Highly diastereoselective cyanation of methyl ketimines obtained from (R)-glyceraldehyde

[reaction: see text] Addition of trimethylsilyl cyanide to ketimines derived from (R)-2,2-dimethyl-1,3-dioxolan-4-yl methyl ketone to generate a quaternary stereocenter has been achieved with high yields and excellent diastereoselectivity. The stereoselectivity was found to be temperature and solvent dependent. The beta-hydroxy-alpha-amino nitrile of syn configuration was the major compound in kinetically controlled reactions, whereas the anti stereoisomer was obtained in excess in thermodynamically controlled reactions. Double stereodifferentiation under kinetic control conditions was successful, and the cyanation reaction occurred with complete syn diastereoselectivity using the matched pair. The versatility of the resulting amino nitrile as a synthetic intermediate was tested by performing the synthesis of orthogonally protected (R)-(2-aminomethyl)alanine.     

Lead-selective membrane electrodes based on dithiophenediazacrown ether derivatives

Three double-armed diazacrown ethers with two thiophene side groups, 7,16-dithenyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTDC), 7,16-dithenoyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTODC), and 7,16-di-(2-thiopheneacetyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTAODC), have been synthesized and used as novel neutral lead(II) ionophores in ion selective electrode applications. The relationship between the molecular structure of these ionophores and electrochemical properties (linear range, response time, selectivity) of the membrane electrode is discussed. The optimum conditions for the preparation of the electrodes are described. The optimized dithenoyldiazacrown had a detection limit of pPb = 5.7, and Nernstian range with slope 29.2 mV decade⁻¹ from pPb = 5.0 to 2.7. Mercury and silver ions are the major interferences. These electrodes are applied to potentiometric titrations of lead(II) ions and show promise for the determination of lead ions in water samples.     

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,...     

Asymmetric allylboration of alpha,beta-enals as a surrogate for the enantioselective synthesis of allylic amines and alpha-amino acids

[reaction: see text] Optically pure allylic amines have been synthesized from alpha,beta-unsaturated aldehydes via allylboration with (-)-B-allyldiisopinocampheylborane, followed by Overman rearrangement. By incorporating crotyl and alkoxyallylboration, functionalization at delta-position was readily accomplished. By applying this methodology, the synthesis of several chiral alpha-amino acids has been achieved.     

Surface tension and density of mixtures of 1,3-dioxolane+alkanols at 298.15 K: analysis under the extended Langmuir model

Surface tensions (sigma) for [1,3-dioxolane+methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 1-pentanol] and excess molar volumes (v(E)) for [1,3-dioxolane+methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol] at the temperature 298.15 K and normal atmospheric pressure have been determined as a function of mole fractions. The magnitude of these experimental quantities is discussed in terms of the nature and type of intermolecular interactions in binary mixtures. In order to analyze the surface tension behavior, the extended Langmuir (EL) model was used and the results obtained for the systems containing 1,3-dioxolane were compared with those of other formerly published series: [1,4-dioxane+alkanes] and [1,4-dioxane+alcohols].     

Synthesis and Spectroscopic Characterization of Two Different Types of Heterobimetallic Glycolate Complexes of Niobium(V)

An entirely new class of heterobimetallic homoleptic glycolate complexes of the type Nb(OGO)₃{Ta(OGO)₂} [where G=CMe₂CH₂CH₂CMe₂ (G¹) (3); CMe₂CH₂ CHMe(G²) (4); CHMeCHMe (G³) (5); CH₂CMe₂CH₂ (G⁴) (6); CMe₂CMe₂(G⁵) (7); CH₂CHMeCH₂ (G⁶) (8); CH₂CEt₂CH₂ (G⁷) (9); CH₂CMe(Prⁿ)CH₂ (G⁸) (10)] have been prepared by the reactions of Nb(OGO)₂(OGOH) [G=G¹ (1a); G² (1b); G³ (1c); G⁴ (1d); G⁵ (1e); G⁶ (1f); G⁷ (1g); G⁸ (1h)] with Ta(OGO)₂ (OPrⁱ) (G=G¹ (2a); G² (2b); G³ (2c); G⁴ (2d); G⁵ (2e) G⁶ (2f); G⁷ (2g); G⁸ (2h). In addition to the novel derivatives (2)–(10), our earlier investigations on heterobimetallic glycolate-alkoxide derivatives have been extended to derivatives of the type Nb(OGO) [where M=A1 n=3, G=G³ (11);G⁴ (12); G⁶ (13) G⁷ (14); G^s (15); G⁹=CH₂CH₂CH₂ (16) and M=Ti (n=4, G=G⁴) (17), Zr(n=4,G=G⁴) (18)], which are conveniently prepared by the reactions of metalloligands Nb(OGO)₂(OGOH) [G=G³ (1c); G⁴ (1d); G⁶ (1f); G⁷ (1g); G⁸ (1h); G⁹ (1i)] with different metal alkoxides. All of these new complexes have been characterized by elemental analyses, molecular weight determinations, and spectroscopic (I.r. and ¹H, ²⁷Al-n.m.r.) studies. Structural features of the new derivatives have been elucidated on the basis of molecular weight and spectroscopic data.     

Schiff base complexes of dioxouranium(VI). VII. Dioxouranium(VI) acetate complexes with monobasic bidentate and bibasic tridentateSchiff bases

11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC₆H₄CH=NR oro-HOC₁₀H₆CH=NR (R=C₂H₅,n-C₃H₇,n-C₄H₉ or C₆H₅) and bibasic tridentateSchiff bases,o-HOC₆H₄CH=NR(OH) oro-HOC₁₀H₆CH=NR(OH) (R=–CH₂CH(CH₃)- or —CH₂CH₂CH₂–) have been studied and derivates of the type UO₂(OAc)₂(SBH), UO₂(OAc)₂(SBH)₂, UO₂(OAc)₂(SBH ₂) and UO₂(OAc)₂(SBH ₂)₂ (whereSBH andSBH ₂ represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.

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UO₂ ²⁺-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen

Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO₂(OAc)₂·2H₂O mitSchiff-Basen (L) Komplexe des Typs UO₂(OAc)₂ L bzw. UO₂(OAc)₂ L ₂ isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.

     

Acylation of α-(N-carbamoyl)alkylcuprates and alkyl- or aryl(halo)cuprates

α-(N-Carbamoyl)alkylcuprates [R₂CuLi·LiX or RCuXLi (X=CN, Cl)] when prepared from THF soluble CuX·2LiCl (X=Cl, CN) undergo a reliable and generally high yield reaction with aroyl, alkanoyl, and alkenoyl chlorides to provide a rapid and efficient synthesis of α-carbamoyl ketones. Cuprates prepared from acyclic, cyclic, and a functionalized carbamate can be utilized. Although yields are a function of cuprate reagent and substrate structure, nearly quantitative yields can be obtained with reagents generated from 2RLi+CuCN·2LiCl. The use of reagents generated from CuCl·2LiCl are more efficient in the α-(N-carbamoyl)alkyl ligand, although yields are slightly lower. Acylation of alkyl(chloro)cuprates generated from one equivalent of CuCl·2LiCl and organolithium or Grignard reagents provides an efficient and high yield procedure for ketone synthesis.     

Effect of grinding on thermal reactivity of ceramic clay minerals

The effect of grinding on thermal behavior of pyrophyllite and talc as commonly used ceramic clay minerals was investigated by DTA, TG, emanation thermal analysis (ETA), B.E.T. surface area (s.a.) measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM). A vibratory mill was used in this study, grinding time was 5 min. It was found that the grinding caused an increase in surface area and a grain size reduction of the samples. From TG and DTA results it followed that grinding caused a decrease of the temperature at which the structure bound OH groups released. The formation of high temperature phases was enhanced with the ground samples. For the ground talc sample the crystallization of non-crystalline phase into orthorhombic enstatite was observed in the range of 800°C. For ground pyrophyllite a certain agglomeration of grains was observed in the range above 950°C. Moreover, for both clays the ETA characterized a closing up of subsurface irregularities caused by grinding as a decrease of the emanation rate in the range 250–400°C. The comparison of thermal analysis results with the results of other methods made it possible to better understand the effect of grinding on the ceramic clays.