β-Fur-2-yl-α-halogenacrylonitrile. VII. Reaktionen von β-(5-Brom-fur-2-yl)-α-bromacrylonitril mit Mercaptan,Thioharnstoff und Thioharnstoffderivaten

β-Fur-2-yl-α-halogenacrylonitriles. VII. Reactions of β-(5-Bromo-fur-2-yl)-α-bromoacrylonitriles with Mercaptans, Thiourea and Thiourea Derivatives β-(5-Bromo-fur-2-yl)-α-bromoacrylonitrile 1 reacts with ethylmercaptan to yield β-(5-bromo-fur-2-yl) β-ethylthioacrylonitrile 3 . With thiourea β,β′-thio-bis[β-(5-bromo-fur-2-yl)]-acrylonitrile 2 is formed. The pyrimidines 4 and 5 have been prepared by the reaction of 1 with s-methylthiourea and 2-aminothiazole, respectively. The structure of the new compounds were determined by means of x-ray analysis, ¹H-n.m.r., ¹³C-n.m.r. and mass-spectroscopy.     

Protein Modification with Ribose Generates Nδ-(5-hydro-5-methyl-4-imidazolone-2-yl)-ornithine

Advanced glycation end products (AGEs) are associated with diabetes and its complications. AGEs are formed by the non-enzymatic reactions of proteins and reducing sugars, such as glucose and ribose. Ribose is widely used in glycation research as it generates AGEs more rapidly than glucose. This study analyzed the AGE structures generated from ribose-modified protein by liquid chromatography–quadrupole time-of-flight mass spectrometry. Among these AGEs, N^δ-(5-hydro-5-methyl-4-imidazolone-2-yl)-ornithine (MG-H1) was the most abundant in ribose-glycated bovine serum albumin (ribated-BSA) among others, such as N^ε-(carboxymethyl) lysine, N^ε-(carboxyethyl) lysine, and N^ω-(carboxymethyl) arginine. Surprisingly, MG-H1 was produced by ribated-BSA in a time-dependent manner, whereas methylglyoxal levels (MG) were under the detectable level. In addition, Trapa bispinosa Roxb. hot water extract (TBE) possesses several anti-oxidative compounds, such as ellagic acid, and has been reported to inhibit the formation of MG-H1 in vivo. Thus, we evaluated the inhibitory effects of TBE on MG-H1 formation using ribose- or MG-modified proteins. TBE inhibited MG-H1 formation in gelatin incubated with ribose and ribated-BSA, but not in MG-modified gelatin. Furthermore, MG-H1 formation was inhibited by diethylenetriaminepentaacetic acid. These results demonstrated that ribose reacts with proteins to generate Amadori compounds and form MG-H1 via oxidation.     

r-5-(α-Halogenbenzyl)-3, t-4-diaryl-c-4-hydroxy-oxazolidin-2-one als Ringtautomere von α-(Arylaminocarbonyloxy)-β-halogen-dihydrochalkonen

r-5-(α-Halogenobenzyl)-3, t-4-diaryl-c-4-hydroxy-oxazolidin-2-ones as Ring Tautomers of α-(N-Arylaminocarbonyloxy)-β-halogeno-dihydrochalcones The reaction of chalcone halogenohydrins ( 1–3 ) with arylisocyanates does not stop at the stage of the α-arylaminocarbonyloxy-β-halogeno-dihydrochalcones ( 7 ), but the cyclic urethanes 4–6 are formed. Compound 7h was synthesized independently. The structure and stereochemistry of 4–6 and 7h were determined by ¹³C n.m.r. spectroscopy.     

Unsymmetrical 3- and 5-substituted bis(pyrazolyl)borate system

An unsymmetrical 3- and 5-substituted bis(azolyl)borate system, the sodium dihydrobis(3-trifluoromethyl-pyrazol-1-yl)(5-trifluoromethyl-pyrazol-1-yl)borate, Na[H₂B(3-(CF₃)pz)(5-(CF₃)pz)], has been synthesized by the reaction of 3-trifuoromethyl-pyrazole with Na[H₃B(5-(CF₃)pz)] in toluene solution. Na[H₂B(3-(CF₃)pz)(5-(CF₃)pz)] reacts with AgNO₃ in the presence of triphenylphosphine to afford the silver(I) bis(phosphane) adduct {[H₂B(3-(CF₃)pz)(5-(CF₃)pz)]Ag[P(C₆H₅)₃]₂}. These compounds have been characterized by elemental analyses, FT-IR, ESI-MS and multinuclear NMR spectroscopy. Solid state structure of {[H₂B(3-(CF₃)pz)(5-(CF₃)pz)]Ag[P(C₆H₅)₃]₂} is also reported. It features a κ²-N,N′ bonded bis(pyrazolyl)borate ligand and a pseudo-tetrahedral silver center.     

HPLC and 13C-NMR study of carboxymethyl-β-(1 → 6)-D-gluco-β-(1 → 3)-D-glucan derived from saccharomyces cerevisiae

Sodium salt of carboxymethyl-β-(1 → 6)-D-gluco-β-(1 → 3)-D-glucan (CMG-Na) was prepared from β-D-glucan isolated from baker's yeast (Saccharomyces cerevisiae). Three samples, Fractions I, II, and III, were further separated from the crude CMG-Na derivative. For the physicochemical characterization of the separated fractions, the methods of high-performance liquid chromatography (HPLC) in the size-exclusion mode and carbon?13 nuclear magnetic resonance (¹³C-NMR) spectroscopy were applied. The HPLC method revealed that the molecular weights, M_n, M_w, and M_z averages, of Fraction II were 9.71 × 10⁴, 2.27 × 10⁵, and 3.59 × 10⁵ Da, respectively, whereas those of Fraction III were 1.52 × 10⁴, 2.13 × 10⁴, and 3.57 × 10⁴ Da, respectively. The ¹³C-NMR spectra of Fraction II showed a ratio of 3 : 1 for β?(1 → 3) / β?(1 → 6), whereas for Fraction III, the content of β-(1 → 3) units was smaller. © 1993 John Wiley & Sons, Inc.     

Chemoenzymatic Preparation of Enantiopure Homoadamantyl β‐Amino Acid and β‐Lactam Derivatives

Racemic cis‐10‐azatetracyclo[7.2.0.1^2,6.1^4,8]tridecan‐11‐one was prepared from homoadamant‐4‐ene by chlorosulfonyl isocyanate addition. The transformation of the β‐lactam to the corresponding β‐amino ester followed by Candida antarctica lipase A‐catalyzed enantioselective (E>>200) N‐acylation with 2,2,2‐trifluoroethyl butanoate afforded methyl (1R,4R,5S,8S)‐5‐aminotricyclo[4.3.1.1^3,8]undecane‐4‐carboxylate and the (1S,4S,5R,8R)‐butanamide with>99% ee at 50% conversion. Alternatively, transformation of the β‐lactam to the corresponding N‐hydroxymethyl‐β‐lactam and the following Pseudomonas cepacia (currently Burkholderia cepacia) lipase‐catalyzed enantioseletive O‐acylation provided the (1S,4S,6R,9R)‐alcohol (ee=87%) and the corresponding (1R,4R,6S,9S)‐butanoate (ee>99%). In the latter method, competition for the enzyme between the (1R,4R,6S,9S)‐butanoate, 2,2,2‐trifluoroethyl butanoate and the hydrolysis product, butanoic acid, tended to stop the reaction at about 45% conversion and finally gave racemization in the (1S,4S,6R,9R)‐alcohol with time.     

Microcomposites of Poly(ε‐caprolactone) and Poly(methyl methacrylate) Prepared by Suspension Polymerization in the Presence of Poly(ε‐caprolactone) Macromonomer

Poly(methyl methacrylate)‐poly(ε‐caprolactone) (PMMA/PCL) microparticles were synthesized by suspension polymerization of methyl methacrylate in the presence of PCL. The incorporation of a small amount of a macromonomer, methacryloyl‐terminated PCL (M‐PCL), into the reaction mixture, led to the formation of grafted systems, namely PMMA‐g‐PCL/PCL. The synthesis of the macromonomer and its characterization by nuclear magnetic spectroscopy (¹H NMR) is described. The role of M‐PCL as an effective compatibilizing agent in the composite was investigated. PMMA/PCL and PMMA‐g‐PCL/PCL composites were fully characterized by ¹H NMR, gel permeation chromatography (GPC) and thermal analysis, including thermogravimetric analysis (TGA), conventional differential scanning calorimetry (DSC), modulated DSC (MDSC) and dynamic mechanical thermal analysis (DMTA). Finally, the morphology of the prepared systems was investigated by scanning electron microscopy (SEM). The addition of compatibilizing agent led the formation of a more homogeneous microcomposite with improved mechanical properties.

SEM picture of PMMA‐g‐PCL/PCL composite surface.     

Oxidation of aroylthioureas during their reactions with 2,3-diphenylcyclopropenone resulting in (E/Z)-3-(aroylthioureido)-2-phenylcinnamic acids

Isolated (E/Z)-3-(aroylthioureido)-2-phenylcinnamic acids have been obtained from the reactions of N-substituted-aroylthioureas with 2,3-diphenylcyclopropenone in acetic acid. The abnormal behavior of the reaction was described as due to nucleophilic addition of N ³ followed by hydrolysis, ring opening and oxidation processes.     

Die Reaktion von α,β-Dihalogen-propionitrilen mit monosubstituierten Hydrazinen - einfache Synthese 1-substituierter 3- bzw. 5-Amino-pyrazole

The Reaction of α,β-Dihalogeno-propionitriles with Monosubstituted Hydrazines — A Simple Synthesis of 1-Substituted 3- or 5-Amino-pyrazoles In methanol hydrazines 3 , and α,β-dihalogeno-propionitriles 1, 2 even at 0°C irreversibly yield 3 · HX, and α-halogenoacrylonitriles 4, 5 (A₁). Fast addition of alkyl- and aralkyl- hydrazines 3 to 4, 5 (C) gives 1-substituted 1-(2′-halogeno-2′-cyan-ethyl)-hydrazines 6 , the addition of arylhydrazines 3 to 4, 5 (D) 1-aryl-2-(2′-halogeno-2′-cyan-ethyl)-hydrazines 8 . In methanol 6 spontaneously cyclise (E) to hydrogen halides 7 · HX of 1-alkyl- and 1-aralkyl-3-amino-pyrazoles, 8 with 2 moles of acids (F) to salts 10 · 2HY of 1-aryl-4-halogeno-5-imino-pyrazolidines, and the free 10 spontaneously (G) to hydrogen halides 9 · HX of 1-aryl-5-amino-pyrazoles. Mechanisms (A₁), (C), (D), (E), (F), and (G) are proved by t.l.c., ¹H-n.m.r., and isolation of intermediates, the structures of 7 resp. 9 , using the significant ¹H-n.m.r.-parameter Δ. Simple general syntheses are described for 3-amino-pyrazoles 7 (R = H, alkyl, aralkyl) or 5-amino-pyrazoles 9 (R = aryl) starting with α,β-dihalogeno-propionitriles 1, 2 , and for α-bromo-acrylonitrile 5 .     

Poly(t-butyl-3α-(5-norbornene-2-carbonyloxy)-7α,12α-dihydroxy-5β-cholan-24-oate-co-maleic anhydride) for a 193-nm photoresist

A copolymer of t-butyl-3α-(5-norbornene-2-carbonyloxy)-7α,12α-dihydroxy-5β-cholan-24-oate and maleic anhydride was synthesized as a matrix polymer for ArF excimer laser lithography. The polymer has an excellent transmittance at 193 nm and possesses good thermal stability up to 255°C. The resist formulated with the polymer showed better dry-etching resistance than the conventional KrF excimer laser resist for chlorine and oxygen mixed gas. A 0.15 μm line and space patterns were obtained at a dose of 18 mJ cm⁻² using an ArF excimer laser stepper.     

(η6‐N‐alkylcarbazole) (η5‐cyclopentadienyl) iron hexafluorophosphate salts in photoinitiated and thermal epoxy polymerization

(η6‐Carbazole)(η5‐cyclopentadienyl) iron hexafluorophosphate salts (CFS PF₆) are capable of photoinitiating cationic polymerization of epoxy monomers directly upon irradiation with long‐wavelength UV light. To improve the solubility of CFS ferrocenium salts in epoxides, two CFS photoinitiators have been prepared: [cyclopentadiene‐Fe‐N‐buylcarbazole] hexafluorophosphate (C4‐CFS PF₆) and [cyclopentadiene‐Fe‐N‐octylcarbazole] hexafluorophosphate (C8‐CFS PF₆), bearing C4 and C8 alkyl chains, respectively, on the nitrogen atom. Studies with real‐time infrared spectroscopy have shown that C4‐CFS and C8‐CFS photoinitiators exhibit high efficiency in polymerization of 3,4‐epoxycyclohexylmethyl‐3,4‐epoxycyclohexane carboxylate (ERL‐4221) epoxy monomer, but lower efficiency in polymerization of di(2,3‐epoxypropyl)‐3,4‐epoxy‐1,2‐cyclohexanedioate (TDE‐85) epoxy monomer. Benzoyl peroxide (BPO) sensitizer was very effective in improving the photoinitiating activities of CFS in polymerization of both ERL‐4221 and TDE‐85. DSC studies have shown that C4‐CFS and C8‐CFS photoinitiators can also be employed as thermal initiators for the cationic ring‐opening polymerization of epoxides at moderate temperatures. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Syntheses and topological networks of two azide complexes based on 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole ligands

Two new azide complexes, [Cd₂(3-abpt)(N₃)₄]_n (1) and [Cu(3-abpt)₂(N₃)₂] (2) (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole), have been prepared and structurally characterized. Complex 1 displays an interesting 2D polymeric structure with rarely reported 3,7-connected (3²;4)(3⁴;4⁶;5⁶;6⁵) network in the Schafli notation. Complex 2 contains mononuclear pieces, and they are linked each other through weak CuN coordination bonds to form a 2D sheet with (4, 4) topology. The thermal stability and fluorescent property of 1 have also been investigated.     

New Efficient Synthesis of tRNA Related Adenosines Bearing the Hydantoin Ring (ct6A,ms2ct6A) by Intramolecular Cyclization of N6-(N-Boc-α-aminoacyl)-adenosine Derivatives

A novel and efficient way for the synthesis of N⁶-hydantoin-modified adenosines, which utilizes readily available N⁶-(N-Boc-α-aminoacyl)-adenosine derivatives, was developed. The procedure is based on the epimerization-free, Tf₂O-mediated conversion of the Boc group into an isocyanate moiety, followed by intramolecular cyclization. Using this method two recently discovered hydantoin modified tRNA adenosines, that is, cyclic N⁶-threonylcarbamoyl-adenosine ( ct⁶A ) and 2-methylthio-N⁶-threonylcarbamoyladenosine ( ms²ct⁶A ) were prepared in good yields.     

Synthesis and characterization of α‐amino acid‐containing polyester: poly[(ε‐caprolactone)‐co‐(serine lactone)]

Novel polyesters, poly[(ε‐caprolactone)‐co‐(N‐trityl‐L ‐serine‐β‐lactone)]s, were prepared by copolymerizing ε‐caprolactone (CL) with N‐trityl‐L ‐serine‐β‐lactone (TSL) using ZnEt₂ as the catalyst. The number‐average molecular weights were determined which ranged from 2.7 × 10⁴ to 4.9 × 10⁴ Da with dispersity values ranging from 1.6 to 1.8. The structures of the copolymers were investigated by means of ¹H NMR, ¹³C NMR and infrared spectroscopies, thermogravimetric analysis and differential scanning calorimetry. The results indicated that CL and TSL monomer units were randomly distributed within the copolymer backbone structures and the ratios of TSL to CL in the copolymers were close to those in the feeds. After removal of the trityl group under mild condition, a new polyester with side amino groups provided by serine units was obtained. L929 cell culturing test indicated good biocompatibility of the polyester with or without protective groups. © 2012 Society of Chemical Industry     

Influence of Poly(ε‐caprolactone) Molecular Weight and Coumarin Amount on Photo‐Responsive Polyurethane Properties

Photo‐reversible polyurethane (PU) coatings based on coumarin diol (CD) are obtained. Initially, pre‐polymers based on different amounts of coumarin (5, 15, and 25 mol%) and 1,6‐hexamethylene diisocyanate are prepared to obtain PUs with a large incorporation of CD and high molecular weight. The pre‐polymer is posterior reacted with poly(ε‐caprolactone) diol (PCL‐diol), either with molecular weight = 530 or 2000 g mol^–1. The thermal stabilities of the PUs are studied using thermogravimetric analysis. Polymers with a higher content of CD present higher stability. The thermal transitions and the mechanical response are analyzed using differential scanning calorimetry and strain‐stress tests, respectively. Moreover, the photo‐reversibility of CD‐based PUs is followed by UV absorption. In general, photo‐dimerization induces better mechanical properties of the final PUs. Materials obtained with short PCL‐diol ( = 530 g mol^–1) and the highest amount of CD present higher reversibility processes. Therefore, these polymers are promising for application as coating systems.

     

Intermediates of Prostanoid Synthesis. Stereospecific conversion of (+)-5β-hydroxycyclopenten-2-yl-1β-acetic acid γ-lactone into (+)-1β-methoxycarbonylmethyl-2β,3β-(p-nitrobenzylidene)-dioxycyclopentan-5-one

Starting from (+)-5β-hydroxycyclopenten-2-yl-1β-acetic acid γ-lactone ( 1 ), (+)-1β-methoxycarbonylmethyl-2β, 3β-(p-nitrobenzylidene)-dioxycyclopentan-5-one ( 7 ) was prepared within 4 steps. Subsequent cleavage of the latter gives (−)-3β-hydroxy-1-methoxy-carbonylmethylcyclopent-1-en-5-one ( 8a ). Hydroxylation of the lactone ( 1 ) was found to give (+)-2β,3β,5β-trihydroxycyclopentyl-1β-acetic acid γ-lactone ( 2a ) with cis-oriented hydroxy groups in respect to the lactone ring. No formation of the trans-isomer, as has been reported earlier [4], was observed.     

The Influence of Steric Configuration of some Nα-Lauroyl Amino-Acid Derivatives on their Antimicrobial Activity

The present study is an attempt to know if the steric configuration of the amino-acid residues of both N^α-Lauroyl-Arginine and N^α-Lauroyl-Lysine methyl ester could influence their antibacterial effect. For this purpose the methyl esters of N^α-Lauroyl-D-Arginine, N^α-Lauroyl-DL-Arginine and N^α-Lauroyl-DL-Lysine have been prepared. Their antibacterial activity has been evaluated and compared to that shown by N^α-Lauroyl-L-Arginine and N^α-Lauroyl-L-Lysine methyl ester derivatives. Our results show that the mechanism of action of these N^α-Lauroyl-amino-acid derivatives against the bacteria cells is not influenced by the stereochemistry of the compound.     

An unprecedented 2D isopolymolybdate with (3·4)(3·5·8)(3·4·5·6·8)(3·4·5·6) topology

A novel two-dimensional molybdenum oxide polymer, [Mo₄O₁₃]_n · 2nH₃O, has been prepared under specific hydrothermal conditions and characterized by IR spectroscopy and TG analysis. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a (3, 4, 5, 6)-connected 2D layer structure with (3²·4)(3²·5³·8)(3·4²·5⁴·6·8²)(3⁴·4³·5⁴·6⁴) topology, which is constructed by two parallel molybdenum oxide dimeric chains (Mo₂O₁₀)_n bound together by the dimer of Mo₂O₉ subunits via the sharing of corners. Additionally, the electrochemistry activity of compound 1 is also reported.     

Crystallization,melting behavior,and wettability of poly(ε‐caprolactone) and poly(ε‐caprolactone)/ poly(N‐vinylpyrrolidone) blends

Both wettability and crystallizability control poly(ε‐caprolactone)'s (PCL) further applications as biomaterial. The wettability is an important property that is governed by both chemical composition and surface structure. In this study, we prepared the PCL/poly(N‐vinylpyrrolidone) (PVP) blends via successive in situ polymerization steps aiming for improving the wettability and decreasing crystallizability of PCL. The isothermal crystallization of PCL/PVP at different PVP concentrations was carried out. The equilibrium melting point (T), crystallization rate, and the melting behavior after isothermal crystallization were investigated using differential scanning calorimetry (DSC). The Avrami equation was used to fit the isothermal crystallization. The DSC results showed that PVP had restraining effect on the crystallizability of PCL, and the crystallization rate of PCL decreased clearly with the increase of PVP content in the blends. The X‐ray diffraction analysis (WAXD) results agreed with that. Water absorptivity and contact angle tests showed that the hydrophilic properties were improved with the increasing content of PVP in blends. The coefficient for the water diffusion into PCL/PVP blends showed to be non‐Fickian in character. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthese eines neuen Thienospirans: 6,7-Dihydro-1′-methyl-spiro[benzo[b]thiophen-4(5H),2′-piperidin]

Synthesis of a New Thienospiran: 6,7-Dihylro-1′-methyl-spiro[benzo[j]thioxhen-4(5H),2′-piperidine] The title spiro compound 6 – a N-methyl derivative of a new parent system - has been synthesized from nitrile 8 via 4-phenoxybutylation, followed by modified Schmidt degradation, ensuing O-deprotection and final cyclization. The constitution of the target compound and of all intermediates is established by ¹H-n.m.r. and ¹³C-n.m.r.-spectroscopy and by microelementary analysis.