Stereoselective acid-catalyzed homoallylic rearrangement of cyclopropylsilylmethanols: an efficient route to Z-homoallyl derivatives

Treatment of cyclopropylsilylmethanols derived from cyclopropyl silyl ketones with acid catalyst gives the corresponding silyl-substituted homoallyl derivatives in high yields with good stereoselectivity, independent of the substituents on the cyclopropyl ring. Cyclopropylsilylmethanols having a n-, s-butyl or phenyl group on the carbinyl carbon react to afford the E-homoallyl derivatives selectively. On the other hand, the reaction of cyclopropylsilylmethanols having a tert-butyl group gives Z-isomers exclusively. The following protiodesilylation of the resulting homoallyl derivatives proceeds with retention of configuration.     

Cloning and sequence analysis of the poly(3-hydroxyalkanoic acid)-synthesis genes ofPseudomonas acidophila

Pseudomonas acidophila can grow with CO₂ as a sole carbon source by the possession of a recombinant plasmid that clones genes that confer chemolithoautotrophic growth ability derived from the H₂-oxidizing bacteriumAlcaligenes hydrogenophilus. H₂-oxidizing bacteria produce poly(3-hydroxybutyric acid) (PHB) from CO₂, but recombinant P.acidophila can produce the more useful biopolymer poly(3-hydroxyalkanoic acid) (PHA). In this study, thepha genes ofP. acidophila were cloned and a sequence analysis was carried out. A gene library was constructed using the cosmid vector pVK102. A recombinant cosmid carrying thepha genes was selected by the complementation of a PHB-negative mutant ofAlcaligenes eutrophus H16. The resulting recombinant cosmid pIK7 contained a 14.8-kb DNA insert. Subcloning was done, and the recombinant plasmid pEH74 was selected by hybridization with theA. eutrophus H16pha genes.Escherichia coli possessing pEH74 produced PHB, indicating that pEH74 contained thepha genes ofP. acidophila. The nucleotide sequences of the PHA-synthesis genesphaA (3-ketothiolase),phaB (acetoacetyl-CoA reductase), andphaC (PHA synthase) in pEH74 were determined. The homologies ofphaA, phaB, andphaC betweenP. acidophila andA. eutrophus H16 were 64.7, 76.1, and 56.6%, respectively.

     

Gas chromatographic-mass spectrometric profile of organic acids in urine and serum of diabetic ketotic patients

The organic acids in the urine and serum of diabetic patients with ketoacidosis and disturbance of consciousness were studied using acidification, extraction, evaporation, methoxime formation and trimethylsilylation, gas chromatographic separation and mass spectrometric identification procedures. The organic acid profile of 1 ml of serum ultrafiltrate was obtained with good separation using a gas chromatograph equipped with a glass capillary column and a splitless injector. 5-Hydroxyhexanoic acid and 3-hydroxyvaleric acid were identified for the first time in the urine of diabetic patients with ketoacidosis. Urinary excretion and serum concentrations of 2,3-dideoxypentonic acid were increased in diabetic patients.     

Synthesis and properties of polymeric azine and thiazine dyes

Some polymeric azine or thiazine dyes were prepared by radical polymerization of dye monomers or by polymer reactions between dyes and suitable prepolymers, and their photoredox reactivities were studied. The thionine polymers containing labile ? OH groups exhibited photochromism and thermochromism, which were extremely sensitive to the moisture content of the polymer film. The reversibility of the photochromism and thermochromism increased with the water content in the film. The water-soluble polymeric dyes were photobleached under the influence of suitable reducing agents. The degree of photobleaching was smaller than for the monomeric systems except for the dye polymers containing ? OH groups, probably because of the large steric hindrance of the polymers.     

Synthesis of poly(2,5-dimethylphenylene sulfide) through oxidative polymerization of sulfur chloride with p-xylene

Poly(2,5-dimethylphenylene sulfide) was prepared by oxidative polymerization of sulfur chloride with p-xylene using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as an oxidizing agent. The reaction proceeded efficiently under atmospheric pressure and at room temperature. The polymer formed had a high melting temperature and linear structure which was confirmed by spectroscopies. The effects of reaction time, solvent, temperature and oxidizing agent on polymerization are also discussed.     

Synthesis of two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids

[structures: see text] Two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids, 6-hydroxy-3-methyl-8-(phenylethyl)-2,5-dihydro-1-benzoxepin-9-carboxylic acid (radulanin E) (1) and 9-hydroxy-3-methyl-2,5-dihydro-1-benzoxepin-7-carboxylic acid (2), were synthesized using Stille coupling followed by Mitsunobu cyclization.     

Hydrodynamic limit for a spin system on a multidimensional lattice

Summary The hydrodynamic limit for a Markov process of [0, )-valued spin fields on a periodic multidimensional lattice is studied. In the process a positive real number, called energy, is attached to each site of the lattice and each couple of adjacent sites exchange thier energy by random amounts at random times. The law of the exchange is such that the sum of the total energy is conserved, and that the process is reversible and of gradient type for the energy distribution. We show that under diffusion type scaling of space and time, the macroscopic energy distribution converges to a deterministic limit which is characterized by a non-linear diffusion equation /t=2^–1P(), whereP is an increasing function which in a typical case equals const·².     

Drying dissipative patterns of colloidal crystals of silica spheres in organic solvents

Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter) in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics of colloidal particles in the drying dissipative pattern formation.     

Anionic polymerization and copolymerization of S-methyl thiomethacrylate

S-Methyl thiomethacrylate (methyl thiolmethacrylate, MTMA) was polymerized with a variety of anionic initiators such as n-BuLi, octylpotassium, PhMgBr, and Et₂AlNPh₂ in toluene and THF. Stereoregularity of the polymer (PMTMA) was determined from the ¹H-NMR spectrum of poly(methyl methacrylate), which had been derived from PMTMA, because the α-methyl resonance in the ¹H-NMR spectrum of PMTMA was not satisfactorily solved owing to the overlap of pentad signals. The ¹³C-NMR spectrum of PMTMA also showed the splitting due to pentad sequences. Stereoregularity of PMTMA was always low compared with that of poly(methyl methacrylate), which was prepared under the same reaction conditions. MTMA was much more reactive than methyl methacrylate and methacrylonitrile in the copolymerization with n-BuLi in toluene and in THF at ?78°C. The lower stereoregulation of the polymerization of MTMA and the higher reactivity of MTMA were mainly ascribed to the higher resonance effect of MTMA.