Vapor–Liquid Equilibria of Nitrogen + Diethyl Ether and Nitrogen + 1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-3-pentanone by Experiment, Peng–Robinson and PC-SAFT Equations of State

The saturated liquid line of the systems nitrogen (N2) + diethyl ether and N2 + 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (Novec 649) is measured along three isotherms, that is, 390, 420, and 450 K and 360, 390, and 420 K, respectively. The employed gas solubility apparatus, based on the synthetic method, allows to measure points up to the critical region of these mixtures. The experimental data are used to correlate the Peng–Robinson and PC-SAFT equations of state (EOS). For the parametrization of the system, N2 + diethyl ether the Peng–Robinson EOS is combined with the Huron–Vidal mixing rule and the non-random two-liquid (NRTL) excess Gibbs energy model; for the system N2 + Novec 649 the quadratic mixing rule is used

Flexible synthesis of polyfunctionalised 3-fluoropyrroles

An efficient and selective approach for the synthesis of polyfunctionalised 3-fluoropyrroles has been developed starting from commercial aldehydes. The methodology is concise, efficient and allows for the modular and systematic assembly of polysubstituted 3-fluoropyrroles. This synthesis provides an alternative and highly convergent strategy for the generation of these chemically and biologically important units

Comparative study of medicinal plants on feeding behaviour of seven day old larvae of Tobacco caterpillar, Spodoptera litura (Fab.) and Bihar hairy caterpillar, Spilarctia obliqua (Walk.)

Eight medicinal plants viz., Sinduri, Bixa orellana (Bixaceae); Dalchini, Cinnamomum zelanicum (Lauraceae); Camphora, Cinnamomum camphora (Lauraceae); Gular, Ficus racemosa (Moraceae); Arjun, Terminalia arjuna (Combretaceae); Nagkesar, Messua ferrea (Calophyllaceae); Sarpgandha, Rauwolfia serpentina (Apocynaceae); Putranjeeva, Putranjeeva roxburghii (Euphorbiaceae) at 5% and 10 % concentrations were tested for the feeding against larvae of Spodoptera litura and Spilarctia obliqua. At 10% conc. C.camphora (hexane, diethyl ether, and acetone) was found extremely antifeedant against the larvae of both insects (S.litura and S.obliqua) while C.zeylanicum (hexane, diethyl ether, and acetone) and P.roxbughii (diethyl ether, and acetone), B.orellana (Acetone) showed extremely antifeedant activity only against the larvae of S.litura. At 5% concentration, the same plants were also effective against the larvae but their efficacy was less than at 10% concentration. The observation showed promising results with these plant extracts against the feeding and management of these two insect pests of agricultural importance

Identification and quantification of cannabinol as a biomarker for local hemp retting in an ancient sedimentary record by HPTLC-ESI-MS

Cannabis products have been used in various fields of everyday life for many centuries, and applications in folk medicine and textile production have been well-known for many centuries. For traditional textile production, hemp fibers were extracted from the stems by water retting in stagnant or slow-moving waters. During this procedure, parts of the plant material‚ among them phytocannabinoids‚ are released into the water. Cannabinol (CBN) is an important degradation product of the predominant phytocannabinoids found in Cannabis species. Thus, it is an excellent indicator for present as well as ancient hemp water retting. In this study, we developed and validated a simple and fast method for the determination of CBN in sediment samples using high-performance thin-layer chromatography (HPTLC) combined with electrospray ionization mass spectrometry (ESI-MS), thereby testing different extraction and cleanup procedures‚ as well as various sorbents and solvents for planar chromatography. This method shows a satisfactory overall analytical performance with an average recovery rate of 73%. Our protocol enabled qualitative and quantitative analyses of CBN in samples of a bottom sediment core‚ having been obtained from a small lake in Northern India, where intense local retting of hemp was suggested in the past. The analyses showed a maximum CBN content in pollen zone 4 covering a depth range of 262–209 cm, dating from approximately 480 BCE to 1050 CE. These findings correlate with existing records of Cannabis-type pollen. Thus, the method we propose is a helpful tool to track ancient hemp retting activities

Highly-functionalised difluorinated cyclohexane polyols via the Diels–Alder reaction : regiochemical control via the phenylsulfonyl group

A difluorinated dienophile underwent cycloaddition reactions with a range of furans to afford cycloadducts whichcould be processed regio- and stereoselectively via episulfonium ions, generated by the reaction between their alkenyl groups and phenylsulfenyl chloride. The oxabicyclic products were oxidised to the phenylsulfonyl level and ring opened via E1CB or reductive desulfonative pathways to afford, ultimately, difluorinated cyclohexene or cyclohexane polyols

Synthesis of Highly Stable 1,3-Diaryl-1H-1,2,3-triazol-5-ylidenes and Their Applications in Ruthenium-Catalyzed Olefin Metathesis

The formal cycloaddition between 1,3-diaza-2-azoniaallene salts and alkynes or alkyne equivalents provides an efficient synthesis of 1,3-diaryl-1H-1,2,3-triazolium salts, the direct precursors of 1,2,3-triazol-5-ylidenes. These N,N-diarylated mesoionic carbenes (MICs) exhibit enhanced stability in comparison to their alkylated counterparts. Experimental and computational results confirm that these MICs act as strongly electron-donating ligands. Their increased stability allows for the preparation of ruthenium olefin metathesis catalysts that are efficient in both ring-opening and ring-closing reactions

Stereoselective synthesis of hydroxylated 3-aminoazepanes using a multi-bond forming, three-step tandem process

A multi-bond forming, three-step tandem process involving a palladium(II)-catalysed Overman rearrangement and a ring closing metathesis reaction has been utilised for the efficient synthesis of a 2,3,6,7-tetrahydro-3-amidoazepine. Substrate directed epoxidation or dihydroxylation of this synthetic intermediate has allowed the diastereoselective synthesis of hydroxylated 3-aminoazepanes including the syn-diastereomer of the balanol core. Asymmetric synthesis of the 2,3,6,7-tetrahydro-3-amidoazepine motif was also achieved using a chiral palladium(II)-catalyst during the Overman rearrangement

1-(Trifluoromethyl)vinyllithium

InChI = 1S/C3H2F3.Li/c1-2-3(4,5)6;/h1H2; InChIKey = YDBNXCHLLXTABG-UHFFFAOYSA-N (reagent used as a versatile vinylation component) Physical Data: thermally unstable; decomposes quickly at temperatures above −78 °C. Solubility: soluble in diethyl ether, pentane, and THF. Form Supplied in: not available commercially. Preparative Method: prepared from the reaction of commercially available 2-bromo-3,3,3-trifluoropropene with n-, sec-, or tert-butyllithium in diethyl ether at −100 to −110 °C. Handling, Storage, and Precautions: prepared and transferred at low temperature (≤ −100 °C) under inert atmosphere (Ar); air and moisture sensitive; handle in fume hood

Synthesis and Characterization of Three-Coordinate Ni(III)-Imide Complexes

A new family of low-coordinate nickel imides supported by 1,2-bis(di-tert-butylphosphino)ethane was synthesized. Oxidation of nickel(II) complexes led to the formation of both aryl- and alkyl-substituted nickel(III)-imides, and examples of both types have been isolated and fully characterized. The aryl substituent that proved most useful in stabilizing the Ni(III)-imide moiety was the bulky 2,6-dimesitylphenyl. The two Ni(III)-imide compounds showed different variable-temperature magnetic properties but analogous EPR spectra at low temperatures. To account for this discrepancy, a low-spin/high-spin equilibrium was proposed to take place for the alkyl-substituted Ni(III)-imide complex. This proposal was supported by DFT calculations. DFT calculations also indicated that the unpaired electron is mostly localized on the imide nitrogen for the Ni(III) complexes. The results of reactions carried out in the presence of hydrogen donors supported the findings from DFT calculations that the adamantyl substituent was a significantly more reactive hydrogen-atom abstractor. Interestingly, the steric properties of the 2,6-dimesitylphenyl substituent are important not only in protecting the Ni═N core but also in favoring one rotamer of the resulting Ni(III)-imide, by locking the phenyl ring in a perpendicular orientation with respect to the NiPP plane