Synthesis of Gingerenone C and 5-Hydroxy-1-(4′-hydroxy-3-methoxyphenyl)-7-(4′′-hydroxyphenyl)-3-heptanone

Diarylheptanoidsconstituteadistinctgroupofmetabolitesofnaturalplantcharacterizedbytwoaromaticringslinkedbyalinearsevenaliphaticchain.Therehavebeenfewreportsonthebiologicalactivitiesofdiarylheptanoids,mostofwhichappearingintheareasofanti-inflammatory,anti-oxidative,superoxidescavengingandanti-hepatotoxiceffects1,2.SomeofthemareusedastraditionalmedicineinAsia3.Compound1and2werefirstlyisolatedfromtherhizomesofZingiberofficalrespectively4,5.Sofarthesynthesisofthesetwocompoundshavenotbeenreportedy…     

Synthesis,physicochemical characterization,and biological activity of nanocomplexes of iron(III) of 3(2′-hydroxyphenyl)-5-(4-substituted phenyl) pyrazolines and dithiophosphoric acid

Complexes of iron(III) with dithiophosphoric acid and 3(2′-hydroxy phenyl)-5-(4-substituted phenyl) pyrazolines, [Fe(C₆O₁₄O₂PS₂)₂(C₁₅H₁₂N₂OX)], and [Fe(C₆O₁₄O₂PS₂)(C₁₅H₁₂N₂OX)₂], where (C₆O₁₄O₂PS₂H) = dithiophosphoric acid, (C₁₅H₁₃N₂OX) = deprotonated 3(2′-hydroxy phenyl)-5-(4-substituted phenyl)pyrazolines (X?=?H, CH₃, OCH₃, Cl), have been synthesized. These complexes have been physicochemically characterized by elemental analysis (C, H, N, S, Cl, and Fe), magnetic moment data, thermogravimetric analysis, molar conductance, cyclic voltammetry, and spectral analysis (UV–visible, IR, and Fast atom bombardment mass spectrometry). Scanning electron microscopy, TEM, and PXRD have been carried out for powdered samples, which show nanometric particles of these derivatives. Antibacterial and antifungal potential of free pyrazoline and iron(III) complexes have been evaluated.     

Synthesis,spectral study and antimicrobial activity of bismuth(III) 3(2′-hydroxyphenyl)-5-(4-substituted phenyl) pyrazolinates

Dichlorobismuth(III) pyrazolinates and chlorobismuth(III) dipyrazolinates of the type BiCl₂(C₁₅H₁₂N₂OX) and BiCl(C₁₅H₁₂N₂OX)₂ have been synthesized in dry benzene by reaction of BiCl₃ and the sodium salt of pyrazoline in 1 : 1 and 1 : 2 molar ratios at elevated temperature [C₁₅H₁₂N₂OX = 3(2′-hydroxyphenyl)-5-(4-X-substituted phenyl) pyrazoline and X = H in compounds 1, 5, CH₃ in 2, 6, OCH₃ in 3, 7 and Cl in 4, 8, respectively]. These newly synthesized derivatives have been characterized by elemental analysis (C, H, N, Cl and Bi), molecular weight measurements and spectral (IR, ¹H NMR, ¹³C NMR) studies. Selected compounds screened against different bacteria and fungi show potential antibacterial and antifungal activities.     

Synthesis of 2-(Substituted Benzylideneamino)-4-(4′-hydroxyphenyl) Thiazoles and Their O-Glucosides

2-Amino-4-(4′-hydroxyphenyl) thiazole 1a was prepared from reaction between p-hydroxyacetophenone, thiourea, and iodine; compound 1a was treated with several (aryl/hetro aryl) aldehydes to form 2-(substituted benzylideneamino)-4-(4′-hydroxyphenyl) thiazoles 2a–j, which were glucosylated by using acetobromoglucose as a glucosyl donor to afford 2-(substituted benzylideneamino)-4-(2, 3, 4, 6-tetera-o-acetyl-4′-o-β-d-glucosidoxyphenyl) thiazoles 3a–j, which further on during deacetylation produced 2-(substituted benzylideneamino)-4-(4′-o-β-d-glucosidoxyphenyl) thiazoles 4a–j. These compounds were evaluated for biological activity, and their structure was confirmed by IR, NMR, mass spectra, elemental, and chemical analysis.

     

Comeplexes of 1-(2′-hydroxybenzyl)-2-(2′-hydroxyphenyl)-benzimidazole with U(VI) and Ce(IV)

Some new U(VI) and Ce(IV) complexes of 1-(2′-hydroxybenzyl)-2-(2′-hydroxyphenyl)-benzimidazole have been prepared and characterized by spectrg magnetic and conductance studies. IR spectral data suggests that the ligand in all the complexes is monodenate through the tertiary nitrogen and that the phenolic oxygen is free from coordination. Conductivity measurements indicate that the nitrate and acetate complexes of U(VI) are non-electrolytes, whereas the nitrate complex of Ce(IV) is a 1:1 electrolyte.     

High-spin complexes of iron(III) with ethylene glycol and 3(2′-hydroxyphenyl)-5-(4′-substituted phenyl) pyrazolines

Complexes of iron(III) with ethylene glycol and 3(2′-hydroxyphenyl)-5-(4′-substituted phenyl) pyrazolines, [Fe(OCH₂CH₂O)(C₁₅H₁₂N₂OX)] _m ? nH₂O and [Fe(C₁₅H₁₂N₂OX)₂(OCH₂CH₂OH)] (where OCH₂CH₂O and OCH₂CH₂OH = ethylene glycol moiety; C₁₅H₁₂N₂OX = 3(2′-hydroxyphenyl)-5-(4-X-phenyl)pyrazoline; X = H, CH₃, OCH₃, or Cl; m = 2–3 and n = 2–3) have been synthesized and characterized by elemental analysis (C, H, N, Cl, and Fe), molecular weight measurement, magnetic moment data, thermogravimetric analysis, molar conductance, spectral (UV-Vis, IR, and FAB mass), scanning electron microscopy, and X-ray diffraction studies. Bonding of ethylene glycol and pyrazolines in these complexes and the particle size of iron(III) complexes are discussed. Antibacterial and antifungal potential of free pyrazoline and some iron(III) complexes are also discussed.     

Reformatsky-type addition of esters of α-halogeno carboxylic acids to aldehydes and ketones in the presence of Fe(CO)5

Reformatsky-type addition of esters of α-halogeno carboxylic acids to aldehydes and ketones in the presence of Fe(CO)₅ and an activating agent (CBrCl₃ or I₂) afforded the corresponding esters of β-hydroxy acids in good yields. Possible reaction mechanisms are discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1132–1138, June, 1999.     

Abnormal Reaction of 1-(2′-Methoxybenzoyl)-1-(2′-hydroxy-5′-methoxycarbonylbenzoyl)methane Treated with Etyyl Orthoformate and Acetic Anhydride

邻羟基二苯甲酰基甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应通常是ＨＣ（ＯＥｔ）３作为酰化剂，得到３－苯甲酰基色酮。本文报道５－甲氧羰基－２－羟基苯甲酰基－（２′－甲氧苯甲酰基）甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应时，是Ａｃ２Ｏ而不是ＨＣ（ＯＥｔ）３作为酰化剂，生成３－苯甲酰基－２－甲基色酮。其结构经ＮＭＲ、ＭＳ、ＩＲ和ＥＡ证实。并对其反应机理作了讨论。     

Deracemization of 5-(4-hydroxyphenyl)-5-phenylhydantoin (HPPH): practical synthesis of (−)-(S)-HPPH

In the presence of 10% NaOH in boiling MeOH enantiomerically enriched HPPH is racemized. This permits the deracemization of HPPH in the presence of brucine, giving enantiomerically pure (−)-(S)-HPPH [(−)-(S)-5-(4-hydroxyphenyl)-5-phenylhydandoin].     

Copper complexes formed by 3,5-bis(2,2′-bipyridin-4-ylethynyl)benzoic acid and its methyl and ethyl esters as studied by electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry was used to study the complexes of ligands containing two bipyridine units, namely 3,5-bis(2,2-bipyridin-4-ylethynyl)benzoic acid (1) and its methyl and ethyl esters (2, 3), with copper cation, with CuCl₂ as a source of copper. It was found that the type of complexes formed strongly depends on CuCl₂ concentration. At lower CuCl₂ concentration, the detected complexes were rather simple and some of them were formed upon electrospray ionization conditions e.g. ions [2₂+Cu₂]²⁺ and [3₂+Cu₂]²⁺ (complexes ligand-Cu(I) of stoichiometry 2:2) which are analogical to the well known, for quaterpyridine, helical complexes. At higher CuCl₂ concentration, the detected complexes were more complicated, and most of them contained copper cations bridged by chlorides. The largest ions were [L₂+Cu₄Cl₆]²⁺. The CID MS/MS spectra of these ions allowed determination of their mass spectrometric fragmentation pathways and as a consequence their structure elucidation.      

Complexing properties of N-[1,1-bis(hydroxymethyl)ethyl]-and N-[tris(hydroxymethyl)methyl]-β-alanine

Russian Chemical Bulletin - Protolytic and complexing properties of N-[1,1-bis(hydroxymethyl)ethyl]- and N-[tris-(hydroxymethyl)methyl]-β-alanine were estimated using the potentiometry. Values...     

An unexpected Pummerer rearrangement in the synthetic route to ethyl (2′-hydroxy-4′,5′-methylenedioxyphenyl)acetate: An alternative approach to 2,3-dimethylthio benzofurans

The synthesis of ethyl (2′-hydroxy-4′,5′-methylendioxophenyl)acetate, a fragment of the antihyperglycemic natural coumarin subcoriacin, is reported. We found an expeditious route to the title compound in five steps. Final metal catalyzed acid ethanolysis of the vinylic 1,1-methylthio methylsulfoxide derivative afforded the required aryl acetic ester, but in the absence of metal catalyst, an unexpected Pummerer rearrangement produced the 2,3-dimethylthiofuran derivative as the major product. This last result provides an alternative entry to 2,3-dimethlythiobenzofurans.     

Lateral protrusion and mesophase behaviour in pure and mixed states of model compounds of the type 4-(4′-substituted phenylazo)-2-(or 3-)methyl phenyl-4'-alkoxy benzoates

Two groups of the title compounds were prepared and investigated for their mesophase formation and stability. Each group constitutes five homologous series that differ from each other by the polar substituent X (CH₃O, CH₃, H, Cl, and NO₂). Within each homologous series, the number (n) of carbons in the alkoxy chain varies between 8, 10, 12, 14 and 16. The difference between the two groups of compounds lies in the orientation protrusion of the lateral methyl group attached to the central benzene ring. In the first group (Group I) the methyl substituent, introduced into the o-position with respect to the ester group, makes an angle of 60° with the long axis of the molecule. In the other series of compounds (Group II), the orientation angle is 120° as it is introduced into the position-3. All possible binary phase diagrams could be constructed in which the two components are corresponding positional isomers from either group. The study aimed to investigate the effect of inclusion of the lateral methyl group, as well as its spatial orientation, on the mesomorphic properties of the produced derivatives in their pure and mixed states. The compounds prepared in both groups were characterised for their mesophase behaviour by differential scanning calorimetry and polarised light microscopy. The nematic phase is the mesophase observed in most of the compounds prepared and their binary mixtures.     

Synthesis,spectral and antimicrobial studies of triorganotin(IV) 3(2′-hydroxyphenyl)-5-(4-substituted phenyl) pyrazolinates

Triorganotin(IV) pyrazolinates of the type R₃Sn(C1₅H₁₂N₂O?·?X) [where C₁₅H₁₂N₂O?·?X?= 3(2′-hydroxyphenyl)-5(4-X-phenyl)pyrazoline {where X?=?H (a); CH₃ (b); OCH₃ (c); Cl (d) and R?=?Me, Pr ⁿ and Ph}] have been synthesized by the reaction of R₃SnCl with the sodium salt of pyrazolines in a 1?:?1 molar ratio, in anhydrous benzene. These newly synthesized derivatives have been characterized by elemental analysis (C, H, N, Cl and Sn), molecular weight measurement as well as spectral studies [IR and multinuclear NMR (¹H, ¹³C and ¹¹⁹Sn)]. The bidentate behaviour of the ligands was confirmed by IR, ¹H and ¹³C NMR spectral data. Trigonal bipyramidal structure around tin(IV) atom for R₃Sn(C₁₅H₁₂N₂O?·?X) has been suggested. The free pyrazoline and a few triorganotin(IV) pyrazolinates have also been screened for their antibacterial and antifungal activities. Some triorganotin(IV) pyrazolinates exhibit higher antibacterial and antifungal effects than free pyrazoline and some of the antibiotics.     

“An efficient synthesis of ethyl (R)-2-hydroxy-4-phenylbutyrate: A useful intermediate in the synthesis of converting enzymeinhibitors”

Optically pure Ethyl (R)-2-hydroxy-4-phenylbutyrate has beensynthesized stereoselectively in 24% overall yield.