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Mono-N-methylation of functionalized anilines with alkyl methyl carbonates over NaY faujasites. 4. Kinetics and selectivity

(Chemical Equation Presented) In the presence of NaY faujasite as the catalyst, the reaction of bifunctional anilines (1-4: XC6H 4-NH2; X = OH, CO2H, CH2OH, and CONH2) with methyl alkyl carbonates [MeOCO2R?: R? = Me or MeO(CH2)2O(CH2)2] proceeds with a very high mono-N-methyl selectivity (XC6H 4NHMe up to 99%), and chemoselectivity as well, with other nucleophilic functions (OH, CO2H, CH2OH, CONH2) fully preserved from alkylation and/or transesterification reactions. Aromatic substituents, however, modify the relative reactivity of amines 1-4: good evidence suggests that, not only steric and electronic effects, but, importantly, direct acid-base interactions between substituents and the catalyst are involved. Weakly acidic groups (OH, CH2OH, CONH2, pKa ? 10) may help the reaction, while aminobenzoic acids (pK a of 4-5) are the least reactive substrates. The solvent polarity also affects the reaction, which is faster in xylene than in the more polar diglyme. The mono-N-methyl selectivity is explained by the adsorption pattern of reagents within the zeolite pores: a BAl2 displacement of the amine on methyl alkyl carbonate should occur aided by the geometric features of the NaY supercavities. Different factors account for the reaction chemoselectivity. Evidence proves that the polarizability of the two nucleophilic terms (NH 2 and X groups) of anilines is relevant, although adsorption and confinement phenomena of reagents promoted by the zeolite should also be considered.

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Isoxazole – Wikipedia,
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Formation of Phenyliodonio-Substituted Spirofurooxindole Trifluoroacetates from N-Substituted 3-Oxopentanediamides via Phenyliodine Bis(trifluoroacetate)-Mediated Oxidative Cascade Reactions

The reaction of N-substituted 3-oxopentanediamides with phenyliodine bis(trifluoroacetate) (PIFA) was found to give a novel class of phenyliodonio-substituted spirofurooxindole trifluoroacetates under metal-free conditions. The reaction is postulated to proceed via a cascade process involving an oxidative C?O bond formation, an oxidative C?C bond formation and a final iodination step. (Figure presented.).

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Properties and Exciting Facts About 5-(4-Hydroxyphenyl)isoxazole-3-carboxylic acid

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Palladium-catalyzed amination of 2,3,3-trifluoroallyl esters: Synthesis of trifluoromethylenamines via an intramolecular fluorine shift and CF3 group construction

The palladium-catalyzed reaction of 2,3,3-trifluoroallyl esters with several types of amines afforded trifluoromethylenamines, which were formed by the addition of a nitrogen nucleophile at the C-2 position and the intramolecular construction of the trifluoromethyl group via the fluorine atom shift from the C-2 to the C-3 position.

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Desulfurization of thioureas, benzimidazoline-2-thiones and 1,3-dihydro-1,3-diaryl-2-thioxopyrimidine-4,6(2H,5H)-diones with nickel boride at ambient temperature

Nickel boride is reported to bring about desulfurization and reductive cleavage of N,N?-diarylthioureas to give corresponding anilines andN-methylanilines while N,N?-dialkylthioureas have been observed to undergo desulfurization to give formamidines; benzimidazoline-2-thiones are reported to undergo desulfurization to benzimidazoles and 1,3-dihydro-1,3-diaryl-2-thioxopyrimidine-4,6(2H,5H)-diones have been observed to yield corresponding hexahydropyrimidine-4,6-diones in high yields in dry methanol at ambient temperature.

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Tunable Visible and Near Infrared Photoswitches

A class of tunable visible and near-infrared donor-acceptor Stenhouse adduct (DASA) photoswitches were efficiently synthesized in two to four steps from commercially available starting materials with minimal purification. Using either Meldrum’s or barbituric acid “acceptors” in combination with aniline-based “donors”, an absorption range spanning from 450 to 750 nm is obtained. Additionally, photoisomerization results in complete decoloration for all adducts, yielding fully transparent, colorless solutions and films. Detailed investigations using density functional theory, nuclear magnetic resonance, and visible absorption spectroscopies provide valuable insight into the unique structure-property relationships for this novel class of photoswitches. As a final demonstration, selective photochromism is accomplished in a variety of solvents and polymer matrices, a significant advantage for applications of this new generation of DASAs.

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METHOD OF TREATING NON-SMALL CELL LUNG CANCER

A method of treating non-small cell lung cancer (NSCLC), and especially NSCLC that has metastasized to brain is disclosed.

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Isoxazole – Wikipedia,
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A facile method for the stereoselective preparation of (1E,3E)-4-substituted-1-amino-1,3-dienes via 1,4-elimination

The 1,4-elimination reaction of 1-amino-4-methoxy-(2Z)-alkenes is shown to proceed with high (1E,3E)-stereoselectivities to afford the corresponding 4-substituted-1-amino-1,3-dienes in good yield. The scope and stereochemical features of the synthetic method are described.

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Erythrosine B Catalyzed Visible-Light Photoredox Arylation?Cyclization of N-Alkyl-N-aryl-2-(trifluoromethyl)acrylamides to 3-(Trifluoromethyl)indolin-2-one Derivatives

3-Trifluoromethylindoline-2-one derivatives were prepared in a visible-light photocatalytic transformation of acrylamides. The arylation?cyclization sequence was initiated by light-induced aryl radical generation from aryldiazonium salts with the utilization of erythrosine B as an organic photocatalyst.

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Isoxazole – Wikipedia,
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The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles

A mild and efficient method for the synthesis of cyanoformamides from N,N-disubstituted aminomalononitriles with CsF as the promoter has been developed. This method features a wide substrate scope and high reaction efficiency, and will facilitate corresponding cyanoformamide-based biological studies and synthetic methodology development.

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Isoxazole – Wikipedia,
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Ru-Catalyzed Switchable N-Hydroxyethylation and N-Acetonylation with Crude Glycerol

Highly efficient Ru-catalyzed selective C?C or C?O bond cleavage of polyols (e.g., crude glycerol) for N-hydroxyethylation or N-acetonylation of amines was achieved through the hydrogen-borrowing approach. A variety of amines were transformed to the desired amino alcohols/ketones in moderate-to-excellent yields, opening up new avenues for generation of oxygenated pharmaceuticals and fine chemicals from renewable raw materials. The use of new redox-active catalysts containing bisphosphine/thienylmethylamine ligands allows this hydrogen-borrowing system to be operated selectively under both basic and acidic conditions.

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Isoxazole – Wikipedia,
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