Practical Method for the Synthesis and Optical Resolution of Axially Dissymmetric 6,6′-Dimethylbiphenyl-2,2′-dicarboxylic Acid

Kanoh, Shigeyoshi; Muramoto, Hiroki; Kobayashi, Natsumi; Motoi, Masatoshi; Suda, Hiroshi

doi:10.1246/bcsj.60.3659

Cited by 27 publications

(16 citation statements)

References 9 publications

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“…[4] Compounds (-)-(M)-9a and (-)-(M)-9b were prepared by homocoupling of the freshly prepared diazonium salt of commercially available 3-methylanthranilic acid [6] (72 % yield, Scheme 2). Optical resolution of the resulting biphen-yldicarboxylic acid rac-8 was achieved by diastereoselective crystallisation of the corresponding brucine salt, [7] and the acid (-)-(M)-8 was obtained in 32 % yield. Finally, esterification with p-ethoxyphenol or 4Ј-(octyloxy)biphenyl-4-ol in the presence of methanesulfonyl chloride gave (-)-(M)-9a (45 % yield) or (-)-(M)-9b (52 % yield), respectively.…”

Section: Synthesismentioning

confidence: 99%

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New 2,2'‐Substituted 6,6'‐Dimethylbiphenyl Derivatives Inducing Strong Helical Twisting Power in Liquid Crystals

Holzwarth

Bartsch

Cherkaoui³

et al. 2005

Eur J Org Chem

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New optically active tetra‐ortho‐substituted biphenyl chiral dopants for nematic liquid crystals are described. It was shown, with respect to our previous results, that biphenyl chiral dopants bearing only mesogenic residues on their 2,2'‐positions and without any substituents on their 4,4'‐positions gave rise to very high twisting powers in nematic liquid crystals. This powerful and unconventional chiral dopant molecular architecture allowed the design of new tetra‐ortho‐substituted biphenyl derivatives, easier to prepare in optically active form. This simplification of the molecular architecture still affords chiral dopants for nematic liquid crystals with large helical twisting powers and allows more economical large‐scale preparation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Synthesismentioning

confidence: 99%

“…The absolute configurations of these new products as well as their high optical purities were deduced by comparison with the known compound carboxylic acid (-)-(M)-8. [7] Scheme 2. Reagents and conditions: a) NaNO 2 , NaOH, 0°C, HCl, NH 4 …”

Section: Synthesismentioning

confidence: 99%

New 2,2'‐Substituted 6,6'‐Dimethylbiphenyl Derivatives Inducing Strong Helical Twisting Power in Liquid Crystals

Holzwarth

Bartsch

Cherkaoui³

et al. 2005

Eur J Org Chem

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“…The synthesis of 5 is based on several reported procedures. Nitration of m ‐toluic acid ( 1 ) yielded 2 in 42 %,39 followed by a Curtius rearrangement in which the carboxylic acid is converted into a primary amine group, giving 3 in 83 % yield 40. The primary amine was then converted into a secondary amine in a methylation reaction to give 4 ,41 followed by hydrogenation of the nitro group to form 5 (both steps are quantitative).…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Grignard Reagent Synthesis for Ionic‐Liquid‐Based Magnesium–Air Batteries

Luder¹,

Ein‐Eli²

2014

ChemElectroChem

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Metal–organic compounds are widely used in the production of fine chemicals and pharmaceutical agents. On large scales, the chemical production of Grignard reagents (GRs) with ether solvents is difficult. The electrochemical synthesis of GRs in ionic‐liquid‐based electrolytes is reported herein. The electrochemical synthesis and presence of the GR product are demonstrated by cyclic voltammetry and 1H nuclear magnetic resonance spectroscopy and by comparing the measured passing charge to the final GR concentration. Additionally, the high‐boiling ether tetraethylene glycol dimethyl ether is shown to be a suitable substitute for volatile tetrahydrofuran ether, which is currently used. A mechanism for the electrochemical synthesis of the GR is suggested and discussed, and the potential importance of the process for high‐energy‐density applications is demonstrated with a magnesium–air cell. Electropolishing of the Mg anode is also observed and discussed.

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“…The chiral ligand 1 was prepared from optically pure 6,6' -dimethylbiphenyl-2,2' -dicarboxylic acid 10 …”

Section: Methodsmentioning

confidence: 99%

New Chiral Catalyst, t-Butyllithium Complexed with Axially Chiral Diamine, for Asymmetric Polymerizations of Triphenylmethyl Methacrylate and Its 2-Pyridyl Derivative

Kanoh

Sumino

Kawaguchi

et al. 1988

Polym J

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ABSTRACT:Asymmetric polymerizations of achiral methacrylates such as bulky triphenylmethyl and diphenyl-2-pyridylmethyl esters were investigated in toluene at -78°C. t-Butyllithium complexed with a tetramethylethylenediamine derivative having an axially chiral 6,6'-dimethylbiphenyl-2,2'-diyl substituent (1) at -78°C was found to be a versatile chiral initiator for the above polymerizations. The produced poly(ester)s were easily soluble in THF, because of the limited molecular weights. The polymers of helical conformation showed large optical rotations, whose signs depended on the chirality of the used 1.KEY WORDS Asymmetric Polymerization / Helix / Triphenylmethyl Methacrylate / Diphenyl-2-pyridylmethyl Methacrylate / Axially Chiral Biphenyl / Tetramethylethylenediamine Derivatives / Butyllithium / PTrMA D2PyMAIn past years, much attention has been focused on optically active polymers obtained from bulky methacrylates such as triphenylmethyl methacrylate (TrMA) 1 -3 and diphenyl-2-pyridylmethyl ester (D2PyMA). 4 · 5 The optical activity of these polymers is attributed to the helical conformation stabilized by the isotactic sequence of bulky ester groups. 6 The conformation prevailing in one screw sense is formed through asymmetric polymerizations with chiral anionic initiators. 1 -5 The molecular weights of the polymers are critical for their solubility. Especially organic solventsoluble parts have been found by Okamoto et al. to be useful materials as chiral solid phases of high performance liquid chromatography for the optical resolution of various racemic substances. 5 • 7 We have already reported that chiral complexes of organolithiums with tetramethylethylenediamine (TMEDA) derivatives (1 and 2) having biaryl substituents also serve as excellent catalysts for the asymmetric polymerization of TrMA. 8 • 9 It is considered that the high stereoselectivities of these catalysts are ascribed to complementary effects between the chirality-recognizing ability of biaryl units and the flexibility of the TMEDA side-arm for

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Practical Method for the Synthesis and Optical Resolution of Axially Dissymmetric 6,6′-Dimethylbiphenyl-2,2′-dicarboxylic Acid

Cited by 27 publications

References 9 publications

New 2,2'‐Substituted 6,6'‐Dimethylbiphenyl Derivatives Inducing Strong Helical Twisting Power in Liquid Crystals

New 2,2'‐Substituted 6,6'‐Dimethylbiphenyl Derivatives Inducing Strong Helical Twisting Power in Liquid Crystals

Electrochemical Grignard Reagent Synthesis for Ionic‐Liquid‐Based Magnesium–Air Batteries

New Chiral Catalyst, t-Butyllithium Complexed with Axially Chiral Diamine, for Asymmetric Polymerizations of Triphenylmethyl Methacrylate and Its 2-Pyridyl Derivative

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