Jorma Matikainen

Relative and inherent reactivities of imidazolium-based ionic liquids: the implications for lignocellulose processing applications

Novel methods for the fractionation of wood, as a major renewable chemical and material feedstock, are in demand. Ionic liquids, such as 1-ethyl-3-methylimidazolium acetate ([emim][OAc]), are promoted as potential media for these processes. However, the chemical stabilities of such ionic liquids are in question as they may have an effect on process sustainability or efficiency. With anion nucleophilicity and basicity being implicated more in ionic liquid reactivity, a rough scale of the relative reactivities for [emim]-based ionic liquids is demonstrated, based upon their TGA decomposition temperatures. These values are compared to the proton affinities for the anions of those ionic liquids, as a crude measure of nucleophilicity or basicity. The implications for the temperature-dependent chemical stability of imidazolium-based ionic liquids are discussed, in regard to their interactions with wood biopolymers. It is observed that for ionic liquids with less diffuse anions (more nucleophilic or basic), such as [emim][OAc], they unfortunately become more unstable. This is exhibited by a decrease in the thermal stability and an increase in the degree of interaction with the biomass, to the point of better solvation and even covalent interactions with dissolved components. The ab initio proton affinities, dipole moments, van der Waals surface area, and volumes, are presented for an extended series of anions, commonly used in ionic liquids.

Effect of hydrogen bonding on coordination in trans-di(Z-animobenzoato-O)di(1,3-diaminopropane-N,N′)copper(II) (Z = 2, 3 or 4) complex units

Abstract The crystal structures of the series of compounds containing the di(Z-aminobenzoato-O)di(1,3-diaminopropane-N,N′)copper(II) (Z = 2, 3 or 4) coordination units were determined by single-crystal X-ray methods. In the ortho- and meta-aminobenzoate analogues the structures are composed of monomeric complex units, where a copper(II) cation is located at a centre of symmetry and the chelate rings display a chair conformation. The benzoate anions in the axial positions are coordinated via one oxygen only. In the para-aminobenzoate analogue the complex units are similar, but there are two additional crystal water molecules in the asymmetric unit. The main differences between the three coordination units are seen in the bite angle of a chelate ring and the declination value of a benzoate anion. The differences are likely due to variation in the participation of an amine group of a chelate ring and a carboxylate group of a benzoate anion to form a hydrogen bonding network. Intramolecular hydrogen bonding seems to be correlated with inclination of a benzoate anion. Small inclination and absolute declination values for a benzoate anion seem to be related with bifurcated intramolecular hydrogen bonding and narrowing of a bite angle NCuN. The hydrogen bonding to the coordinated oxygen atom changes its hybridisation from approximate sp2 towards sp4. The existence of hydrogen bonding is supported by IR spectra. The crystallographic data are as follows (tn: 1,3-diaminopropane: bzO: a benzoate anion): [Cutn2(2NH2b/O)2], C20H42CuN6O4, monoclinic, space group P24/a No. 14, a = 10.513(2), b = 9.1789(12), c = 12.126(2) A , β = 99.82(2)° , V = 1153.0(4) A 1 : [Cutn2(3NH2bzO)2], C20H2CuN6O4, monoclinic, space group P21/n No. 14, a = 6.7128(12), b = 16.503(4), c = 10.268(2) A , β = 92.022(15)°, V = 1136.8(1) A : [Cutn2(4NH2bzO)2] · 2H2O, C20H30CuN40O6, monoclinic, space group P2/n No. 14, a = 9.484(2), b = 8.938(2), c = 16.30(3) A , β = 103.910(14)°, V = 1334.6(5) A 1 .

A study of 1,5-hydrogen shift and cyclization reactions of an alkali isomerized methyl linolenoate

Abstract Heating a mixture formed by alkali isomerization of methyl linolenoate ( 1 ) produces a complex mixture with the bicyclic hexahydroindenoic esters 4β-(7-methoxycarbonylheptyl)-5α-methyl-2,3,3aα,4,5,7aαhexahydroindene (CL5) and 4β-ethyl-5α-(6-methoxycarbonylhexyl)-2,3,3aα,4,5,7aα-hexahydroindene (CL6) as main components. Similar isomerization reactions of three synthetic model compounds, methyl 9 Z ,13 E ,15 Z -octadecatrienoate ( 2 ), 9 Z ,14 E ,16 E -octadecatrienoate ( 4 ) and 9 Z ,11 E ,15 Z -octadecatrienoate ( 5 ) corroborated the results obtained with alkali isomerized methyl linolenoate.

1,5-Hydrogen shift and other isomerization reactions of certain ethyl octadecatrienoates

Abstract Four new octadecatrienoic acid ethyl esters (4–7) were synthesized. On heating these undergo cyclization, via an intramolecular Diels-Alder (IMDA) reaction, mainly to stereoisomers of ethyl 4-(5-pentyl-1,2,3,3a,4,5,7a-hexahydroindenyl)-butanoate (CP-1, CP-2, CP-3, CP-4 and CP-5) and 3-(6-pentyl-1,2,3,4,4a,5,6,8a-octahydronaphthyl)propanoate. 1,5-Sigmatropic hydrogen shift reactions of the trienoic esters 4–7, all possessing a conjugated Z,E structure, precede the IMDA reactions. The 1,5-hydrogen shift reaction occurs in Z,E dienoic structures at a lower temperature than the Z,E to E,E isomerization.

Development of a Novel Hapten for Radioimmunoassay of the Lignan, Enterolactone in Plasma (Serum). Total Synthesis of (±)-trans-5-Carboxymethoxyenterolactone and Several Analogues

Abstract A recently developed method for the analysis of the mammalian lignan, enterolactone 1 , is based on time-resolved fluoroimmunoassay (TR-FIA) using an europium chelate as a label. This RIA utilizes enterolactone derivatives carrying a carboxylic acid appendage for the production of antiserum and tracer. The synthesis of 5-carboxymethoxyenterolactone 6 and analogues 5 , 7 and 8 is described, and their suitability for the method are discussed.

Cellulose fatty acid esters as sustainable film materials – effect of side chain structure on barrier and mechanical properties

Cellulose is mainly utilized by industry for paper and packaging materials. Due to ecological awareness this biopolymer has recently received an increasing amount of attention as a renewable alternative for replacing traditional oil based products. In this work, hydrophobic cellulose based materials were prepared by acylation of cellulose with tall oil fatty acid based saturated, unsaturated and branched fatty acids. Films were prepared by casting, and their oxygen and water vapour permeabilities as well as mechanical and thermal properties were characterized. Unsaturation and branching had a significant effect on the properties of the films. Comparing these materials with already existing commercial products showed that fatty acid modification of cellulose yields films with increased thermal stability, low water vapour transmission rates and enhanced tensile and elastic properties.

Antimicrobial activity of the marine alkaloids haminol and pulo'upone and related compounds.

The marine alkaloids haminol A, haminol B and pulo’upone as well as 17 related compounds (twelve 2-substituted pyridine derivatives, four 3-substituted ones and one analogue of the bicyclic terminus of pulo’upone) were tested for antimicrobial activity against a panel of six microbes (Bacillus cereus, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus epidermidis, Candida albicans and Saccharomyces cerevisiae) using the paper disc agar diffusion method. Six compounds were tested also against the mold Aspergillus niger. Some of the compounds displayed noteworthy antimicrobial activity, only one congener being completely devoid of activity. Nearly all compounds had activity against B. cereus and S. epidermidis. The growth of E. coli, C. albicans and S. cerevisiae was also distinctly inhibited by many compounds. In contrast, most compounds were inactive or had minimal activity against P. aeruginosa. Interestingly, most of the compounds tested against the opportunistic pathogen A. niger were active, one of them having noteworthy inhibitory potency.

Cyclopinolenic acids: Synthesis, derivatives and thermal properties

The two isomeric cyclopinolenic acids (CP-1 and CP-2), components of distilled tall oil, have been synthesized by means of an intramolecular Diels-Alder reaction of isomers of 5,10,12-octadecatrienoic esters, themselves synthesized in a stereocontrolled manner. The 5cis,10-trans,12trans isomer cyclizes at 200°C to a 1:3 mixture of esters of CP-1 and CP-2. At 200°C, the 5cis,10trans,12cis isomer is unreactive, but at 240°C it gives the same CP-1 + CP-2 ester mixture, presumably by way of prior isomerization to the 5cis,10trans,12trans isomer. A subambient thermal study of CP-1 and CP-2 and their derivatives shows that the compounds, excluding CP-1, lack crystalline structures or melting points, and display glass transitions only, below −80°C for esters and below −50°C for the carboxylic acids.

SYNTHESIS OF ISOPULO'UPONE

Abstract Two routes are reported for the synthesis of the title marine metabolite 1. The routes converge at the trienoic aldehyde 4, and are completed by chain extension to the tetraenoic ketone 5 and intramolecular Diels-Alder cyclization. - Daylight lamp irradiation offers a convenient means for converting a cis/trans mixture from a Wittig reaction into the pure trans isomer.

Intramolecular Diels-Alder reaction of 5,10,12-(5E,10E,12E)-octadecatrienoic and 2,7,9-(2E,7E,9E)-pentadecatrienoic esters

Abstract In stereochemical outcome of intramolecular Diels-Alder reactions, the non-activated 5,10,12-octadecatrienoate system is intermediate between the activated 2,7,9-isomer and the parent hydrocarbon 1,6,8-nonatriene