Antimicrobial,Mosquito Larvicidal and Antioxidant Properties of the Leaf and Rhizome of Hedychium coronarium

The essential oil, methanolic and aqueous extracts of the leaves and rhizomes of Hedychium coronarium Koen. (Zingiberaceae) were assayed for their antimicrobial, mosquito larvicidal and antioxidant properties. The chemical composition of the essential oil of two organs was analyzed by GC/MS analysis. β‐Pinene (33.9%), α‐pinene (14.7%), 1,8‐cineole (13.3%), r‐elemene (11.0%) and carotol (9.1%) were the main components in the leaf oil, including 82.0% terpenoid compounds. The major constituents of the rhizome oil were 1,8‐cineole (37.3%), β‐pinene (23.0%), α‐terpineol (10.4%) and α‐pinene (9.9%), comprising 80.6% of the oil. The leaf and rhizome essential oil displayed significant antimicrobial activity, as determined by the disc‐diffusion method, inhibiting the growth of all five fungal and four bacterial strains tested. The antimicrobial nature of the essential oil is related to high terpenoid contents. The leaf oil exhibited the mosquito larvicidal activity with 2 h and 24 h LC₅₀ values of 111 and 90 ppm, respectively, while the rhizome oil showed the larvicidal activity with 2 h and 24 h LC₅₀ values of 86 and 47 ppm, respectively. β‐Pinene, α‐pinene and 1,8‐cineol in H. coronarium serve as the principal larvicidal components of both oils. The individual antioxidant assays such as DPPH scavenging activity, chelating effect of ferrous ions and reducing power have been used. The present study demonstrated that the polar extracts of H. coronarium possessed anti‐oxidant. Appreciable total phenolic content (18.5‐26.3 mg/g) was also detected by Folin‐Ciocalteu test.     

An improved procedure for phenylselenoetherification of some Δ5-alkenols using pyridine,Ag2O,and some Lewis acids as catalysts

An improved procedure for intramolecular cyclization of some Δ⁵-alkenols, using PhSeX (X = Cl, Br) has been developed. We found that cyclization can be facilitated in the presence of pyridine, Ag₂O, and some Lewis acids as catalysts. Thus catalytic amount of additives (pyridine and Ag₂O) influences higher yields but equimolar amount achieves almost quantitative yield under extremely mild experimental conditions. In the presence of Lewis acids (ZnCl₂ and FeCl₃) high yields of cyclic ether products are obtained with catalytic amounts. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:146–149, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10227     

3‐miktoarm star terpolymers using triple click reactions: Diels–Alder,copper‐catalyzed azide‐alkyne cycloaddition,and nitroxide radical coupling reactions

Well‐defined linear furan‐protected maleimide‐terminated poly(ethylene glycol) (PEG‐MI), tetramethylpiperidine‐1‐oxyl‐terminated poly(ε‐caprolactone) (PCL‐TEMPO), and azide‐terminated polystyrene (PS‐N₃) or ‐poly(N‐butyl oxanorbornene imide) (PONB‐N₃) were ligated to an orthogonally functionalized core ( 1 ) in a two‐step reaction mode through triple click reactions. In a first step, Diels–Alder click reaction of PEG‐MI with 1 was performed in toluene at 110 °C for 24 h to afford α‐alkyne‐α‐bromide‐terminated PEG (PEG‐alkyne/Br). As a second step, this precursor was subsequently ligated with the PCL‐TEMPO and PS‐N₃ or PONB‐N₃ in N,N‐dimethylformamide at room temperature for 12 h catalyzed by Cu(0)/Cu(I) through copper‐catalyzed azide‐alkyne cycloaddition and nitroxide radical coupling click reactions, yield resulting ABC miktoarm star polymers in a one‐pot mode. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and ring‐opening polymerization of new monoalkyl‐substituted lactides

New monoalkyl‐substituted lactides were synthesized by reaction of α‐hydroxy acids with 2‐bromopropionyl bromide, and polymerized with various catalysts in the presence of benzyl alcohol by ring‐opening polymerization (ROP). The classic tin(II) 2‐ethylhexanoate (Sn(Oct)₂) catalyst was leading to polymers with narrow distribution and predictable molecular weights, in polymerizations in bulk or toluene at 100 °C. The polymerization rate was corresponding to the steric hindrance of the alkyl substituents, such as butyl, hexyl, benzyl, isopropyl, and dimethyl groups. A yield of 83% was obtained with the hexyl‐substituted lactide after 1 h of polymerization. Excellent conversions (97%) could be achieved by using the alternative catalyst 4‐(dimethylamino)pyridine (DMAP). This latter organic catalyst was most efficient in polymerizing the more steric‐hindered lactides with good molecular weight and polydispersity control, in comparison to the tin(II) 2‐ethylhexanoate and tin(II) trifluoromethane sulfonate [Sn(OTf)₂] catalysts. The efficiency of the DMAP catalyst and the variability of the monomer synthesis route for new alkyl‐substituted lactides allow to prepare and to envision a wide range of new functionalized polylactides for the elaboration of tailored materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4379–4391, 2004     

Investigations of Scope and Mechanism of Nickel‐Catalyzed Transformations of Glycosyl Trichloroacetimidates to Glycosyl Trichloroacetamides and Subsequent,Atom‐Economical,One‐Step Conversion to α‐Urea‐Glycosides

The development and mechanistic investigation of a highly stereoselective methodology for preparing α‐linked‐urea neo‐glycoconjugates and pseudo‐oligosaccharides is described. This two‐step procedure begins with the selective nickel‐catalyzed conversion of glycosyl trichloroacetimidates to the corresponding α‐trichloroacetamides. The α‐selective nature of the conversion is controlled with a cationic nickel(II) catalyst, [Ni(dppe)(OTf)₂] (dppe=1,2‐bis(diphenylphosphino)ethane, OTf=triflate). Mechanistic studies have identified the coordination of the nickel catalyst with the equatorial C₂‐ether functionality of the α‐glycosyl trichloroacetimidate to be paramount for achieving an α‐stereoselective transformation. A cross‐over experiment has indicated that the reaction does not proceed in an exclusively intramolecular fashion. The second step in this sequence is the direct conversion of α‐glycosyl trichloroacetamide products into the corresponding α‐urea glycosides by reacting them with a wide variety of amine nucleophiles in presence of cesium carbonate. Only α‐urea‐product formation is observed, as the reaction proceeds with complete retention of stereochemical integrity at the anomeric C?N bond.     

A concise synthesis of sex pheromone of mediterranean fruit fly,Ceratitis capitata via lithiated carbanion derived from enephosphoramide

A novel and versatile synthetic approach to the preparation of (E)‐non‐6‐en‐1‐ol, a sex pheromone of the Mediterranean fruit fly, Ceratitis capitata, is presented. This pheromone can be viewed as potential active component for lures designed to control and eradication of Mediterranean fruit fly. The described protocol is a six‐step reaction sequence producing the desired compound with 28% overall yield from commercially available and inexpensive starting material and total E stereoselectivity of the double bond present in final structure. The key to the success of the presented strategy is application of lithiated α‐allylphosphoramido carbanions and their reaction with halogenated acetals. © 2010 Wiley Periodicals, Inc. 21:139–147, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20588     

The multieffects of DMF and DBU on the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals: Hydrogen bonding and electrostatic interactions

A density functional theory (DFT) study was performed to elucidate the mechanism for the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals. The calculation results are consistent with experimental findings, showing that the reaction proceeds via deprotonation of nitroethane, nucleophilic addition, intramolecular cyclization, elimination of HNO₂, and the keto‐enol tautomerization sequence. It was disclosed that N,N‐dimethylformamide (DMF) and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) act as not only solvent and nonnucleophilic base, respectively, but also catalysts in the reaction by stabilizing the transition states (TSs) and intermediates via intermolecular hydrogen bonds and electrostatic interactions. Besides, the effective orbital interaction of the reaction site in TS also contributes to the intramolecular cyclization step. The new mechanistic insights obtained by DFT calculations highlight that the hydrogen bonds and electrostatic interactions are key factors for the [5 + 1] benzannulation of nitroethane and α‐alkenoyl ketene‐(S,S)‐acetals. © 2015 Wiley Periodicals, Inc.     

Crystallographic report: Bis{[diacetyl‐bis(2,6‐isopropylphenylimine)]nickel(I)(µ‐chloro)}

The first α‐diimine nickel(I) complex having a chloro bridge is reported. The centrosymmetric dinuclear structure of {[ArN?C(Me)C(Me)?NAr]NiCl}₂[Ar?2,6?C₆H₃(i‐Pr)₂] features two chelating α‐diimine ligands and two bridged chlorine atoms, so that a distorted tetrahedral N₂Cl₂ coordination geometry for nickel results. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of α‐cyclodextrin on the crystallization of poly (3‐hydroxybutyrate)

The effect of α‐cyclodextrin (α‐CD) on the crystallization behavior of poly(3‐hydroxybutyrate) (PHB) was investigated with polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. We found that the addition of α‐CD can greatly accelerate the crystallization of PHB and that α‐CD has a potential not only to enhance the nucleation but also to accelerate the crystallization of PHB. Compared to a conventional nucleation agent, such as talc, α‐CD is a natural product and has many advantages because it is environmentally friendly and safe to humans. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3461–3469, 2004     

A facile and efficient synthesis of diethyl α,α‐chlorofluoroalkanephosphonates

A facile and efficient synthetic methodo‐ logy for the preparation of diethyl α,α‐chlorofluoro‐ alkanephosphonates is described. A wide variety of diethyl α‐hydroxyphosphonates were investigated by a two‐step halogenation procedure, which includes nucleophilic chlorination with PPh₃ and CCl₄ and electrophilic fluorination with N‐fluorobisbenzene‐ sulfonimide. Aromatic and aliphatic α,α‐chlorofluoro‐ phosphonates could be prepared by this method with acceptable yields. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:250–255, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20604     

Heterocyclic synthesis with ethyl α‐(3‐carbamoyl‐4,5,6,7‐tetrahydrobenzo[b]thiophen‐2‐ylhydrazono)acetates: An expeditious synthetic approach to polyfunctionally substituted pyran,pyridine, and pyridazine derivatives

Ethyl α‐(3‐carbamoyl‐4,5,6,7‐tetrahydrobenzo[b]thiophen‐2‐ylhydrazono)acetates 1 were prepared and established as previously described by our research group. Their reactivity toward a variety of active methylene reagents was studied to give pyran, pyridine, and pyridazine derivatives. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:300–306, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20019     

Ferrocenylalkyl azoles: bioactivity,synthesis, structure

The toxicity of ferrocenylethyl benzotriazole ( 1 ) and other ferrocene compounds including ferrocenylmethyl benzimidazoles ( 4,5,6,11 ), ferricenium salts ( 3,9,10 ) and ferrocenylmethyl adenine ( 7 ), was studied. All ferrocene complexes under investigation showed low or medium toxicities. On the basis of an earlier model of chemical carcinogenesis, the antitumor activity of ferrocenylalkyl azoles 1, 8 and ferricenium salts 9, 10 was studied in vivo in the so‐called sub‐capsular test on human tumors. This effectiveness was compared with that of cisplatin. A series of ferrocenylalkyl azoles were synthesized by interacting azoles either with α‐hydroxyalkyl ferrocenes FcC(OH)R₁R₂ in organic solvent in the presence of aqueous HBF₄ in quantitative yields or with trimethyl(aminomethyl)ferrocene iodide in an aqueous‐basic medium in good yields. The X‐ray determinations of molecular and crystal structures of α‐(1‐benzotriazolyl)ethylferrocene ( 1 ) and α‐(1‐naphthatriazolyl)ethylferrocene ( 12 ) were performed. Copyright © 2008 John Wiley & Sons, Ltd.     

Diels‐alder click reaction for the preparation of polycarbonate block copolymers

The Diels‐Alder reaction as a click reaction strategy is applied to the preparation of well‐defined polycarbonate (PC)‐block copolymers. A well‐defined α‐anthracene‐terminated polycarbonate (PC‐anthracene) is prepared using 9‐anthracene methanol as an initiator in the ring opening polymerization of benzyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate in CH₂Cl₂ at room temperature for 5 h. Next, a well‐defined α‐furan protected maleimide‐terminated‐poly(ethylene glycol) (PEG₁₁‐MI or PEG₃₇‐MI), ‐poly(methyl methacrylate) (PMMA₂₆‐MI), and ‐poly(ε‐caprolactone) (PCL₂₇‐MI) were clicked with the PC‐anthracene at reflux temperature of toluene to yield their corresponding PC‐based block copolymers (PC‐b‐PEG, PC‐b‐PMMA, and PC‐b‐PCL). The homopolymer precursors and their block copolymers were characterized by using the GPC, NMR and UV analysis. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Enantiomeric distribution of major chiral volatile organic compounds in juniper‐flavored distillates

The enantiomeric ratios of chiral volatile organic compounds in juniper‐flavored spirits produced by various processing technologies in different EU countries were determined by multidimensional GC using solid‐phase microextraction and liquid–liquid extraction as a sample pretreatment procedure. In total, more than 260 compounds were detected in studied spirits from which linalool, α‐terpineol, 4‐terpineol, linalool oxides, α‐pinene, and verbenone were selected for enantiomeric separation. The significant differences in enantiomeric ratio of linalool and cis‐linalool oxide allowed us to distinguish between samples produced in Slovakia and the United Kingdom from those produced in Germany, Czech Republic, and Belgium. The pure enantiomer of trans‐linalool oxide was found only in samples from Germany. It was shown that the enantiomeric ratio is independent of the sample treatment procedure, and only small differences up to 1% were observed.     

Asymmetric polymerization using C1 resources

Two examples of asymmetric alternating copolymerization, (1) the alternating copolymerization of α‐olefins (monosubstituted ethenes) with carbon monoxide and (2) the alternating copolymerization of meso‐epoxide with carbon dioxide, are described, and the meaning of chirality in polymer synthesis is emphasized. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 215–221, 2004     

Anomerization reaction of bare and microhydrated d‐erythrose via explicitly correlated coupled cluster approach. Two water molecules are optimal

We present a comprehensive benchmark computational study which has explored a complete path of the anomerization reaction of bare d ‐erythrose involving a pair of the low‐energy α‐ and β‐furanose anomers, the former of which was observed spectroscopically (Cabezas et al., Chem. Commun. 2013, 49, 10826). We find that the ring opening of the α‐anomer yields the most stable open‐chain tautomer which step is followed by the rotational interconversion of the open‐chain rotamers and final ring closing to form the β‐anomer. Our results indicate the flatness of the reaction's potential energy surface (PES) corresponding to the rotational interconversion path and its sensitivity to the computational level. By using the explicitly correlated coupled cluster CCSD(T)‐F12/cc‐pVTZ‐F12 energies, we determine the free energy barrier for the α‐furanose ring‐opening (rate‐determining) step as 170.3 kJ/mol. The question of the number of water molecules (n ) needed for optimal stabilization of the erythrose anomerization reaction rate‐determining transition state is addressed by a systematic exploration of the PES of the ring opening in the α‐anomer‐(H₂O)_n and various β‐anomer‐(H₂O)_n (n = 1–3) clusters using density functional and CCSD(T)‐F12 computations. These computations suggest the lowest free energy barrier of the ring opening for doubly hydrated α‐anomer, achieved by a mechanism that involves water‐mediated multiple proton transfer coupled with the furanose C O bond breakage. Among the methods used, the G4 performed best against the CCSD(T)‐F12 reference at estimating the ring‐opening barrier heights for both the hydrated and bare erythrose conformers. Our results for the hydrated species are most relevant to an experimental study of the anomerization reaction of d ‐erythrose to be carried out in microsolvation environment. © 2016 Wiley Periodicals, Inc.     

A convenient synthesis of N‐t‐butyl‐N′‐aminocarbonyl‐N‐(substituted)benzoyl‐hydrazine containing α‐aminoalkylphosphonate groups in a one‐pot procedure

A variety of novel N‐t‐butyl‐N′‐aminocarbonyl‐N‐(substituted)benzoylhydrazines containing α‐aminoalkylphosphonate groups were synthesized. Treatment of α‐aminoalkylphosphonates with triphosgene yielded α‐isocyanatoalkylphosphonates, and subsequent addition with N‐t‐butyl‐N‐substituted benzoylhydrazines provided the title compounds in a one‐pot procedure with good yields. The triphosgene‐mediated reaction for the synthesis of α‐isocyanatoalkylphosphonates enjoys a number of advantages: the reaction is carried out under mild condition in good yield, triphosgene is relatively safe to handle because of its low vapor pressure and high stability, and the experimental procedure is simple. This method can be applicable to the synthesis of other α‐isocyanatoalkyl‐phosphonates and urylenediphosphonates. The structures of all of the products and by‐products were confirmed by ¹H NMR, ³¹P NMR, IR and mass spectroscopy, and elemental analysis. We also found that some of the compounds possess potential antitobacco mosaic virus (TMV) activities and anticancer activities. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:68–72, 2001     

Modeling the free radical polymerization of acrylates

Acrylates have gained importance because of their ease of conversion to high‐molecular‐weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well‐known monomer for free radical polymerization, but its α‐methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl α‐hydroxymethylacrylate (MHMA), methyl α‐methoxymethylacrylate (MC₁MA), methyl α‐acetoxymethylacrylate (MAcMA) show even better conversions to high‐molecular‐weight polymers than MMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl α‐hydroxymethylacrylate (EHMA) and t‐butyl in t‐butyl α‐hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6‐31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC₁MA, MAcMA, EHMA, TBHMA, MC₁AN (α‐methoxymethyl acrylonitrile), and MC₁AA (α‐methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Mechanism of asymmetric hydrogenation of enamides with [Rh(BisP*)]+ catalyst: Model DFT study

The potential energy profile for the [Rh(R,R)‐Et‐BisP*]⁺‐catalyzed asymmetric hydrogenation of prochiral enamides, α‐acetamidoacrylonitrile, was studied by the nonlocal density functional method (B3LYP). As illustrated, this hydrogenation is exothermic and goes mainly through association of [Rh(R,R)‐Et‐BisP*]⁺ with α‐acetamidoacrylonitrile, oxidative addition of hydrogen, migratory insertion of an olefin carbon into a Rh? H bond, reductive elimination of the C? H bond from the alkyl hydride, and dissociation of product–catalyst adducts with regeneration of the catalyst. The turnover‐limiting step for this reaction is the oxidative addition of hydrogen. The main product predicted theoretically is the R‐conformer. Our results are consistent with available empirical data and experiments for rhodium‐catalyzed asymmetric hydrogenation. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Isolation of terpenoids from Pimpinella anisum essential oil by high‐performance counter‐current chromatography

High‐performance counter‐current chromatography was successfully used for the isolation and purification of terpenoid compounds from the essential oil of Pimpinella anisum L. A two‐phase solvent system composed of n‐heptane/methanol/ethyl acetate/water (5:2:5:2, v/v/v/v) was suitable for the purification of linalool, terpinen‐4‐ol, α‐terpineol, p‐anisaldehyde, while n‐heptane/methanol (1:1, v/v) was used for the isolation of anethole and foeniculin. A scale‐up process from analytical to preparative was developed. Additionally, a stepwise gradient elution was applied and instead of two different runs, 40 min each, one 80 min separation was performed; although the time of separation remains the same, it was possible to repeat the efficiency even if the water‐containing mobile phase was changed to a nonaqueous system. The obtained essential oil, as well as purified compounds, was analyzed by GC. A total of 0.64 mg of linalool, 0.52 mg of terpinen‐4‐ol, 0.10 mg of α‐terpineol, 0.62 mg of p‐anisaldehyde, 15 mg of anethole, and 2.12 mg of foeniculin were obtained from 210 mg of the essential oil of P. anisum L. in a short time with purities of 99, 98, 94, 93.54, 93, and 93.6%, respectively.