- CARBONATE DERIVATIVE PRODUCTION METHOD
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The objective of the present invention is to provide a method for producing a carbonate derivative in a safe and efficient manner. The method for producing a carbonate derivative according to the present invention is characterized in comprising irradiating light on a composition containing a C1-4 halogenated hydrocarbon having one or more kinds of halogen atoms selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom, a nucleophilic functional group-containing compound and the specific base in the presence of oxygen.
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Paragraph 0139-0140
(2020/04/09)
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- Photochemical molecular storage of Cl2, HCl, and COCl 2: Synthesis of organochlorine compounds, salts, ureas, and polycarbonate with photodecomposed chloroform
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Chloroform is available as not only an organic solvent but also photochemical molecular storage for synthetically important chemicals such as Cl2, HCl, and COCl2. We have succeeded in synthesizing organochlorine compounds, hydrochloric salt of amines, ureas, organic carbonates, and polycarbonate in practical high yields with photodecomposed chloroform.
- Kuwahara, Yuki,Zhang, Ailing,Soma, Haruka,Tsuda, Akihiko
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supporting information; experimental part
p. 3376 - 3379
(2012/08/08)
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- Hydrolysis of orthocarbonates. Evidence for charge imbalance in the transition state for the general acid catalyzed process
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Catalytic constants have been measured for the hydrolysis of a range of aryl orthocarbonates, in which both the leaving group and trioxocarbenium ion moiety have been systematically varied, by neutral carboxylic acids (trichloroacetic, difluoroacetic, dichloroacetic, malonic, chloroacetic, and acetic) at 70.0°C in 60% water-40% acetonitrile, I = 1.0 M (KCI). Curvature cannot be detected in Br?nsted plots involving carboxylic acids only, but inclusion of the point for H3O+ suggests downward curvature (i.e. px ≥ 0). β1g Plots are curved downward (i.e. py′ = -?β1g/?pK1g > 0). Substitutent effects in the tris(aryloxy)carbenium ion fragment were quantitated by use of the experimental aqueous pKa alues of the phenol (pKrc), rather than Hammett σ values, since this gave better correlations for the spontaneous reactions (Kandanarachchi, P.; Sinnott, M. L. J. Am. Chem. Soc., preceding paper in this issue). Cross coefficients are large and not constant: pxy′ (measured as ?α/?pK1g rather than -?β1g/?pKHA) varies from 0.26 for (PhO)3C+ to 0.16 for (PMeOC6H4O)3C+. Likewise,pxy (measured as -?α/?pKrc rather than -?βrc/?pKHA) experiences large changes with the leaving group pK. Data to estimate pyy′ (?βrc/?pK1g) are more limited, but it too changes with the pKa of the catalyzing acid. These data indicate that a two-dimensional More O'Ferrall-Jencks diagram, with one axis representing both C-O cleavage and the ability of substituents in the tris(aryloxy)carbenium ion moiety to sense positive charge development, is inadequate to represent this reaction: separate axes are required for carbon-oxygen bond cleavage and development of carbon-oxygen double-bond character.
- Kandanarachchi, Pramod,Sinnott, Michael L.
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p. 5601 - 5606
(2007/10/02)
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- Process for producing an organic carbonate
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A process for producing an organic carbonate which comprises reacting an organic hydroxy compound, carbon monoxide and oxygen in the presence of a catalyst comprising(a) palladium or a palladium compound, (b) a cuprous or cupric compound such as cupric acetate, (c) a quinone or an aromatic diol formed by reduction of the quinone or a mixture thereof such as hydroquinone, and (d) a halogenated onium compound such as (C4 H9)NBr is disclosed. According to the invention, an organic carbonate such as diphenyl carbonate can be produced efficiently and economically.
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