Reactivity of methyl (3,6-dichloropyridazin-4-yl)acetate towards nucleophiles

Methyl (3,6-dichloropyridazin-4-yl)acetate (II), prepared from methyl (3,6-dihydroxypyrid-azin-4-yl)aeetate (1) by chlurination with phosphorus oxychloride, was used for studies of nucleo-philic displacement reactions and it has been found that only the chlorine atom at position 6 was displaced with hydrazine. With diluted hydrochloric acid both chlorine atoms were displaced with the 6-oxo isomer predominating. By turning the aromatic ring of pyridazine into an o-quinoid system, the chlorine atom at position 3 became mobile. Cyelization of (6-hydrazino-s-triazolo-[4,3-b ]pyridazin-7-yl)acetic acid hydrazide (XIX) gave 6-aminopyrrolo[3,2-e ]s-triazlo[ 4,3-b ]-pyridazm-7(8H)one (XXI).     

Spiro-dihydrofuran-pyrazolidinones from tetraacetylethylene andazo-dicarbonyl compounds

Tetraacetylethylene (1) reacted with electron-withdrawing azo compounds to give spiro furan-pyrazoles. Their structure was confirmed by an X-ray crystallographic analysis on a derivative of the spiro furan-3(2H),5′(7′H)-pyrazolo 1,2-a1,2,4 triazole-1′,3′,6′-trione. The cycload-ducts show ring-open chain tautomerism.     

Free radical substitution reaction on zirconium and hafnium organometallics

Di-t-butyl nitroxide readily substitutes alkyl zirconocenes and hafnocenes, Cp₂MR₂, by a rate-determining displacement of alkyl radicals to give high yields of O-alkyl-N,N-di-t-butylhydroxylamine and Cp₂M(R)ONBu^t₂. A free radical substitution of di-benzylzirconocene by benzenethiyl radicals yields Cp₂Zr(SPh)₂.     

The first three anisotropy constants of nickel

The technique of ferromagnetic resonance at 23 GHz has been used to determine the first three anisotropy constants of pure Ni down to 4.2K. A temperature and orientation dependent linewidth has also been observed.     

Bio-electrosprayed living composite matrix implanted into mouse models

We show that composite de novo structures can be generated using bio-electrosprays. Mouse lung fibroblasts are bio-electrosprayed directly with a biopolymer to form cell-bearing matrices, which are viable even when implanted subcutaneously into murine hosts. Generated cell-bearing matrices are assessed in-vitro and found to undergo all expected cellular behaviour. Subsequent in-vivo studies demonstrate the implanted living matrices integrating as expected with the surrounding microenvironment. The in-vitro and in-vivo studies elucidate and validate the ability for either bio-electrosprays or cell electrospinning to form a desired living architecture for undergoing investigation for repairing, replacing and rejuvenating damaged and/or ageing tissues.     

Selectivity in cycloadditions: Crystal and molecular structure of (1a,4β,5a)-1,5-diacetyl-4-hydroxy-4-methylbicyclo[3.1.0]Hexan-2-one

The stereochemistry of (1a,4β,5a)-1,5-diacetyl-4-hydroxy-4-methylbicyclo[3.1.0]hexan-2-one, the main cycloadduct of 2,3-diacetyl-4-hydroxy-4-methylcyclopent-2-en-1-one and diazomethane, was unambiguously established from a single crystal X-ray analysis.