30752-18-2Relevant academic research and scientific papers
Method for decarboxylation and in-situ methylation of alkyl active carboxylic ester
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Paragraph 0047-0054; 0123-0129; 0203, (2020/06/20)
The invention relates to a method for decarboxylation and in-situ methylation of alkyl active carboxylic ester. The method comprises the following step: in the presence of a cobalt catalyst, a phosphine ligand and an organic solvent, reacting alkyl active carboxylic ester with a trimethyl aluminum reagent to obtain a target methylated product. According to the provided method, trimethyl aluminum is used as a methylation reagent, so that a series of important secondary carbon and tertiary carbon centers are commercially and conveniently constructed successfully; the used carboxylate substrate is rich in source and simple to synthesize; compared with a traditional synthesis method reported before, the method avoids the use of a noble metal catalyst, and meets the requirements of green environment-friendly chemistry; the functional group compatibility is wide, the method is successfully applied to gram-scale reaction, the conversion rate is high, and the method has an important syntheticchemical value.
Cobalt-Catalyzed Decarboxylative Methylation and Ethylation of Aliphatic N-(Acyloxy)phthalimides with Organoaluminum Reagents
Wang, Ze-Zhong,Wang, Guang-Zu,Zhao, Bin,Shang, Rui,Fu, Yao
supporting information, p. 1221 - 1225 (2020/08/17)
A cobalt-catalyzed decarboxylative methylation of aliphatic redox-active esters [ N-(acyloxy)phthalimides; RAEs] with trimethylaluminum under mild conditions was developed, providing a method for transforming a carboxylate group into a methyl group without redox fluctuation. Primary and secondary RAEs were both amenable substrates, whereas a tertiary RAE delivered an elimination product. Triethylaluminum was also used to deliver a decarboxylative ethylation product.
Thermotropic MIDA Boronates as a Case Study for the Role of Dipolar Interactions in Liquid Crystalline Self-Assembly
W?hrle, Tobias,Gündemir, Rafet,Frey, Wolfgang,Knecht, Friederike,K?hn, Andreas,Laschat, Sabine
supporting information, p. 4149 - 4159 (2017/03/31)
A series of MIDA (N-methylimino diacetic acid) boronates carrying 4-alkoxy, 3,4-bisalkoxy, or 3,4,5-trisalkoxyphenyl substituents were synthesized and their mesomorphic properties characterized by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD) techniques such as small- and wide-angle X-ray scattering (SAXS and WAXS, respectively). Most derivatives were liquid crystalline. In the case of mono- and bisalkoxy-substituted derivatives, C6 chains already induced smectic A (SmA) mesophases despite the bulky MIDA head group. With increasing chain length, columnar hexagonal (Colh) phases replaced SmA phases in the disubstituted series. Quantum chemical calculations on a series of MIDA boronates show that the B?N bond is a dative bond with a positive charge on the boron atom and negative charges on the nitrogen and oxygen atoms. In addition, no π-interaction between the aryl moiety and B?N bond was found, thus the mesogenic unit is electronically decoupled from the MIDA head group. These theoretical findings were supported by IR and Raman spectra as well as by asingle crystal structure analysis of 4-ethoxyphenyl MIDA boronate. Calculations of the electrostatic potential of the MIDA boronate reveal a special polarity pattern that can support the formation of a two-dimensional network and is likely to explain the liquid crystalline self-assembly. The absence of any electronic cross-talk between the MIDA head group and B-aryl or B-alkyl substituents allows the efficient tailoring of the mesophase type through variation of the substituents.
Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
Stridfeldt, Elin,Lindstedt, Erik,Reitti, Marcus,Blid, Jan,Norrby, Per-Ola,Olofsson, Berit
supporting information, p. 13249 - 13258 (2017/09/12)
A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by-product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4-coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron-deficient diaryliodonium salts.
Novel biphenyl-3-carboxamide derivatives or salt thereof and pharmaceutical composition for treating or preventing autoimmune diseases comprising the same
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Paragraph 0121; 0123-0126; 0150-0153, (2021/10/21)
The present invention refers to novel biphenyl-3-carboxamide amide derivatives or a salt thereof and a self effect because of having immunosuppressive effect and the treatment of auto-immune diseases in relates to pharmaceutical compositions for the treat
CYCLOHEXADIENE FULLERENE DERIVATIVES
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Page/Page column 78; 79; 85, (2015/03/28)
The invention relates to novel fullerene derivatives, to methods for their preparation and educts or intermediates used therein, to mixtures and formulations containing them, to the use of the fullerene derivatives, mixtures and formulations as organic semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising, or being prepared from, these fullerene derivatives, mixtures or formulations.
Synthesis and Characterization of a New Series of Paramagnetic Ferroelectric Liquid Crystalline Nitroxide Radicals
Uchida, Yoshiaki,Tamura, Rui,Suzuki, Katsuaki,Takahashi, Hiroki,Aoki, Yoshio,Nohira, Hiroyuki
, p. 89 - 106 (2015/09/01)
A new series of all-organic liquid-crystalline (LC) chiral radical compounds,trans-1-alkoxyphenyl-4-[(4-(4-alkoxyphenyl)-2,5-dimethylpyrrolidine-1-oxy-2-yl)-benzylideneamino]benzenes (1) with various alkyl chains, containing a chiral nitroxide unit in the mesogen core were synthesized and their LC properties were fully characterized. The enantiomerically enriched compounds (2S,5S)-1 showed N, TGBA, SmA and SmC phases, while the racemates (±)-1 exhibited N, SmA and SmC phases. The phase transition behavior and the ferroelectric properties of the SmC phase of (2S,5S)-1 differed from those of previously reported analogues with an ester group as a substitute for the imino group of (2S,5S)-1. Some of the (2S,5S)-1 series showed a temperature-dependent spontaneous polarization PS (θ) inversion. We discuss the origin of this difference in terms of their molecular structures optimized by molecular orbital calculations. The phase transition behavior supports the hypothesis that the large φ, which is defined as the angle between the molecular long axis (one of the principal axes of inertia) and the direction of the dipole moment in each molecule, results in the stabilization of the SmA (SmA) phase.
Copper-catalyzed reduction of alkyl triflates and iodides: An efficient method for the deoxygenation of primary and secondary alcohols
Dang, Hester,Cox, Nick,Lalic, Gojko
supporting information, p. 752 - 756 (2014/01/23)
We describe an effective method for catalytic reduction of 1°alkyl sulfonates, and 1°and 2°iodides in the presence of a wide range of functional groups. This Cu-catalyzed reaction provides a means for the effective deoxygenation of alcohols, as demonstrated by the highly selective reduction of 1°alcohols using a triflation/reduction sequence. A preliminary study of the reaction mechanism suggests that the reduction does not involve free-radical intermediates. Primarily reduced: The copper-catalyzed reduction of 1°alkyl sulfonates, and 1°and 2°iodides, which is effective in the presence of a wide range of functional groups, provides a means for the effective deoxygenation of alcohols. A preliminary study of the reaction mechanism suggests that the reduction does not involve free-radical intermediates. Copyright
NHC-copper hydrides as chemoselective reducing agents: Catalytic reduction of alkynes, alkyl triflates, and alkyl halides
Cox, Nick,Dang, Hester,Whittaker, Aaron M.,Lalic, Gojko
, p. 4219 - 4231 (2014/06/09)
The NHC-copper-catalyzed Z-selective semi-reduction of terminal and internal alkynes, as well as the NHC-copper-catalyzed reduction of primary alkyl triflates and primary and secondary alkyl iodides and bromides are described. The high chemoselectivity demonstrated in these examples illustrates the mild nature of copper hydride complexes as reducing agents, which have applications in synthetic chemistry beyond their traditional role in the reduction of activated alkenes and carbonyl compounds.
