824-55-5Relevant articles and documents
Mechanism of solvolysis of substituted benzyl chlorides in aqueous ethanol
Denegri, Bernard,Mati?, Mirela,Va?ko, Monika
supporting information, (2021/11/22)
The mechanism of solvolyses of activated ortho-, meta- and para-substituted benzyl chlorides in aqueous ethanol has been studied by using the Hammett-Brown and Yukawa-Tsuno treatments as well as by correlating logarithms of solvolysis rate constants with relative stabilities of corresponding benzyl carbocations in water calculated at the IEFPCM-M06–2X/6-311+G(3df,3pd) level of theory. Benzyl chlorides containing strong conjugative electron-donors in the para-position solvolyze by the SN1 mechanism, whereas other activated benzyl chlorides solvolyze by the SN2 mechanism via loose transition states.
Ir-Catalyzed Asymmetric and Regioselective Hydrogenation of Cyclic Allylsilanes and Generation of Quaternary Stereocenters via the Hosomi-Sakurai Allylation
Rabten, Wangchuk,Margarita, Cristiana,Eriksson, Lars,Andersson, Pher G.
supporting information, p. 1681 - 1685 (2018/01/05)
A number of cyclic dienes containing the allylsilane moiety were prepared by a Birch reduction and subjected to iridium-catalyzed regioselective and asymmetric hydrogenation, which provided chiral allylsilanes in high conversion and enantiomeric excess (up to 99 % ee). The compounds were successively used in the Hosomi–Sakurai allylation with various aldehydes employing TiCl4 as Lewis acid, providing adducts with two additional stereogenic centers in excellent diastereoselectivity.
Aromatic cation activation: Nucleophilic substitution of alcohols and carboxylic acids
Nguyen, Thanh V.,Bekensir, Alp
supporting information, p. 1720 - 1723 (2014/04/17)
A new method for the nucleophilic substitution of alcohols and carboxylic acids using aromatic tropylium cation activation has been developed. This article reports the use of chloro tropylium chloride for the rapid generation of alkyl halides and acyl chlorides under very mild reaction conditions. It demonstrates, for the first time, the synthetic potential of tropylium cations in promoting chemical transformations.
An experimental and theoretical study on imidazolium-based ionic liquid promoted chloromethylation of aromatic hydrocarbons
Wang, Yun,Xi, Yanli
, p. 2196 - 2199 (2014/03/21)
The chloromethylation of aromatic hydrocarbons proceeded efficiently using the reusable imidazolium-based ionic liquid as promoter. Mild reaction conditions, enhanced rates, improved yields, recyclability of ionic liquids, and reagents' reactivity which is different from that in conventional organic solvents are the remarkable features observed in ionic liquids. The ionic liquids were recycled in three subsequent runs with no decrease in activity. In addition, the results of calculations with the Gaussian 98 suite of program are in good accordance with the experimental outcomes.
An inexpensive and convenient procedure for chloromethylation of aromatic hydrocarbons by phase transfer catalysis in aqueous media
Hu, Yu Lin,Lu, Ming,Ge, Qiang,Wang, Peng Cheng,Zhang, Sheng Bin,Lu, Ting Ting
experimental part, p. 97 - 102 (2010/08/05)
Reaction of aromatic hydrocarbons catalyzed by a novel catalytic system consisting of zinc chloride, acetic acid, sulfuric acid and PEG-800 in aqueous media under PTC conditions results in chloromethylation in good to excellent yield.
Identification of alkylarene chloromethylation products using gas-chromatographic retention indices
Zenkevich,Makarov
, p. 611 - 619 (2008/03/18)
Gas-chromatographic retention indices on standard nonpolar polydimethylsiloxane stationary phases allow identification of products formed by known organic reactions even without using mass-spectrometric data. The efficiency of this approach was demonstrated by the example of identification of previously uncharacterized chloromethyl derivatives of alkylarenes, including structural isomers of compounds containing several chloromethyl groups, directly in reaction mixtures. Chromatographic analysis of such reaction mixtures allows identification of positional isomers of the starting alkylarenes even when they are present simultaneously. The retention indices were determined for the first time for more than 50 alkyl-(chloromethyl)arenes, by-products of chloromethylation, and chloromethyl derivatives of the simplest alkyl phenyl ketones. Nauka/Interperiodica 2007.
[emim]BF4-promoted chloromethylation of aromatic hydrocarbons
Wang, Yun,Shang, Zhi-Cai,Wu, Tian-Xing
, p. 3053 - 3059 (2007/10/03)
The chloromethylation of aromatic hydrocarbons proceeded efficiently using the reusable ionic liquid [emim]BF4 as promoter. The reactions were completed in 5 h at 70°C with good yields and easy workup. Copyright Taylor & Francis Group, LLC.
Synthesis, pharmacological evaluation, and molecular modeling studies of novel peptidic CAAX analogues as farnesyl-protein-transferase inhibitors
Santagada, Vincenzo,Caliendo, Giuseppe,Severino, Beatrice,Lavecchia, Antonio,Perissutti, Elisa,Fiorino, Ferdinando,Zampella, Angela,Sepe, Valentina,Califano, Daniela,Santelli, Giovanni,Novellino, Ettore
, p. 1882 - 1890 (2007/10/03)
Fifteen analogues of the C-terminal CA1A2X motif were synthesized and evaluated for their inhibition potency against farnesyltransferase (FTase). Replacement of the A2 residue by phenylalanine or tyrosine-derived analogues, in which a different number of methyl groups were introduced on the aromatic ring, resulted in compounds less active than the reference compound CVFM against FTase except for compounds I and VI (IC50 = 1 μM and 2.5 μM, respectively) that were comparable to CVFM and compound IV (IC50 = 0.1 μM), which was 6-fold more active than the reference compound. Because pseudopeptidic derivatives I-IX were inactive in the cellular assays, the N-formyl- and methyl-ester derivatives (compounds X-XV) were synthesized and tested on different cell lines, showing, in some cases, activity and appreciable selectivity against transformed cells. To rationalize the obtained results, molecular modeling experiments were carried out suggesting the molecular basis of FTase inhibition by these products.
Synthesis and molecular structures of zirconium and hafnium complexes bearing dimethylsilandiyl-bis-2,4,6-trimethylindenyl and dimethylsilandiyl-bis- 2-methyl-4,6-diisopropylindenyl ligands
Izmer, Vyacheslav V.,Sorokin, Denis A.,Kuz'Mina, Lyudmila G.,Churakov, Andrei V.,Howard, Judith A.K.,Voskoboynikov, Alexander Z.
, p. 1067 - 1079 (2007/10/03)
Zirconium and hafnium ansa-complexes containing 2,4,6-trialkyl-substituted indenyl fragments were synthesized and unambiguously characterized. Mixtures of rac- and meso-Me2Si(2-Me-4,6-R2C9H 3-η5)2MCl2, where R = Me, i-Pr and M = Zr, Hf, were obtained by a treatment of MCl4 by dilithium salts of the respective bis(2,4,6-trialkylindenyl)dimethylsilanes in toluene. Alternatively, better yields of the same complexes can be obtained by the reaction between metal tetrachlorides and indenyl-tin derivatives gave the desired ansa-metallocenes. All rac- and meso-complexes of Zr and Hf were isolated in an analytically pure form, and six of these ansa-metallocenes were characterized by X-ray crystal structure analysis.
Interpretation of retention indices in gas chromatography for establishing structures of isomeric products of alkylarenes radical chlorination
Zenkevich
, p. 270 - 280 (2007/10/03)
By an example of previously uncharacterized products obtained by alkylarenes radical chlorination was demonstrated that combination of various interpretation methods applied to the retention indices (RI) in the gas chromatography on the standard nonpolar phases (comparison of RI of products and initial compounds, characteristics of succession of the chromatographic elution of the structural isomers with the use of estimation of molecular dynamic parameters, application of the additive schemes to RI calculation, and using of structural analogy CH3?Cl for testing the results obtained) permitted unambiguous identification of the structure even without data of mass spectrometry.
