Ph₂PCH₂CH₂PPh₂), which are easily derived from bis(dinitrogen) complexes [M(N₂)₂(dpe)₂], undergo consecutive one- and two-electron oxidations and reductions under voltammetric conditions at a platinum electrode. The ESR spectra of the species generated by the controlled potential electrolysis show that primary oxidation occurred on the metal atom (M = Mo) and reduction on the two nitrogen atoms in the diazoalkane ligands (M = Mo or W).     

Multiplex amplified product-length polymorphism analysis of 36 mitochondrial single-nucleotide polymorphisms for haplogrouping of East Asian populations

We present a reliable, rapid, and economical multiplex amplified product-length polymorphism (APLP) method for analyzing the haplogroup-diagnostic mitochondrial single-nucleotide polymorphisms (mtSNPs) in East Asian populations. By examining only 36 haplogroup-specific mtSNPs in the coding region by using four 9-multiplex polymerase chain reaction (PCR) and subsequent electrophoresis, we could safely assign 1815 individuals from 8 populations of Japanese, Korean, Chinese, and Germans to 45 relevant haplogroups. This multiplex APLP analysis of coding-region mtSNPs for haplogrouping is especially useful not only for molecular phylogenetic studies but also for large-scale association studies due to its rapid and economical nature. This is the first panel of mtSNPs in the coding region to be used for haplogrouping of East Asian populations.