Marian Olejnik

SELECTIVE DEHYDRATION OF GLUCOSE TO HYDROXYMETHYLFURFURAL AND A ONE-POT SYNTHESIS OF A 4-ACETYLBUTYROLACTONE FROM GLUCOSE AND TRIOXANE IN SOLUTIONS OF ALUMINIUM SALTS

Abstract Saturated water solutions of Al 2 (SO 4 ) 3 and AlCl 3 were applied as solvent/matrices for dehydration of Glc to hydroxymethylfurfural (HMF). Addition of oxygen ligands: methanol, ethanol, THF, furan, dibutyl ether, ethyl orthoformate and trioxane influenced the yield and selectivity, the best being observed with ethanol. When Glc and trioxane were present together in reacting solution, formation of a 4-acetylbutyrolactone was observed.

Concentrated water solutions of salts as solvents for reaction of carbohydrates. Part 2. Influence of some magnesium salts and some ruthenium species on catalysis of dehydration of glucose

Saturated water solutions of MgCl2 and MgSO4 were applied as solvents/matrices for dehydration of glucose. The product of reaction between RuCl3(aq.) and Ag2SO4 abbreviated as ‘RuSO4’ was used as catalyst. As the most selective systems are: MgSO4/benzene(ethanol)/RuSO4 the mechanistic hypothesis was designed for these cases. Interaction of glucose with MgSO4RuSO4 consists of: Mg2+ complexation of glucose oxygens; hydrogen bonds between the glucose OH groups and the SO2−4 groups; between the glucose OH groups and water, hydroxy ligands in the Ru complex and SO2−4 donation to the glucose carbons.

Generation and reactions of aza-ortho-xylylenes in the injector of GC/MS system

Abstract Nitro derivatives of 2,1-benzisothiazoline 2,2-dioxide (benzosultams) undergo thermal elimination of sulfur dioxide yielding very reactive, non-isolable azo-ortho-xylylenes. It was found that this reaction can be performed in the injector of the gas chromatograph at 300 – 350°C and the formed aza-ortho-xylylenes can be trapped by appropriate reagents added to the injected solution. In the preliminary experiments aza-ortho-xylylenes were reacted with dienophiles (methyl acrylate, dimethyl maleate, vinyl acetate, N-phenylmaleimide etc.) resulting in the formation of the [4+2] cycloaddition reaction products, and also with nucleophilic reagents (alcohols, amines) to give appropriate adducts. In the absence of the trapping reagent dimers of aza-ortho-xylylenes were formed.

Investigation of the reaction product of 1,4,7,10-tetraphenyl-cyclododecahexa-1,2,3,7,8,9-ene with dodecacarbonyl-triiron by X-ray diffraction and MS: comparative structural study of the hexacarbonyl-μ2-(1η2-1,2-ene-2η3-3,4,5-allyl-1σ1-5)diiron(FeFe) system

Abstract Reaction of dodecacarbonyl-triiron with the 12-membered bis(butatriene) results in phenyl ring metallation and an intramolecular crosslinking of the macrocycle with the formation of a system of three condensed rings. The central core of the complex is formed by Fe2(CO)6 unit bridged by an organic ligand which is η3:η1-bonded by the π-allylic system and η2-bonded by the olefinic group. The molecular structure of the complex was determined by X-ray diffraction. Differences in fragmentation patterns in MS (EI and LSIMS) were examined. Comparative studies of the geometry of the complex obtained and a series of compounds with isostructural core have been carried out.

The synthesis, mass spectrometric properties and identification of some N,N-di-(β-arylisopropyl)formamides related to the synthesis of ring-modified amphetamines

This study examines the electron impact (EI) induced mass spectrometric behavior of several N,N-di-(β-arylisopropyl)formamides, which are connected to the Leuckart synthesis of some amphetamine analogues. Emphasis is laid on the fragmentation paths, which are common for all compounds under investigation and may be used in construction of the prediction scheme useful for identification of similar impurities, especially in absence of desirable authentic material. On the basis of this scheme several new N,N-di-(β-arylisopropyl)formamides have been identified in selected amphetamine analogues synthesized by the Leuckart method, including 4-methylthioamphetamine (4-MTA), 4-fluoroamphetamine (4-FA), 4-methylamphetamine, 3-trifluoromethylamphetamine, 3,4-methylenedioxyamphetamine (MDA), 2,5-dimethoxyamphetamine (2,5-DMA), 2,4,5- and 3,4,5-trimethoxyamphetamines (2-TMA and 3-TMA).

Methyleneglucoses — Transition metal catalyzed synthesis from formaline and glucose; importance of heterobimetallic catalyst

Abstract Iron III, ruthenium III and tin (II) chlorides catalyze the synthesis of methyleneglucoses with a yield of 13–20%. Chlorides of remaining metals and many different iron salts are considerably inferior. The yields of methyleneglucoses is further increased up to 36% when a heterobimetallic system (FeCl 3 + SnCl 2 2H 2 O) is applied as a catalyst. Hypothesis of the mechanism implies formation of a heterobimetallic complex bridged by Cl, gem-diol and glucose. The structure of two methyleneglucoses was established as 1,2:5,6-di-O-methylene-α-glucofuranose and 1,2:3,5-di-O-methylene-α-glucofuranose.