- Novel process for producing phenyl fluoride, diphenyl ketone fluoride, and derivatives thereof
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The invention relates to a novel process for producing phenyl fluoride, diphenyl ketone fluoride, and derivatives thereof, especially the phenyl fluoride and derivatives thereof. The invention especially relates to a novel environment-friendly process for synthesizing phenyl fluoride and diphenyl ketone fluoride, which are the raw materials for preparing polyaryl-ether-ketone PAEK. The invention discloses the method that is more effective and environment-friendly for preparing the compounds through a Friedel-Crafts reaction, and further a more environment-friendly process, and provdies beneficial catalysts. Another object of the present invention is to employ the Friedel-Crafts reaction and adopts the beneficial catalysts, wherein the catalyst can be easily combined with the fluoridation reaction which can be carried out before, or after the Friedel-Crafts reaction. Herein, another object of the invention is to use the catalyst in the Friedel-Crafts reaction, wherein the catalyst can work in both the Friedel-Crafts reaction and the fluoridation reaction.
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Paragraph 0285; 0291-0292
(2020/07/02)
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- Dual Nickel- And Photoredox-Catalyzed Reductive Cross-Coupling of Aryl Halides with Dichloromethane via a Radical Process
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The first catalytic strategy to harness a new chloromethane radical from dichloromethane under dual Ni/photoredox catalytic conditions has been developed. Compared with traditional two-electron reductive process associated with metallic reductants, this method via a single-electron approach can proceed under exceptionally mild conditions (visible light, ambient temperature, no strong base) and exhibits complementary reactivity patterns. It affords a broad scope of many functional groups, including alkenyl, which suffers cyclopropanation in previous routes. The diarylmethane-d2 compounds can be readily available with this transformation.
- Xu, Tao,Xu, Wenhao,Zheng, Purui
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supporting information
(2020/11/13)
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- Super electron donor-mediated reductive desulfurization reactions
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The desulfurization of thioacetals and thioethers by a pyridine-derived electron donor is described. This methodology provides efficient access to the reduced products in high yields and does not require the use of transition-metals, elemental alkali-metals, or hydrogen atom donors.
- Nozawa-Kumada, Kanako,Ito, Shungo,Noguchi, Koto,Shigeno, Masanori,Kondo, Yoshinori
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supporting information
p. 12968 - 12971
(2019/11/05)
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- +: A Masked Potent Boron Lewis Acid
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The chemistry of the boron cation has been revitalized in the past decade due to its newfound application in stoichiometric and catalytic organic reactions. To extend the frontier of boron cation catalysis, we came to discover that a mesityl-substituted η5-Cp*-coordinated boron cation could serve as a powerful Lewis acid for organic catalytic transformations. The boron cation [Cp*B-Mes][B(C6F5)4] ([1][B(C6F5)4]) stabilized in a boronium-like electronic structure binds to Et3PO readily and displays an acceptor number exceeding that of B(C6F5)3 on the Gutmann-Beckett acidity scale. The steric and electronic stabilization exerted by the electron-donating Cp? renders the highly Lewis acidic boron cation an easy-to-handle catalyst for hydrodeoxygenation of aryl ketones at ambient temperature. The exceptional catalytic performance of [1]+ implies that the incorporation of a coordinatively flexible substituent at boron is critical in bringing catalytic activity and stability to boron cation catalysts.
- Tseng, Hsi-Ching,Shen, Chao-Tang,Matsumoto, Kentaro,Shih, Ding-Nan,Liu, Yi-Hung,Peng, Shie-Ming,Yamaguchi, Shigehiro,Lin, Ya-Fan,Chiu, Ching-Wen
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supporting information
p. 4516 - 4521
(2019/11/14)
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- Chlorotrimethylsilane and Sodium Iodide: A Remarkable Metal-Free Association for the Desulfurization of Benzylic Dithioketals under Mild Conditions
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A novel metal-free process allowing the reductive desulfurization of various benzylic dithioketals to afford diarylmethane and benzylester derivatives with good to excellent yields is reported. At room temperature, this mild reduction process requires only the use of TMSCl and NaI in CH2Cl2 and tolerates a large variety of functional groups. (Figure presented.).
- Zhao, Guangkuan,Yuan, Ling-Zhi,Alami, Mouad,Provot, Olivier
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p. 2522 - 2536
(2018/05/14)
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- Reversible Generation of Labile Secondary Carbocations from Alcohols in the Nanospace of H-Mordenite and Their Long-Lasting Preservation at Ambient Temperature
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Secondary carbocations are rarely observed spectrometrically for prolonged durations at ambient temperatures because of their instability. In this study, when 4,4′-difluorobenzhydrol (1) was mixed with H-mordenite (H-Mor), the 4,4′-difluorodiphenylmethyl cation (2) was generated as the main product, identified by UV-vis and 13C-MAS NMR spectroscopies, and was preserved for over 1 week at ambient temperature. Surprisingly, the polymerization and disproportionation of 1 barely proceeded within the micropores of H-Mor. However, these side reactions prevailed in TfOH and formation of 2 was not observed. Preservation of other secondary carbocations from benzhydrol, 4,4′-dichlorobenzhydrol, and 9-fluorenol was also realized in H-Mor. It was confirmed that the generation of 2 from 1 was controlled by thermodynamic equilibrium rather than kinetic regulations. The equilibrium between 2 and 1 was accompanied by reversible chromism, which could be easily controlled by altering the moisture content in H-Mor. Moreover, novel insights into specific acid catalysis in zeolites densely populated with acid sites on the inner surface of micropores are described herein.
- Masui, Yoichi,Hattori, Taiki,Onaka, Makoto
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supporting information
p. 8612 - 8620
(2017/07/06)
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- Preparation method of 4,4'-difluorobenzophenone
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The invention discloses a preparation method of 4,4'-difluorobenzophenone, wherein the method includes the following preparation steps: (1) preparing a fluoroboric diazonium salt; (2), adding the fluoroboric diazonium salt obtained in the step (1), a catalyst and a solvent into a beaker provided with a distillation device and a BF3 gas absorption device, and carrying out reduced pressure distillation, to obtain 4,4'-difluorodiphenylmethane; (3), loading 4,4'-difluorodiphenylmethane into a flask, adding 24% dilute nitric acid and a catalyst, heating to a reflux temperature, dropping a 55% nitric acid, completing dropping within about 4 h, after the dropping is completed, continuing to carry out a reaction for 2 h, cooling to room temperature, separating crystals out, filtering, reused the filtrate, recrystallizing the filter material with 70% ethanol, and drying to obtain white flaky 4,4'-difluorobenzophenone crystals. The process and operation practicability is high, the steps are simple, requirements on equipment are low, the method is suitable for industrialized production, the product yield reaches 95% or more and the content reaches 99.8% or more.
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Paragraph 0006
(2018/02/04)
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- Ethers as hydrogen sources in BF3·OEt2 promoted reduction of diphenylmethyl alcohols, ethers and esters to hydrocarbons
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A novel ether/BF3 reductive system has been described, in which diphenylmethanols and their ether and ester derivatives are used as starting materials. Reductions are performed in ether under reflux and an argon atmosphere, and the addition of extra water is beneficial to this reduction. A series of alkanes are able to be prepared with good to excellent yields. A deuterated experiment exhibits that the reductive hydrogen is generated from ether. The mechanism is discussed in detail to explain the observed reactivity.
- Li, Jiaqiang,Liu, Qing,Shen, Hang,Huang, Ruofeng,Zhang, Xiaohui,Xiong, Yan,Chen, Changguo
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p. 85291 - 85295
(2015/11/02)
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- N-Heterocyclic carbene-palladium(II)-1-methylimidazole complex-catalyzed Suzuki-Miyaura coupling of benzyl carbamates with arylboronic acids
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The Suzuki-Miyaura coupling of benzyl carbamates with arylboronic acids was achieved in an environmentally benign medium. Using water as the sole solvent, such transformation took place very well to give the desired diarylmethane derivatives in good to almost quantitative yields in the presence of a well-defined NHC-Pd(ii)-Im complex under mild conditions. It is worth noting here that this is the first example of benzyl carbamates used in coupling reaction, thus affording a new method for the formation of diarylmethanes by palladium-catalyzed C-O bond activation.
- Wang, Xiao-Xia,Luo, Mao-Jun,Lu, Jian-Mei
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p. 11438 - 11444
(2015/12/04)
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- N-heterocyclic carbene-palladium(II)-1-methylimidazole complex-catalyzed Suzuki-Miyaura coupling of benzyl sulfonates with arylboronic acids
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The first example of palladium-catalyzed Suzuki-Miyaura coupling between benzyl sulfonates and arylboronic acids was reported in this paper. In the presence of a well-defined, air-stable and easily available NHC-Pd(ii)-Im complex, all reactions worked well to give the desired products in good to almost quantitative yields under the optimal conditions. Electron-rich, -neutral, -poor and sterically-hindered substituents on both substrates are tolerated in such transformation, providing a convenient, efficient and alternative method for the synthesis of diarylmethanes.
- Wang, Xiao-Xia,Xu, Bin-Bin,Song, Wen-Ting,Sun, Kai-Xin,Lu, Jian-Mei
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p. 4925 - 4930
(2015/05/05)
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- Deoxygenation of tertiary and secondary benzylic alcohols into alkanes with triethylsilane catalyzed by solid acid tin(IV) ion-exchanged montmorillonite
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We discovered an efficient protocol for the conversion of tertiary and secondary benzylic alcohols into the corresponding alkanes in good to quantitative yields by employing tin(IV) ion-exchanged montmorillonite (Sn-Mont) as a solid acid catalyst and Et3SiH as the hydride source. The reaction is likely to proceed via the SN1-type reaction mechanism, that is, the formation of carbenium ions, followed by the addition of a hydride from the silane. The work-up of the reaction only requires simple filtration of the solid acid without any neutralization of the acid catalyst.
- Tandiary, Michael Andreas,Masui, Yoichi,Onaka, Makoto
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supporting information
p. 4160 - 4162
(2014/07/22)
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- Facile one-pot palladium-catalyzed sequential coupling to diarylmethanes by using aryl methyl ketones as the methylene donors
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A novel palladium-catalyzed coupling reaction of an aryl methyl ketone with two molecules of an aryl halide to yield symmetric diarylmethanes is described. In the facile one-pot reaction, the aryl methyl ketone acts as a formal methylene donor. The experimental facts, including TLC monitoring, speculated intermediates as the raw materials, analysis of the cesium benzoate coproduct by ex situ IR spectroscopy, and the cross-coupling reactions of two different aryl halides, indicate a mechanism involving a palladium-catalyzed sequential two-step coupling process, in which the presence of a trace amount of H 2O is indispensable. The reaction is applicable to a broad spectrum of substrates and delivers the products in good to excellent yields. Access to unsymmetrical diarylmethanes with this method is also explored and various factors are discussed. An aryl methyl ketone is used as the methylene donor to couple with two molecules of an aryl halide for the synthesis of various symmetric diarylmethanes under palladium catalysis. The mechanism involves a two-step coupling process in which the presence of a trace amount of H 2O is indispensable. The cross-coupling to unsymmetrical diarylmethanes with this method is also explored. Copyright
- Wang, Xing,Liu, Lian-Hua,Shi, Jin-Hua,Peng, Ji,Tu, Hai-Yang,Zhang, Ai-Dong
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p. 6870 - 6877
(2013/11/06)
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- One-pot synthesis of symmetrical and unsymmetrical diarylmethanes via diborylmethane
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A one-pot synthesis of diarylmethanes from air-stable diborylmethane via the Suzuki-Miyaura cross-coupling reaction is described. The present approach realizes the synthesis of various symmetrical and unsymmetrical diarylmethanes in good to excellent yields.
- Endo, Kohei,Ishioka, Takafumi,Ohkubo, Takahiro,Shibata, Takanori
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p. 7223 - 7231
(2012/10/29)
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- Catalytic double C-Cl bond activation in CHlby iron(III) salts with grignard reagents
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Cross-coupling of Grignard reagents with dichloromethane is achieved using iron(III) catalysts. Aryl- and benzylmagnesium bromides show a range of activity toward double C-Cl bond activation resulting in the insertion of methylene fragments between two equivalents of the nucleophilic partner. Georg Thieme Verlag Stuttgart.
- Qian, Xin,Kozak, Christopher M.
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experimental part
p. 852 - 856
(2011/06/21)
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- Reduction of carbonyl to methylene: Organosilane-Ga(OTf)3 as an efficient reductant system
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Direct carbonyl reduction to methylene has been achieved by mild reductant system obtained from the combination of organosilane and gallium (III) trifluoromethanesulfonate {Ga(OTf)3}, a water tolerant, recyclable, catalyst. Among a series of organosilanes studied, dimethylchlorosilane (Me 2SiHCl, DMCS) showed the highest efficiency. Both aromatic and aliphatic ketones were effectively reduced to the corresponding methylene products with high functional groups tolerance, under very mild conditions in a relatively short period of time with good to excellent yields. Graphical Abstract: [Figure not available: see fulltext.]
- Surya Prakash,Do, Clement,Mathew, Thomas,Olah, George A.
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experimental part
p. 507 - 511
(2012/01/04)
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- Deoxygenation of benzylic alcohols using chloroboranes
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New boron-based methods for deoxygenating benzylic alcohols via the corresponding alkoxides are reported.
- Yao, Min-Liang,Pippin, Adam B.,Kabalka, George W.
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scheme or table
p. 853 - 855
(2010/03/24)
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- Palladium-catalyzed synthesis of diarylmethanes: Exploitation of carbanionic leaving groups
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A novel route to the synthesis of diarylmethanes via a Pd-catalyzed α-arylation of benzyl ketones is rseported. By harnessing the inherent reactivity of enolates, it is possible to circumvent the need for a transmetalating reagent such as boron for the co
- Schmink, Jason R.,Leadbeater, Nicholas E.
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scheme or table
p. 2575 - 2578
(2009/10/02)
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- Synthetic and mechanistic aspects of acid-catalyzed disproportionation of dialkyl diarylmethyl ethers: A combined experimental and theoretical study
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The disproportionation reactions of various dialkyl diarylmethyl ethers have been carried out in the presence of a catalytic amount (10 mol-%) of o-benzenedisulfonimide as a Bronsted acid catalyst; the reaction conditions were mild, and the yields of the diarylmethane target products were good. The catalyst was easily recovered and purified, ready to be used in further reactions. The theoretical study confirmed that the reaction proceeds in two steps: The formation of a carbocation from the protonated ether followed by hydride transfer. Although the hydride transfer is the rate-determining step, it is the stability of the carbocation that determines the reaction rate and therefore the yields.
- Barbero, Margherita,Bazzi, Stefano,Cadamuro, Silvano,Dughera, Stefano,Ghigo, Giovanni
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experimental part
p. 4346 - 4351
(2011/02/24)
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- Facile synthesis of 3-(diarylmethylene)isobenzofuranones, 4-(diarylmethyl)-1(2H)-phthalazinones and diarylmethanes
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Reflux of 2,2-diaryl-1,3-indanediones in ethyleneglycol with a catalytic amount of triethylamine affords 3-(diarylmethylene)isobenzofuranones in very good yields. The latter produces 4-diarymethyl-1(2H)-phthalazinones under reflux in hydrazine hydrate (99%), and diarylmethanes upon stirring in ethylenediamine.
- Das, Suven,Froehlich, Roland,Pramanik, Animesh
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- PROCESS FOR THE PREPARATION OF ARYL DIAZONIUM SALTS AND REACTION WITH NUCLEOPHILES
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A process for performing nucleophilic substitution reactions on aryl diazonium salts or derivatives thereof wherein the aryl diazonium salt is first generated in an aqueous solvent system followed by partitioning of the aryl diazonium salt with a hydrophobic ionic liquid thereby allowing subsequent reaction of the aryl diazonium salt with an appropriate nucleophilic species in the hydrophobic ionic liquid to the desired product without the need to first isolate the aryl diazonium salt.
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- 6-(α-hydroxy-α-aryl/naphthyl)methyl-3,4-dihydro-2, 5-benzodiazocin-1(2H)-ones and diphenylmethanes from C-2 arylated 1,3-indanediones
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Stirring 2-hydroxy-2-aryl-1,3-indanediones in ethylenediamine at room temperature for 1-2 h produces 6-(α-hydroxy-α-aryl/naphthyl)methyl- 3,4-dihydro-2,5-benzodiazocin-1(2H)-ones in high yields. Under similar reaction conditions 2,2-diaryl-1,3-indanediones furnish diphenylmethanes.
- Kundu, Sandip Kumar,Das, Suven,Pramanik, Animesh
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p. 781 - 783
(2007/10/03)
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- Preparation process of fluorine substituted aromatic compound
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A preparation process of a fluorine substituted aromatic compound comprising reacting an alkali metal or alkali earth metal salt of an aromatic compound having a hydroxy group with an organic fluorinating agent is disclosed. As a representative fluorinating agent, a bis-dialkylamino-difluoromethane compound, for example, 2,2′-difluoro-1,3-dimethylimidazolidine, is exemplified. According to the process, an industrially useful fluorinated aromatic compound, for example, a fluorobenzene, a fluorine substituted benzophenone, a fluorine substituted diarylsulfone can be prepared with ease in economy without specific equipment.
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- Extended scope of in situ iodotrimethylsilane mediated selective reduction of benzylic alcohols
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Iodotrimethylsilane, generated in situ from chlorotrimethylsilane and sodium iodide in acetonitrile, selectively reduces moderately electron deficient benzylic alcohols to the analogous toluenes; other reduction sensitive functional groups such as ketone, aldehyde, nitrile, and nitro are unaffected.
- Cain,Holler
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p. 1168 - 1169
(2007/10/03)
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- Facile preparation of aromatic fluorides by deaminative fluorination of aminoarenes using hydrogen fluoride combined with bases
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One-pot deaminative fluorination of aminoarenes including heteroaromatics, namely, diazotization of aminoarenes followed by in situ fluoro-dediazoniation of the corresponding diazonium ions, was successfully accomplished to produce fluoroarenes in high yields by using hydrogen fluoride combined with base solutions. The diazotization stage has been found to play the most important part in yielding fluoroarenes effectively. It was greatly influenced by the composition of the HF solution and enhanced by employing appropriate amounts of bases such as pyridine under carefully controlled conditions. The fluoro-dediazoniation stage was effectively accelerated photochemically to afford fluoroarenes having polar substituents such as hydroxyl, nitro and so on in high yields.
- Yoneda,Fukuhara
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- Carbon Acidity. 66. Equilibrium Ion Pair Acidities of Substituted Diphenylmethanes in Cyclohexylamine
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The pKCsCHA values are reported for a number of symmetrically meta- and para-substituted diphenylmethanes.The pKCsCHA values for the meta series (Me, 33.8; OMe, 32.7; F, 29.9; CF3, 28.9; Ph, 32.3; H, 33.4) give a normal Hammett plot with ρ = 9.69.The para series (Me, 35.1; OMe,37.6; Ph, 30.8; NMe2, 38.6; SPh, 28.8; CN, 23.0; SO2Me, 22.4) do not fit attempted correlations with ?, the Yukawa-Tsuno modifications, or dual substituent parameter approaches.Electron-donating groups are more anion destabilizing than in other reference systems. "Amphoteric" substituents, those that stabilize both anions and cations (phenyl, thio, etc.), cause special problems in generalized correlations.
- Streitwieser, Andrew Jr.,Vorpagel, Erich R.,Chen, Chia-Chung
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p. 6970 - 6975
(2007/10/02)
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