Synthesis and Solvolysis of [(ω-(Dimethylphenoxysilyl)alkyl]-diphenylphosphines,Phosphine Oxides and Phosphine Sulfides

Abstract

Kinetics of base catalysed solvolytic cleavage of phenoxy group from compounds of general structure X (CH₂)nSiMe₂OPh, where n=1,2,3 and X=Me,Ph₂P, Ph₂P (p), Ph₂P(s) has been investigated. The main purpose was to study the effect of phosphorus groups on the reactivity in substitution reaction at silicon. We wanted to answer the question whether there is any direct interaction of the phosphorus groups with silicon moiety, modifying this reactivity. Complementary NMR studies have also been performed for this purpose.     

Synthesis and characterization ofα-{3-[(2,3-dihydroxy) propoxy]propyl}-ω-butylpolydimethylsiloxanes

Hydrosilylation has been carried out between Si-H terminated polydimethylsiloxanes with narrow molecular weight distribution and protected 3-allyloxy-1,2-propanediol,and after subsequently alcoholyzed,α-{3-[(2,3-dihydroxy)propoxy]propyl}-ω-butyl -polydimethylsiloxanes with varying number of((Si(CH_3)_2-O) unit were obtained.At each step,the produced compounds were carefully characterized.The results showed that each step was successfully carried out and target products were achieved.     

Synthesis of β-Substituted-α-[(trimethylsilyl)oxy]acrylonitriles from α, β-Unsaturated Aldehydes

The condensation of trimethylsilylcyanide with α, β-unsaturated aldehydes, followed by DBU catalyzed isomerization of the intermediate 0-silylated cyanohydrins, constitutes a facile synthesis of β-substituted- α-[(trimethylsilyl)oxy]acrylonitriles.     

Structural characterization,thermal investigation,and liquid crystalline behavior of 4-[(4-chlorobenzyl)oxy]-3,4′-dichloroazobenzene

Using the Williamson method, a new dye 4-[(4-chlorobenzyl)oxy]-3,4′-dichloroazobenzene (CODA) with liquid crystalline properties was synthesized. The structure and the thermal behavior of CODA were investigated by means of nuclear magnetic resonance, X-ray diffraction, differential scanning calorimetry, and light polarized optical microscopy techniques. The thermophysical processes were monitored by heating–cooling cycles, but the formation of liquid crystal phases were exhibited only for small values of the cooling rates. For the first heating–cooling cycle, the melting and the solidification processes, thus the characteristic temperatures, are shifted to higher values when compared to the following cycles.     

Synthesis and Structure of μ-Oxobis[(nitrito)triphenylantimony]

Triphenylantimony dibromide was reacted with sodium nitrite in aqueous acetone to obtain -oxobis[(nitrito)triphenylantimony]. According to single-crystal X-ray diffraction data, the Sb atoms in the molecule have a trigonal bipyramidal coordination. The molecule is centrosymmetric, the two Sb atoms are linked with each other by a bridging oxygen atom [the SbOSb angle is 141.8(2)°, and the Sb···Sb distance is 3.7354(5) Å]. The Sb-Obr and Sb-Oterm bond lengths are 1.9768(1) and 2.257(3) Å, and the Sb···O and Sb···N distances are 3.020(4) and 3.070(6) Å, respectively.     

Electric Field-Controlled Synthesis and Characterisation of Single Metal–Organic-Framework (MOF) Nanoparticles

Achieving control over the size distribution of metal–organic-framework (MOF) nanoparticles is key to biomedical applications and seeding techniques. Electrochemical control over the nanoparticle synthesis of the MOF, HKUST-1, is achieved using a nanopipette injection method to locally mix Cu²⁺ salt precursor and benzene-1,3,5-tricarboxylate (BTC³⁻) ligand reagents, to form MOF nanocrystals, and collect and characterise them on a TEM grid. In situ analysis of the size and translocation frequency of HKUST-1 nanoparticles is demonstrated, using the nanopipette to detect resistive pulses as nanoparticles form. Complementary modelling of mass transport in the electric field, enables particle size to be estimated and explains the feasibility of particular reaction conditions, including inhibitory effects of excess BTC³⁻. These new methods should be applicable to a variety of MOFs, and scaling up synthesis possible via arrays of nanoscale reaction centres, for example using nanopore membranes.     

Synthesis of [(π-cyano-P-nacnac)Cp] and [(π-cyano-nacnac)Cp]-zirconium complexes, and their remote activation for ethylene polymerization

In this contribution the synthesis and characterization of two distinct, yet similar, zirconium complexes, [(π-P-nacnac-CN)Cp] and [(π-nacnac-CN)Cp] zirconium dichloride were discussed. In addition to the complexes, Lewis acid adducts [B(C(6)F(5))(3)] of the complexes were isolated and characterized as well. It was found that while structurally similar, the complexes behave distinctly upon adduct formation and in their ethylene polymerizations.     

Synthesis and characterization ofα-butyl-ω-{3-[(2,2-dihydroxymethyl)-propionyloxy]}propylpolydimethylsiloxanes

A series of polydimethylsiloxanes containing two primary hydroxyl groups at one single chain end were synthesized by five-step reactions which included esterification, hydroxyl protection, anionic ring-opening polymerization, hydrosilylation and deprotection. The prepared compounds in each step were characterized. The results showed that each step synthesis was successfully carried out and objective products could be achieved.     

Synthesis and Antioxidant Properties of Bis[ω-(3,5-dialkyl-4-hydroxyphenyl)alkyl] Sulfides

The reaction of -(3,5-dialkyl-4-hydroxyphenyl)-1-chloroalkanes with sodium sulfide yielded the corresponding sulfides, which were tested as antioxidants in two model reactions: oxidation of lard and Vaseline oil.     

Synthesis and crystal structure of (E)-[(2-cyclohexenyl) vinyl]triaryltin

(E)-[(2-Cyclohexenyl)vinyl]triaryltin (aryl=phenyl, p-tolyl) were synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy. The crystal structure of (E)-[(2-cyclohexenyl)vinyl]triphenyltin was also determined by the X-ray diffraction. Experiments show that this compound has the conjugated system, which makes it have possible bioactivity and anti-tumor activity.     

Synthesis and structure of bis-μ-[(methylenedicyclopentanone-2,2′-dioximato)triphenylantimony]

The reaction of pentaphenylantimony with methylenedicyclopentanone-2,2 dioxime affords bis--[(methylenedicyclopentanone-2,2-dioximato)triphenylntimony] having, according to the X-ray diffraction data, a centrosymmetric structure with two Ph₃Sb moieties linked by dioxime bridges. The antimony atom has a distorted trigonal bipyramidal coordination. The Sb-C bond lengths vary in an interval of 2.111(1)–2.137(3) , and the Sb-O distances are equal to 2.064(1) and 2.0663(9) . The molecule contains short intramolecular contacts SbN of 2.876(1) and 2.910(1) .Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 172–176.Original Russian Text Copyright © 2005 by Sharutin, Molokova, Sharutina, Alyabeva, Kukharev, Akimova, Pushilin.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Design, Synthesis and Biological Activity of Substituted-N-[4-（substituted-phenylsulfamoyl）phenyl]benzamide as Potential AHAS Inhibitors

Acetohydroxyacid synthase (AHAS) is an ideal target for the design of environmental benign herbicides, because it catalyzes the first step in the biosynthesis of branched chain amino acids, which does not exist in mammal bodies1-4. Typical AHAS inhibitors…     

Synthesis of Polyacrylaminothiourea Chelating Fiber and Properties of Concentration and Separation of Trace Noble Metal Ions from Samples

A novel polyacrylaminothiourea chelating fiber was synthesized simply and rapidly from nitrilon (an acrylonitrile-based synthetic fiber), which was applied to preconcentrate and separate of trace amount of Au(Ⅲ）,Pt(Ⅳ）,Pd(Ⅳ） and Ir (Ⅳ） ions from solution of samples.The analyzed ions can be quantitatively concentrated by the fiber up to a flow rate of 20.0mL/min at pH2, and can also be desorbed with 15 mL of 4mol/L HCl 3% thiourea from the fiber column with recoveries of 96.5%-100%.The chelating fiber can be reused for ten times,the recoveries of these ions are still over 92%,and hundred to thousand times of excess of Fe(Ⅲ）,Al（Ⅲ）,Ca(Ⅱ），Mg（Ⅱ）,Ni(Ⅱ）,Mn（Ⅱ),Cu(Ⅱ），Zn(Ⅱ），and Cd(Ⅱ） cause no interference on the determination of the analyzed ions by inductively-coupled plasma atomic emission spectrometry (ICP-AES).The static saturation adsorption capacities of the fiber for the analytes are in the range of 1.15-2.80mmol/g.The relative standard deviations for the determination of 20.0ng/mL each of Au(Ⅲ）,Pt(Ⅳ）,Pd(Ⅳ）and Ir(Ⅳ） are in the range of 0.7%-3.0%.The recoveries for test from standard additions to real solution samples are between 96% and 100%.The concentration of each ion in powder sample detected by the method is in good agreement with the certified value.     

Synthesis and Crystal Structure of 2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol-copper(Ⅱ)

2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol-copper(Ⅱ) has been designed and synthesized.The structure was determined by UV,IR and single-crystal X-ray study.The title complex crystallizes in the triclinic system,space group P1 with a=6.6090(13),b=10.377(2),c=12.550(3),α=113.29(3),β=93.84(3),γ=98.31(3)°,V=774.9(3)3,Dc=2.215g/cm3,C26H30CuO4N4I4,Mr=1033.68,F(000)=487,μ=4.726 mm-1,Z=1,the final R=0.0563 and wR=0.1475 for 2101 observed reflections(I2σ(I)).The central copper(Ⅱ) is four-coordinated by two nitrogen atoms and two oxygen atoms from two 3,5-diiodosalicylaldehyde-2-morpholinoethylamine Schiff bases.The complex is linked into a column by π-π stacking interaction.The complex was assayed for antibacterial activities against three Gram positive bacterial strains(B.subtilis,S.aureus and S.faecalis) and three Gram negative bacterial strains(E.coli,P.aeruginosa and E.cloacae) by MTT method.Fortunately,the title complex shows potent antibacterial activity against these six bacterial strains.     

Preparation and properties of copper tetra-4-[(4′-carboxy)phenylamino]phthalocyanine

Interaction of 4-nitrophthalonitrile with 4-aminobenzoic acid in dimethylsulfoxide in the presence of potassium carbonate has led to 4-[(4′-carboxy)phenylamino]phthalonitrile. From the latter, copper tetra-4-[(4′-carboxy)phenylamino]phthalocyanine has been prepared via the template synthesis. The spectral properties of the product have been studied. It has been demonstrated that in aqueous alkaline solutions the complex associates, whereas in dimethylformamide it predominantly exists in the monomeric form.     

New Synthesis of (±)-Cherylline and Mono- and Dimethyl Ethers

The synthesis of 4-aryl-1,2,3,4-tetrahydroisoquinolines is achieved via the ether rearrangement methodology. Subsequent reactions yielded cherylline and ether derivatives of amaryllidaceac alkaloids.     

Synthesis and Crystal Structure of N-phenyl-N-[（o-nitrophenylacetyl）oxy]benzamide

The compound N-phenyl-N-[（o-nitrophenylacetyl）oxy]benzamide （C21HI6N2Os, Mr = 376） has been synthesized by the reaction of N-hydroxy-N-phenylbenzamide with 2-（2-nitro- phenyl）acetyl chloride in dichlorom-ethane and its structure Was characterized by 1H NMR, 13C NMR, IR, H RMS（ESI） and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group C2/c with a = 32.30（2）, b = 8.400（5）, c = 15.099（9） A, fl = 114.256（10）°, V = 3735（4） A3, Z = 8, D, = 1.339 g/cm3, F（000） = 1568, p = 0.097 mm-1, the final R = 0.0506 and wR = 0.1176 for 2318 observed reflections （1 〉 2a（/））. The title molecule contains three branched chains with its center placed at the midpoint of N. The phenyl ring （C（1）＇-C（6）） makes a dihedral angle of 70.3（1）° with the phenyl ring （C（10）-C（15）） of benzoyl group, and 14.3（1）° with the phenyl ring （C（16） - C（21））, Hydrogen bonds C（5）-H（5）...O（1） and C（12）-H（12）...O（3） together with it-Jr stacking interactions contribute to the stability of the structure.     

Synthesis of a Novel Diamine 4-[(4''''-Butoxyphenoxy)carbonyl]phenyl-3",5"-diaminobenzoate and Corresponding Polyimides

A novel diamine 4-[(4'-butoxyphenoxy)carbonyl]phenyl-3",5"-diaminobenzoate (BCDA) was synthesized from 4-butoxyphenol, 4-hydroxybenzoic acid and 3,5-dinitrobenzoic acid through four main intermediates, and a series of polyimides were also synthesized. All the intermediates and the final product were characterized by FTIR and 1H-NMR. The key step in synthesis route is selective hydrolyzation of two ester groups in 4-butoxyphenyl-4'-acetoxybenzoate, by adjusting the reaction temperature and the concentration of ammonia, shorteding the reaction time. The properties of the novel polyimides, such as the aggregation structures, glass transition temperature, solubility and the pretilt angles, were carried out.