Synthesis and Properties of Phosphabetaine Structures: III. Phosphabetaines Derived from Tertiary Phosphines and α,β-Unsaturated Carboxylic Acids. Synthesis, Structure, and Chemical Properties

Methods of synthesis of acylate phosphabetaines by reactions of triphenylphosphine with methacrylic, cinnamic, and p-methoxycinnamic acids are developed. The phosphabetaine form is proposed to exist in equilibrium with the ⁵-oxaphospholane form. The features of methylation of the phosphabetaines are discussed.     

Synthesis and Acid-Base Properties of α-Aminophosphoryl Compounds

-Aminophosphoryl compounds of the phosphonate, phosphine oxide, and ,-bis(phosphine oxide) series and some of their thiophosphoryl analogs were synthesized. Potentiometric measurements of the pK_a of the conjugate acids revealed an insignificant effect of variation of substituents on the phosphorus, nitrogen, and -carbon atoms on the basicity of the phosphorylated amines. The latter are weak bases. Organophosphorus groups decrease the basicity of the amines by almost 5 pK _a units. The role of the hydrophobic effect and intramolecular H-bonding in the obtained substances was discussed.     

Synthesis and Properties of Phosphorylated and Silylated α-Mercaptocarbonyl Compounds

Abstract

Phosphorylation and silylation of α -mercaptooarbonyl compounds have been investigated. A novel type of 1.4 S-O migration trimethylsilyl and P(III) groups has been discovered. The thiophosphite-thiophosphonate rearrangement when exposed to oxygen as well as heterocyclization with the formation of 1,3,2-oxathiaphospholenes and 1,3,2-oxathiasilalenes were also found. Some regularities of these processes and the properties of heterocycles synthesized have also been brought out.     

Synthesis and Three-photon Induced Nonlinear Properties of a Novel Organic Chromophore

A novel organic chromophore 4, 4＇-bis（9-carbazyl-trans-styryl）-biphenyl （BCSBP） has been synthesized and characterized by IHNMR and elemental analysis. Three-photon absorption（3PA） induced upconvention fluorescence was observed and large 3PA cross section as high as 10^-74 cm^6 s^2 was obtained for nanosecond laser pulses at 1064 nm from optical limiting measurements.     

1,4-Diphenyl-5H-[1,2,5]triazepino[5,4-a]benzimidazole—A New Heterocyclic System. Synthesis and Properties

Russian Journal of Organic Chemistry - The first representative of a new heterocyclic system, 1,4-diphenyl-5H-[1,2,5]triazepino[5,4-a]-benzimidazole, has been synthesized by condensation of ethyl...     

Synthesis of Antipyrine Derivatives Derived from Dimedone

Coupling of dimedone with the diazonium salt of 4-aminoantipyrine afforded 2,3-dimethyl-4-[2-（5,5-dimethyl- 2,6-dioxocyclohex-2-ylidend）-hydrazino]-5-oxo-1-phenylpyrazoline （3）. Reaction of 3 with excess phenylhydrazine gave the mixed trishydrazone derivative 4. Treatment of 3 with hydroxylamine produced the bisoxime 5 which upon dehydrative cyclization with acetic anhydride gave the corrsponding tetrahydrobenzo[d][1,2,3]triazole derivative 7. A one-pot synthesis of 7 was done by reacting 3 with hydroxylamine hydrochloride in pyridine, followed by heatment with acetic anhydride.     

Synthesis and Mesomorphic Properties of Some ω′-Alkoxy-ω-benzoxypolyfluorotolane Compounds

Four homologue series of 4-cyano-nd 4-nitro-substituted benzoate-tolanes were synthesized and char-acterized by IR,NMR,MS spectra and elemental analysis.Their phase transition behaviors were investigated byDSC and polarized optical microscope.The effects on the mesomorphic properties of different positions of the per-fluorophenyl in the molecular core unit,the terminal cyano-substituted systems and the terminal nitro-substitutedones were discussed.     

Design and Synthesis of Novel Molecular Tweezers Derived from Chenodeoxycholic Acid

A novel type of chiral molecular tweezers has been designed and synthesized by usingchenodeoxy cholic acid as spacer and the aromatic compounds as arm. Their structures werecharacterized by 1HNMR, IR, MS spectra and elemental analysis. These chiral molecular tweezersshowed good enantioselectivity for D-amino acid methyl esters.     

Diastereospecific synthesis of β-heterosubstituted alcohols from 1,2-diols via 1,3,2λ5-dioxaphospholanes

The stereochemistry of the ring opening of (R,S) or (R,R)-4,5-dimethyl-2,2,2-triphenyl-1,3,2λ⁵-dioxaphospholanes (prepared by reaction of (R,S) or (R,R)-butane-2,3-diol with dibromotriphenylphosphorane) by aniline or thiophenol was investigated. The reaction affords stereoselectively the corresponding β-anilino- or β-phenylthioalcohols with a nearly complete inversion of stereochemistry at the stereogenic reaction centre.     

Synthesis on Multifunctional Groups and Multibranched Compounds Ⅷ.Synthesis of Dendritic Polyestrone

Eversincethel99o's,studiesondendrimershavesparkedmuchinterest,andthemainresearchworkdonehavebeenfocusedonthesynthesisandphysicalandchemicalpropertiesofdendrimers.Recently,thepotentialofdendrimersinpharmaceuticalandmedicalapplications,diagnosticimagingandradiationtherapyhasbeenincreasinglydiscussedl.However,therehasbeenonlyafewreportsconcerningtheincorporationofnaturalproductsordrugsintoadendrimerstructure2.Previously,ourgrouphasreported'onthefacileconvergentapproachtotheoctopuspolyestrone.Inth…     

Highly Diastereoselective Synthesis of Anomeric β-O-Glycopyranosyl σ3λ3-and σ4λ5-Phosphorus Compounds

Abstract

A new method for the highly stereoselective synthesis of β-O-σ³λ³ and σ⁴λ⁴ phosphorus-substituted 2,3,4,6-tetrabcnzylglucose is presented. The β-diastereoselective synthesis of the carbohydrates containing σ³λ³ and σ⁴λ⁵ phosphorus groups could be accomplished via two main synthetic routes. The first involves the addition of the σ³λ³-phosphorus derivative 3 to the 2,3,4,6-tetrabenylglucose derivative 1 (αβ = 1:l) in toluene and triethylamine as a catalyst to provide the σ³λ³ phosphorus derivative 4 with practically 100% β-diastereoselectivity.     

Synthesis of New Surfactants Mono and Bipolar Derived from 1,2,4‐Triazole‐5‐thione

Abstract

3‐Phenyl‐1,2,4‐triazole‐5‐thione (PTS) and 3‐methyl‐1,2,4‐triazole‐5‐thione (MTS) are prepared in two steps. The first is a condensation of the thiosemicarbazide with the benzoyl chloride and the acetyl chloride for the PTS and MTS respectively in pyridinic medium. This step leads to the formation of 1‐benzoylthiosemicarbazide and 1‐acetylthiosemicarbazide. The 1‐acetylthiosemicarbazide is also prepared with a new method consisted of a simple solvolysis the thiosemicarbazide in acetic acid for 4 hr. The second is the intramolecular cyclization in methanol with the presence of the sodium methalate leads to the formation of the PTS and the MTS in good yields. The alkylation of MTS and PTS under the conditions of solid–liquid phase transfer catalysis (PTC) allowed us to synthesize some new mono and bipolar surfactants compounds derived from 1,2,4‐triazole‐5‐thione in good yields.     

Synthesis,Electrocatalytic Properties and Crystal Structure of a New Organic—Inorganic Hybrid Constructed from Dodecamolybdophosphoric Acid and Benzotriazole

IntroductionIn the last few years there has been a rapidlygrowing number of reports in the literature ad-dressing the use of polyoxometalate- based hybridmaterials as catalysts,non- linear optical materialsand anti- virus drugs[1— 5] . In all the cases men-tioned above,the size,the shape and the chargesof the inorganic counter anions strongly affect theproperties of the materials. Polyoxometalates arelarge in size and high in electron accepting abili-ty[6] .They can form novel compounds with …     

Synthesis and Properties of Polyurethane Resins from Liquefied Benzylated Wood

In this paper, polyurethane resins were synthesized from liquefied benzylated wood and TDI (toluene diisocyanate)-TMP (trihydromethylene propane) prepolymer. And the relation between microphase structure and properties of PU samples were also studied. The results indicated that coatings obtained had good mechanical and thermal properties. The amount of the curing agent has great effect on the degree of phase segregation. In addition, with increased the curing agent amount, the thermal stabilities were also improved.     

Synthesis of Peroxy-Containing Acetylenic Alcohols and Ethers Derived from γ-Amino Ketones

A series of peroxy-containing tertiary alcohols were prepared by the reactions of lithium peroxy acetylenides with -amino ketones. The reactions of the intermediate lithium peroxy alcoholates with alkyl iodides in the presence of hexamethylphosphoramide yielded the corresponding peroxy ethers. The thermal stability of the compounds synthesized was evaluated by thermal analysis.     

Advanced Bifunctional Oxygen Reduction and Evolution Electrocatalyst Derived from Surface-Mounted Metal–Organic Frameworks

Metal–organic frameworks (MOFs) and their derivatives are considered as promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which are important for many energy provision technologies, such as electrolyzers, fuel cells and some types of advanced batteries. In this work, a “strain modulation” approach has been applied through the use of surface-mounted NiFe-MOFs in order to design an advanced bifunctional ORR/OER electrocatalyst. The material exhibits an excellent OER activity in alkaline media, reaching an industrially relevant current density of 200 mA cm⁻² at an overpotential of only ≈210 mV. It demonstrates operational long-term stability even at a high current density of 500 mA cm⁻² and exhibits the so far narrowest “overpotential window” ΔE_ORR-OER of 0.69 V in 0.1 m KOH with a mass loading being two orders of magnitude lower than that of benchmark electrocatalysts.     

Synthesis and Properties of Dinuclear Cu( Ⅱ ) Complexes Derived from Oxamidobis(propionato)cuprate( Ⅱ )

Three dinuclear complexes were synthesized and designated as Cu(obp)CuL where obp =oxamidobis(propionato), L=2,2' -bipyridyl(bpy) (1), 1 , 10-phenathroline(phen)(2) and 5-nitro-1, 10-phenathroline(NO2-phen)(3). The complexes were characterized by elemental analyses, in fared and electronic spectra, magnetic susceptibilities and ESR spectra, indicating antiferromagnetic spin exchange interactions between metal ions.     

Triarylborane-Based Helical Donor–Acceptor Compounds: Synthesis,Photophysical, and Electronic Properties

The synthesis and characterization of 10-(dimesitylboryl)-N,N-di-p-tolylbenzo[c]phenanthren-4-amine (3-B(Mes)₂-[4]helix-9-N(p-Tol)₂ 1 ) and 13-(dimesitylboryl)-N,N-di-p-tolyldibenzo[c,g]phenanthren-8-amine (3-B(Mes)₂-[5]helix-12-N(p-Tol)₂ 2 ) are reported herein. Their electrochemical and photophysical properties have been studied experimentally and theoretically. The donor and acceptor-substituted helicene derivatives exhibit moderate fluorescence quantum yields in THF (Φ_f=0.48 and 0.61 for 1 and 2 , respectively), which are higher than unsubstituted ones (Φ_f=0.18 for [4]helicene; Φ_f<0.05 for [n]helicenes (n≥5)). In the solid state, the Φ_f values are higher (Φ_f=1.00 and 0.55 for 1 and 2 , respectively) than those in solution, most likely due to the restrictions of molecular motions. The S₁←S₀ transitions of 1 and 2 are predominately HOMO→LUMO transitions. Upon excitation with UV light, the interplanar angle between the two terminal aryl rings of the [5]helix core of 2 decreases (S₁ state compared with S₀ state), which is similar to placing a spring under an external force.     

Polystannanes—Synthesis and Properties

Abstract

Polystannanes were prepared from H₂SnR₂ with the catalyst [RhCl(PPh₃)₃], or by reaction of Cl₂SnR₂ with Na in liquid ammonia. The polymers showed a characteristic peak in ¹¹⁹Sn NMR and UV-vis spectra, and a yellow color. Using common techniques, the polymers could be processed into films and oriented, the latter leading to a dichroism. The polystannanes are sensitive to light, more pronounced for R = alkyl than for R = aryl.

GRAPHICAL ABSTRACT     

Two Novel Organic–Inorganic Hybrid Compounds Constructed from Anderson-type Clusters and Transition-Metal Complexes

Abstract  Two organic–inorganic hybrid compounds based on the Anderson-type clusters [TeMo₆O₂₄]⁶⁻, [(H₂O)₂Co(TeMo₆O₂₄)][(C₁₀N₂H₁₀)₂] · 9.5H₂O (1), [(C₁₀N₂H₉)Ni(H₂O)₃]₂[TeMo₆O₂₄] · 8.5H₂O (2), have been synthesized by hydrothermal reactions and characterized by elemental analyses, IR spectra, thermal stability analyses, and single-crystal X-ray diffraction. Compound 1 displays a 1D chain structure constructed from alternating [TeMo₆O₂₄]⁶⁻clusters and Co²⁺ along the a axis with two pendant ligands 4,4′-bpy (4,4′-bipyridine). Compound 2 is composed of [TeMo₆O₂₄]⁶⁻ clusters coordinated by [Ni(bpy)(H₂O)₃]²⁺ moieties, and a supramolecular architecture is further formed through extensive hydrogen bonds interactions. Graphical Abstract  Two organic–inorganic hybrid compounds based on the Anderson-type clusters [TeMo₆O₂₄]⁶⁻and the unit [M(4,4′-bpy)] have been synthesized under the hydrothermal conditions. Compound 1 displays a 1D chain structure constructed covalently from alternating polyoxoanions [TeMo₆O₂₄]⁶⁻ and Co²⁺ along the a axis with two pendant ligands 4,4′-bipyridine. Compound 2 is composed of [TeMo₆O₂₄]⁶⁻ polyoxoanion coordinated by [Ni(bpy)(H₂O)₃]²⁺ moieties and shows a 1D chain structure through the hydrogen bonds interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.