Phenyl iodonium bis(perfluoroalkanesulphonyl)-methide-dimethyl sulphoxide complex——Its formation and X-ray structure analysis

Irradiation of phenyl iodonium bis(perfluoroalkanesulphonyl)methide in DMSO yieldsan 1:1 adduct, DMSO·PhI=C(SO_2R_F)_2 (2) which was confirmed by X-ray crystal structure analysis.     

Benzoylation and Properties of 14-π Nickel(II)-Tetraazaannulene Complexes with Substituents on the Phenyl Ring

The benzoylated asymmetrical nickel(II) complexes, 2,4,9,11-tetramethyl-3,10-dibenzoyl-1,5,8,12-([14]-Xbenzo)tetraazacyclotetradecinato(2-)nickel(II) ( A_1-4) and 2,4,10,12-tetramethyl-3,11-dibenzoyl-1,5,9,13-([15]-Xbenzo)tetraazacyclotetradecinato(2-)nickel(II) (B_1-4), wherein X = CH₃(A₁ and B₁), H ( A₂ and B₂), Cl (A₃ and B₃) and NO₂(A₄ and B₄), have been synthesized and characterized by analysis, IR, electronic, ¹H- and ¹³C-NMR spectra. An intense IR band due to C=O stretching is present in the range 1630-1650 cm^-1 upon benzoylation. Electronic spectra show bands at 375-390 nm with k_max = 10000-26000 M^-1cm^-1 due to π→π* transitions of macrocycles and at 500-550 nm with k_max = 1000-5000 M^-1cm^-1 attributable to LMCT for each of the complexes. The proton peaks of methine sites in the NMR spectra disappear on benzoylation. Results of the carbon-13 NMR spectra are compatible with those of the proton NMR. Cyclic voltammograms of the complexes in acetonitrile exhibit two successive and reversible (irreversible in DMSO) oxidation peaks for the macrocycle (Mc M Mc ^{” +} and Mc ^{” +} M Mc ²⁺) in the ranges +0.31 - +0.51 and +0.60 - +0.84 V, respectively. In the reduction area, a reversible wave is followed by reduction of metal {Ni(II) M Ni(I) at around m 2.32 V}. Unlike analogous complexes without the benzoyl group, those compounds are not electropolymerized by cyclic voltammetry.     

Polymesomorphism and orientation in liquid crystalline poly(triethylene glycol p,p′-bibenzoate)

The phase transitions and the orientational behavior of liquid crystalline poly(triethylene glycol p,p′-bibenzoate) have been studied. The real-time synchrotron diffraction results indicate that, on cooling from the isotropic melt, an orthogonal SmA mesophase is formed first, and later it is transformed into a tilted SmC mesophase. However, the SmA mesophase is stable in a rather wide temperature interval, and the transformation into the SmC phase occurs at temperatures close to the glass transition, so that not very high tilting angles are attained. The uniaxial deformation of the SmC mesophase indicates that usual parallel orientation of the molecular axes in relation to the stretching direction is obtained at high strain rates, while anomalous perpendicular orientation occurs at low deformation rates, with the smectic layers aligned with the stretching direction and the molecular axes almost perpendicular. A mixture of the two types of orientation is observed at intermediate rates, with rather interesting features.     

Comparison of the Separation Characteristics of the Organic–Inorganic Hybrid Stationary Phases XBridge C8 and Phenyl and XTerra Phenyl in RP-LC

Differences in the system constants of the solvation parameter model and retention factor correlation plots for varied solutes are used to study the retention mechanism on XBridge C₈, XBridge Phenyl and XTerra Phenyl stationary phases with acetonitrile–water and methanol–water mobile phases containing from 10 to 70% (v/v) organic solvent. These stationary phases are compared with XBridge C₁₈ and XBridge Shield RP₁₈ characterized in an earlier report using the same protocol. The XBridge stationary phases are all quite similar in their retention properties with larger difference in absolute retention explained by differences in cohesion and the phase ratio, mainly, and smaller changes in relative retention (selectivity) by the differences in individual system constants and their variation with mobile phase type and composition. None of the XBridge stationary phases are selectivity equivalent but XBridge C₁₈ and XBridge Shield RP₁₈ have similar separation properties, likewise so do XBridge C₈ and XBridge Phenyl, while the differences between the two groups of two stationary phases is greater than the difference within either group. The limited range of changes in selectivity is demonstrated by the high coefficient of determination (>0.98) for plots of the retention factors for varied compounds on the different XBridge phases with the same mobile phase composition.     

Indole derivatives. 138. Synthesis of α-(5-indolyl)ethylamine and 5-(2-aminoethoxy)- and 5-(aminoethylthio)tryptamines

The reaction of 5-acetylindole with hydroxylamine with subsequent reduction of the resulting oxime gave -(5-indolyl)ethylamine. Coupling of 4-(2-phthalimidoethoxy)- and 4-(2-phthalimidoethylthio)phenyldiazonium chlorides with ethyl -acetyl--phthalimidovalerate, subsequent cyclization of the resulting hydrazones, hydrolysis, decarboxylation, and removal of the phthalyl protecting group led to the formation of 5-(2-aminoethoxy)- and 5-(2-aminoethylthio)tryptamines, respectively.For Communication 137, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 46–48, January, 1992.     

Die argentometrische Bestimmung von N-Methyl-cyclohexenyl-methylbarbiturs?ure (Evipan) (I) und Phenyl?thylbarbiturs?ure (Luminal) (II)

Ohne Zusammenfassung     

Phenyl bismuth β-diketonate complexes: Synthesis and structural characterization

The first examples of arylbismuth diketonate complexes are reported. Phenylbismuth(III) bis(hexafluoroacetylacetonate), BiPh(hfac)₂ (1) and its adducts [BiPh(hfac)₂(L)] (Hhfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; L = H₂O (1a), Me₂CO (1b), THF (1c), DMA (N,N-dimethylacetamide) (1d), DMSO (1e), PhCN (1f), as well as a mixed hexafluoroacetylacetonate-trifluoroacetate complex, [BiPh(hfac)(O₂CCF₃)]₂ (2), have been synthesized and characterized. Compound 1 is isolated from the reaction of BiPh₃ with 2 equiv. of Hhfac in dry hexanes. Compound 2 can be synthesized using two different routes: one utilizes the reaction between stoichiometric amounts of 1 and CF₃CO₂H, while the second method involves the interaction of the previously described BiPh₂(O₂CCF₃) (3) with Hhfac. Crystallographic analysis of the [BiPh(hfac)₂(L)] adducts reveals a pentagonal pyramidal geometry around the metal center; similarly, the dinuclear [BiPh(hfac)(O₂CCF₃)]₂ complex is composed of two distorted pentagonal pyramids connected into dimers by the bridging carboxylate groups. The effect of replacing the Lewis base in the coordination sphere of Bi(III) on the coordination polyhedron and crystal packing is discussed. The ¹H and ¹⁹F NMR spectra of the title complexes at room temperature indicate single environments for the hfac group and suggest that they are fluxional in solutions on the NMR time scale. Compounds 1 and 2 are promising starting materials in the chemistry of bismuth(III) and as building blocks for the construction of heterometallic species.     

Solvolysis of 1-Chloro-1-Alkenyl Phenyl Sulfides. Synthesis of α-Bromo Phenyl Thiocarboxylic Esters, α-Bromo Alkyl Carboxylic Esters and α-Phenylthio Methyl Carboxylic Esters

1-chloro-1-alkenyl phenyl sulfides treated with bromine followed by hydrolysis or methanolysis give α-bromo phenyl thiocarboxylic esters and α-phenyl-thio methyl carboxylic esters. Direct oxidative solvolysis with bromine and alcohol give α-bromo alkyl carboxylic esters.     

Synthesis and Characterization of Cardo Polysulfonates of 1,1′-Bis(4-Hydroxy Phenyl)Cyclohexane with 1,3-Benzene and 2,4-Toluene Disulfonyl Chlorides

Abstract

Cardo polysulfonates (PSBCB and PSBCT) of 1,1′-bis(4-hydroxy phenyl)cyclohexane with benzene-1,3 and toluene-2,4-disulfonyl chlorides have been synthesized by interfacial polycondensation of 1,1′-bis(4-hydroxy phenyl)cyclohexane (0.005 mol) with benzene-1,3/toluene-2,4-disulfonyl chlorides (0.005 mol) using water-chloroform (4:1, v/v) as interphase, alkali (0.015 mol) as acid acceptor, and cetyl trimethyl ammonium bromide (0.125 g) as emulsifier at 0°C for 3 hours. The structures of the polymers were supported by IR and NMR spectral data. The PSBCT was fractionated into several fractions by using 1,2-dichloroethane as solvent and n-butanol as precipitant. The fractions were characterized by GPC and viscometry in different solvents at four different temperatures. Viscosity studies showed that the PSBCT is flexible in solutions and has a specific solvent effect. PSBCB and PSBCT have good biological activity against E. coli and S. citrus organisms, and they possess excellent hydrolytic stability toward acids and alkalis.     

A Facile Synthesis of 0,0-Dialkyl-α-(Phenyl Carbamyloxy) Alkyl Phosphonates

TheC-ph0sphorylatedcarbamatederivativeshavereceivedspecialattentionbecauseoftheirpesticidalactivity.Wewereinterestedinfindingafacilemethodf0rthesynthesis0fthetitlec0mpounds.Therehavebeens0mereportsonthesynthesis0f(dialkylph0sphono)arylmethylcarbamates',whichwerepreparedbytreatingdialkylis0cyanat0phosphitewithsubstitutedbenzaldehydefoll0wedbyhydr0lysiswithwater.However,thismeth0dhassomelimitationsduetol0wyield,anddialkylisocyanatophosphiteisnoteasytoprepare.Inthestudy0fthenucIeophilicadditionr…     

Phenyl­phosphinic acid

The crystal structure of the title compound, C₆H₇O₂P, shows continuous hydrogen-bonding chains in the x direction, with a P—O⋯O=P distance of 2.513 (3) Å.     

The molecular and crystal structure of N-(4-n-butyloxybenzylidene)-4′-ethylaniline (4O.2) and N-(4-n-heptyloxybenzylidene)-4′-hexylaniline (7O.6)

Abstract

The molecular and crystal structure of N-(4-n-butyloxybenzylidene)-4′-ethylaniline (4O.2) and the homologue N-(4-n-heptyloxybenzylidene)-4′-hexylaniline (7O.6) have been solved (at room temperature) by direct methods. The crystals of both compounds belong to the triclinic system with space group P1 with two molecules per unit cell. 4O.2: a = 5·531(2), b = 7·592(3), c = 19·746(7) Å, α = 86·66(2), β = 88·15(2), γ = 90·29(2)° 7O.6: a = 5·420(2), b = 8·307(3), c = 28·057(7) Å, α = 91·69(2), β = 89·76(2), γ = 108·02(2)°. The structures were refined by full-matrix least-squares calculations to R = 0·036 for 2297 observed reflections for 4O.2 and to R = 0·037 for 2150 reflections for 7O.6. The conformations in the asymmetric units of the two compounds differ considerably: The planes of the two phenyl rings of 4O.2, forming the mesogenic core of the molecule, are twisted at 61·2° to each other and the butoxy group contains a gauche conformation. In contrast the heptoxy chain of 7O.6 forms an all trans-conformation which lies almost in one plane with the two coplanar phenyl rings. The hexyl group also exists in an extended form, in a plane which is rotated against the plane of the mesogenic unit. The packing in the crystalline state of the two homologues exhibits a layered structure along c*; in 4O.2 these layers are separated, but in 7O.6 they are interdigitated. The compensation of the dipole moments of the C?O?C and C?N?C bonds occurs similarly in both structures: molecular orientations parallel to the a, c-plane in which the long axes of the molecules points in the same direction are packed in antiparallel fashion along b*.     

Cyclization of α- and β-amino ketones. (Review)

In this review data on the synthesis of three-, four-, five-, and six-membered heterocycles, as well as of condensed heterocyclic compounds from -amino ketones and Mannich bases are classified for the first time.Samara State Technical University, Samara 433100, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 723–735, June, 1999.