PHOSPHORUS-NITROGEN COMPOUNDS. PART 52.1 THE SYNTHESIS OF SOME 1,3,2-BENZODIAZAPHOSPHORINE 2-OXIDES AND 2-SULPHIDES

Abstract

The reactions of 4-methyl-2-[N-(p-toluidinyl)methyl]aniline with phosphorus oxychloride, thiophosphoryl chloride, and their derivatives yield 1,3,2-benzodiazaphosphorine 2-oxides and 2-sulphides. Their ¹H NMR and infrared spectra are discussed. Related 1,3,2-benzodiazophosphorine and 1,3,2-dibenzodiazaphosphocine 2-oxides and 2-sulphides are compared.     

Synthesis,Characterization, and Biological Screening of Some Novel Thiazolidin-4-One and α-Aminophosphonate Derivatives

Abstract

Synthesis of some new functionalized thiazolidin-4-ones and α-amino phosphonate derivatives has been reported. The imines were synthesized from the reaction of various substituted anilines with 1-phenyl-3-(pyridine-4-yl)-1H-pyrazole-4-carbaldehyde in ethanol at reflux condition. The corresponding thiazolidin-4-ones and α-aminophosphonates were prepared by reaction of imines with mercaptoacetic acid and triethyl phosphite, respectively. The structures of the newly synthesized compounds were confirmed by IR, ¹H NMR, and mass spectral data and were evaluated for their antimicrobial activities.

GRAPHICAL ABSTRACT      

Optically Active Helical Polymer From Anionic Polymerization of (S)-6-Acrylyl-2,2’-dimethoxy-1,1’-binaphthyl

(S)-6-Acrylyl-2,2’-dimethoxy-1,1’-binaphthyl (ADBN) was synthesized and anionically polymerized using n-BuLi as an initiator. The absolute value of specific optical rotation [α]²⁵₅₈₉ of poly-ADBN is ?118.0 and that is about 8 times that of the starting monomer ADBN. Poly-ADBN was confirmed to exist in the form of one-handed helical structure in solution by means of comparing the specific optical rotation, the CD and UV-Vis spectra with that of ADBN and the model compounds such as (S)-6-propionyl-2,2’-dimethoxy-1,1’-binaphthyl (PDBN) and (S)-6-heptanoyl-2,2’-dimethoxy-1,1’-binaphthyl (HDBN). This conclusion was also confirmed by the fact that the g-value of poly-ADBN is about 13 times as high as that of its monomer and model compounds     

Synthesis of Sub-100 nm Nanoparticles by Emulsifier-free Emulsion Polymerization of α-Methylstyrene,Methyl Methacrylate and Acrylic Acid

The emulsifier-free emulsion copolymerization of α-methylstyrene (AMS) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process, giving birth to sub-100 nm nanoparticles. The kinetics of polymerization was investigated. The morphology and size of particles were monitored by TEM. The influences of the functional monomer AA concentration, initiator ammonium persulfate (APS) concentration, and polymerization temperature were studied. It was found that AMS caused a drastic decrease in both the rate of polymerization and the average degree of polymerization. The activation energy calculated from Arrhenius plot turned out to be 83.6 kJ/mol.     

Amino Acid Based Epoxy-Poly(Ester Amide)s—A New Class of Functional Biodegradable Polymers: Synthesis and Chemical Transformations

A new class of biodegradable functional polymers – epoxy-poly(ester amide)s (EPEAs), was synthesized for the first time on the basis of naturally occurring α-amino acids, fatty diols and cis- and trans-epoxysuccinic acids. The syntheses were conducted via both solution Active Polycondensation and Interfacial Polycondensation using, accordingly, either activated di-p-nitrophenyl esters or dichlorides of cis- and trans-epoxysuccinic acids as bis-electrophilic monomers. Di-p-toluenesulfonic acid salts of bis-(L-phenylalanine)-1,6-hexylene and bis-(L-leucine)-1,6-hexylene diesters were used in both cases as bis-nucleophilic counter-partners. High-molecular-weight polymers (M_w up to 67.000) with desirable material properties were obtained via solution polycondensation using di-p-nitrophenyl-trans-epoxy succinate. The EPEAs were chemically modified further under mild conditions: oxirane groups along the backbone were reacted with both nucleophilic and electrophilic reagents, and also subjected to thermal and chemical curing. The macromolecular transformations of EPEAs substantially broaden material properties and, hence, the potential to apply amino acid-based biodegradable poly(ester amide)s as absorbable drug carriers and surgical devices.     

The Simple Synthesis of Chiral Polyazaoxacoronands Derived from α-Amino Acids

Abstract

Bisamidation of oxaloyl chloride using L-amino acid methyl ester hydrochlorides afforded chiral diesters. The following reactions of diesters with 2,2-(ethylene-dioxy)diethylamine, afforded tetramides possessing C₂ symmetry. Coupling of N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine with 1,5-diamino-3-oxapentane, followed by cleavage of protecting groups, afforded an optically active diamine, which was transformed consequently into tetramide via the reaction with diglycolic acid dimethyl ester under high pressure conditions.     

1H-NMR Study on Inclusion Modes of 2-Chloronaphthalene and α-Cyclodextrin in D2

Abstract

With a 1:1 and a 2:1 host-guest stoichiometry, α-cyclodextrin (α-CD) forms inclusion complexes with 2-chloronaphthalene. From simulations concerning observed chemical-shift differences (Δδ_obs) of proton signals of 2-chloronaphthalene, intrinsic Δδ values are estimated for all the guest protons in the 1:1 and 2:1 inclusion complexes. The intrinsic Δδ values indicate that α-CD first binds to a part of a naphthalene ring bearing a C1 atom to form the 1:1 inclusion complex. In the 1:1 and 2:1 inclusion complexes, the symmetry axes of α-CD are tilted approximately 30° relative to a naphthalene longitudinal axis. In the 2:1 inclusion complex, the association through hydrogen bonding most likely occurs between two α-CD molecules whose symmetry axes are laterally shifted.     

A novel amperometric biosensor based on a co-crosslinked l-lysine-α-oxidase/overoxidized polypyrrole bilayer for the highly selective determination of l-lysine

An amperometric biosensor for the determination of l-lysine based on l-lysine-α-oxidase immobilized by co-crosslinking on a platinum electrode previously modified by an overoxidized polypyrrole film is described. The optimization of experimental parameters, such as pH and flow rate, permitted to minimize significantly substrate interferences even using a low specific, commercial enzyme. The relevant biases introduced in the measurement of lysine were just about 1% for l-arginine, l-histidine and l-ornithine, roughly 4% for l-phenylalanine and l-tyrosine. The developed approach allowed linear lysine responses from 0.02 mM up to 2 mM with a sensitivity of 41 nA/(mM × mm²) and a detection limit of 4 μM (S/N = 3). No appreciable loss in lysine sensitivity was observed up to about 40 days. Allowing polypyrrole layer to remove interference from electroactive compounds, the present method revealed suitable to detect l-lysine in a pharmaceutical and cheese sample, showing a good agreement with the expected values.     

The Reaction of 1-Nitro-4-(4-nitrophenylsulfonylmethyl)benzene with α,β-Unsaturated Esters

Under solid-liquid PTC conditions, treatment of 1-nitro-4-(4-nitrophenylsulfonyl-methyl)benzene(1) with α,β -unsaturated esters (2a-h) at 35–75°C gave tandem addition-rearrangement products(3a-h). While at higher temperature(75°C), addition-rearrangement-addition products (4a-b) were obtained when acrylates were used. Finally a possible mechanism is proposed.