Durable Modification of Wood by Benzoylation-Proof of Covalent Bonding by Solution State NMR and DOSY NMR Quick-Test.

A convenient, broadly applicable and durable wood protection was recently published by Kaufmann and Namyslo. This procedure efficiently allows for esterification of wood hydroxyl groups with (1H-benzotriazolyl)-activated functionalized benzoic acids. The result of such wood-modifying reactions is usually monitored by an increase in mass of the wood material (weight percent gain value, WPG) and by infrared spectroscopy (IR). However, diagnostic IR bands suffer from overlap with naturally occurring ester groups, mainly in the hemicellulose part of unmodified wood. In contrast to known NMR spectroscopy approaches that use the non-commonly available solid state techniques, herein we present solution state NMR proof of the covalent attachment of our organic precursors to wood. The finding is based on a time-efficient, non-uniformly sampled (NUS) solution state 1H,13C-HMBC experiment that only needs a tenth of the regular recording time. The appropriate NMR sample of thoroughly dissolved modified wood was prepared by a mild and non-destructive method. The 2D-HMBC shows a specific cross-signal caused by spin-spin coupling over three bonds from the ester carbonyl carbon atom to the α-protons of the esterified wood hydroxyl groups. This specific coupling pathway requires a covalent bonding as a conditio sine qua non. An even more rapid test to monitor the covalent bonding was achieved with an up-to-date diffusion-ordered spectroscopy sequence (Oneshot-DOSY) based on 1H or 19F as the sensitive nucleus. The control experiment in a series of DOSY spectra gave a by far higher D value of (1.22 ± 0.06)∙10-10 m2∙s-1, which is in accordance with fast diffusion of the "free" and thus rapidly moving small precursor molecule provided as its methyl ester. In the case of a covalent attachment to wood, a significantly smaller D value of (0.12 ± 0.01)∙10-10 m2∙s-1 was obtained.

Experimental and theoretical studies of quadrupolar oligothiophene-cored chromophores containing dimesitylboryl moieties as π-accepting end-groups: syntheses, structures, fluorescence, and one- and two-photon absorption.

Quadrupolar oligothiophene chromophores composed of four to five thiophene rings with two terminal (E)-dimesitylborylvinyl groups (4 V-5 V), and five thiophene rings with two terminal aryldimesitylboryl groups (5 B), as well as an analogue of 5 V with a central EDOT ring (5 VE), have been synthesized via Pd-catalyzed cross-coupling reactions in high yields (66-89%). Crystal structures of 4 V, 5 B, bithiophene 2 V, and five thiophene-derived intermediates are reported. Chromophores 4 V, 5 V, 5 B and 5 VE have photoluminescence quantum yields of 0.26-0.29, which are higher than those of the shorter analogues 1 V-3 V (0.01-0.20), and short fluorescence lifetimes (0.50-1.05 ns). Two-photon absorption (TPA) spectra have been measured for 2 V-5 V, 5 B and 5 VE in the range 750-920 nm. The measured TPA cross-sections for the series 2 V-5 V increase steadily with length up to a maximum of 1930 GM. We compare the TPA properties of 2 V-5 V with the related compounds 5 B and 5 VE, giving insight into the structure-property relationship for this class of chromophore. DFT and TD-DFT results, including calculated TPA spectra, complement the experimental findings and contribute to their interpretation. A comparison to other related thiophene and dimesitylboryl compounds indicates that our design strategy is promising for the synthesis of efficient dyes for two-photon-excited fluorescence applications.

Sydnone anions and abnormal N-heterocyclic carbenes of O-ethylsydnones. Characterizations, calculations and catalyses.

Deprotonated sydnones, which can be represented as anionic N-heterocyclic carbenes, were prepared as Li adducts and compared with deprotonated O-ethylsydnones (5-ethoxy-1,2,3-oxadiazol-4-ylidenes) which belong to the class of abnormal NHCs. The Pd complexes of the sydnone anions (X-ray analysis) as well as of the O-ethylsydnone carbenes proved to be efficient catalysts in aryl couplings of thiophenes.

Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles.

Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes) which can be trapped as rhodium complexes (X-ray analysis). In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole-indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole-indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis). Results of DFT calculations are presented.

Pericyclic rearrangements of N-heterocyclic carbenes of indazole to substituted 9-aminoacridines.

On deprotonation, 1-arylindazolium salts form 1-arylindazol-3-ylidenes which rearrange spontaneously via ring cleavage, ring closure and subsequent proton transfer to substituted 9-aminoacridines. By contrast, the N-heterocyclic carbene of 2-phenylindazolium cannot rearrange similarly and was trapped by sulfur.

Betaine-carbene interconversions. From N-ylides to zwitterionic N-heterocyclic carbene-borane adducts.

In the presence of NBS 3-methylindole reacted with various imidazoles to give the (indol-2-yl)imidazolium salts 21a-f, which were converted in aqueous solution into the 2-(imidazolium-3-yl)-3-methylindolates 22a-f by base. These conjugated ylides--which represent a subclass of mesomeric betaines--are the exclusively detectable form in the NMR spectra taken in DMSO-d(6). A DFT calculation revealed that the betaine 22a is -9.3 kJ/mol more stable than the tautomeric N-heterocyclic carbene 23a and that the energy for the betaine-carbene interconversion is ΔG(‡) = 66.4 kJ/mol. The N-heterocyclic carbenes (3-methyl-indol-2-yl)imidazol-2-ylidenes, however, can be trapped by sulfur, triethylborane, and triphenylborane. Whereas the first trapping reaction yielded the expected imidazolethiones, the borates gave the first representatives of new zwitterionic borane adducts, imidazo[2',1':3,4][1,4,2]diazaborolo[1,5-a]indolium-11-ides 26a-h. We performed DFT calculations on the structures of mesomeric betaine 22a, the carbene 23a, and the mechanisms of the borane adduct formation to 26a-h, NMR spectroscopic investigations including (15)N, (7)Li, and (11)B NMR spectroscopy, and an X-ray single-crystal analysis of one of the borane adducts.

Selective mono- to perarylations of tetrabromothiophene by a cyclobutene-1,2-diylbisimidazolium preligand.

(Cyclobut-1-ene-1,2-diyl)bis(1-methylimidazolium)tetrafluoroborate is applied as preligand in palladium-catalyzed cross-coupling reactions starting from tetrabromothiophene for the synthesis of mono-, bi-, tri-, and tetraaryl-substituted thiophenes bearing up to four different aryl rings. A synthetic kit for preparations of nine different substitution patterns of arylated thiophenes is presented by application of only one single catalyst system. In agreement with DFT calculations, which predict energetically low rotational barriers in triaryl-3-bromothiophenes and tetraarylthiophenes, no NOE effects between adjacent aryl rings are detectable. The regioselectivity of their syntheses has therefore been elucidated by reduction of triaryl-3-bromothiophene to 2,3,5-triarylthiophene followed by HMBC, HSQC, and NOESY NMR measurements. Additionally, results of an X-ray single structure analysis are presented.