Transformation from a heat-set organogel to a room-temperature organogel induced by alcohols

A unique transformation from a heat-set organogel to a room-temperature organogel induced by ethanol (EtOH) was reported here. When the system containing β-cyclodextrin, 4,4′-isopropylidenediphenol, N,N-dimethylacetamide and LiCl was heated to the gelling temperature (T _gel), a heat-set organogel would be formed. In contrast, a semitransparent organogel (room-temperature organogel) could be obtained by injecting EtOH into the system at ambient temperature. In this transformation process, EtOH played a role in the formation of hydrogen bonds, which was critical for the self-assembly. The influence of other guest molecules, solvents and alcohols on this transformation was also investigated. These organogels were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, thermal gravity analysis and differential thermal gravity. Further, the formation mechanism of the organogels was proposed based on the above measurements.     

Triple-transforming gel prepared byβ-cyclodextrin,diphenylamine and lithium chloride in N,N-dimethylacetamide

<正>This paper describes a triple-transforming gel system(gel-sol-gel') for the first time,which is a thermo-responsive and multicomponent organogel prepared byβ-cyclodextrin(β-CD),diphenylamine(DPA) and lithium chloride(LiCl) in N,N-dimethylacetamide (DMAC) in a suitable proportion based on the supramolecular interactions.In the triple-transforming gel system,a gel(gel A) could be formed byβ-CD,DPA and LiCl in DMAC at room temperature based on stirring,then the gel could transform into a clear solution based on heating,and then the other gel(gel B) can be formed at a relatively high temperature(T_(gel),the gelation temperature by heating).The two gel states in the triple-transforming gel system have different microstructures.This gel system was characterized by OM,SEM,IR and rheology.     

Organogelation‐Controlled Topochemical [2+2] Cycloaddition and Morphological Changes: From Nanofiber to Peculiar Coaxial Hollow Toruloid‐Like Nanostructures

Novel amphiphilic molecules composed of naphthylacryl and L ‐glutamide moieties (1‐NA and 2‐NA) have been designed and their organogel formation in various organic solvents as well as their self‐assembled nanostructures have been investigated. Both compounds formed organogels in many organic solvents, ranging from nonpolar to polar, and self‐assembled into essentially nanofiber structures, although some twist or belt structures could be observed in certain solvents. A gel of compound 2‐NA in ethanol initially self‐assembled into nanofibers and then these were transformed into a family of coaxial hollow toruloid‐like (CHTL) nanostructures under irradiation, in which various toroids and disks of different sizes were stacked coaxially. We have established that a topochemical [2+2] cycloaddition in the organogel triggers this transformation. When the gel was fabricated into xerogels in which no ethanol remained, such morphological changes could not happen. This might be the first report of an organogel, in which both organized nanofibers and solvent coexist, controlling a topochemical reaction as well as the self‐assembled nanostructures formed. Due to the formation of the toruloid‐like nanostructures, the gel collapsed to a precipitate. However, upon heating this precipitate with ethanol, it redissolved and then formed a gel and self‐assembled into nanofibers once more. Thus, a reversible morphological transformation between nanofibers and an unprecedented series of toruloid‐like nanostructures can be induced by alternately heating and irradiating the gel.     

The wittig synthesis of allylic organosilicon compounds

The reactions of β-silylalkylidenetriphenylphosphoranes (prepared by the action of alkylidenetriphenylphosphoranes on iodomethylsilicon compounds, followed by deprotonation of the resulting β-silylalkyltriphenylphosphonium iodides) with aldehydes and ketones provide a useful route to allylic silicon compounds. The β-silyl Wittig reagents prepared and utilized in this study include Pha₃P=CHCH₂SiMe₃, Ph₃P=C(CH₃)CH₂,SiMe₃, Ph₃P=C(C₆H₅)CH₂SiMe₃, Ph₃P=CHCH₂SiMe₂H, Ph₃P=CHCH₂SiMe₂OSiMe₃ and Ph₃P=CHCH₂SiMe-(OSiMe₃)₂.     

New Possible Applications of Heavy Main-Group Elements in Organic Synthesis

Aside from elements of the 2nd row, and one element of the 3rd row of the periodic system—Si, P, S, and Se, respectively, whose organoelement groups such as Me₃Si and Ph₃P^⊕ have proven useful in numerous organic syntheses—other elements of the 3rd as well as 4th and 5th row (Ge, As, Sn, Sb, Te, Pb, Bi) can also be used as components of synthetically useful organoelement groups, the elements As, Sn, and Pb, in particular, offering certain advntages over the others. Some of these organoelement groups are suitable equivalents for Li- or halogen-substituents attached to carbon; they stabilize carbanionic centers (minimum of this effect at the 3rd-row elements), and owing to their suitability as leaving groups in β-eliminations, also open up interesting synthetic possibilities. The thermally unduced syn- and silica-gel induced anti-elimination of Ph₃Sn, Ph₂Sb, Ph₃Pb, together with β-OH, are novel. With the newly synthesized compounds Ph_nEl—Ch₂—Li (El = Sn, Pb, As, Sb, Bi) and other α- and β-lithiated R_nEl- and Ph₂As(O)-reagents such organoelement groups can be introduced into organic compounds and exploited in organic and organoelement synthesis.     

A new photo-responsive organogel containing benzophenone group

Benzophenone group was introduced into the gel system in order to fabricate a new ALS₂ organogel which was photo-responsive. In the gel state with mixed solvent of acetone and water (5%), helical fibres were formed. The light control on the morphological change from fibres to core–shell spheres was followed by transmission electron microscope, which supplied a new paradigm for the morphology control triggered by stimulus. Moreover, the gel could serve as light absorbent without being mixed with polymer.     

Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study

Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph₂POTEMP), which was obtained by the reaction of Ph₂PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph₂P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph₂P(S)H ( 6 ) or Ph₂P(BH₃)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph₂P(O)STEMP) in CDCl₃ at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP‐H₂][Ph₂P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates.     

Reactivity of mixed organozinc and mixed organocopper reagents: 11. Nickel‐catalyzed atom‐economic aryl–allyl coupling of mixed (n‐alkyl)(aryl)zincs

Group selectivity in the allylation of mixed (n‐butyl)(phenyl)zinc reagent can be controlled by changing reaction parameters. CuCN‐catalyzed allylation in tetrahydrofuran (THF)–hexamethylphosphoric triamide is n‐butyl selective and also γ‐selective in the presence of MgCl₂, whereas CuI‐catalyzed allylation in THF in the presence of n‐Bu₃P takes place with a n‐butyl transfer:phenyl transfer ratio of 23:77 and an α:γ transfer ratio of phenyl of 76:24. NiCl₂(Ph₃P)₂‐catalyzed allylation in the presence of LiCl is phenyl selective with an α:γ ratio of 65:35. The reaction of methyl‐ or n‐butyl(aryl)zinc reagents with an allylic electrophile in THF at room temperature in the presence of NiCl₂(Ph₃P)₂ catalyst and LiCl as an additive provides an atom‐economic alternative to aryl–allyl coupling using diarylzincs. Copyright © 2014 John Wiley & Sons, Ltd.     

Ultrasound induced formation of organogel from a glutamic dendron

New l-glutamic acid based dendritic compounds: N-(2-naphthacarbonyl)-l-glutamic acid diethyl ester (NGE) and N-(2-naphthacarbonyl)-1,5-bis(l-glutamic acid diethyl ester)-l-glutamic diamide (NBGE) were designed. Although NGE could not form any gels in common solvents, NBGE could form stable gels in hexane, toluene, and water under ultrasound. Three dimensional network structures composed of fibers with various diameters were observed in the gel by SEM and TEM. FTIR spectral measurement revealed that ultrasound during cooling of the solution could destroy some of the hydrogen bond interactions and caused the gel formation. In solution, no CD signal was detected because the naphthyl chromophore is far from the chiral center. In the gel, however, CD signals assigned to the naphthyl group were observed, which indicated that the chirality of the chiral center could be transferred to the chromophore in the supramolecular organogel system.     

Zur Oxydation von Nickel(0)-Komplexen mit Halogenverbindungen des Kobalt(II), Kupfer(II) und Zink(II)

Oxidation of Nickel(0) Complexes by Halogen Compounds of Cobalt(II), Copper(II), and Zine(II) In aceton as a solvent Ni(PPh₃)₄ is oxidized by; cobalt(II) complexes of the type (Ph₃P)₂CoX₂ to nickel(I) compounds. In the case of X = Cl (Ph₃P)₃NiCl and (Ph₃P)₃CoCl separately crystallize, while for X = Br the lattice compound CoNi(PPh₃)₆Br₂ and for X = I CoNi(PPh₃)₅I₂ are formed. CuBr₂ and Ni(PPh₃)₄ react to (Ph₃P)₂NiBr and (Ph₃P)_nCuBr. With (Ph₃P)₂ZnCl₂ also (Ph₃P)₃NiCl is formed But in this case the oxidant is hydrogen chloride originating from hydrolysis. The magnetic moments of the new compounds were measured and their vis and fir spectra compared with those of the simple compounds (Ph₃P)_nNiX (n = 2, 3) and (Ph₃P)₃CoX. The M–X stretching frequencies are assigned. The cobalt (I) complexes (Ph₃P)₃CoCl have identical (distorted tetrahedral) structures, but most probably the nickel (I) complexes have not.     

Effect of Solvent and Molecular Structure on the Enhanced Fluorescence and Supramolecular Chirality of Schiff Bases in Organogels

The structures and properties of some Schiff base compounds doped in organogels were investigated. It was found that although individual Schiff bases could not form organogels with organic solvents, they can gel by mixing with an organogelator, N,N′-bisoctadecyl-L-Boc-glutamic-diamide, which formed transparent organogels in dimethyl sulfoxide (DMSO) or toluene (Tol). The enhancement of doping Schiff bases fluorescence in the organogel was observed in comparison with that of the corresponding solution. Furthermore, in the DMSO organogel, the induced chirality was obtained from the doping Schiff base with long alkyl chain. In contrast, the Schiff bases without long alkyl chain could not form supramolecular chiral assemblies in organogel. It was suggested that through gel formation the chirality of the gelator could be transferred to the Schiff base through hydrophobic interaction among the long alkyl chains.     

Palladium(II) Chloride Interaction with Chelating BIS(Phosphine Sulfides). Effect of the Ligand Structure on the Complex Geometry

Abstract

Interaction of PdCl₂ in chloroform with bis(phosphine sulfides) Ph₂P(S)?X?P(S)Ph₂ (X?CH₂, C(CH₃)₂, CH₂CH₂, NH, S, and SCH₂S) has been studied. Mechanism of the reaction has been found to vary dramatically with the identity of X. The structures of the resultant complexes were evaluated by UV and IR spectroscopy. Crystal structures were were determined by X-ray diffraction for two of the compounds (A: [Ph₂P(S)?(CH₂)₂?P(S)Ph₂]PdCl₂ · CH₃CN, P2₁/n, Z = 4, a = 10.104(2), b = 20.939(4), c = 14.034(3) Å, γ = 102.54(2)· B: [Ph₂P(S)?N?P(S)Ph₂]₂Pd · 2CHCl₃, Pl, Z = 1, a = 9.539(1), b = 12.333(3), c = 12.866 Å, α = 111.83(2)°, β = 96.70(3)° γ = 99.84(3)°).     

Pyrene-containing peptide-based fluorescent organogels: inclusion of graphene into the organogel

The N-terminally pyrene-conjugated oligopeptide, Py-Phe-Phe-Ala-OMe, (Py=pyrene 1-butyryl acyl) forms transparent, stable, supramolecular fluorescent organogels in various organic solvents. One of these organogels was thoroughly studied using various techniques including transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), Fourier-transform infrared (FTIR) spectroscopy, photoluminescence (PL) spectroscopy, and rheology. Unfunctionalized and non-oxidized graphene was successfully incorporated into this fluorescent organogel in o-dichlorobenzene (ODCB) to form a stable hybrid organogel. Graphene is well dispersed into the gel medium by using non-covalent π-π stacking interactions with the pyrene-conjugated gelator peptide. In the presence of graphene, the minimum gelation concentration (mgc) of the hybrid organogel was lowered significantly. This suggests that there is a favorable interaction between the graphene and the gelator peptide within the hybrid organogel system. This hybrid organogel was characterized using TEM, AFM, FTIR, PL, and rheological studies. The TEM study of graphene-containing hybrid organogel revealed the presence of both graphene sheets and entangled gel nanofibers. The AFM study indicated the presence of 3 to 4 layers in exfoliated graphene in ODCB and the presence of both graphene nanosheets and the network of gel nanofibers in the hybrid gel system. The rheological investigation suggested that the flow of the hybrid organogel had become more resistant towards the applied angular frequency upon the incorporation of graphene into the organogel. The hybrid gel is about seven times more rigid than that of the native gel.     

Salt resistivity of poly (4-vinyl benzoic acid) gel

Salt resistivity of poly (4-vinyl benzoic acid) (P4VBA) gel was investigated to compare with the super salt-resistivity that was found for poly (4-vinyl phenol)(P4VPh) gel containing an acidic proton and π-electron system. Poly(acrylic acid) (PAA) gel was also prepared and used as a reference gel containing only an acidic proton. P4VBA gel showed a moderate salt resistivity, which was less significant than that for P4VPh gel, in many kinds of inorganic salt solutions (MgCl₂, LiCl, NaCl, KCl, CsCl, KI, KSCN, Na₂SO₄). On the other hand, PAA gel showed a drastic deswelling in the presence of concentrated MgCl₂, LiCl, Na₂SO₄, and (NH₄)₂SO₄ solutions, and a significant swelling for KSCN solution. These contrastive behaviors between P4VBA and PAA gels strongly suggest that the combination of acidic proton and π-electron system is essential and necessary for polymer gels to be endowed with the salt resistivity.     

Copolymerization of 1,3‐butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine

The homopolymerization and copolymerization of 1,3‐butadiene and isoprene were achieved at 0 °C with cobalt dichloride in combination with methylaluminoxane and triphenylphosphine (Ph₃P). For 1,3‐butadiene, highly cis‐specific and 1,2‐syndiospecific polymerization proceeded in the absence or presence of Ph₃P, respectively, although the activity with Ph₃P was much higher than that without Ph₃P. Only a trace of the polymer was, however, obtained in isoprene polymerization when Ph₃P had been added. For copolymerization, the polymer yield in the presence of Ph₃P was about three times higher than that in its absence. Copolymerization in the presence of Ph₃P was, therefore, investigated in more detail. Unimodal gel permeation chromatography elution curves with narrower polydispersity (weight‐average molecular weight/number‐average molecular weight ≈ 1.5) indicated that the propagation reaction proceeded by single‐site active species. Both the yield and molecular weight of the copolymer decreased with an increasing amount of isoprene in the feed, and this was followed by an increase in the isoprene content in the copolymer. The monomer reactivity ratios, r₁ (1,3‐butadiene) and r₂ (isoprene), were estimated to be 2.8 and 0.15, respectively. Although the 1,3‐butadiene content in the copolymer was strongly dependent on the comonomer composition in the feed, the ratio of 1,2‐inserted units to 1,4‐inserted units of 1,3‐butadiene was constant. Concerning the isoprene unit, the percentage of 1,2‐ and 3,4‐inserted units was increased at the expense of 1,4‐inserted units with an increasing isoprene content in the feed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3086–3092, 2002     

Reaction of coordinated phosphines: VI. Divalent palladium promoted cleavage of carbon—phosphorus bonds in tertiary phosphines

The important role of divalent palladium in the cleavage of carbon—phosphorus bond of tertiary phosphines is revealed by the study of the phenylation in the Pd(OAc)₂Ph₃P-styrene system under various conditions; reaction atmosphere, ratio of Ph₃P/Pd(OAc)₂, and addition of ethanol or Cu^II(OAc)₂ · H₂O.     

Triphenyltin hydroxide as a precursor for the synthesis of nanosized tin‐doped TiO2 photocatalysts

¹H and ¹¹⁹Sn NMR results indicate that, when Ph₃SnOH is dissolved in CD₂Cl₂, it dehydrates to (Ph₃Sn)₂O, only a small amount of Ph₃SnOH remaining in equilibrium at room temperature. As a result, the reaction of TiCl₄ with Ph₃SnOH in CH₂Cl₂ proceeds via hydrolysis of the halide to precipitate amorphous TiO₂ that contains adsorbed organotin species. Calcination of the amorphous precursor to 723 K yields nanoparticles of tin‐doped TiO₂ photocatalysts, that contain anatase and rutile phases, and may also contain a segregated SnO₂ phase. The reaction conditions that lead to the formation of a SnO₂ phase have been studied and we have found that it is formed when the amorphous precipitate is not thoroughly washed with CH₂Cl₂ or when non‐recrystallized commercial Ph₃SnOH is used as a starting material. The catalysts obtained have a high activity for the photooxidation of toluene in the gas phase. In particular, a material obtained from non‐recrystallized Ph₃SnOH is particularly promising because the toluene photooxidation rate is more than twice as high as when using Degussa P25. Copyright © 2005 John Wiley & Sons, Ltd.     

2-Phosphinothioyl- and 2-phosphinoylethylcyclopentadienyl zirconium and titanium complexes. Crystal structure of [η5:η1-C5H4CH2CH2P(O)Ph2]TiCl3

The intracomplex conversion of (2-diphenylphosphanoethyl)cyclopentadienyl zirconium and titanium complexes into the corresponding 2-phosphinothioyl and 2-phosphinoyl derivatives, viz., (η⁵-C₅H₅)[η ⁵-C₅H₄CH₂CH₂P(S)Ph₂]ZrCl₂, [η⁵-C₅H₄CH₂CH₂P(S)Ph₂]ZrCl₃, [η⁵:η¹C₅H₄CH₂CH₂P(O)Ph₂]ZrCl₃·THF, and [η⁵:η ¹-C₅H₄CH₂CH₂P(O)Ph₂]TiCl₃ (7), was performed. The NMR spectroscopy data revealed the following order of the coordination ability of the functional groups with respect to the Zr center: Ph₂P=O > Ph₂P > Ph₂P=S. An analogous order was found for the monodentate ligands (Ph₃P=O > Ph₃P > Ph₃P=S) with respect to (η⁵-C₅H₅)ZrCl₃. The molecular structure of complex 7 was established by X-ray diffraction analysis. Coordination of the Ph₂P=O group to the titanium atom was found retained both in the crystalline state and solution.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116–122, January, 2005.     

Reduction of Phosphine Oxide by Using Chlorination Reagents and Dihydrogen: DFT Mechanistic Insights

Extensive DFT calculations provide detailed mechanistic insights into the metal-free reduction of phosphine oxide Ph₃P=O by using chlorination reagents O=CClX (X=COCl, Cl, OCCl₃ and Ph) and H₂. Fast electrophilic attack to the P=O group oxygen atom is favored by exergonic CO₂ release to form phosphonium Ph₃PCl⁺ and chloride Cl⁻, which may slowly cleave H₂ by an unstable HPh₃PCl complex yielding Ph₃PH⁺ and Cl⁻ ions in solution. Moderate heating is required to accelerate the slow H₂-activation step and to eliminate HCl to form phosphine Ph₃P instead of Ph₃PH⁺Cl⁻ salt as the desired product. Though partially quenched by Ph₃P (and reactant Ph₃P=O if present), borane B(2,6-F₂C₆H₃)₃ can be still combined with Cl⁻ and Ph₃P as reactive frustrated Lewis pair (FLP) catalysts.