- Mechanism of solvolysis of substituted benzyl chlorides in aqueous ethanol
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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.
- Denegri, Bernard,Mati?, Mirela,Va?ko, Monika
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supporting information
(2021/11/22)
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- Photochemical C(sp)-C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM-CP
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The photochemical activation of the C(sp)-C(sp2) bond in Pt(0)-ν2-aryl-phosphaalkyne complexes leads selectively to coordination compounds of the type LnPt(aryl)(CP). The oxidative addition reaction is a novel, clean, and atom-economic route for the synthesis of reactive terminal Pt(II)-cyaphido complexes, which can undergo [3 + 2] cycloaddition reactions with organic azides, yielding the corresponding Pt(II)-triazaphospholato complexes. The C-C bond cleavage reaction is thermodynamically uphill. Upon heating, the reverse and quantitative reductive elimination toward the Pt(0)-phosphaalkyne-π-complex is observed.
- Boback, Nico,Coles, Nathan T.,Dittrich, Birger,Frost, Daniel S.,G?rlich, Tim,Jones, William D.,Müller, Christian,Müller, Peter
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supporting information
p. 19365 - 19373
(2021/11/26)
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- Selective Pd-catalyzed monoarylation of small primary alkyl amines through backbone-modification in ylide-functionalized phosphines (YPhos)
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Ylide-substituted phosphines have been shown to be excellent ligands for C-N coupling reactions under mild reaction conditions. Here we report studies on the impact of the steric demand of the substituent in the ylide-backbone on the catalytic activity. Two new YPhos ligands with bulky ortho-tolyl (pinkYPhos) and mesityl (mesYPhos) substituents were synthesized, which are slightly more sterically demanding than their phenyl analogue but considerably less flexible. This change in the ligand design leads to higher selectivities and yields in the arylation of small primary amines compared to previously reported YPhos ligands. Even MeNH2 and EtNH2 could be coupled at room temperature with a series of aryl chlorides in high yields.
- Rodstein, Ilja,Prendes, Daniel Sowa,Wickert, Leon,Paa?en, Maurice,Gessner, Viktoria H.
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p. 14674 - 14683
(2020/12/29)
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- α-Diimine-Niobium Complex-Catalyzed Deoxychlorination of Benzyl Ethers with Silicon Tetrachloride
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α-Diimine niobium complexes serve as catalysts for deoxygenation of benzyl ethers by silicon tetrachloride (SiCl4) to cleanly give two equivalents of the corresponding benzyl chlorides, where SiCl4 has the dual function of oxygen scavenger and chloride source with the formation of a silyl ether or silica as the only byproduct. The reaction mechanism has two successive trans-etherification steps that are mediated by the niobium catalyst, first forming one equivalent of benzyl chloride along with the corresponding silyl ether intermediate that undergoes the same reaction pathway to give the second equivalent of benzyl chloride and silyl ether.
- Parker, Bernard F.,Hosoya, Hiromu,Arnold, John,Tsurugi, Hayato,Mashima, Kazushi
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supporting information
p. 12825 - 12831
(2019/10/19)
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- 1,3-dipolar compound bearing an imidazole functional group
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In a 1,3-dipolar compound of formula Q-A-B, Q comprises a dipole containing at least and preferably one nitrogen atom, A, which is preferably divalent, is an atom or a group of atoms connecting Q to B, and B comprises an imidazole ring. An unsaturated polymer modified by grafting the 1,3-dipolar compound is also disclosed.
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Page/Page column 10-11
(2019/02/20)
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- Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols
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Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol-%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded (2-methoxyphenyl)methyl sulfoxide as optimal catalyst. In contrast to reported formamide catalysts, sulfoxides also enable the application of plain acetyl chloride (AcCl) as reagent. In addition, it was demonstrated that weakly electrophilic carboxylic acid chlorides like BzCl promote Pummerer rearrangement of sulfoxides already at room temperature. This side-reaction also provided the explanation, why sulfoxide catalyzed SN-reactions of alcohols do not allow the effective production of aliphatic and electron deficient chloro alkanes. Comparison experiments provided further insight into the reaction mechanism.
- Motsch, Sebastian,Schütz, Christian,Huy, Peter H.
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supporting information
p. 4541 - 4547
(2018/09/13)
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- METHOD OF CONVERTING ALCOHOL TO HALIDE
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The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.
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Page/Page column 98; 99
(2017/01/02)
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- 2-OXO-3,4-DIHYDROPYRIDINE-5-CARBOXYLATES AND THEIR USE
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The present invention is directed to novel compounds of Formula (I), pharmaceutically acceptable salts or solvates thereof, and their use.
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Page/Page column 126
(2016/04/20)
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- A 2, 4, 6-Trimethylbenzene acetyl chloride synthesis process
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The invention relates to a synthesis technology for 2, 4, 6-trimethylbenzene acetyl chloride, comprising the following steps of: putting thionyl chloride, a catalyst and 2, 4, 6-trimethylbenzene acetic acid into a reaction kettle in batches, and controlling temperature to carry out reaction; and after the reaction, distilling (high vacuum) in a heating way in the reaction kettle, and acquiring a final product. The preparation method of the 2, 4, 6-trimethylbenzene acetic acid can comprise the following steps of: carrying out chloromethylation reaction by taking trimethylbenzene, formaldehyde and concentrated hydrochloric acid as raw materials, adding toluene to extract after reacting, and washing to obtain a toluene solution of 2, 4, 6-trimethyl benzyl chloride; taking the toluene solution of 2, 4, 6-trimethyl benzyl chloride and the sodium cyanide as raw materials, adding a phase transfer catalyst, reflowing in a heating way to carry out cyanation reaction, washing by adding water after reacting, distilling oil phase to recover toluene and mesitylene, and rectifying to obtain 2, 4, 6-trimethylbenzene acetonitrile; and hydrolyzing the 2, 4, 6-trimethylbenzene acetonitrile, centrifuging to obtain a 2, 4, 6-trimethylbenzeneacetic acid crude product, and optionally selecting and carrying out the aftertreatment to obtain the 2, 4, 6-trimethylbenzeneacetic acid. The content of the 2, 4, 6-trimethylbenzene acetyl chloride synthesized by the method disclosed by the invention is more than or equal to 98.0%, and the content of the 2, 4, 6-trimethylbenzene acetonitrile is less than or equal to 0.5%.
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Paragraph 0063
(2017/02/09)
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- Rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagent precursors in halogenation reactions
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Heterogeneous polymer-supported triphenylphosphine oxides based on the rasta resin architecture have been synthesized, and applied as reagent precursors in a wide range of halogenation reactions. The rasta resin-triphenylphosphine oxides were reacted with either oxalyl chloride or oxalyl bromide to form the corresponding halophosphonium salts, and these in turn were reacted with alcohols, aldehydes, aziridines and epoxides to form halogenated products in high yields after simple purification. The polymersupported triphenylphosphine oxides formed as a byproduct during these reactions could be recovered and reused numerous times with no appreciable decrease in reactivity.
- Xia, Xuanshu,Toy, Patrick H.
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supporting information
p. 1397 - 1405
(2014/07/22)
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- Chlorination of benzylic and allylic alcohols with trimethylsilyl chloride enhanced by natural sodium montmorillonite
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A new and practical method for the efficient chlorination of tertiary, secondary, and primary benzylic and allylic alcohols is described. The method is characterized by the formation of hydrogen chloride from trimethylsilyl chloride and trace water, the formation of a carbenium ion through the protonation of an alcohol and subsequent dehydration, and the chlorination of the carbenium ion. During the process, sodium ion-exchanged montmorillonite plays a crucial role in capturing the generated hydrogen chloride, stabilizing the carbenium intermediate as well as promoting the chlorination.
- Tandiary, Michael Andreas,Masui, Yoichi,Onaka, Makoto
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supporting information
p. 2639 - 2643
(2015/01/09)
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- Identification of alkylarene chloromethylation products using gas-chromatographic retention indices
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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.
- Zenkevich,Makarov
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p. 611 - 619
(2008/03/18)
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- NOVEL BETA MIMETICS WITH EXTENDED DURATION OF ACTION, METHOD FOR PRODUCTION AND USE THEREOF AS MEDICAMENTS
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The invention relates to compounds of general formula (I), where the groups R1, R2 and R3 can have the meanings given in the claims and the description, method for production and use thereof as medicaments, in particular for the treatment of inflammatory and obstructive bronchial diseases.
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Page/Page column 8
(2010/02/06)
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- Spirodiclofen and spiromesifen - Novel acaricidal and insecticidal tetronic acid derivatives with a new mode of action
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The broad spectrum acaricides spirodiclofen (BAJ2740, trade name: Envidor) and spiromesifen (BSN2060, trade name: Oberon) with an additional excellent activity against whiteflies, both belong to the new chemical class of tetronic acid derivatives discovered at Bayer CropScience during the 1990s. The discovery process starting from herbicidal PPO (protoporphyrinogen oxidase) chemistry, the synthetic routes leading to the products, and some insight into process development of central intermediates is given. Spirodiclofen and spiromesifen have a new mode of action (interference with lipid biosynthesis), show no cross-resistance to any resistant mite or whitefly field population and are therefore valuable tools for resistance management.
- Bretschneider, Thomas,Benet-Buchholz, Jordi,Fischer, Reiner,Nauen, Ralf
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p. 697 - 701
(2007/10/03)
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- ROMPgel-Supported Triphenylphosphine with Potential Application in Parallel Synthesis
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(Equation Presented) ROMPgel-supported triphenylphosphine was synthesized in three steps (67%) from norbornadiene, 4-bromoiodobenzene, and chlorodiphenylphosphine. The supported reagent has a high loading (2.5 mmol/g) and favorable swelling properties in organic solvents. It has been utilized for the conversion of alcohols to halides, the reduction of ozonides, and the isomerization of α,β-acetylenic esters and in the Staudinger reaction. In general, filtration of the resin from the reaction mixtures and evaporation gave the corresponding products in high yield and purity.
- Arstad, Erik,Barrett, Anthony G. M.,Hopkins, Brian T.,Koebberling, Johannes
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p. 1975 - 1977
(2007/10/03)
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- Phase-Transfer Catalysis in Electrophilic Substitution Reactions. V. Reactivities of Aromatic Compounds in Chloromethylation under Conditions of Phase-Transfer Catalysis
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Regioselectivity of chloromethylation of aromatic compounds under conditions of phase-transfer catalysis linearly correlates with the ?+Ar constants, the correlations significantly depending on the catalyst; moreover, the nature of the catalyst is the factor that governs the fine mechanism of the reaction.Only one of the two detected reaction mechanisms yields chloromethyl derivatives as the final products.
- Kachurin, O. I.,Velichko, L. I.,Zaraiskaya, N. A.,Zaraiskii, A. P.
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p. 657 - 659
(2007/10/03)
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- ARYLMETHYL ISOCYANATES
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Chloromethyl isocyanate reacts readily with aromatic hydrocarbons in the presence of anhydrous ferric chloride or other catalysts of the Friedel-Crafts reaction with the formation of arylmethyl isocyanates.The latter add alcohols and amines readily, being converted into the corresponding substituted urethanes and ureas.When heated in the presence of catalytic amounts of 1,3-dimethylphosphol-3-ene they give substituted carbodiimides.
- Kozhushko, B. N.,Lomakina, A. V.,Paliichuk, Yu. A.,Shokol, V. A.
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p. 654 - 660
(2007/10/02)
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- Antihypertensive Activity of 6-Arylpyridopyrimidin-7-amine Derivatives
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A series of 51 6-arylpyridopyrimidin-7-amine derivatives was prepared and evaluated for antihypertensive activity in the conscious spontaneously hypertensive rat.A number of these compounds, notably 6-(2,6-dichlorophenyl)-2-methylpyridopyrimidin-7-amine (36), lowered blood pressure in these rats in a gradual and sustained manner to normotensive levels at oral doses of 10-50 mg/kg.Normalized blood pressure levels could then be maintained by single daily oral doses.The effect of structural variation in the 6-aryl group and in the 2 and 4 positions of the pyridopyrimidine ring on activity is reported and discussed.
- Bennett, Lawrence R.,Blankley, C. John,Fleming, Robert W.,Smith, Ronald D.,Tessman, Deirdre K.
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p. 382 - 389
(2007/10/02)
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- 9-Phenyl-nonate traene compounds
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Novel 9-phenyl 5,6-dimethyl-nona-2,4,6,8-tetraenoic acid, tetraenal or tetraenol derivatives useful as anti-tumor agents.
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- Process for tris(aralkyl)phosphines
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In a solution that is free of bases and free of oxygen and which contains at least four molar proportions of the reactant tris(hydroxymethyl)phosphine for every three molar proportions of an aralkyl halide reactant, the following reaction produces tris(aralkyl)phosphine product: after separation of the phosphine product, the phosphonium salt by-products can be converted to tris(hydroxymethyl)phosphine by the addition of a base.
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