Caewoalljmination of Diphenylacetylene

It was found that diphenylacetylene reacts at 90[ddot]C with Et₃Al to form cis-ethylvinylalane. On the other hand, Et₃Al adds mostly in an anti-manner to diphenylacetylene at 140°C.     

Reduction of silicon halides and alkoxides with diisobutylaluminum hydride. Stereochemistry-rate law correlations for the SNiSi and SN2Si mechanisms

Stereochemistry-rate law correlations are given for the reduction of R₃Si*X compounds with i-Bu₂ AlH in either and n-hexane.     

An effect of application of chiral aluminium alkoxides and amides as adducts to zirconium catalyzed carbo- and cycloalumination of olefins

This paper is dedicated to a study of properties of the following novel optically active organoaluminium compounds (OACs): (1S,2S)-l,7,7-trimethyl-2-[(dialkylalumina)oxy]-bicyclo[2.2.1]heptanes and (1S)-N-(dialkylalumina)-6,7-dimethoxy-1-methyl-1,2,3,4- tetrahydroisoquinolines. The synthesis of the chiral OACs was carried out in the reaction of either natural camphor or salsolidine with both AlEt₃ and i-Bu₂AlH. The main goal of the research was to investigate the stereodifferentiating activity of the chiral OACs in the olefin carbo- and cycloalumination reactions, catalyzed by Cp₂ZrCl₂.     

Solar State 1H and 13C NMR Studies of Melanoidins Synthesized from D-Xylose and Glycine

Parameters affecting ¹³C CP/MAS NMR spectra of solid melanoidins (in particular ¹H T₁, T₁₀ and the cross polarization time t_cp) have been obtained with the aim of determining the optimum conditions necessary for quantitative studies. Melanoidins were synthesized at 22[ddot], 68[ddot] and 100 [ddot]C, from molar solutions of D-xylose and glycine. The ¹H T₁₀ values for all melanoidins were similar. Single exponential ¹H T₁ and ¹H T₁₀ relaxation curves were observed for all three polymers, suggesting that the mace-rials were relatively homogenenous. An increase in T₁'s with an increase in unsaturation was also observed. The optimum conditions for quantifying the different types of C were found to be t_cp = 2 msec., recycling time 2 sec. and for these conditions, the melanoidins synthesized at 22[ddot]C showed 18% unsaturation, 18% carboxyl and amide C, while the melanoidin synthesized at 100 [ddot]C showed 28 and 11% respectively. Solid state ¹H NMR lineshapes were obtained and these consisted in all three melanoidins of a broad and a narrow component attributed to the protons of the polymer core and the protons of the mobile side chains or methyl groups respectively.     

Characteristic features of reduction with i-Bu2AlH of products of ring opening with (?)-α-methylbenzylamine of (3aS,4R,7R,7aS)-3a,4,7,7a-tetrahydro-4,7-epoxy-2-benzofuran-1,3-dione

A special procedure of synthesis was developed for amidoaminals of atypical topology through a reduction with i-Bu₂AlH of primary products of thermodynamical opening of (3aS,4R,7R,7aS)-3a,4,7,7a-tetrahydro-4,7-epoxy-2-benzofuran-1,3-dione at treating with (−)-α-methylbenzylamine. Characteristic spectral criteria are described for assignment of diastereomeric compounds; possible routes of reaction stages are considered.     

Volatile mixed-ligand complexes of bis(diisobutyldithiocarbamato)zinc with 1,10-phenanthroline, 2,2′-bipyridyl,and 4,4′-bipyridyl. Crystal and molecular structure of the binuclear complex [Zn2(C10H8N2){(i-C4H9)2NCS2∼4]

Mixed-ligand complexes ZhPhen(i-Bu₂Dtc)₂, Zn(2,2′-Bipy)(i-Bu₂Dtc)₂, and Zn₂(4,4′-Bipy)(i-Bu₂Dtc)₄, where i-Bu₂Dtc=(i-C₄H₉)₂NCS ₂ ⁻ , have been synthesized. The structure of Zn₂(4,4′-Bipy)(i-Bu₂Dtc)₄ was determined by X-ray diffraction analysis; it consists of centrosymmetric binuclear molecules with trigonal-bipyramidal coordination of the central Zn atom. When heated in vacuum, the compounds quantitatively sublimate or evaporate. Thermal decomposition of the compounds in air (350°C) gives α-ZnS. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 6, pp. 1114–1121, November–December, 1996. Translated by L. Smolina     

The synthesis and characterization of isobutylantimony compounds

Six new isobutyl derivatives of antimony have been synthesized in good yields, including the five-coordinate i-Bu₃SbI₂ and the three-coordinate i-Bu₂SbI, i-Bu₂SbBr, i-BuSbBr₂, i-Bu₂SbH, and i-BuSbH₂. The iodides were made from addition of iodine to i-Bu₃Sb and subsequent thermal decomposition of i-Bu₃SbI₂. The bromides were synthesized by thermal exchange reactions of i-Bu₃Sb with SbBr₃, and the hydrides from reduction of the bromides with LiAlH₄. All compounds have been characterized by elemental analysis, IR, and NMR spectroscopy.     

Propene polymerization with rac-Me2Si(2-Me-Benz[e]Ind)2ZrX2 [X = Cl,Me] using different cation-generating reagents

Propene was polymerized with methylaluminoxane (MAO) and cationic activated rac-dimethylsilylene-2-methylbenz[e]indenylzirconocene [ MBI-Cl ₂] and [ MBI-Me ₂]. For cationic activation of the MBI-Me ₂ system tris(pentafluorophenyl)borane [I], N,N-dimethylanilinium tetra(pentafluorophenyl)borate [III] were used. The MAO-activated dimethyl complex showed higher activity with respect to the dichloride system using high catalyst concentrations and [Al]/[Zr] ratios. Most effective cationic activator for MBI-Me ₂ was N,N-dimethylanilinium tetra(pentafluorophenyl)borate [II] in combination with Al(i-Bu₃). Using tris(pentafluorophenyl)borane [I] at different polymerization conditions or N,N-dimethylanilinium tetra(pentafluorophenyl)borate [II] in combination with Al(Et)₃ no propene polymerization was observed due to the occurrence of reduction of the catalytically active site.     

Synthesis of sulfonated poly(diphenylacetylene)s with high CO2 permselectivity

High‐molecular‐weight poly[1‐phenyl‐2‐(4‐t‐butylphenyl)acetylene], poly[1‐phenyl‐2‐(4‐trimethylsilylphenyl) acetylene], and their copolymers were synthesized by the polymerization with TaCl₅–n‐Bu₄Sn. The obtained polymers were sulfonated by using acetyl sulfate to give sulfonated poly(diphenylacetylene)s with different degrees of substitution. The degrees of sulfonation of poly[1‐phenyl‐2‐(4‐t‐butylphenyl)acetylene] and copolymers were in the range of 0.57–0.85. When poly[1‐phenyl‐2‐(4‐trimethylsilylphenyl)acetylene] was sulfonated, the sulfonated poly(diphenylacetylene) with the highest degree of sulfonation was obtained among all the polymers in this study. Its degree of sulfonation was 1.55. All the sulfonated polymers exhibited high CO₂ permselectivity, and their CO₂/N₂ separation factor were over 31. The sulfonated poly(diphenylacetylene) with the highest degree of sulfonation showed the highest CO₂/N₂ separation factor of 75. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6463–6471, 2009     

Production of Organometallic Polymers by the Interfacial Technique. XXXII. Reaction Variables in the Synthesis of Oligomeric Tin Poly(cobalticinium Esters) and Thermal Properties of the Products

The synthesis of oligomeric tin poly(cobalticinium esters) is presented as a function of the particular reaction variables stirring rate, pH and amount of added base, mole ratio of reactants, concentration of reactants, and volume of organic phase. Factors which decrease the solubility of the stannane apparently act to increase the yield of polyester. The thermal characterization of I was carried out via DSC and TGA. The products generally exhibit endotherms below 150 to 200[ddot]C which may be related to T_g. Above 200[ddot]C, degradation occurs in air by an oxidative mode.     

Spectrophotometric Determination of Cystine with O-Phthalaldehyde in the Absence of Thiol

Abstract

A spectrophotometric method for the determination of cystine with o-phthalaldehyde (OPA) in the absence of thiol is described. When cystine is heated at 60[ddot]C for 30 min in a low excess of OPA (pH 9.5), a very stable derivative with 1:2 stoichiometry (cystine:OPA) and an absorption maximum at 335 nm (E = 4600) is formed. At pH < 1 the derivative is protonated (protonation constants: log K¹ = 5.88 and log K² = 3.70 at I = 0.1 and 20[ddot]C) and another absorption band at 440 nm (E = 3800) appears, which allows the determination of cystine in the presence of other amino acids.     

Activation of biscyclopentadienyl hydride complexes of titanium and aluminum by NH- and OH-acids in the reactions of hydrogenation of olefins. Crystal and molecular structures of {(η5−Cp)2Ti(μ−H)2AlH]μ−N(C2H4)4O]}2 and [(η5−Cp)2Ti(μ−H(2AlH]2(μ−OC2H4OMe)[(μ1:μ5−C5H4)Ti(μ5−Cp)(μ−H)]2*

The reactions of Cp₂TiH₂AlH₂·Et₂O (1) with HN(C₂H₄)₂O, HOC₂H₄OMe, and water afforded the complexes {Cp₂TiH₂AlH[μ-N(C₂H₄)₂O]}₂ (5), [Cp₂TiH₂AlH(μ-OC₂H₄OMe)]₂ (6) and (Cp₂TiH₂AlH)₂O (4), respectively. Compounds 5 and 6 are dimers containing bridging Al?E₂?Al fragments (E=N or O). Complex 6 in solution converted to the hexanuclear compound [(η⁵?Cp)₂Ti(μ?H(₂AlH]₂(μ?OC₂H₄OMe)[(μ¹:μ⁵?C₅H₄)Ti(μ⁵?Cp)(μ?H)]₂ (8). The structures of complexes 5 and 8 were established by X-ray diffraction analysis. The rates of hydrogenation of hex-1-ene were determined using compounds 4–6 and the complexes [Cp₂TiH₂AlH(NEt₂)]₂ and [Cp₂TiH₂AlH(OEt)]₂ as catalysts. The probable mechanism of hydrogenation with the participation of bimetallic hydride complexes of aluminum and titanocene is discussed.     

Rapid TLC Separation of some Closely Related 1-(2-Benzothiazolyl)-3- Methyl-5-Phenyl Pyrazole Derivatives

Abstract

Some closely related 1-(2-Benzothiazolyl)-3-methyl-5-phenyl pyrazole derivatives have been separated by TLC on silica gel-G[ddot] Most suitable solvent systems tried are (A) Pet. ether (40[ddot]-60[ddot])- Benzene (1:3) and (B) cyclohexane: ethylacetate (50:3).     

GC-MS Derivatization Studies: The Formation of Dexamethasone MO-TMS

Abstract

The 16α-methyl group in dexamethasone increases drastically the steric hindrance to reaction of both the 20-ketone and 17α-hydroxyl groups, as shown by kinetic studies with GC-MS techniques. A procedure is described for the preparation of the MO derivative (reaction et 60[ddot]C for 3 hr) and complete conversion of all hydroxyl groups to TMS ether groups (reaction at 100[ddot]C for 6 hr). The resulting MO-TMS derivative is thermostable and suitable for use in GC-MS methods. The procedures usually employed in urinary steroid studies are satisfactory for prednisone and prednisolone.     

SYNTHESIS AND PROPERTIES OF COPOLYMERS FROM 1-[3,5-BIS(TRIMETHYLSILYL)PHENYL]-2-PHENYLACETYLENE

Copolymerization of 1-[3,5-bis(trimethylsilyl)phenyl]-2-phenylacetylene (m,m-(Me₃Si)₂DPA) with other diphenylacetylene derivatives and their copolymer properties were investigated. Homopolymerization of m,m-(Me₃Si)₂DPA by TaCl₅─n-Bu₄Sn (1:2) did not give the polymer due to steric hindrance. However, m,m-(Me₃Si)2DPA copolymerized with diphenylacetylene (DPA), 1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene (p-Me₃Si DPA), and 1-phenyl-2-[m-(trimethylsilyl)phenyl]acety-lene (m-Me₃SiDPA) in the presence of TaCl₅─n-Bu₄Sn at various feed ratios to give copolymers in moderate yields. The formed copolymers were yellow to orange solids, which were soluble in common organic solvents such as toluene and CHCl₃. The highest weight-average molecular weights (M_w) of these copolymers reached ca. 6 × 105 and tough films could be obtained by solution casting. Their onset temperatures of weight loss in air were observed around 400°C, indicating high thermal stability. The oxygen permeability coefficients at 25°C of copoly(m,m-(Me₃Si)₂ DPA/DPA) (feed ratio 1:1) and copoly(m,m-(Me₃Si)₂DPA/p-Me₃SiDPA) (feed ratio 1:2) were 21 and 100 barrers, respectively, medium in magnitude among polymers from substituted acetylenes.     

Hydrodefluorination of non-activated C-F bonds by diisobutyl-aluminiumhydride via the aluminium cation [i-Bu2Al]

A novel system for the hydrodefluorination (HDF) of non-activated C-F bonds at room-temperature is described. The reaction of i-Bu₂AlH with [Ph₃C][B(C₆F₅)₄] (1), [Ph₃C][Al(C₆F₅)₄] (2) and [Ph₃C][Al{OC(CF₃)₃}₄] (3) as precatalysts leads under formation of triphenylmethane to the aluminium cation [i-Bu₂Al]⁺ and the non-coordinating anions [M(C₆F₅)₄]⁻ (M = B, Al) and [Al{OC(CF₃)₃}₄]⁻. The formed aluminium cation is very reactive towards C-F bonds and easily forms i-Bu₂AlF releasing a carbocation that abstracts the hydride of excess i-Bu₂AlH and yields the corresponding hydrocarbon. Thereby, the active species [i-Bu₂Al]⁺ is regenerated and can realize a catalytic cycle. For 1-fluorohexane as an example including non-activated C-F bonds different activities were found (TON: 1: 20; 2: 12; 3: 30) in cyclohexane as solvent.     

Solute Retention in Column Liquid Chromatography. V. the Column Dead Volume

Abstract

Methods of determination of the column void volume with two homologous series of solutes (alkyl-substituted aromatic hydrocarbons and phenyl-substituted aliphatic alcohols) are considered in terms of correlation coefficients r of plots of log V'_R against carbon number over the temperature range 10[ddot]-30[ddot]C. The homologous series methods provide self-consistent fits as well as temperature-invariant data for the aromatic hydrocarbons, but not for the alcohols, for which a mixed retention mechanism is said to obtain. A new graphical method of determining the best-fit value of V_A is introduced that makes use of plots of r against assumed V_A. In contrast to work reported elsewhere by others, each of the series of compounds studied in this work clearly exhibits a maximum. Those for the aromatic hydrocarbons are temperature-invariant; however, this is not so for the alcohols, which is taken as evidence of thermal and/or multiple sorption interactions of these solutes with the stationary phase.     

Phyllohydroquinone (Vitamin K1 H2) and Phylloquinone (Vitamin K1): Purification and Spectral Analysis

Abstract

Simple procedures for the preparation of pure phyllohydroquinone and phylloquinone are described. Phylloquinone is reduced by sodium dithionite and the reduced vitamin is purified by reverse phase high performance liquid chromatography. The essential spectral properties of the pure vitamins in ethanol and methanol are cited. The data provide a convenient spectral method for the accurate determination of the absolute concentrations of the oxidized and reduced vitamins and the rates of oxidation of the reduced vitamin. Pure, dry phyllohydroquinone may be safely stored at -70[ddot]C under nitrogen for a period of months. The stability of Phyllohydroquinone in methanol at 25.0 ± 0.1[ddot]C is also reported.     

A novel reducing agent. The reduction of dicarbonyls,acyloins, alkynes,and alkenes with active uranium

Active uranium, prepared in hydrocarbon solvents from UCl₄ and [(TMEDA)Li]₂[naphthalene] is a novel reducing agent. The unprecedented stepwise reduction of benzil and benzoin to bibenzyl has been shwon to proceed via the unsaturated species diphenylacetylene, cis-stilbene, and trans-stilbene. Active uranium also effects oligomerizations of diphenylacetylene and trans-stilbene.     

Synthesis and some transformations of (−)-carveol

Reduction of the oxo group in (?)-carvone with LiAlH₄, NaBH₄, and (i-Bu)₂AlH was performed. It was found that the reduction with the system CeCl₃ · 7 H₂O-NaBH₄ in methanol at 20°C is the most practical procedure for the synthesis of (?)-carveol. Solvolysis of (?)-carvyl methanesulfonate gave products of S_N2 and S_N2′ replacement of the methylsulfonyloxy group, the latter slightly prevailing. Overman rearrangement of (?)-carveol resulted in the formation of the corresponding trichloroacetamide derivative, and intramolecular iodoetherification of the title compound afforded 6-iodomethyl-2,6-dimethyl-7-oxabicyclo[3.2.1]oct-2-ene.