A study of HPLC separation and spectrophotometric, polarographic and voltammetric detection of 4-substituted derivatives of N-nitroso-N-methylaniline

Optimised conditions have been found for the separation of N-nitroso-N-methylaniline derivatives substituted in the position 4 (4-R-NMA, where R =- H,- CH₃, - OCH₃, - Cl, - CN, - OH and - NO₂), using reversed phase HPLC with a C18 chemically bonded stationary phase. Suitable mobile phases are mixtures of aqueous 0.01 mol l^–1 KH₂PO₄ with methanol (4+6) or acetonitrile (7+3), or a mixture of water, methanol, acetonitrile and 80% H₃PO₄ (200+200+200+3). Four detection techniques have been investigated: Direct UV photometry, polarography on a hanging mercury drop electrode, anodic voltammetry on a glassy carbon fibre array electrode and indirect anodic voltammetric detection after photolytic denitrosation of the analytes. The UV photometry is the most universal and yields limits of detection around 10^–6 mol l^–1. Polarography exhibits the poorest sensitivity (with a limit of detection of ca. 10^–5 mol l^–1) but it can be used for selective detection of 4-NO₂-NMA. Direct voltammetric detection is selective for the oxidizable derivatives and the limits of detection attained are lower than those obtained by UV photometry (for 4-OH-NMA) or comparable with (for 4-OCH₃-NMA). When the analytes are photolytically denitrosated to yield oxidizable derivatives, the voltammetric detection of 4-H-NMA, 4-Cl-NMA, 4-CH₃-NMA and 4-NO₂-NMA has limits of detection one order of magnitude lower than those obtained UV photometrically.     

Morphological structures formed by grafted polymers in poor solvents

We study a system of grafted polymers in a poor solvent by self-consistent-field methods as well as Monte-Carlo simulation methods. We observe a number of different morphological structures including an inverted solvent micelle or hole in the polymer layer, a lamella-like micelle structure, and fused, spherical micelle structures. These structures can be obtained by either varying the grafting density or chain length. We also develop a scaling theory for the existence of these structures and find reasonable agreement between this theory and our numerical calculations.     

Computer-assisted site-specific functionalization in the gibberellin series; norrish type II photocyclization via a 9-membered transition state

The site-specific Norrish II type reaction of the gibberellin oxo ester , prepared in two steps from tetraacetyl- GA₃, anhydride , to the photolactone , is reported. By potential energy calculations based on the X-ray analysis of , it is shown that the regio- and stereoselectivity of the photocyclization can be predicted involving a 9-membered cyclic transition state in the H-abstraction step. The structure of the photolactone was determined by spectroscopic data, especially NOE measurements.     

The influence of intermolecular interactions on polymerization—2. Polymers of 1-naphthyl methacrylate and 2-naphthyl methacrylate obtained by radical polymerization

1-Naphthyl methacrylate and 2-naphthyl methacrylate were polymerized with azoisobutyronitrile in n-hexane, cyclohexane and benzene in the absence and in the presence of tetracyanoethylene. Products were transformed into poly(methyl methacrylate) by hydrolysis and methylation; tacticities were then determined by proton NMR.     

Polymérisation anionique des diènes. VI. Microstructure des polybutadiène et polyisoprène par résonance magnétique protonique à 250 MHz et mécanismes de propagation

Analysis by 250-MHz proton magnetic resonance (PMR) allows more precise examination of the microstructure of anionic polyisoprenes and polybutadienes obtained in the presence of organo-alkali metals. Besides vinyl addition, the propagation of contact ion pairs in dioxane solvent gives a mixture of cis and trans products with isoprene, whereas only trans product is obtained with butadiene. The presence of 1,4-trans-polyisoprene appears to be inconsistent with the cis configuration of the polyisoprenyllithium living end in dioxane or tetrahydrofurane media. In taking into account the existence of complexation phenomena, it was suggested that propagation mechanisms should involve a transition state which should begin with the trans configuration before isomerization into the more stable cis configuration. For the free ions, the living end of the carbanion should be entirely trans.     

Anion Selectivity of Tetravalent Tin Compounds in Membranes Studied by 119Sn-, 13C- and 1H-NMR

The fundamental molecular aspects of trialkyltin compounds of the type R₃SnY have been investigated in view of their applicability as ion-selective components in solvent polymeric membranes. The interaction between these compounds and anions has been studied using ¹¹⁹Sn- and ¹³C-NMR. Neutral tetracoordinated trialkyltin compounds form a negatively charged pentacoordinated complex upon interaction with Cl-ions in homogeneous organic phases as well as in membranes in contact with aqueous solutions. Although in a homogeneous phase, the electronegative substituent Y determines the complex-formation constant, it has no influence on the potentiometric anion selectivity in liquid membranes containing trialkyltin carriers R₃SnY with different Y. The observed selectivity pattern is not given by the magnitude of the stability constants in a homogeneous phase but is dictated by the prevailing association-dissociation process leading to tetracoordinated compounds which change in constitution due to varying sample composition, The results obtained from equilibrium studies of tetravalent mono tin compounds with anions in both homogeneous phase and in two-phase systems confirm the earlier hypothesis that trialkyltin compounds incorporated in solvent polymeric membranes act as electrically neutral carriers for anions.     

Complexation du chlorure de vinyle par le tetrahydrofuranne et le n-butyraldéhyde: Étude par résonance magnétique nucléaire haute résolution

Examination of the HR-NMR spectra of vinyl chloride in the presence of tetrahydrofuran and n-butyraldehyde suggests the formation of donor-acceptor type complexes. The equilibrium quotients and NMR constants were estimated by using the Benesi-Hildebrand method. The existence of these complexes would explain the anomalies observed: first, in the anionic polymerization of vinyl chloride initiated by tert-butylmagnesium chloride is tetrahydrofuran. The initiation step seems to be governed by this complexation phenomenon; second, in the radical polymerization of the same monomer in n-butylaldehyde the obtained poly(vinyl chloride) is more syndiotactic than the radical polymer prepared in bulk by the usual methods.     

Précisions apportées au mécanisme de la polymérisation du chlorure de vinyle par le chlorure de tertiobutyle-magnésium en milieu tétrahydrofurannique. Etude par résonance magnétique nucléaire

NMR analysis of the low molecular weight poly(vinyl chloride) obtained from polymerizations initiated by t-BuMgCl in THF solution suggests that all the polymer chains have the structure: Enhanced signal/noise ratio by NMR spectrum accumulation confirms this structure in products of higher molecular weights. Examination of the NMR spectrum of vinyl chloride monomer in THF solution reveals the formation of a monomer–THF complex; it seems that the initiation step of the polymerization is governed by this complexation phenomenon.     

Lewis base catalyzed aldol additions of chiral trichlorosilyl enolates and silyl enol ethers

[structures: see text] The consequences of double diastereodifferentiation in chiral Lewis base catalyzed aldol additions using chiral enoxysilanes derived from lactate, 3-hydroxyisobutyrate, and 3-hydroxybutyrate have been investigated. Trichlorosilyl enolates derived from the chiral methyl and ethyl ketones were subjected to aldolization in the presence of phosphoramides, and the intrinsic selectivity of these enolates and the external stereoinduction from chiral catalyst were studied. In the reactions with the lactate derived enolate, the strong internal stereoinduction dominated the stereochemical outcome of the aldol addition. For the 3-hydroxyisobutyrate- and 3-hydroxybutyrate derived enolates, the catalyst-controlled diastereoselectivities were observed, and the resident stereogenic centers exerted marginal influence. The corresponding trimethylsilyl enol ethers were employed in SiCl4/bisphosphoramide catalyzed aldol additions, and the effect of double diastereodifferentiation was also investigated. The overall diastereoselection of the process was again controlled by the strong external influence of the catalyst.     

Serre's Theorem on the Cohomology Algebra of a p-Group

The purpose of this note is to give a proof of a theorem ofSerre, which states that if G is a p-group which is not elementaryabelian, then there exist an integer m and non-zero elementsx₁, ..., x_m H¹ (G, Z/p) such that with ß the Bockstein homomorphism. Denote by m_G thesmallest integer m satisfying the above property. The theoremwas originally proved by Serre [5], without any bound on m_G.Later, in [2], Kroll showed that m_G p^k – 1, with k =dim_Z/pH¹ (G, Z/p). Serre, in [6], also showed that m_G (p^k –1)/(p – 1). In [3], using the Evens norm map, Okuyamaand Sasaki gave a proof with a slight improvement on Serre'sbound; it follows from their proof (see, for example, [1, Theorem4.7.3]) that m_G (p + 1)p^k–2. However, m_G can be sharpenedfurther, as we see below. For convenience, write H^*(G, Z/p) = H^*(G). For every x_i H¹(G),set 1991 Mathematics SubjectClassification 20J06.