Nucleophilic substitution in certain bicyclic sesquiterpene alcohols under chemical lonization conditions

Substitution of amino for hydroxyl groups in certain sesquiterpene alcohols has been studied by chemical ionization mass spectrometry using ammonia and ammouia-d₃ as the reagent gases, and by mass-analysed ion kinetic energy spectrometry and collision-induced decomposition mass-analysed ion kinetic energy measurements. Depending upon the source conditions and the nature of the substrates, both S_Ni and S_N1 mechanisms have been found to operate. No evidence is obtained for an S_N2 mechanism in these compounds. In centdarol and isocentdarol, addition of NH₃ to the double bond, followed by elimination of H₂O, also contributes to the substitution process. Attack of [NH₄]⁺ on the epoxide function, followed by loss of H₂O, appears to lead to the substitution ions in epoxycentdarol, epoxyisocentdarol and epoxyhimachalol.     

Halogen oxidation and nitrosylation of some aldimine and ketimine carbonyl complexes of chromium and molybdenum

Summary The halogen oxidation and nitrosylation of cis-[(SB)M-(CO)₄] [M = Cr or Mo, SB = N,N-ethylenebis(p-tolualideneimine), N,N-ethylenebis(p-N,N-dimethylaminobenzalideneimine) or N,N-ethylenebis(methyl-p-methoxyphenylketimine); M = Mo, SB = N,N-ethylenebis-(cinnamylideneimine) or N,N-ethylenebis(methyl-p-methylphenylketimine)] have been studied. Halogenation of [(SB)Cr(CO)₄] yielded [(SB)CrX₂] (X = Cl, Br or I) where-as [(SB)Mo(CO)₄] gave [(SB)Mo(CO)₃X₂] (X = Br or I) and [(SB)MoX _x ] (X = I, n = 2; X = Cl or Br, n = 4). NOCl produced [(SB)Cr(NO)₂Cl₂] and [(SB)Mo(CO)₂(NO)Cl] when reacted with the corresponding [(SB)M(CO)₄]. The complexes were characterized by physico-chemical and spectroscopic measurements.     

Complexometric titration of copper(II) using nitrosochromotropic acid as a new metal indicator

Summary Nitrosochromotropic acid gives a violet coloured soluble complex with Cu^II in ammonium chloride-ammonium hydroxide buffer solution, which is less stable than Cu^II-EDTA complex. When microquantities of Cu^II solution containing 1 or 2 drops of nitrosochromotropic acid in the ph range 7.25 to 8.00, are titrated with EDTA, a sharp colour change from violet to orange occurs at the end point. The method of titration can be carried out from 20° to 40° C, but the copper complex dissociates at higher temperature and gives low results. The separation of Zn²⁺, Cd²⁺, Co²⁺, Ni²⁺, Pb²⁺ and alkaline earths, is necessary as they interfere in the titrations with EDTA.

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Zusammenfassung Nitrosochromotropsäure bildet mit Kupfer(II) in Ammoniumchlorid-Ammoniak-Pufferlösung einen violett gefärbten löslichen Komplex, der weniger stabil ist als der Kupfer(II)-ÄDTA-Komplex. Mikromengen Kupfer(II) können imph-Bereich von 7,25–8,00 unter Zusatz von 1–2 Tropfen Nitrosochromotropsäurelösung als Indicator mit ÄDTA-Lösung titriert werden, wobei am Endpunkt ein scharfer Umschlag von Violett nach Orange erfolgt. Die Temperatur der Lösung soll 20–40° C betragen; bei höherer Temperatur erhält man zu niedrige Werte, da der Kupferkomplex dann dissoziiert. Zn²⁺, Cd²⁺, Co²⁺, Ni²⁺, Pb²⁺ und Erdalkalien müssen vor der Titration abgetrennt werden.

     

Polymerization initiated by ylide: Polymerization of ethyl methacrylate with the use of 4-picolinium p-chloro phenacylide as initiator

The ylide 4-picolinium, p-chloro phenacylide-initiated thermal polymerization of ethyl methacrylate (EMA) was studied. 4-Picolinium p-chloro phenacylide induces the thermal polymerization of ethyl methacrylate at 65°C. The rate of polymerization (R_p) rose as the initiator concentration increased from 2 × 10^?3 to 4 × 10^?3 M and the initiating exponent was computed as 1.9. The R_p decreased as the concentration of ylide increased from 6 × 10^?2 to 1M. The greater initiator concentration also affected the molecular weight inversely. The polymerization was carried out at different temperatures and the overall activation energy was computed as 4.08 Kcal/mol. Polymerization was inhibited in the presence of hydroquinone as a radical scavenger. Kinetic studies and other data show that the overall polymerization takes place in a radical mechanism. The various kinetic parameters, such as the rate and average degree of polymerization, molecular weight, and energy of activation of the present system, were evaluated.     

Thermal studies on copper(II)-5,5′-thiodisalicylic acid complexes

Aquo, ammonia and pyridine complexes of copper(II) with 5,5-thiodisalicylic acid have been investigated by TG and DTG. All these complexes decompose in three distinct steps, viz. dehydration, loss of axial bases and decarboxylation of the aromatic ligand. The thermal curves of the aquo and pyridine complexes show water loss in two distinct steps. The decreasing order of thermal stability of the complexes is py > NH₃ > H₂O.

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Zusammenfassung Aquo-, Ammoniak- und Pyridinkomplexe von Kupfer(II) mit 5,5-Thiodisalicylsäure wurden durch TG und DTG untersucht. Diese Komplexe werden in den drei Stufen, Dehydratisierung, Verlust axialer Basen und Decarboxylierung des aromatischen Liganden zersetzt. Die Abbaukurven der Aquo- und Pyridinkomplexe zeigen einen Wasserverlust in zwei Stufen. Die abnehmende Reihenfolge der Thermostabilität der Komplexe ist py > NH₃ > H₂O.

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, (II) 5,5- . , : , . - , . : > NH₃ > ₂.

     

Use of HPTLC,HPLC, and Densitometry for Qualitative Separation of Indole Alkaloids from Rauvolfia serpentina Roots

JPC – Journal of Planar Chromatography – Modern TLC - High-performance thin-layer chromatography (HPTLC) has been used for normal-phase separation of the components of hexane,...     

Force constants,coriolis coupling constants and mean amplitudes of vibration of GaF63− and FeF63−

The force constants, Coriolis coupling constants and mean amplitudes of vibration at 0, 298.16 and 500 K for GaF₆^3?FeF₆^3? have been reported for the first time employing recent vibrational data. The results are discussed in the light of available information.     

Membrane oscillations involving electrokinetic phenomena

Semi theoretical models have been proposed to account for the mechanism of membrane oscillations involving, electrokinetic phenomena in systems where (i) concentration difference deltaC is finite and deltaP is varying but the current is fixed, and (ii) deltaC=0, pressure difference deltaP is fixed across the membrane and imposed current is fixed. The formalism leads to the van der Pol equation in both cases. Computer simulation has also been attempted, which indicates oscillations in the former case.     

Synthesis and biodistribution of p-iodophenyl analogues of a naturally occurring imidazole ribonucleoside

A model iodophenyl imidazole ribonucleoside has been synthesized to study biodistribution properties in laboratory animals. The key intermediate 5-amino-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)imidazole-4-[N-(p-iodophenyl)carboxamide] ( 5 ) was synthesized by coupling N-succinimidyl-5-amino-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)imidazole-4-carboxylate ( 4 ) and p-iodoaniline. Deacetylation of the intermediate compound gave 5-amino-1-β-D-ribofuranosylimidazole-4-[N-(p-iodophenyl)]carboxamide ( 6 ). Ring annulation via diazotization of 5 gave 7-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)imidazo[4,5-d]-v-triazin-[3-N-(p-iodophenyl)]-4-one ( 7 ). Subsequent deacetylation of 7 afforded 7-β-D-ribofuranosylimidazo[4,5-d]-v-triazin-[3-N-(p-iodophenyl)]-4-one ( 8 ). The radiolabeled compounds, [¹²⁵I] 5 and [¹²⁵I] 6 were prepared in a manner similar to the corresponding unlabeled compounds except that p-[¹²⁵I]iodoaniline was used for coupling with 4 . Biodistribution studies of iodine-125-labeled 5 and 6 were performed in female Fischer rats and tumor bearing nude mice. Compound 6 showed uptake in the brain and proliferating tissues such as tumor and bone-marrow.     

The integration of certain products of the multivariableH-function with a general class of polynomials

The authors present six general integral formulas (four definite integrals and two contour inegrals) for theH-function of several complex variables, which was introduced and studied in a series of earlier papers by H. M. Srivastava and R. Panda (cf., e.g., [25] through [29]; see also [14] through [18], [20], [24], [32], [34], [35], [37], and [38]). Each of these integral formulas involves a product of the multivariableH-function and a general class of polynomials with essentially arbitrary coefficients which were considered elsewhere by H. M. Srivastava [21]. By assigning suiatble special values to these coefficients, the main results (contained in Theorems 1, 2 and 3 below) can be reduced to integrals involving the classical orthogonal polynomials including, for example, Hermite, Jacobi [and, of course, Gegenbauer (or ultraspherical), Legendre, and Tchebycheff], and Laguerre polynomials, the Bessel polynomials considered by H. L. Krall and O. Frink [9], and such other classes of generalized hypergeometric polynomials as those studied earlier by F. Brafman [3] and by H. W. Gould and A. T. Hopper [8]. On the other hand, the multivariableH-functions occurring in each of our main results can be reduced, under various special cases, to such simpler functions as the generalized Lauricella hypergeometric functions of several complex variables [due to H. M. Srivastava and M. C. Daoust (cf. [22] and [23])] which indeed include a great many of the useful functions (or the products of several such functions) of hypergeometric type (in one and more variables) as their particular cases (see,e. g., [1], [10] and [39]). Many of the aforementioned applications of our integral formulas (contained in Theorems 1, 2 and 3 below) are considered briefly. Further usefulness of some of these consequences of Theorems 1 and 2 in terms of the classical orthogonal polynomials is illustrated by considering a simple problem involving the orthogonal expansion of the multivariableH-function in series of Jacobi polynomials. It is also shown how these general integrals are related to a number of results scattered in the literature. 0261 0262 V