Cinnoline chemistry XIII. 4-aziridinocinnolines

Nine substituted 4-aziridinoeinnolines have been prepared and subjected to anticancer screening. J. Heterocyclic Chem., 15 , 1039 (1978)     

Spin-free quantum chemistry. XIV. The infinite interaction range model for ferromagnetism

The infinite interaction range model (IIRM ) for ferromagnetic systems is presented in its spin-free formulation. In this formulation the states are labelled by partitions which provide a natural variable for thermodynamic computation. We have extended the calculations of Kittel and Shore by computing to a practical thermodynamic limit (N ～ 100,000). The heat capacity, magnetic susceptibility and the magnetization of the first two functions exhibit a critical temperature while the magnetization is zero at zero field for all temperatures. Spontaneous magnetization is obtained by linear extrapolation from high field or equivalently by a polarized partition function. Relationships are explored among IIRM , the Heisenberg model and the mean field model. Application to IIRM of the Yang-Lee condition for a phase transition yields a critical temperature identical to that obtained by the direct calculation.     

Metal carbonyl chemistry : XIV. Reactions of rhodium carbonyls with ligands

Dodecacarbonyltetrarhodium [Rh₄(CO)₁₂] reacts with phosphine and phosphite ligands under an atmosphere of nitrogen to give the compounds Rh₄(CO)₁₀L₂, Rh₄(CO)₉L₃ and Rh₄(CO)₈L₄ [where L = Ph₃P or P(OCH₂)₃CEt (ETPO)¹] in which the metal atom cluster is retained. Under similar conditions hexadecacarbonyl-hexarhodium [Rh₆(CO)₁₆] reacts with Ph₃P, P(OCH₂)₃CEt or P(OMe)₃ to give complexes of the type Rh₆(CO)₁₀L₆. When the reaction of either Rh₄(CO)₁₂ or Rh₆(CO)₁₆ with the ligands Ph₃P or Ph₃As is carried out in the presence of carbon monoxide, breakdown of the metal clusters occurs to give the bridged compounds L₂(CO)Rh(CO)₂Rh(CO)L₂ (where L = Ph₃P or Ph₃As) in high yields; reaction of Rh₄(CO)₁₂ with n-Bu₃P under similar conditions gives the compound [(n-Bu₃P)₃-(CO)Rh]₂. Dodecacarbonyltetrarhodium has also been shown to react with PhC₂Ph or CF₃C₂CF₃ to give the compounds Rh₄(CO)₁₀(RC₂R) (R = CF₃ or Ph).Some of these ligand-substituted rhodium carbonyls have been shown to be extremely active hydroformylation catalysts for 1-alkenes.     

Radiation chemistry of polyethylene. XIV. Allyl radical decay kinetics in different types of polyethylene

The decay kinetics of the chain allyl free radical has been studied in the following morphological forms of polyethylene (PE): Marlex bulk film, hydrogenated PE, and extended-chain PE. Coupled with previous work on single-crystalline PE it can be seen that the decay rate is greater the more amorphous the sample. In the Marlex bulk film and hydrogenated PE the decay can be interpreted in terms of a simultaneous fast and slow decay process by means of our Q-function equation, but with rising temperature the decay approximates a single rate process. With extended-chain PE the allyl decay rate does not become appreciable until the melting range is approached. The fraction of allyl radicals decaying by the slow process is 2 to 10 times greater than the fraction of fast decaying radicals. The ratio of the fast decay rate constant to that of the slow rate constant is greater for the bulk Marlex film than for the hydrogenated PE. All ratios decrease with rising temperature. For times up to about 150 min the allyl decay in the extended-chain PE accurately follows a single second-order decay law with a time-independent diffusion controlled reaction rate constant.     

Reactions of Cinnoline, Cinnoline N-Oxides, and Their Chloro Derivatives with Alkylamines: the First Case of Nucleophilic Substitution of Hydrogen in the Cinnoline Series

In contrast to cinnoline and cinnoline N₍₁₎-oxide, cinnoline N₍₂₎-oxide reacts with primary and secondary amines on prolonged heating or in the presence of oxidants to give 3-alkylaminocinnolines.     

α-Halogenoketones—XIV: Studies in the chemistry of 2''-hydroxyacrylophenones

The chromone epoxide ring system has been synthesised. Base-catalysed cyclization and dehydrobromination of α-bromo-o-acyl (aroyl) oxyacetopheones or 2-bromo-1, 3-diones yielded 3-substituted chromone epoxides. Acid-catalysed rearrangement of a 2-methylchromone epoxide in an aprotic solvent gave a 2-methylenech-romanonol, while a 3-methoxymethylchromone epoxide fragmented to chromonol under these conditions; in alchols, chromone epoxides gave 2-alkoxychromanonols.     

Chelatometrie. XIV

Zusammenfassung Eisen(III)-ionen lassen sich mit 0,1 m Äthylendiamintetraessigsäurelösung gegen Rhodanid als Indicator bei p_H 3,0–3,5 und 20° C titrieren. In Gegenwart einer sehr hohen Acetationenkonzentration sind die Titrationsergebnisse von der Indicatorkonzentration unabhängig. Daher kann auch eine große Rhodanidmenge zur Lösung gegeben werden und es ist möglich, den Titrationsendpunkt scharf zu indicieren.Mitteilung XIII dieser Reihe: diese Z. 154, 182 (1957).     

Aromatic λ<Superscript>3</Superscript> heterocycles XIV. Fosfinine-ether macrocyclesheterocycles XIV. Fosfinine-ether macrocycles

The geometry and electronic structure of several phosphinine-ether macrocycles were investigated at semiempirical level. The calculated geometries are in good agreement with experimental data. Compared to phosphinine, the coordinative abilities of phosphinineether macrocycles based on energy considerations suggest a little lowered π acceptor character, while π donor character is improved. The molecular environment causes a significant mixing of phosphinine and phenyl substituent π levels. The geometry and electronic properties of phosphinine-ether macrocycles can provide significant host coordination properties for guest species.     

Nitroxide chemistry. Part XIV [1]. Reactions of trifluoromethyl 2,3-dimethylbut-3-en-2-yl and trifluoromethyl 2,3-dimethylbut-2-yl nitroxides

The nitroxide CF₃N(?)CMe₂CMeCH₂ abstracts the aldehydic hydrogen from benzaldehyde, yielding the benzoyl compound PhCO₂N(CF₃)CMe₂CMeCH₂ (82%), the benzylic hydrogen from cumene, yielding PhCMe₂ON(CF₃)CMe₂CMeCH₂ (80%), and the methylene group hydrogen from fluorene, oxidises benzoin to benzil, and hydroquinol to quinone, attacks the Si'&'2.sbnd;H bond of trimethylsilane, and adds to tetrafluoroethylene to give the compound R¹N(CF₃)OCF₂CF₂ON(CF₃)R¹ (R¹ = CMe₂CMeCH₂, 97%), and to hexafluoropropene to give the 2:1-adduct.In a similar manner, the nitroxide CF₃N(?)CMe₂CHMe₂ adds to tetrafluoroethylene to give the compound R²N(CF₃)OCF₂CF₂ON(CF₃)R² (R² = CMe₂CHMe₂, 75%) and to hexafluoropropene to give a similar adduct (71%), and abstracts a benzylic hydrogen from toluene.     

Studies in group IV organometallic chemistry : XIV. Ultraviolet absorption due to bonds between group IV metals

Ultraviolet absorption spectra are discussed for a number of molecules containing metal-metal bonds, viz. (C₆H₅)₆Sn₂, (C₆H₅)₆Pb₂, (cyclohexyl)₆Pb₂, [(C₆H₅)₃Sn]₄M, and [(C₆H₅)₃Pb]₄M with M  Pb, Sn, and Ge. Long wavelength absorptions are attributed to the metallic part of the molecules.     

New Synthetic Route to Cinnoline Derivatives and Their Microbiological Activity

Russian Journal of Organic Chemistry - New cinnoline derivatives have been synthesized by reductive cyclization of hydrazones obtained by condensation of various 2-nitrophenylhydrazine derivatives...