Synthesis of phosphinodiselenoic acid esters and their application as RAFT agents in styrene polymerization

Phosphinodiselenoic acid esters are synthesized from the reaction of chlorodiphenylphosphine and aryl- or alkyl-magnesium bromide in the presence of selenium powder. They are employed as RAFT agents in thermally initiated, styrene polymerization. The phosphinodiselenoic acid esters 6a and 6b showed some degree of control over the radical polymerization of styrene.     

A synthesis of licofelone using Fenton’s reagent

An efficient synthesis of licofelone, an anti-inflammatory drug currently undergoing phase-III clinical studies, based on Fenton-type radical alkylation of 2,3-dihydro-1H-pyrrolizine 3 with iodoacetonitrile or iodoacetates is reported. The iodoacetates can be replaced by NaI and by the corresponding bromoacetate.     

Chirale Halbsandwich‐Pentamethylcyclopentadienyl‐Rhodium(III)‐ und Iridium(III)‐Komplexe mit Schiff‐Basen aus Salicylaldehyd und α‐Aminosäureestern [1]

Chiral Half‐sandwich Pentamethylcyclopentadienyl Rhodium(III) and Iridium(III) Complexes with Schiff Bases from Salicylaldehyde and α‐Amino Acid Esters [1] A series of diastereoisomeric half‐sandwich complexes with Schiff bases from salicylaldehyde and L‐α‐amino acid esters including chiral metal atoms, [(η⁵‐C₅H₅)(Cl)M(N,O‐Schiff base)], has been obtained from chloro bridged complexes [(η⁵‐C₅Me₅)(Cl)M(μ‐Cl)]₂ (M = Rh, Ir). Abstraction of chloride from these complexes with Ag[BF₄] or Ag[SO₃CF₃] affords the highly sensitive compounds [(η⁵‐C₅Me₅)M(N,O‐Schiff base]⁺X^? (M = Rh, Ir; X = BF₄, CF₃SO₃) to which PPh₃ can be added under formation of [(η⁵‐C₅Me₅)M(PPh₃)(N,O‐Schiff base)]⁺X^?. The diastereoisomeric ratio of the complexes ( 1 ‐ 7 and 11 ‐ 12 ) has been determined from NMR spectra.     

Solution and fluorous phase synthesis of β,β-difluorinated 1-amino-1-cyclopentane carboxylic acid derivatives

An efficient protocol for the preparation of β,β-difluorinated 1-amino-1-cyclopentane carboxylic acid derivatives was developed. 2,2-Difluro-4-phenyl-3-butenoic acid 6 was used as substrate for the preparation of the starting vinyl difluoro imino esters 8. The key steps of this methodology rely on the chemo- and diastereoselective addition of allylzinc bromides over the iminic functionality of 8 and subsequent RCM reaction. This synthetic sequence was successfully applied to fluorous synthesis.     

Multivariate near infrared spectroscopy models for predicting the methyl esters content in biodiesel

Biodiesel is the main alternative to fossil diesel. The key advantages of its use are the fact that it is a non-toxic renewable resource, which leads to lower emissions of polluting gases. European governments are targeting the incorporation of 20% of biofuels in the general fuels until 2020.Chemically, biodiesel is a mixture of fatty acid methyl esters, derived from vegetable oils or animal fats, which is usually produced by a transesterification reaction, where the oils/fats react with an alcohol, in the presence of a catalyst. The European Standard (EN 14214) establishes 25 parameters that have to be analysed to certify biodiesel quality and the analytical methods that should be used to determine those properties.This work reports the use of near infrared (NIR) spectroscopy to determine the esters content in biodiesel as well as the content in linolenic acid methyl esters (C18:3) in industrial and laboratory-scale biodiesel samples. Furthermore, calibration models for myristic (C14:0), palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2) acid methyl esters were also obtained. Principal component analysis was used for the qualitative analysis of the spectra, while partial least squares regression was used to develop the calibration models between analytical and spectral data. The results confirm that NIR spectroscopy, in combination with multivariate calibration, is a promising technique to assess the biodiesel quality control in both laboratory-scale and industrial scale samples.     

Determination of volatile fatty acid ethyl esters in raw spirits using solid phase microextraction and gas chromatography

An analytical method for the determination of fatty acid ethyl esters in raw spirits of different quality or produced from various raw materials has been developed and optimized. A combination of headspace solid phase microextraction (HS-SPME) as the extraction technique and gas chromatography with flame ionization detection (GC-FID) as the determination technique was utilized. HS-SPME conditions such as: type of the stationary phase of the fiber, ethanol content, sample volume, extraction temperature and time, salt addition and sample agitation were investigated to determine the most suitable conditions for the analysis of volatile fatty acid ethyl esters in raw spirits. The quantification method was an internal standardization using methyl octanoate as the internal standard. The method's detection limits (MDLs) for the individual ethyl esters ranged from 26.8 to 0.0470 μg L⁻¹ 20% EtOH. The feasibility of SPME for the quantitative analysis of fatty acid ethyl esters in raw spirits of different organoleptic quality was demonstrated. High precision and simple sample preparation enable the use of this method for routine investigations in both industrial and research laboratories.     

Investigations of 2,3′-biquinolines 23. Synthesis of 1′-R-1′,4′-dihydro-2,3′-biquinolin-4′-ones by Claisen condensation

A method has been developed for the synthesis of 1′-R-1′,4′-dihydro-2,3′-biquinolin-4′-ones based on the interaction of quinaldine with N-alkyl-N-formylanthranilic acid methyl esters under the conditions of the Claisen condensation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 409–410, March 2008.     

Monohydroxy‐Substituted Polyunsaturated Fatty Acids from Swertia japonica

Fourteen monohydroxy‐substituted polyunsaturated fatty acids, including two new compounds, (9Z,12S,13E,15Z)‐12‐hydroxyoctadeca‐9,13,15‐trienoic acid ( 10 ) and (9Z,12Z,14E,16R)‐16‐hydroxyoctadeca‐9,12,14‐trienoic acid ( 13 ), and 12 known ones, i.e., 1 – 9, 11, 12 , and 14 , were isolated from the whole plants of Swertia japonica Makino , and characterized as the corresponding methyl esters 1a – 14a . Their structures were elucidated by analysis of the corresponding spectroscopic data, and the absolute configurations of 10a and 13a were determined by the Mosher‐ester method. The CD spectra (Table) of compounds 1a – 14a are briefly discussed. This is the first report on the isolation of monohydroxy‐substituted polyunsaturated fatty acids from the Swertia genus in Gentianaceae.     

Coordination of iron(III) cations to beta-keto esters as studied by electrospray mass spectrometry: implications for iron-catalyzed Michael addition reactions

Solutions of Fe(III) salts and beta-keto esters have been investigated by means of electrospray ionization mass spectrometry. The complexes formed in such solutions have been considered previously as active intermediates in Fe(III)-catalyzed Michael additions. By using different Fe(III) salts with a set of beta-keto esters, cation and anion mass spectra were analyzed and the effects of ester concentration, the role of the counterion, and the structure of the ester employed are discussed. Depending on the basicity of the ester, an increase of its concentration may lead to a decrease in the concentration of iron complexes observed in the mass spectra. Counterions with strong binding affinities to iron are found to capture the metal as ferrates, thereby removing the metal from the catalytic cycle.