- Desulfonylative Electrocarboxylation with Carbon Dioxide
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Electrocarboxylation of organic halides is one of the most investigated electrochemical approaches for converting thermodynamically inert carbon dioxide (CO2) into value-added carboxylic acids. By converting organic halides into their sulfone derivatives, we have developed a highly efficient electrochemical desulfonylative carboxylation protocol. Such a strategy takes advantage of CO2as the abundant C1 building block for the facile preparation of multifunctionalized carboxylic acids, including the nonsteroidal anti-inflammatory drug ibuprofen, under mild reaction conditions.
- Zhong, Jun-Song,Yang, Zi-Xin,Ding, Cheng-Lin,Huang, Ya-Feng,Zhao, Yi,Yan, Hong,Ye, Ke-Yin
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supporting information
p. 16162 - 16170
(2021/09/02)
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- An improved method for the synthesis of phenylacetic acid derivatives via carbonylation
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2,4-Dichlorophenylacetic acid is synthesized in high yield via the carbonylation of 2,4-dichlorobenzyl chloride, and various experimental conditions are evaluated. Xylene, bistriphenylphosphine palladium dichloride, tetraethylammonium chloride and sodium hydroxide in solution are added to the reaction system and held at 80 °C under a CO atmosphere. 2,4-Dichlorophenylacetic acid is obtained in a maximum yield of 95percent, and a mechanism for 2,4-dichlorobenzyl chloride carbonylation is proposed. The reaction system provides a mild, effective and novel means by which to prepare phenylacetic acid derivatives from their corresponding benzyl chloride derivatives.
- Li, He,Zhang, Yijun,Liu, Dinghua,Liu, Xiaoqin
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p. 548 - 552
(2019/11/13)
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- Carboxylation of benzylic and aliphatic C-H bonds with CO2 induced by light/ketone/nickel
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A photoinduced carboxylation reaction of benzylic and aliphatic C-H bonds with CO2 is developed. Toluene derivatives capture gaseous CO2 at the benzylic position to produce phenylacetic acid derivatives when irradiated with UV light in the presence of an aromatic ketone, a nickel complex, and potassium tert-butoxide. Cyclohexane reacts with CO2 to furnish cyclohexanecar-boxylic acid under analogous reaction conditions. The present photoinduced carboxylation reaction provides a direct access from readily available hydrocarbons to the corresponding carboxylic acids with one carbon extension.
- Ishida, Naoki,Masuda, Yusuke,Imamura, Yuuya,Yamazaki, Katsushi,Murakami, Masahiro
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supporting information
p. 19611 - 19615
(2019/12/24)
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- PROCESS FOR SYNTHESIZING PHENYLACETIC ACID BY CARBONYLATION OF TOLUENE
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A production process for substituted phenylacetic acids or ester analogues thereof is disclosed. In this process toluene or toluene substituted with various substituents, an alcohol, an oxidant and carbon monoxide are used as raw materials to obtain compounds comprising structure of phenylacetic acid ester or analogues thereof by catalysis of the complex catalyst formed from transition metal and ligand, and such compounds are hydrolyzed to obtain various substituted phenylacetic acid based compounds. This type of compounds and their derivatives serve as important fine chemicals used widely in the industries of pharmaceuticals, pesticides, perfume and the like.
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Paragraph 0018; 0058; 0059
(2013/11/19)
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- Exalted resonance demands in the substituent effects on the acetolyses of 2-arylethyl trifluoromethanesulfonates destabilized by cn and cf3 groups
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Substituent effects on the acetolysis rates of 2-aryl-l-cyano-l- (trifluoromethyl)ethyl trifluoromethanesulfonates (α-OTf) and 2-aryl-2-cyano-2-(trifluoromethyl)ethyl trifluoromethanesulfonates (ss-OTf) were investigated by using LArSR equation. The obtained p and r+ values were p = -3.28, r+ = 0.98 and p = -3.48,r+ = 0.93 for the acetolysis of α-OTf and ss-OΥi, respectively. The obtained p values are comparable to those for typical aryl-assisted solvolyses, but the r+ values are much larger. The large r+ values suggest that the ester bond cleavages in the deactivated aryl-assisted solvolyses are assisted by the strong participation of the ss-aryl group.
- Usui, Satoshi,Tsuboya, Shoko,Umezawa, Yukthiro,Hazama, Ken,Okamura, Mutsuo
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experimental part
p. 254 - 260
(2009/05/30)
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- Quinolones as gonadotropin releasing hormone (GnRH) antagonists: Simultaneous optimization of the C(3)-aryl and C(6)-substituents
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A series of 3-arylquinolones was prepared and evaluated for their ability to act as gonadotropin releasing hormone (GnRH) antagonists. A variety of substitution patterns of the 3-aryl substituent are described. The 3,4,5-trimethylphenyl substituent (23h) was found to be optimal. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Young, Jonathan R.,Huang, Song X.,Chen, Irene,Walsh, Thomas F.,DeVita, Robert J.,Wyvratt Jr., Matthew J.,Goulet, Mark T.,Ren, Ning,Lo, Jane,Yang, Yi Tien,Yudkovitz, Joel B.,Cheng, Kang,Smith, Roy G.
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p. 1723 - 1727
(2007/10/03)
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- THE DIPHENYLMAFNESIUM/ALKALI METAL ALKOXIDE SYSTEM. HYDROCARBON-SOLUBLE ORGANOALKALI METAL REAGENTS
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Unsolvated diphenylmagnesium is solubilized in aromatic hydrocarbon solvents by an alkali metal 2-ethoxyethoxide.The mode of interaction between Ph2Mg and MOCH2CH2OEt (M=Li, Na, K) varies with M.For M=Li the complex formed has an Mg/Li ratio equal to 1.3/1.0, and is evidently different from the PhLi/Mg(OCH2CH2OEt) complex.For M=Na the metal-metal interchange apparently leads to a complex identical to thaht derived from PhNa and Mg(OCH2CH2OEt).For M=K the results are not conclusive.The width of the resonance 13C from the ipso-carbon, increases with increasing ionic radius, and for M=K the signal is too broad to be clearly observed .The ipso-carbon in the NMR spectrum of the PhNa/Mg(OCH2CH2OEt) complex has now been shown to give rise to resonance at 175.95 ppm.Metalation experiments involving Ph2Mg along with two equivalents of MOCH2CH2OEt indicated that reactivity increases in the order Li Na K.
- Screttas, Constantinos G.,Micha-Screttas, Maria
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- Carbanions. 23. Cleavage of 1,2-Diphenylethane and Derivatives by Cs-K-Na Alloy. Cometitive Rates of Bond Scission
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The following hydrocarbons are cleaved at a C-C bond to allylic and or/benzylic cesium compounds within 2 h by Cs-K-Na alloy in THF at -75 deg C: meso-2,3-diphenylbutane, 2,3-dimethyl-2,3-diphenylbutane, 1,2,2-triphenylpropane, 4-phenyl-1-butene, bibenzyl, and eight o-,m-, or p-methyl derivatives of bibenzyl.Under the same conditions 2-methyl- and 3-methyl-4-phenyl-1-butene were partially cleaved, 4,4'-dimethylbibenzyl was only slightly cleaved, and 9,10-dihydrophenanthrene was not detectably cleaved, while 10,11-dihydro-5H-dibenzocycloheptene underwent alternative C-H bond cleavage.Under the present reaction conditions 4,4'-dimethylbibenzyl and 9,10-dihydrophenanthrene were converted largely to dianions.It is suggested that all of the compounds undergoing cleavage are converted to dianions prior to cleavage.From competitive experiments the rates of reductive cleavage of most of these hydrocarbons relative to bibenzyl have been measured at -75 deg C.The relative rates of cleavage of m- and p-methylderivatives of bibenzyl may be correlated with the relative equilibrium acidities of toluene, m-xylene, and p-xylene in a modified Hammett relationship.Cleavages of benzylic C-C bonds are believed to occur by way of a preferred transition-state geometry,7, which permits the ?* orbital of the bond undergoing cleavage to interact with the HOMO's of both aromatic rings.Compounds that cannot attain this transition-state geometry are cleaved slowly if at all.The variable effect upon reaction rate of methyl groups near the bond undergoing cleavage are discussed in terms of ground-state and transition-state atrain, solvation, and polarizability of methyl groups.According to labeling experiments (o-methylbenzyl)cesium undergoes ready intramolecular sigmatropic migration of hydrogen from the methyl group to the methylene group when warmed from -75 deg C to near room temperature.
- Grovenstein, Erling,Bhatti, Amjad M.,Quest, Dean E.,Sengupta, Dibyendu,VanDerveer, Don
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p. 6290 - 6299
(2007/10/02)
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