Hydroarylation of cinnamic acid with phenols catalyzed by acidic ionic liquid [H-NMP]HSO<Subscript>4</Subscript>: computational assessment on substituent effect

Hydroarylation of cinnamic acid with different substituted phenols, in the presence of acidic ionic liquid, N-methyl-2-pyrrolidonum hydrosulfate ([H-NMP]HSO₄) gave the corresponding dihydrocoumarins in high yields and excellent selectivity. Among these substituted phenols, while methyl phenol afforded the corresponding dihydrocoumarin, nitrophenol under the same reaction conditions diverted the course of reaction, affording 3-(4-nitrophenyl)-3-phenylpropanoic acids. We investigated this behavior from the energetic and electronic points of view, using quantum chemistry computational methods. In this respect, the electronic energy change values for the conversion reaction of substituted phenyl cinnamate esters to dihydrocoumarin compounds have been obtained via density functional theory calculations. We demonstrated that the conversion reaction in the presence of CH₃ substituent is more favorable energetically than NO₂ substituent. Moreover, we have concentrated on topological analysis of electron density on some key bond and ring critical points and their associated bond paths to assess the conversion of substituted phenyl cinnamate esters to dihydrocoumarins. Our calculated results showed that para-methyl phenyl cinnamate has more of electronic tendency to undergo the intramolecular cyclization step and, consequently, generate the corresponding dihydrocoumarin.     

N-Methyl Piperidinium Chlorochromate Adsorbed on Alumina: A New and Selective Reagent for the Oxidation of Benzylic Alcohols to their Corresponding Carbonyl Compounds

Summary.  N-Methyl piperidinium chlorochromate adsorbed on alumina oxidizes a wide variety of benzylic alcohols to the corresponding carbonyl compounds. Received May 18, 2000. Accepted (revised) July 4, 2000     

Amine modified nanozeolites for the three component synthesis of chromenes

Research on Chemical Intermediates - New amine modified nanozeolites were prepared and characterized using FT-IR, TGA, DTG, SEM, and TEM. Then the synthesized nanozeolites were employed as novel,...     

Synthesis of bio-based poly(methacrylates) using SG1-containing amphiphilic macroinitiators by nitroxide mediated miniemulsion polymerization

SG1-based amphiphilic macroinitiators were synthesized from oligoethylene glycol methyl ether methacrylate and 10 mol% acrylonitrile or styrene (as the controlling comonomer) to conduct the nitroxide mediated polymerization of bio-based methacrylic monomers (isobornyl methacrylate (IBOMA) and C13 alkyl methacrylate (C13MA)) in miniemulsion. The effect of the addition of surfactant (DOWFAX 8390), co-stabilizer (n-hexadecane) and different reaction temperatures (80, 90 and 100°C) on polymerization kinetics was studied. We found that the NMP of IBOMA/C13MA using amphiphilic macroalkoxyamines were most effective during miniemulsion polymerization (linear trend of M_n versus conversion and high latex stability) in presence of 2 wt% surfactant and 0.8 wt% co-stabilizer (relative to monomer) at 90°C. The effect of surfactant, co-stabilizer and temperature on particle size during the polymerization was studied and suggested a decrease in initial particle size with the addition of surfactant and co-stabilizer. Finally, the thermal properties of IBOMA/C13MA polymers, prepared by amphiphilic macroinitiators, were examined thoroughly, indicating a T_g in the range of −44°C < T_g < 109°C.     

Indoline derivatives I: synthesis and factor Xa (FXa) inhibitory activities

A series of bisamidine derivatives each having a ring structure in the center of the molecule was synthesized and their Factor Xa (FXa) inhibitory activities were evaluated. Among them, some indoline derivatives showed potent inhibitory activities in vitro. In particular, (R)-18a having an (R)-configuration at the 2-position of the indoline ring exhibited the most potent FXa inhibitory activity in vitro, more potent than DX-9065a. Furthermore, (R)-18a exhibited more potent anticoagulant activity than DX-9065a. We also succeeded in obtaining an X-ray crystal structure of FXa bound with (R)-18a.     

Reductive Amination of Aldehydes and Ketones Under Heterogeneous and Solvent-Free Conditions Using Sodium-Borohydride and Silica-Gel–Supported Sulfuric Acid

A regioselective and convenient procedure for preparation of amines by reductive amination of aldehydes and ketones using sodium borohydride in the presence of sulfuric acid supported on silica gel as an active, inexpensive, and recoverable catalyst under heterogeneous and solvent-free conditions at room temperature is described.     

DABCO–Bromine Complex: A Novel Oxidizing Agent for Oxidative Deprotection of THP and Silyl Ethers and Semicarbazones to Corresponding Carbonyl Compounds

A tetrameric DABCO–bromine complex was synthesized, characterized, and utilized as a novel active bromine complex for the oxidative deprotection of THP and silyl ethers and semicarbazones to carbonyl compounds.     

Efficient Synthesis of Symmetrical Bisamides from Aldehydes and Amides Catalyzed by Silica-Bonded S-Sulfonic Acid Nanoparticles

Silica-bonded S-sulfonic acid nanoparticles (SBSSANPs) were easily synthesized from silica nanoparticles and showed to be an efficient catalyst in the synthesis the symmetrical N,N′-alkylidene bisamides. Reaction of aldehydes and amides in the presence of the catalyst afforded the corresponding bisamides in good to excellent yields. The extensive range of substrates suggests general applicability of the method. Reusability of the catalyst, simple workup procedure, and short reaction times are other advantages of this protocol.

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