Reaction of [α-(trimethylsilyl)benzyl]ferrocenes with α-ferrocenylbenzyl cations

Although methanolysis of [α-(trimethylsilyl)benzyl]ferrocene (I) and [p-methyl-α-(trimethylsilyl)benzyl]ferrocene (II) in the presence of anhydrous ferric chloride merely gave α-ferrocenylbenzyl methyl ether (III) and p-methyl-α-ferrocenylbenzyl methyl ether (IV), respectively, acid-catalyzed methanolysis of (I) and (II) in the presence of an equimolar amount of (III) or (IV) afforded 1,2-diferrocenyl-l,2-diarylethanes. It is suggested that one electron oxidation of [α-(trimethylsilyl)benzyl]ferrocene by α-ferrocenylbenzyl cation generated from α-ferrocenylbenzyl methyl ether, and subsequent methanolysis of the resulting substituted ferricenium ion may occur to give the two species of α-ferrocenylbenzyl radical, which in turn undergo an approximately statistical coupling.     

A new Zn(II) coordination polymer with 4-pyridylthioacetate: assemblies of homo-chiral helices with sulfide sites

A coordination polymer [Zn(pyta)(OH)] (pyta = 4-pyridylthioacetate), was synthesized and structurally characterized; it is constructed by an alternating assembly of two types of homo-chiral helices, [Zn-OH] and [Zn-pyta], in which the sulfide moieties are fastened in the latter columns.     

KINETICS OF ENZYMATIC PHOTOREACTIVATION STUDIED WITH PHAGE T1 AND ESCHERZCHZA COLI Bs-1*

Abstract— The kinetics of enzymatic photoreactivation (PR) of u.v.-induced killing was compared among E. coli B_s-1, phage T1 in B_s-1 and phage T1 in irradiated B_s-1. The PR action spectrum showed no substantial difference between PR of B_s-1 and PR of T1 in B_s-1. The PR D₃₇ (i.e. the PR dose required to reactivate all but 37 per cent of the reactivable lethal lesions) was found to decrease linearly with decreasing U.V. dose whether U.V. was given to produce pyrimidine dimers in B_s-1 DNA, which then compete with irradiated T1 DNA for PR enzyme, or to B_s-1 or T1 DNA to produce dimers serving as substrate for the PR enzyme. A generalized Michaelis-Menten formula was used to analyze the data and the following conclusions were drawn. (1) The number of PR enzyme molecules per cell available for PR of T1 DNA inside the B_s-1 host is only a quarter of the number available for PR of the B_s-1 host itself. (2) The Michaelis constant K_m for reaction of host-DNA-damage and PR-enzyme becomes larger when the host damage acts as competitive inhibitor to PR of T1 DNA than when it is the substrate for PR enzyme. (3) PR enzyme retains almost all its initial catalytic efficiency even after about two-hundred rounds of catalytic functioning. Conclusions (1) and (2) suggest that PR enzyme is concentrated within the nuclear area surrounding the host DNA.     

1,6,11,16‐Tetra­oxacyclo­eicosane‐2,5,12,15‐tetra­one

The 20‐membered ring of the title compound, C₁₆H₂₄O₈, adopts an approximately flat rectangular structure with three‐ and seven‐bond sides and lies across a crystallographic center of inversion. The corners of the ring occur at both ends of one of the planar ester segments. All of the carbonyl O atoms are involved in inter­molecular C—H⋯O hydrogen bonds.     

Copolyamides and copolyesters containing the phenoxasilin ring

Copolyamides and copolyesters containing the phenoxasilin ring were prepared from 2,8-dichloroformyl-10,10-diphenylphenoxasilin, isophthaloyl chloride and m-phenylenediamine or bisphenol A by interfacial polycondensation in chloroform-aqueous alkali mixture. They were obtained in yields of 80% or above and at relatively high viscosities up to 1.30 dl/g. The copolymers with high phenoxasilin content were freely soluble in dimethylacetamide, dimethylformamide and N-methyl-2-pyrrolidone, but decreasing phenoxasilin content led to copolymers with slight solubilities in these solvents; the copolyesters also dissolved in chloroform, m-cresol and phenol-sym tetrachloroethane (60:40 in wt%). Flexible transparent films were obtained from chloroform solutions of the copolyesters, but the films cast from DMF solutions of the copolyamides became brittle as the phenoxasilin content decreased. The phenoxasilin-containing copolymers hardly degraded below 400° and had good thermal stability. Introduction of the phenoxasilin ring into the polymer backbones by copolycondensation did not reduce thermal stability.     

Mechanical properties of fiber reinforced styrene-butadiene rubbers using surface-modified UHMWPE fibers under EB irradiation

Aiming to develop a high performance fiber reinforced rubber of SBR, a special technique using electron beam (EB) irradiation-induced graft-polymerization was applied to ultra-high molecular-weight polyethylene (UHMWPE) fibers. Although UHMWPE is chemically inert, N-vinyl formamide (NVF) could be graft-polymerized onto the UHMWPE fiber surface with this special technique. A maximum grafting percentage of 23.6% was achieved. The composite of SBR and grafted UHMWPE fibers with maximum grafting indicated a linear increase in the initial modulus and strength with the fiber content. At the fiber content of 10%, the initial modulus was improved about five times with respect to that of the pure SBR, while the strength was done about twice. At this moment, only a small reduction could be observed in the strain compared with that of pure SBR. The fiber reinforced rubber with a good performance was obtained in the system of SBR and grafted UHMWPE fibers.     

Reactions of sulfoxonium allylides with nitrile oxides and ring transformations of their reaction products

Reactions of allylides ($\text{1}$) with nitrile oxides ($\text{2}$) afforded furanylglyoxylate oxime ($\text{3}$) and 6H-l,2-oxazine ($\text{4}$). Ring transformations of $\text{3}$ and $\text{4}$ gave $\text{4}$ and pyrrolinone ($\text{6}$), respectively.