Efficient Method for Aromatic‐Aldehyde Oxidation by Cleavage of Their Hydrazones Catalysed by Trimethylsilanolate

Bürglová, Kristýna; Окороченков, С. А.; Budêšínský, Miloś; Hlaváč, Jan

doi:10.1002/ejoc.201601238

Cited by 8 publications

(4 citation statements)

References 34 publications

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“…Higher temperatures produced a mixture of products assigned to oxidation of the perylene ring. The formylation-oxidation method is straightforward when compared to methods previously reported for the synthesis of 6 , including the reaction of 5 with phenyl hydrazine followed by reaction with potassium trimethylsilanolate, or oxidative esterification of 5 in the presence of a catalyst . Our initial approach to 6 by metal-halogen exchange of 4 with t -BuLi, followed by carboxylation (Table , entry 4), however, was unsuccessful, producing mixtures of 3 and unreacted 4 , whereas the same procedure with 1-bromonaphthalene yields readily 1-naphthoic acid.…”

Section: Resultsmentioning

confidence: 96%

Synthesis and Properties of Perylene-Bridge-Anchor Chromophoric Compounds

et al. 2020

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The quest to control chromophore/semiconductor properties to enable new technologies in energy and information science requires detailed understanding of charge carrier dynamics at the atomistic level, which can often be attained through the use of model systems. Perylene-bridge-anchor compounds are successful models for studying fundamental charge transfer processes on TiO 2 , which remains among the most commonly investigated and technologically important interfaces, mostly because of perylene's advantageous electronic and optical properties. Nonetheless, the ability to fully exploit synthetically the substitution pattern of perylene with linker (= bridge-anchor) units remains little explored. Here we developed 2,5-di-tertbutylperylene (DtBuPe)-bridge-anchor compounds with t-Bu group substituents to prevent π-stacking and one or two linker units in both the peri and ortho positions, by employing a combination of Friedel−Crafts alkylations, bromination, iridium-catalyzed borylation, and palladium-catalyzed cross-coupling reactions. Photophysical characterization and computational analysis by density functional theory (DFT) and time-dependent DFT (TD-DFT) were carried out on four DtBuPe acrylic acid derivatives with a single or a double linker in peri (12b), ortho (15b), peri,peri (18b), and ortho,ortho (21b). The energies of the unoccupied orbitals {LUMO, LUMO + 1, LUMO + 2} are strongly affected by the presence of a π-conjugated linker, resulting in a stabilization of these states and a red shift of their absorption and emission spectra, as well as the loss of vibronic structure in the spectrum of the peri,peri compound, consistent with the strong bonding character of this substitution pattern.

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Section: Resultsmentioning

confidence: 96%

Synthesis and Properties of Perylene-Bridge-Anchor Chromophoric Compounds

et al. 2020

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“…In a subsequent study, we demonstrated a more detailed substrate scope and a possible mechanism for this reaction, wherein we described the TMSOK-induced oxidation of the aldehyde moiety via formation of their hydrazones and the release of carboxylic acids (Scheme 26). 61 The study was performed both on solid support and in solution, hence offering a new possibility for very mild aldehyde oxidation.…”

Section: Scheme 25 Tmsok As a Hydrazone Cleavage Reagent In Solid-phamentioning

confidence: 99%

Application of Trimethylsilanolate Alkali Salts in Organic Synthesis

Bürglová

Hlaváč

2018

Synthesis

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Trimethylsilanolate alkali salts are widely used in organic synthesis, mainly due to their solubility in common organic solvents. They are frequently used as nucleophiles in ester hydrolysis, both in solution and solid-phase chemistry. However, they have also been used as mild bases or as specific reagents in some chemical transformations. Reactions employing trimethylsilanolate alkali salts as the key component are typically performed under mild reaction conditions. This review summarizes the utilization of trimethylsilanolate alkali salts in various organic transformations.1 Introduction2 Properties of Alkali Metal Trimethylsilanolates (TMSO[M])3 Trimethylsilanolate Alkali Salts in Organic Synthesis4 Conclusion

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“…The title compound is known 26 and was prepared according to general (E)-1-Benzylidene-2-phenylhydrazine (6i). The title compound is known 27 and was prepared according to general procedure 1 using benzaldehyde and phenylhydrazine (0.33 g, 83% yield): (E)-Benzaldehyde Oxime (6j). The title compound is known 28 and was prepared according to general procedure 1 using benzaldehyde and hydroxylamine (0.21 g, 85% yield): 1 H NMR (400 MHz, CDCl 3 ) δ (ppm) 9.22 (s, 1H, OH), 8.22 (s, 1H, CH), 7.62−7.59 (m, 2H, ArH), 7.49−7.40 (m, 3H, ArH).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The title compound is known and was prepared according to general procedure 1 using benzaldehyde and phenylhydrazine (0.33 g, 83% yield): 1 H NMR (400 MHz, CDCl 3 ) δ (ppm) 7.68–7.65 (m, 3H, ArH+CH), 7.39–7.35 (m, 2H, ArH), 7.31–7.25 (m, 4H, ArH), 7.13–7.11 (m, 2H, ArH+NH), 6.89–6.85 (m, 1H, ArH).…”

Section: Experimental Sectionmentioning

confidence: 99%

Transition-Metal-Free Trifluoromethylation of Aldehyde Derivatives with Sodium Trifluoromethanesulfinate

Tan

Zhang

et al. 2017

J. Org. Chem.

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A metal-free and cost-effective synthetic protocol for the trifluoromethylation of N,N-disubstituted hydrazones with Langlois's reagent (CFSONa) to afford the corresponding functionalized trifluoromethyl ketone hydrazones has been established. It is proposed that a radical/SET mechanism proceeding via a trifluoroalkyl radical may be involved in the reaction. Applications of the methodology in industry will be found and the development of new methods for trifluoromethylation with Langlois's reagent will be continued in our laboratory.

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Efficient Method for Aromatic‐Aldehyde Oxidation by Cleavage of Their Hydrazones Catalysed by Trimethylsilanolate

Cited by 8 publications

References 34 publications

Synthesis and Properties of Perylene-Bridge-Anchor Chromophoric Compounds

Synthesis and Properties of Perylene-Bridge-Anchor Chromophoric Compounds

Application of Trimethylsilanolate Alkali Salts in Organic Synthesis

Transition-Metal-Free Trifluoromethylation of Aldehyde Derivatives with Sodium Trifluoromethanesulfinate

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