SYNTHESIS OF DINITRAMIDE SALT 1-AMINO-1,2,3-TRIAZOLE

Показано, что динитразовая кислота легко взаимодействует с 1-амино-1,2,3-триазолом с количественным выходом образуя соответствующую высокоэнергетическую ионную соль. В ходе процесса солеобразования используется более безопасный и доступный растворитель, чем описано в литературе для ионных солей динитразота на основе различных триазолов. It was shown that dinitratic acid easily interacts with 1-amino-1,2,3-triazole in quantitative yield to form the corresponding high-energy ionic salt. During the salt formation process, a safer and more affordable solvent is used than described in the literature for dinitrazot ionic salts based on various triazoles.

Free-radical cyclization approach to polyheterocycles containing pyrrole and pyridine rings

A wide range of derivatives with new pyrido[2,1-a]pyrrolo[3,4-c]isoquinoline skeleton was synthesized by free-radical intramolecular cyclization of o-bromophenyl-substituted pyrrolylpyridinium salts using the (TMS)3SiH/AIBN system. The cyclization provides generally good yields of pyrido[2,1-a]pyrrolo[3,4-c]isoquinoline hydrobromides having no additional radical-sensitive substituents. The free bases can be obtained from the synthesized hydrobromides in quantitative yield by basification at room temperature. The selectivity control of intramolecular arylation was achieved by replacing the halogen: the use of 1-(2-(ortho-bromophenyl)-4-(ortho-iodophenyl)pyrrol-3-yl)pyridinium bromide makes it possible to obtain a monocyclization product, and the bicyclization product from the dibromo derivative. The procedure is also applicable to obtain 3-arylpyrido[2,1-a]pyrrolo[3,2-c]isoquinoline derivatives including 2-unsubstituted skeletons that are inaccessible via Pd-catalyzed cyclization.

An Easy Synthesis of Monofluorinated Derivatives of Pyrroles from β-Fluoro-β-Nitrostyrenes

The catalyst-free conjugate addition of pyrroles to β-Fluoro-β-nitrostyrenes was investigated. The reaction was found to proceed under solvent-free conditions to form 2-(2-Fluoro-2-nitro-1-arylethyl)-1H-pyrroles. The effectiveness of this approach was demonstrated through the preparation of a series of the target products in a quantitative yield. The kinetics of a conjugate addition of pyrrole was studied in detail to reveal the substituent effect and activation parameters of the reaction. The subsequent base-induced elimination of nitrous acid afforded a series of novel 2-(2-Fluoro-1-arylvinyl)-1H-pyrroles prepared in up to an 85% isolated yield. The two-step sequence herein proposed is an indispensable alternative to a direct reaction with elusive and unstable 1-Fluoroacetylenes.

Development of enantioselective intramolecular N-arylation reactions for the desymmetrization of achiral dinitrogen malonamide derivatives

An effective methodology for the enantioselective intramolecular (Buchwald-Hartwig) amidation of prochiral dinitrogen malonamide derivatives has been developed in quantitative yield and good enantioselectivities. The best result was obtained based on an enantiopure (R)-MOP/Pd(OAc)₂ catalytst system with either Cs₂CO₃ or K₃PO₄ in refluxing THF affording the 4-methoxybenzyl substituted diamide derivative, 3-methyl-N, 1-bis(4-methoxbenzyl)-2-oxo-1,2,3,4-tetrahydroquinoline-3-carboxamide, in 99% yield and 75% enantiomeric excess. This example serves as a preliminary example of a desymmetrization of prochiral dinitrogen nucleophiles by preferential N-arylation. The intermolecular version of this reaction proved to be more challenging than its intramolecular counterpart and no coupling products were obtained. Other malonamide derivatives were prepared with a pendant bromovinyl substituent at the αposition and cyclized intramoleculary employing a mild Goldberg reaction to form 5-membered rings in good yield and unknown enantioselectivity.

Development of enantioselective intramolecular N-arylation reactions for the desymmetrization of achiral dinitrogen malonamide derivatives

An effective methodology for the enantioselective intramolecular (Buchwald-Hartwig) amidation of prochiral dinitrogen malonamide derivatives has been developed in quantitative yield and good enantioselectivities. The best result was obtained based on an enantiopure (R)-MOP/Pd(OAc)₂ catalytst system with either Cs₂CO₃ or K₃PO₄ in refluxing THF affording the 4-methoxybenzyl substituted diamide derivative, 3-methyl-N, 1-bis(4-methoxbenzyl)-2-oxo-1,2,3,4-tetrahydroquinoline-3-carboxamide, in 99% yield and 75% enantiomeric excess. This example serves as a preliminary example of a desymmetrization of prochiral dinitrogen nucleophiles by preferential N-arylation. The intermolecular version of this reaction proved to be more challenging than its intramolecular counterpart and no coupling products were obtained. Other malonamide derivatives were prepared with a pendant bromovinyl substituent at the αposition and cyclized intramoleculary employing a mild Goldberg reaction to form 5-membered rings in good yield and unknown enantioselectivity.

Influence of Growing Medium on the Parameters and Yield Capacity of the Mini Tuber Potato of the Charoite Variety

The creation of original seed grains of the Charoite variety, healed of pathogenic infections of various etiologies, was carried out through reproduction of the certified meristematic material of the microplants class. Mini tubers microplants were grown in 5.5 liter vessels on a “Agrobalt S” soil (control) mixed with peat and supplemented with 10% and 20% (of the volume) of the “ORVI” substrate. The use of the substrate “ORVI” mixed with peat and “Agrobalt S” soil positively influenced the growth, development and formation of tubers. The appliance of 10% of the “ORVI” substrate significantly increased the quantitative yield of mini tubers by 17% and the weight of tubers by 12.3%. The increase in the total number of mini tubers was due to the increase in tuber fraction from 10 to 30 mm. The appliance of a 20% “ORVI” substrate also led to an increase in the total number and mass of mini tubers. According to the EIA results, the mini tubers grown from microplants did not contain any latent viral infection. Tests on the seeds did not reveal symptoms of fungal diseases. Keywords: breed, potatoes, mini tubers, mass of tubers, peat fertilizer, substrate

Synthesis of optically inactive cellulose via cationic ring-opening polymerization

Cellulose, which comprises D-glucose and L-glucose (D,L-cellulose), was synthesized from D-glucose (1D) and L-glucose (1L) via cationic ring-opening polymerization. Specifically, the ring-opening copolymerization of 3-O-benzyl-2,6-di-O-pivaloyl-β-D-glucopyranoside (2D) and 3-O-benzyl-2,6-di-O-pivaloyl-β-D-glucopyranoside (2L), synthesized from compounds 1D and 1L, respectively, in a 1:1 ratio, afforded 3-O-benzyl-2,6-di-O-β-D,L-glucopyranan (3DL) with a degree of polymerization (DPn) of 28.5 (Mw/Mn = 1.90) in quantitative yield. The deprotection of compound 3DL and subsequent acetylation proceeded smoothly to afford acetylated compound 4DL with a DPn of 18.6 (Mw/Mn = 2.08). The specific rotation of acetylated compound 4DL was + 0.01°, suggesting that acetylated compound 4DL was optically inactive cellulose triacetate. Furthermore, before acetylation, compound 4DL was an optically inactive cellulose comprising an almost racemic mixture of D-glucose and L-glucose. Compound 4DL was an amorphous polymer. This is the first reported synthesis of optically inactive D,L-cellulose.

Constructing a triangular metallacycle with salen-Al and its application to a catalytic cyanosilylation reaction

A triangular metallosalen-based metallacycle was constructed in quantitative yield by the self-assembly of a 180° bis(pyridyl) + salen-Al complex and a 60° diplatinum(II) acceptor in a 1:1 stoichiometric ratio. This...

Reversible PtII-CH3 deuteration without methane loss: metal-ligand cooperation vs ligand-assisted PtII-protonation

Di(2-pyridyl)ketone dimethylplatinum(II), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo complete deuteration of Pt-CH3 fragments in ~5 h without loss of methane to form (dpk)PtII(CD3)2 in virtually quantitative yield. The deuteration can...

Breaking thiacalix[4]arene into pieces – a novel synthetic approach to higher calixarenes bearing mixed (–S–, –CH2–) bridges

A novel approach is based on the cleavage of thiacalix[4]arene monosulfoxide with BuLi providing a linear tetramer in an essentially quantitative yield which is used as a building block for further cyclization.