An Improved and Plant Viable Synthesis of Vitamin K1

An improved and simplified process of vitamin K1 preparation. The article confers the new reagent BF3. Acetic acid complex as a condensation reagent for phytol with compound III in vitamin K1 synthesis, which eludes the use of ethereal reagent and make the process hazard free. Further innovation presents base catalyzed synthesis of vitamin K1 which is an oxidative product of compound IV. Sodium methoxide base is used in synthesis which eliminates use of metal oxidant, costly and hazardous reagent. The new approach ensures the non-generation of epoxide impurity (V) which tends to form during Ag2O catalyzed synthesis. Finally, article also focused on formation and conformation of 7R and 11R diastereomeric centers and ensure the formation of vitamin k1 with desired stereochemistry also article submit proof of concept and supporting literature survey for desired stereochemistry.

Asymmetric Aldol Reaction of Alkenyl Esters with α-Ketoesters Catalyzed by Chiral Tin Alkoxides

A catalytic enantioselective aldol reaction of alkenyl esters with α-ketoesters was achieved using an (R)-BINOL-derived chiral tin dibromide possessing a 4-t-butylphenyl group at 3- and 3’-positions as the chiral precatalyst in the presence of sodium methoxide and methanol. Optically active aldol products possessing a chiral tertiary carbon with up to 92% ee were diastereoselectively obtained in moderate to high yields not only from cyclic alkenyl esters but also from acyclic ones under the influence of the in situ generated chiral tin methoxide.

Synthesis of thiophenylazolyl pyrrolylsulfamoyl acetamides as potential antimicrobial agents

A variety of thiophenylazolyl pyrrolylsulfamoyl acetamides were prepared by the reaction of azolylsulfamoyl acetate with pyrrolylamine in the presence of sodium methoxide in methanol under ultrasonication. Chloro, nitro and dinitro substituted thiophenylthiazolyl pyrrolylsulfamoyl acetamides (9d, 9e, 9f) and dinitro substituted thiophenylimidazolyl pyrrolylsulfamoyl acetamide (10f) exhibited potential antibacterial activity against B. subtilis. The compound 9f also displayed prominent antibacterial activity against S. aureus. The compounds 9f, chloro and nitro substituted thiophenylimidazolyl pyrrolylsulfamoyl acetamide (10d, 10e) and 10f exhibited prominent antifungal activity against A.niger.

Benzofuran-oxadiazole hybrids: Design, Synthesis and antimicrobial activity studies

The six benzofuran-oxadiazole derivatives (4a-d) and (5a-b) have been designed, synthesized, characterized and evaluated for antimicrobial activity. The key synthetic intermediate 5-bromo-N'-hydroxybenzofuran -2-carboxamidine (3) was prepared from 5-bromobenzofuran-2-carboxylic acid (1) in two consecutive steps involving reaction with NaN3, in presence of TEA, Xtalfluor-E, PPh3 in dry DCM at 0oC followed by the treatment of resulting carbonitrile (2) with hydroxylamine hydrochloride in presence of sodium methoxide under reflux in aqueous ethanol. Reaction of carboxamidine (3) with different aryl esters in presence of K2CO3 under reflux conditions in toluene afforded 3-(5-bromobenzofuran-2-yl)-5-substituted phenyl-1,2,4-oxadiazoles (4a-d) while the refluxion of a solution of carboxamidine (3) in dichloromethane with chloro/bromo acetyl chloride in presence of TEA and a catalytic amount of HBTU furnished 3-(5-bromobenzofuran-2-yl)-5-(chloromethyl)-1,2,4-oxadia zole (5a) and 3-(5-bromobenzofuran-2-yl)-5-(bromomethyl)-1,2,4-oxadiazole (5b).

Synthesis of macro-RAFT agent containing M13-10 and its application in surface sizing agent

A novel macro-RAFT emulsifier was synthesized with S, S’-bis(α, α’-dimethyl-α”-acetic acid)-trithiocarbonate (BDATT), M13-10 (self-made emulsifier) and acrylate monomer, which was further used to prepare surface sizing agent. On the other hand, M13-10 was synthesized with iso-tridecanol polyoxyethylene ether, sodium methoxide and sulfamic acid as the starting materials. The hydrophilicity of macro-RAFT emulsifier and the performance of surface sizing agent were affected by BDATT used as the chain transfer agent and M13-10 as the hydrophilic monomer. So, the CMC and HLB of the emulsifier prepared with different M13-10 content and BDATT content, were compared, as well as the particle size of the prepared surface sizing agent, and the cobb, bursting resistance, tensile resistance, folding endurance and roughness of paper sized. The results reveal that surface sizing agent with macro-RAFT emulsifier of which the amount of M13-10 is 7 w% and the amount of BDATT is 2.5 w% demonstrates the best sizing effect on paper with the contact angle of 119°, the surface water absorption (cobb) of 48.8 g/m2, the bursting strength of 285 kPa, the folding endurance of 19 and the tensile strength of 59.6 kN/m.

Palladium carbene complexes – efficient catalysts for hydrodehalogenation of haloarenes

The work is aimed at solving the problem of neutralization of persistent organic pollutants by catalytic methods. In order to identify the relationship between electronic and steric factors of carbenes with catalytic efficiency in the reaction of hydrodehalogenation of haloarenes, the parameters for estimating the ligand influences are proposed (electronic - Ie indices, Ph philicities, ED electron donicities, and EA electron acceptabilities, steric - dimerization energies) using theoretical methods (DFT, B3LYP5, RHF). Synthesis of new heteroaromatic carbenes of the series of sterically shielded 1,3-diarylphenanthro-[9,10-d]imidazol-2-ylidene, 1,3-diaryl-2-methy­lene­phenan­thro-[9,10-d]imidazoline, tetrahydropyrimidin-2-ylidene, 1,3-diaryl­imidazol-2-ylidene, 1,3,4-triaryl-1,2,4-triazol-5-ylidenes, their carbene complexes with palladium iodide, as well as the carbene complex of the superbasic anionic carbene 1,3-bis-(4-oxidophenyl)-imidazol-2-ylidene with nickel(II) ion. 1H and 13C NMR spectroscopy, mass spectrometry and X-ray diffraction study methods were used to establish the structures of the synthesized compounds. A high catalytic effect of a number of sterically shielded carbene complexes (2.4b, 3.5, 4.6a) in the reaction of hydrodehalogenation of p-dichlorobenzene haloarenes with sodium methoxide in isopropanol at 80 °С (TON 98000–110000) was revealed that can be applied to solve the problem of neutralization of persistent organic pollutants. The efficiency of catalysis by sterically open compounds 4.6b and 6.7 appeared to be low (TON 74, 128). The high catalytic effect of sterically shielded compounds is explained by the increased stability of the complexes under the conditions of an alkaline medium caused by metal alkoxides.