Alkaline Decomposition of Cyclic Nitramines

Treatment of 1,3,5-trinitro-1,3,5-triazacyclohexane and 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclo-octane with potassium hydroxide gives dipotassium salt of methylenedinitramine.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 130–132.Original Russian Text Copyright © 2005 by Il’yasov, Lobanova.     

Comparison of Carboxamides Reactivity with Respect to Benzoyl Chloride and Diphenyl Chlorophosphate in Acetonitrile

For amides belonging to series RCONH₂ (I), RCONHMe (II), RCONHPh (III), and RCONMe₂ (IV) rate constants k₁ (l mol^-1 s^-1) were determined (in acetonitrile at 25°C) specifying the nucleophilic reactivity of the oxygen atom in amides toward benzoyl chloride and diphenyl chlorophosphate. The lack of substrate selectivity in the reactions in question was established. For equal values of inductive constants ^* of the R substituents the reactivity sequence of amides with respect to both substrates is the same (I >> IV > II, and III > II), and it does not follow the corresponding sequence of basicities. A conclusion was drawn that both groups of reactions proceed through cyclic transition states resembling reagents: six-membered with amides I and III, and five-membered with amides II and IV.     

(2-Vinyloxyethyl)hydrazines

Reaction of hydrazine hydrate with 2-chloroethyl vinyl ether afforded (2-vinyloxyethyl)hydrazine and 1,1-bis(2-vinyloxyethyl)hydrazine in 20-38% yield.     

Synthesis of 5-hydroxy-N-(2-vinyloxyalkyl)indoles from dicarbonyl compounds and vinyloxyalkylamines

N-(Vinyloxyalkyl)enaminoketones were obtained by the condensation of vinyloxyalkylamines with acetylacetone or ethyl acetoacetate. Their subsequent reactions with 1,4-benzoquinone produce the corresponding 5-hydroxy-2-methyl-N-(2-vinyloxyalkyl)indoles in 17–43% yields. The structures of the compounds obtained were confirmed by IR and¹H NMR spectroscopy.     

Catalytic properties of polyvanadomolybdic acids in oxidation of 1,2,4-trimethylbenzene by peracetic acid

Polyvanadomolybdic acids catalyze the process of peracid oxidation of 1,2,4-trimethylbenzene. The selectivity with respect to 2,3,5-trimethyl-1,4-benzoquinone increases with increasing degree of replacement of vanadium atoms in the PVMA by molybdenum; this is related to increased stability of the intermediate peroxides of the heteropolyvanadates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1967–1969, September, 1989.     

Express detection of nonylphenol in water samples by fluorescence polarization immunoassay

The development of express method for detection of endocrine-disrupting chemicals (EDC) such as alkylphenols is required for ecological monitoring. Several attempts have been made to produce antibodies against 4-nonylphenol (NP) in recent years. This work describes the production of new antibodies against NP and also summarizes the characterization of antibodies obtained earlier. Three approaches used to produce alkylphenol-specific antibodies are compared; these are based on: 1. omega-(4-hydroxyphenyl)nonanoic or omega-(4-hydroxyphenyl)heptanoic acid NP derivatives designed to mimic the linear NP isomer; 2. 4-aminophenol, which potentially mimics various substituted phenolic compounds with different side-chain structures at position 4 of the benzene ring; and 3. a mixture of branched NP isomers, conjugated to the carrier protein via a benzene ring by the Mannich reaction, and expected to be the closest mimic of NP structure by preserving its natural alkyl moiety.Fluorescence polarization immunoassays based on different combinations of antibody and labeled antigen for screening detection of NP were developed and structural aspects of assay sensitivity and specificity were investigated. The assays based on the antisera raised against omega-(4-hydroxyphenyl)nonanoic acid and NP conjugate via Mannich reaction are capable of express detection of NP with detection limit of 7 microg mL(-1 )and assay dynamic range of 18-300 microg mL(-1).     

Reaction of ω-Vinyloxyalkylamines with Isatin

3-(-Vinyloxyalkylimino)-2,3-dihydroindol-2-ones and 3-(vinyloxyphenylimino)-2,3-dihydroindol-2-ones were synthesized in 34-93% yield by reactions of -aminoalkyl and aminophenyl vinyl ethers with isatin.     

Reaction of exo-nido-ruthenacarborane [Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 with bromine

The reaction of bromine with exo-nido-ruthenacarborane [Cl(Ph₃P)₂Ru]-5,6,10-(-H)₃-10-H-7,8-C₂B₉H₈ (1) led to the replacement of the chlorine atom by the bromine atom in the octahedral environment of the ruthenium atom rather than to the substitution in the carborane cage. The structure of [Br(Ph₃P)₂Ru]-5,6,10-(-H)₃-10-H-7,8-C₂B₉H₈ was established by NMR and IR spectroscopy and X-ray diffraction analysis.