- Method for decarboxylation and in-situ methylation of alkyl active carboxylic ester
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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.
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Paragraph 0047-0054; 0123-0129; 0203
(2020/06/20)
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- Cobalt-Catalyzed Decarboxylative Methylation and Ethylation of Aliphatic N-(Acyloxy)phthalimides with Organoaluminum Reagents
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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.
- Wang, Ze-Zhong,Wang, Guang-Zu,Zhao, Bin,Shang, Rui,Fu, Yao
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supporting information
p. 1221 - 1225
(2020/08/17)
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- Thermotropic MIDA Boronates as a Case Study for the Role of Dipolar Interactions in Liquid Crystalline Self-Assembly
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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.
- W?hrle, Tobias,Gündemir, Rafet,Frey, Wolfgang,Knecht, Friederike,K?hn, Andreas,Laschat, Sabine
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supporting information
p. 4149 - 4159
(2017/03/31)
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- Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
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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.
- Stridfeldt, Elin,Lindstedt, Erik,Reitti, Marcus,Blid, Jan,Norrby, Per-Ola,Olofsson, Berit
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supporting information
p. 13249 - 13258
(2017/09/12)
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- Novel biphenyl-3-carboxamide derivatives or salt thereof and pharmaceutical composition for treating or preventing autoimmune diseases comprising the same
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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
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Paragraph 0121; 0123-0126; 0150-0153
(2021/10/21)
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- CYCLOHEXADIENE FULLERENE DERIVATIVES
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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.
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Page/Page column 78; 79; 85
(2015/03/28)
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- Synthesis and Characterization of a New Series of Paramagnetic Ferroelectric Liquid Crystalline Nitroxide Radicals
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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.
- Uchida, Yoshiaki,Tamura, Rui,Suzuki, Katsuaki,Takahashi, Hiroki,Aoki, Yoshio,Nohira, Hiroyuki
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- NHC-copper hydrides as chemoselective reducing agents: Catalytic reduction of alkynes, alkyl triflates, and alkyl halides
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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.
- Cox, Nick,Dang, Hester,Whittaker, Aaron M.,Lalic, Gojko
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supporting information
p. 4219 - 4231
(2014/06/09)
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- Copper-catalyzed reduction of alkyl triflates and iodides: An efficient method for the deoxygenation of primary and secondary alcohols
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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
- Dang, Hester,Cox, Nick,Lalic, Gojko
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supporting information
p. 752 - 756
(2014/01/23)
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- Synthesis of 1,4-bis[2,2-bis(4-alkoxyphenyl)vinyl]benzenes and side chain modulation of their solid-state emission
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Figure Presented. A series of 1,4-bis[2,2-bis(4-alkoxyphenyl)vinyl]benzene molecules with aggregation-induced emission (AIE) activity were synthesized. The conformations and packing arrangements of these molecules in the solid state can be adjusted by changing the side chains, which subsequently modulates their solid-state emission. The fluorescence quantum yield of 1e with the n-C 6H13 side chain in the solid state could reach up to 60.3% in the solid state.
- An, Peng,Shi, Zi-Fa,Dou, Wei,Cao, Xiao-Ping,Zhang, Hao-Li
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supporting information; experimental part
p. 4364 - 4367
(2010/11/17)
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- Design, synthesis and biological evaluation of new ionone derivatives as potential neuroprotective agents in cerebral ischemia
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A new series of ionone derived allylic alcohols have been evaluated for anti-ischemic activity. Out of them, 12f and 13b decreased infarct volume to 23.98?±?4.7?mm3 and 93.98?±?24.8?mm3 as compared to ischemic group.
- Srivastava, Ajay Kumar,Dohare, Preeti,Ray, Madhur,Panda, Gautam
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supporting information; body text
p. 1964 - 1971
(2010/06/20)
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- High birefringence nematic liquid crystals for display and telecom applications
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Several compounds with high birefringence and, having tolane structure were synthesized. For a high polarizability, isothiocyanato (NCS) terminal group was introduced. Another goal of this study was reduction of melting point and smectic phases by introduction of fluorine as lateral substituent. The transition temperatures for all the synthesized compounds and the refractive and dielectric indices for one of the compounds have been determined. Electro-optic (EO) measurements were also performed.
- Catanescu, Carmen Otilia,Chien,Wu, Shin-Tson
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p. 93/[1135]-102/[1144]
(2007/10/03)
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- Discotic liquid crystals of transition metal complexes, 31: Establishment of mesomorphism and thermochromism of bis[1,2-bis(4-n-alkoxyphenyl)ethane-1,2-dithiolene]nickel complexes
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Two series of bis[1,2-bis(4-n-alkylphenyl)ethane-1,2-dithiolene]nickel, Cn-Ni (n= 1-12), and bis[1,2-bis(4-n-alkoxyphenyl)ethane-1,2-dithiolene]nickel, CnO-Ni(n = 1-12, 14, 16, 18), have been synthesized. Their mesomorphism, thermochromism, supramolecular structures and π-acceptor property have been investigated by using different scanning calorimetry, polarizing microscopy, temperature-dependent X-ray diffraction technique, electronic spectroscopy and cyclic voltammetry. From the X-ray diffraction and electronic spectral results, it was established that the CnO-Ni complexes for n ≤ 10 exhibit two differently colored discotic lamellar (DL) mesophases whereas none of the Cn-Ni complexes has a mesophase, and that the thermochromism (brown→green) is attributable to a slow transformation from the Ni-Ni bonded dimers to the Ni-S bonded dimers.
- Horie,Takagi,Hasebe,Ozawa,Ohta
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p. 1063 - 1071
(2007/10/03)
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- The X-ray crystal structures and computational analysis of NH...π hydrogen bonded banana-shaped carbazole derivatives and thermal analysis of higher mesogenic homologues
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The synthesis of a series of banana-shaped mesogenic structures has been carried out, in which the bend unit is formed by the 3,6-substitution of carbazole by 4-alkoxyphenyl moieties. The crystal structures of the methoxy and propyloxy derivatives are reported with an analysis of the N-H...π interactions that are observed in the crystalline state. This analysis was aided by semi-empirical molecular orbital calculations. Additionally, the thermal analysis of the complete series has been carried out in order to investigate the phase properties of these materials. The 4-nonyloxyphenyl derivative displays two melting points by DSC and normal light microscopy, but yields non-birefringent liquids. The incorporation of photorefractive molecular units, such as carbazole. into anisotropic materials may offer many advantages over conventional electrical poling of photorefractive polymers.
- Belloni, Maura,Manickam,Ashton, Peter R.,Kariuki, Benson M.,Preece, Jon A.,Spencer, Neil,Wilkie, John
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- Kaolin-assisted Aromatic Chlorination and Bromination
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Moist kaolin catalyses the regioselective and high-yielding chlorination and bromination of C6H5OR (R = C1-C8 alkyl. Bu1, allyl, cyclohexyl, benzyl) to 4-XC6H4OR (X = Cl and Br, respectively) with NaCl02 and Mn(acac)3 in CH2Cl2 in the absence and presence of NaBr, respectively, under mild and neutral conditions.
- Hirano, Masao,Monobe, Hiroyuki,Yakabe, Shigetaka,Morimoto, Takashi
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p. 662 - 663
(2007/10/03)
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- Nuclear monobromination of alkyl phenyl ethers with NaClO2, NaBr, Mn(acac)3, and moist silica gel in aprotic solvent
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Nuclear monobromination of aromatic ethers can be achieved with a NaClO2/NaBr/Mn(acac)3 catalyst/silica gel system in dichloromethane in regioselective and high-yielding manner under mild conditions.
- Hirano, Masao,Monobe, Hiroyuki,Yakabe, Shigetaka,Morimoto, Takashi
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p. 1463 - 1470
(2007/10/03)
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- Regioselective aromatic monobromination of alkyl phenyl ethers with NaClO2, NaBr, Mn(acac)3, and Montmorillonite K10 in dichloromethane
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Regioselective and high-yielding nuclear monobromination of aromatic ethers can be accomplished with a combination of NaClO2, NaBr, and Mn(acac)3 catalyst in dilchloromethane under mild and neutral conditions with the aid of Montmorillonite K10.
- Hirano, Masao,Yakabe, Shigetaka,Monobe, Hiroyuki,Morimoto, Takashi
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p. 669 - 676
(2007/10/03)
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- Cyclic peptide antifungal agents
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Provided are pharmaceutical formulations, and methods of inhibiting fungal and parasitic activity using a compound of formula I STR1 wherein: R', R", R'", Rx1, Rx2, Ry1, Ry2, Ry3, Ry4, and R0 are as defined herein below; R2 is a novel acyl side chain. Also provided are novel formulations and methods of inhibiting fungal and parasitic activity.
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- Synthesis of Mesogenic Compounds, Catalyzed by Metal Complexes. I. Monoalkylation and Monoarylation of 1,4-Dibromobenzene in the Synthesis of 4-n-Alkyl- and 4-n-Alkoxy-4'-Cyanobiphenyls Catalyzed by Palladium
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New methods of synthesis of mesomorphic 4-n-alkyl- and 4-n-alkoxy-4'-cyanobiphenyls are developed, based on the palladium catalyzed highly selective reactions of 1,4-dibromobenzene with alkyl and aryl Grignard reagents.
- Bumagin, N. A.,Luzikova, E. V.,Beletskaya, I. P.
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p. 1480 - 1486
(2007/10/03)
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- Ethanolamine benzoate compounds
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New ethanolamine benzoate compounds which can be used as medicaments and correspond to the formula: STR1 wherein R is as defined in the description, in the form of racemic compounds and enantiomers. These new compounds and their physiologically tolerable salts can be used therapeutically for treatment of insulin-resistance states.
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- Monohalogenation of alkyl phenyl ethers in micellar and vesicular media
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The rates and regioselectivities of monohalogenation of C6H5OR (1: a, R = C5H11;b, R = C9H19; c, R = C12H25) by chlorine water and bromine water to give 4-XC6/su
- Jaeger, David A.,Clennan, Malgorzata Wegrzyn,Jamrozik, Janusz
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p. 1171 - 1176
(2007/10/02)
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- POLY(ETHYLENE GLYCOL)S AS PHASE TRANSFER CATALYSTS IN THE ALKOXYLATION OF HALOBENZENES OF ALKYL ARYL ETHERS
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Mono and di-halobenzenes and alkoxide ions gave monoalkoxybenzenes, but no phenols, when catalyzed by high molecular weight poly(ethylene glycol)s as phase transfer catalysts.Bromobenzenes were more reactive than chlorobenzenes but gave more side products, and for alcohols the reactivity was primary>secondary>tertiary.
- Neumann, R.,Sasson, Y.
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p. 3437 - 3440
(2007/10/02)
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