Lignin, obtained through steam explosion\ud from straw, was completely characterized via elemental\ud analysis, gel permeation chromatography, ultraviolet and\ud infrared spectroscopy, and 13C and 1H nuclear magnetic\ud resonance spectrometry. Polyurethanes were obtained by\ud treating steam-exploded lignin from straw with 4,4-methylenebis(\ud phenylisocyanate), 4,4-methylenebis(phenylisocyanate)\ud –ethandiol, and poly(1,4-butandiol)tolylene-2,4-diisocyanate\ud terminated. The obtained materials were characterized\ud by using gel permeation chromatography, infrared\ud spectroscopy, and scanning electron microscopy. Differential\ud scanning calorimetry analysis showed a Tg at 6°C,\ud assigned to the glass transition of the poly(1,4-butandiol) chains. The presence of ethylene glycol reduced the yields of\ud the polyurethanes. The use of the prepolymer gave the best\ud results in polyurethane formation. Steam-exploded lignin\ud was used as the starting material in the synthesis of polyesters.\ud Lignin was treated with dodecanoyl dichloride. The\ud products were characterized by using gel permeation chromatography,\ud infrared spectroscopy, 13C and 1H nuclear\ud magnetic resonance spectrometry, and scanning electron microscopy

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The reaction of (S)-1-methylpropylbenzoylformate with furan gave (1'S)-1'-methylpropyl (1S,5R,6R)-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate with de = 15%. The reaction of (S)-2-methylbutyl benzoylformate with furan gave (2'S)-2-methylbutyl (1SR,5RS,6RS)-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate as a mixture of stereoisomers. (1R,2S,5R)-5-Methyl-2-(1-methylphenylethyl)cyclohexyl benzoylformate gave (1R,2S,5R)-5-methyl-2-(1-methylphenylethyl)cyclohexyl (1R,5S,6S)-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate with de = 95%. The stereochemical behaviour can be explained considering the energy gap between the biradical intermediates in the coupling reaction. When the reaction was performed in the presence of zeolite, the diastereoisomeric excess increased (37, 18 and 98%, respectively). The reaction of (S)-1-methylpropylbenzoylformate with 2-methylfuran gave (1'S)-1'-methylpropyl (1S,5R,6R)-1-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate (yield: 12%) with de = 94%. The main product was (1'S)-1'-methylpropyl (1SR,5RS,6RS)-3-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate as a mixture of diastereoisomers. The reaction of (S)-2-methylbutyl benzoylformate with 2-methylfuran gave (2'S)-2-methylbutyl (1S,5R,6R)-1-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate (yield: 9%) with de = 10%. The main product was (2'S)-2-methylbutyl (1SR,5RS,6RS)-3-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate as a mixture of stereoisomers. The stereochemical behaviour can be explained on the basis of the energy gap between the possible biradical intermediates. The reaction of (S)-1-methylpropylbenzoylformate and (S)-2-methylbutyl benzoylformate with 2-furylmethanol gave the corresponding adducts as a mixture of diastereoisomers. The reaction of (S)-1-methylpropylbenzoylformate and (S)-2-methylbutyl benzoylformate with 2-furylphenylmethanol gave the corresponding adducts with high diastereoselectivity. In this case, the stereochemical behaviour is determined by the presence of the hydroxy group in a molecule with a preferntial conformation.

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) of a steam-exploded lignin from wheat straw showed that fragments with a mass higher than 4534 Da cannot be obtained. Furthermore, FT-ICR-MS showed that lignin is not a completely random polymer, but shows some regularity with a difference of 44.026 m/z (C₂H₄O) between the peaks. The distribution of Kendrick mass defect in the function of Kendrick nominal masses showed the same behaviour. FT-ICR-MS analysis of bagasse lignin (Granit) showed that the largest value of mass found was 4347 Da. The peaks show regularities with a difference of 44.026 m/z between the peaks. The organosolv lignin showed that the polymer with the largest mass value was 3699 Da in FT-ICR-MS. The analysis of the peaks did not show regularity; however, the Kendrick diagram for this lignin showed the same slope as in the other samples, in agreement with the C₂H₄O regular difference between peaks.

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The photochemical reaction of 1-(2-furyl)-1-phenylethanol with benzaldehyde gave a mixture of regioisomeric products. The adduct obtained on the more hindered side of the molecule was obtained with complete diastereoselectivity. The same substrate with benzophenone gave only one product with a diastereoisomeric excess of 48%. The reaction of 2-(2-furyl)-3,3-dimethylbutan-2-ol with benzaldehyde and benzophenone gave the corresponding adducts on the more hindered side of the molecule with diastereoisomeric excesses of 42 and 71%, respectively. These results, and also those obtained using 2-furylphenylmethanol with benzophenone and acetone (complete diastereoselectivity and absence of diastereoselectivity, respectively), were explained assuming the attack of the excited carbonyl compound on the same side as the hydroxy group, through the formation of a hydrogen bond or of a complex. This type of attack gave the biradical intermediate in preferential conformations. The relative energies of these conformers account for the observed diastereoselectivity.

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