Mechanosynthesis of YIG and GdIG: A Structural and Mössbauer Study

We have investigated the mechanosynthesis of gadolinium and yttrium iron garnets by high-energy ball-milling of α-Fe₂O₃ and Gd₂O₃ or α-Fe₂O₃ and Y₂O₃, respectively, followed by short thermal annealings conducted at moderate temperatures. The samples were characterized by X-ray diffraction and Mössbauer spectroscopy, in order to determine the influence of the milling time and annealing conditions on the final products. For as-milled samples of each rare-earth system, the results revealed the formation of perovskite phases, in relative amounts that depend on the milling time. The formation of garnet phases was observed in as-annealed samples treated at 1000°C for 2 h or 1100°C for 3 h, i.e., at very modest annealing requirements when compared with ordinary solid-state-reaction processes performed without previous high-energy milling. Also, the occurrence was verified of a milling time for which the relative amount of garnet phases formed by annealing was maximized. This time depends on the rare-earth composing the garnet phase and on the annealing temperature.     

A convenient two-step synthesis of 6-methylenesubstituted-4-trichloromethyl-2-methylsulfanyl pyrimidines

This work reports a two-step synthetic strategy to obtain a series of 6-methylenesubstituted-4-trichloromethyl-2-methylsulfanylpyrimidines from the cyclization of 5-bromo-4-methoxy-1,1,1-trichloro-pent-3-en-2-ones with 2-methyl-2-pseudothiourea sulfate, followed by nucleophilic substitution of 6-bromomethyl-4-trichloromethyl-2-methylsulfanylpyrimidine with a series of nucleophiles. Alternative strategies to obtain 6-halomethyl-4-trichloro[fluoro]methyl-2-methylsulfanyl pyrimidines have been addressed.     

Synthesis of 4‐(trihalomethyl)dipyrimidin‐2‐ylamines from β‐alkoxy‐α,β‐unsaturated trihalomethyl ketones

The synthesis of a novel series of twelve 4‐(trihalomethyl)dipyrimidin‐2‐ylamines, from the cyclo‐condensation reaction of 4‐(trichloromethyl)‐2‐guanidinopyrimidine, with β‐alkoxyvinyl trihalomethyl ketones, of general formula: X₃C‐C(O)‐C(R²)=C(R¹)‐OR, where: X = F, Cl; R = Me, Et, ‐(CH₂)₂‐, ‐(CH₂)₃‐; R¹ = H, Me; R² = H, Me, ‐(CH₂)₂‐, ‐(CH₂)₃‐, is reported. The reactions were carried out in acetonitrile under reflux for 16 hours, leading to the dipyrimidin‐2‐ylamines in 65‐90% yield. Depending on the substituents of the vinyl ketone, tetrahydropyrimidines or aromatic pyrimidine rings were obtained from the cyclization reaction. When X = Cl, elimination of the trichloromethyl group was observed during the cyclization step. The structure of 4‐(trihalomethyl)dipyrimidin‐2‐ylamines was studied in detail by ¹H‐, ¹³C‐ and 2D‐nmr spectroscopy.     

A Convenient Method to Obtain 4,5-Dihydro-1H-Methylpyrazoles by A Ring Transformation Reaction

A convenient method for the synthesis of alkyl[aryl]-substituted 5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-methylpyrazole (2) from a new ring transformation reaction of alkyl[aryl]-substituted-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-pyrazolethiocarboxyamide (1) with methylhydrazine in THF, and the thermal dehydration of 2, are reported.     

Brominated Trihalomethylenones as Versatile Precursors to 3‐Ethoxy, ‐Formyl, ‐Azidomethyl, ‐Triazolyl,and 3‐Aminomethyl Pyrazoles

5‐Bromo[5,5‐dibromo]‐1,1,1‐trihalo‐4‐methoxy‐3‐penten[hexen]‐2‐ones are explored as precursors to the synthesis of 3‐ethoxymethyl‐5‐trifluoromethyl‐1H‐pyrazoles from a cyclocondensation reaction with hydrazine monohydrate in ethanol. 3‐Ethoxymethyl‐carboxyethyl ester pyrazoles were formed as a result of a substitution reaction of bromine and chlorine by ethanol. The dibrominated precursor furnished 3‐acetal‐pyrazole that was easily hydrolyzed to formyl group. In addition, brominated precursors were used in a nucleophilic substitution reaction with sodium azide to synthesize the 3‐azidomethyl‐5‐ethoxycarbonyl‐1H‐pyrazole from the reaction with hydrazine monohydrate. These products were submitted to a cycloaddition reaction with phenyl acetylene furnishing the 3‐[4(5)‐phenyl‐1,2,3‐triazolyl]5‐ ethoxycarbonyl‐1H‐pyrazoles and to reduction conditions resulting in 3‐aminomethyl‐1H‐pyrazole‐5‐carboxyethyl ester. The products were obtained by a simple methodology and in moderate to good yields.     

The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

1‐n‐Butyl‐2,3‐dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2‐Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl₃ and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D₂O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.     

4-Trichloroacetyl-1,2,3-triazoles: A versatile building block for rapid assessment of carbohydrazides and rufinamide derivatives

This work reports the synthesis of a series of (1H-1,2,3-triazol-4-yl)carbohydrazides (2), which were obtained from 4-trichloroacetyl-1H-1,2,3-triazoles (1). Triazoles 1 were synthesized by 1,3-dipolar cycloaddition reaction, starting from 4-alkoxy-1,1,1-trichloroalk-3-en-2-ones and benzyl azides and easily (15 min) converted to 2 by reaction with hydrazine hydrate (73–82% yield). Carbohydrazides 2 proved to be a versatile building block for constructing a series of fluorinated heterocycles analogous to rufinamide, i.e., 1H-1,2,3-triazol-4-yl-1,3,4-oxadiazoles, a pyrrole derivative, and a 2-pyrazoline, through [4+1]–, [1+4]–, and [3+2]–cyclocondensation reactions, respectively. Finally, and according to the Lipinski’s rule of five, 2,6-difluorobenzylated 1,2,3-triazoles can be considered as potential candidates for further biological activity assays.     

New,simple, and efficient method for the synthesis of N-substituted 4-trifluoromethyl-5-(alkan-1-ol)-pyridin-2(1H)-imines

A new, simple, and efficient method for the synthesis a novel series of 1-substituted 4-(trifluoromethyl)-5-(alkan-1-ol)-pyridin-2(1H)-imines from the reaction of 3-(5,6-dihydro-4H-pyran-3-yl)-4,4,4-trifluorobut-2-enenitrile and 3-(4,5-dihydrofuran-3-yl)-4,4,4-trifluorobut-2-enenitrile with primary amines – is described. The products were obtained in 29–82% yield.