Novel copolymers of styrene. 15. Halogen ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel halogen ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C3H7 (where R is 2-fluoro-5-methyl, 3-iodo-4-methoxy, 5-iodo-2-methoxy, 3,5-dichloro, 3,4-difluoro, 3,5-difluoro, 2-chloro-4-fluoro, 2-chloro-6-fluoro, 3-chloro-2-fluoro, and 3-chloro-4-fluoro) were prepared and copolymerized with styrene. The propenoates were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and propyl cyanoacetate, and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the propenoates were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500ºC range with residue (1-3% wt.), which then decomposed in the 500-800ºC range.

Novel copolymers of vinyl acetate. 4. Halogen ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates

Novel copolymers of vinyl acetate and halogen ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C2H5 (where R is 2-Br, 3-Br, 4-Br, 2-Cl, 3-Cl, 4-Cl, 2-F, 3-F, 4-F, 2,3-dichloro, 2,4-dichloro, 2,6-dichloro, 3,4-dichloro, 2,4-difluoro, 2-bromo-3,4-dimethoxy) were prepared in solution with radical initiation at 70C. The propenoates were synthesized by the piperidine catalyzed Knoevenagel condensation of halogen ring-substituted benzaldehydes and ethyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Thermal behavior of the copolymers was studied by DSC (Tg) and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 159-500ºC range with residue (8.8-15.2 wt%), which then decomposed in the 500-650ºC range.

Novel copolymers of vinyl acetate. 3 Ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates

Novel copolymers of vinyl acetate and ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C2H5 (where R is 4-acetoxy, 4-acetamido, 2-cyano, 3-cyano, 4-cyano, 4-dimethylamino, 4-diethylamino, 2,4,6-trimethyl, 2,3-dimethyl-4-methoxy, 2,4-dimethoxy-3-methyl were prepared in solution with radical initiation at 70C. The propenoates were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and ethyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Thermal behavior of the copolymers was studied by DSC (Tg) and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 160-350ºC range with residue (1.5-15.1 wt%), which then decomposed in the 500-650ºC range.

N-Alkoxyimidazolylidines (NOHCs): Nucleophilic carbenes based on oxidized imidazolium core

We report the first preparation of a N-alkoxyimidazolylidene (NOHC), a nucleophilic carbene based on an oxidized imidazolium core. The carbene carbon shows the highest upfield 13C NMR shift compared to...

Acid Catalyzed Multicomponent One-Pot Synthesis of New Quinazolinone based Unsymmetrical C-N Linked Bis Heterocycles

A novel series of unsymmetrical C-N linked bis heterocycles bearing quinazolinone and acridinedione skeletons have been synthesized in an acid promoted one pot multicomponent reaction. A blend of 6-aminoquinazolin-4-(3H)-one, aromatic aldehydes and cyclohexane-1,3-dione in a simple and efficient condensation-cyclization reaction using hydrochloric acid in catalytic amount as catalyst afforded unsymmetrical bis hybrids in good to excellent yields. Multiheterocyclic hybrid compounds were also synthesized using heterocyclic ring containing aldehyde in three component reaction. The synthesized quinazolinone-acridindione hybrids were characterized using spectroscopic techniques such as a IR, 1H NMR, 13C NMR, ESI-mass and HRMS.

Humus formation in soils of the Lena River Delta

The aim of the study. Nowadays close attention is paid to polar soils due to the expected landscape transformation rate under the predicted climate crisis. Intensive degradation of permafrost and the release of nutrients from their frozen state can lead to an increase in the emission of greenhouse gases into the atmosphere, as well as the loss of landscapes. The aim of the study was to investigate the peculiarities of organic residues formation and humification degree as well as humus structure and functioning in soil the Lena River Delta. Location and time of the study. The study was conducted on the Samoylov and Sardach Islands in the Lena River Delta (Yakutia, Russia). Field studies were performed during the summer of 2019. Objects and methodology. Soils of the Lena River Delta from the Samoylov Island (flooded area) and Sardakh (non-flooded zone), i.e. Subaquatic Fluvisol (Arenic) and Histic Cryosol (Siltic) were the objects of the study, respectively. To examine the features of humification chemical-analytical, sedimentation, micromorphological methods were used, as well as CP/MAS 13C-NMR spectroscopy. Main results. The data obtained indicate a high diversity of soils and soil formation conditions in the Lena River Delta. Under non-flooded conditions Histic Cryosol (Siltic) were formed in the flooded parts of the Samoylov Island, Subaquatic Fluvisol (Arenic) were formed. These soils play an important role in the global carbon cycle, accumulation, transformation and deposition of condensed high- and low molecular mass organic compounds in the composition of soils and permafrost. The main soil micromorphology features were identified. In the young landscapes the soil microstructure was represented by poorly sorted sand with a circular type of optical orientation of the soil plasma (which indicated the influence of the river), as well as vertically oriented micas (muscovite/biotite). Soils influenced by the floodplain process were characterized by the presence of coarse amorphous humus. Due to the long-term effect of the freezing/thawing processes on the permafrost-affected soils the biogenic aggregates were formed. In such organo-mineral microaggregates humus is fixed in the composition of mineral components consisting of particles of quartz, micas and Mn-Fe nodules and is in a stable state (physical stabilization of humus). To analyze the molecular composition the 13C NMR spectroscopy method was used. According to 13C NMR spectroscopy data, up to 37% of aromatic structural fragments accumulated in soils, which indicates the process of condensation of molecules in humic acids, thus showing a relatively high level of humus stabilization in the soils of the Lena River delta. From the data obtained, three main groups of chemical structural fragments that accumulate in the delta soils can be distinguished, such as C,H - alkyls ((CH2)n/CH/C and CH3), aromatic compounds (C–C/C–H, C–O) and the OCH group (OCH/OCq). In the studied humic preparations aliphatic structural fragments of HAs (63–64%) predominated, which indicated a deficiency of lignin and lignin-like compounds in the composition of humification precursors. The predominance of aliphatic structures is typical of humic substances formed under reduction conditions, including the aqueous humic substances, as well as in soils, the precursors of humification of which are typical tundra vegetation (mosses and lichens) with a predominance of carbohydrates (up to 80%). A significant amount of aromatic fragments accumulated in the delta in the alluvial soils of the first terrace of the river (flooded zone). This is apparently due to the formation of vascular plants in the flooded areas of the Lena River Delta. The chemical composition of vascular plants includes components such as tannins, flavonoids and lignin (arenas). Thus in the samples formed under vascular plants with a lignin content of about 30%, an increase in signals in the range of 110-160 ppm were observed. Aromatic and carboxyl fragments in the structure of HA were formed during the transformation of lignin, which leads to the resistance of HAs to biodegradation. Conclusion. Under the floodplain condition humus is represented by coarse amorphous forms, whereas without the influence of flooding humus is fixed in mineral microaggregates. Specific humic acids composition in the studied regions is determined by bioclimatic conditions, cryogenic processes and the composition of humification precursors. High abundance of aromatic structures in humus substances suggests relatively stable humus status (most likely due to the putative condensation of humic acids) in the Lena River Delta during the study period.

Cyclic Methacrylate Tetrahydropyrimidinones: Synthesis, Properties, (Co)Polymerization

During radical polymerization of novel biocidal methacrylate guanidine monomers, a cyclic byproduct was discovered and identified as 2-imino-5-methyltetrahydropyrimidin-4(1H)-one (THP). Its methacrylate salt (MTHP) was synthesized and characterized via 1H and 13C NMR and pyrolysis chromatography. Synthesis conditions of both THP and MTHP were optimized to high yields, and both MTHP homopolymerization (in aqua) and copolymerization with diallyldimethylammonium chloride (in aqua in salt form) were successfully carried out with middle to high yields, providing a promising platform for potential tailored biocide polymers.

Novel copolymers of vinyl acetate. 2. Oxy ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates

Novel copolymers of vinyl acetate and oxy ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C2H5 (where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 2,3-dimethoxy, 2,4-dimethoxy, 2,5-dimethoxy, 3,4-dimethoxy, 2,3,4-trimethoxy, 2,4,5-trimethoxy, 2,4,6-trimethoxy, 3,4,5-trimethoxy) were prepared in solution with radical initiation at 70C. The propenoates were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and ethyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Thermal behavior of the copolymers was studied by DSC (Tg) and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 160-350ºC range with residue (2.2-25.3 wt%), which then decomposed in the 500-650ºC range.

Synthesis and Characterisation of 1,1′-{[3,5-Bis(dodecyloxy-carbonyl)-4-(thiophen-3-yl)-1,4-dihydropyridine-2,6-diyl]bis-(methylene)}bis(pyridin-1-ium) Dibromide

In the present work, construction of double-charged cationic amphiphilic 1,1′-{[3,5-bis(dodecyl¬oxy-carbonyl)-4-(thiophen-3-yl)-1,4-dihydropyridine-2,6-diyl]bis-(methylene)}bis(pyridin-1-ium) dibromide (7) was performed in four steps. Dodecyl 3-oxobutanoate (1) was condensed with thiophene-3-carbaldehyde (2) which was necessary for Hantzsch cyclisation dodecyl (E/Z)-3-oxo-2-(thiophen-3-ylmethylene)butanoate (3). Two-component Hantzsch type cyclisation of dodecyl (E/Z)-3-aminobut-2-enoate (4) and dodecyl (E/Z)-3-oxo-2-(thiophen-3-ylmethylene)butanoate (3) gave 3,5-bis(dodecyloxycarbonyl)-2,6-dimethyl-4-(thiophen-3-yl)-1,4-dihydropyridine (5). Bromination of compound 5 followed by nucleophilic substitution of bromine with pyridine gave the desired cationic amphiphilic 1,4-dihydropyridine 7. The obtained target compound 7 and new intermediates 3, 5 and 6 were fully characterised by IR, UV, 1H NMR, 13C NMR, HRMS or microanalysis. Characterisation of nanoparticles formed by the cationic 1,4-dihydropyridine 7 in an aqueous solution was performed by DLS measurements.

Sesquiterpenoids and Xanthones from the Kiwifruit-Associated Fungus Bipolaris sp. and Their Anti-Pathogenic Microorganism Activity

Nine previously undescribed sesquiterpenoids, bipolarisorokins A–I (1–9); two new xanthones, bipolarithones A and B (10 and 11); two novel sativene-xanthone adducts, bipolarithones C and D (12 and 13); as well as five known compounds (14–18) were characterized from the kiwifruit-associated fungus Bipolaris sp. Their structures were elucidated by extensive spectroscopic methods, electronic circular dichroism (ECD), 13C NMR calculations, DP4+ probability analyses, and single crystal X-ray diffractions. Many compounds exhibited anti-pathogenic microorganism activity against the bacterium Pseudomonas syringae pv. actinidiae and four pathogenic microorganisms.