Solvent Effects in the Menschutkin Reaction

Reinheimer, John D.; Harley, J. D.; Meyers, Wayne W.

doi:10.1021/jo01041a035

Cited by 39 publications

(14 citation statements)

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“…26 High solvent polarity resulting in high reaction rates of the Menshutkin reaction can be attributed to stabilization of the reaction path of ion separation by the solvent. 94 Purification was carried out by precipitation into cold Et2O afforded by the high polarity of quaternary ammonium compound. From 1 H NMR analysis, the new signals indicated the addition of triethylamine.…”

Section: Coating Preparation Of Poly(vbbp-b-p N Bu3mentioning

confidence: 99%

Robust UV-Curable Antimicrobial Polymeric Coatings for Medical Plastics Prepared by Controlled Radical Polymerization

Shum¹

2021

Preprint

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In response to hospital acquired infections stemming from biofilms and the impending antibiotic resistance crisis, the development of non-traditional, non-leachable antimicrobials have gained significant traction. Contact-active antimicrobial coatings physically attached to surfaces with cationic active sites, such as ammonium and phosphonium, are of particular interest in the prevention of pathogenic bacterial transfer. Previously reported antimicrobial coatings are found to be susceptible to abrasion, significantly limiting their potential applications. In this work, a range of robust, antimicrobial polymeric coatings synthesized by control radical polymerization are presented. Polymeric thin film coatings possessing cationic groups with n-alkyl substituents of n ≤ 4 demonstrated antimicrobial properties against gram-positive bacteria, while species containing bulkier substituents were biologically inactive, contradictory of previously reported monomeric coatings. Cationic polymeric brush coatings were found to have a higher antibacterial activity against the gram-positive model compared to its non-brush equivalent, but failed against the gram-negative model. These polymeric thin films demonstrate the complexity of antimicrobial coating designs and facilitates the investigation into the architecture of these coatings.

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Section: Coating Preparation Of Poly(vbbp-b-p N Bu3mentioning

confidence: 99%

Robust UV-Curable Antimicrobial Polymeric Coatings for Medical Plastics Prepared by Controlled Radical Polymerization

Shum¹

2021

Preprint

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“…27 Alkyl (sp 3 ) carbons can be effortlessly connected to most amines by this nucleophilic substitution. Since its discovery in 1890, the reaction has been thoroughly investigated, [28][29][30][31][32] and it has been shown that it can be accelerated by polar aprotic solvents, [33][34][35] increased pressure, 36,37 and increased leaving-group ability. 38 The reaction scope includes alkyl, allyl, and benzyl halides, which react with a wide range of alkylamines, piperidines, pyridines, and anilines, among others.…”

Section: Alkylation Of Anilines: the Menshutkin Reactionmentioning

confidence: 99%

Strategies for the Synthesis of N-Arylammonium Salts

Arava

Diesendruck

2017

Synthesis

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The N-arylation of tertiary amines to provide sp3 quaternary ammonium salts is a challenge in organic chemistry. To date, no general method for such arylations has been established. Here, we summarize a variety of strategies that have been tested, starting with harsh nucleophilic aromatic substitutions, through to the use of copper catalysis and the application of strong electrophiles, such as phenyl cations and benzynes. The achievements and limitations of each method are summarized, and the challenges yet to be met in the synthesis of charged ammonium compounds are described.1 Introduction2 Alkylation of Anilines: The Menshutkin Reaction3 Arylations3.1 Nucleophilic Aromatic Substitutions by Tertiary Amines3.2 Preparation of N-Arylpyridinum Salts from Zincke and Pyrylium Salts3.3 Arylations Using Phenyl Cations3.4 Copper-Catalyzed Arylation of N-Heteroarenes3.5 Benzynes as Aryl Electrophiles4 Conclusions and Perspective

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“…In accordance with the S N 2 mechanism, the reaction is accelerated by more nucleophilic amines, increased leaving group ability, increased pressure and elevated temperatures (Figure ) . Polar solvents also kinetically enhance the reaction by stabilizing the charged transition state . With alkyl tosyl or mesylates, the reaction is often carried out at lower temperatures and in polar protic solvents in order to avoid a competing elimination reaction…”

Section: Introductionmentioning

confidence: 99%

“…[9] Polar solvents also kinetically enhance the reaction by stabilizing the charged transition state. [10] With alkyl tosyl or mesylates, the reaction is often carried out at lower temperatures and in polar protic solvents in order to avoid a competing elimination reaction. [11] In this study, we describe the preparation and characterization of a series of functionally terminated long chain quaternary ammonium salts ( Figure 2).…”

Section: Introductionmentioning

confidence: 99%

A C₁₈ Quaternary Ammonium Library

et al. 2016

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A library of precursor and functionally active quaternary ammonium cations (QACs) for use as corrosion resistant and or antimicrobial coatings, or alternatively as polymer modifiers, is described. High yielding and improved routes to a series of functionally terminated allyl ([(CH2=CH‐CH2)m‐N+(Me)n‐C18H37][X−], 1: m=1, n=2, X−=Br−, 3: m=2, n=1, X−=I−, 4: m=3, n=0, X−=Br−) vinyl ([CH2=CHCH2CH2‐N+Me2‐C18H37][Br−] 5), hydroxy ([HO‐(CH2)m‐N+Me2‐C18H37][Br−], 6: m=3, 7: m=4), haloalkyl ([X1‐(CH2)3‐N+Me2‐C18H37][X−] 8: X1=Br, X=Br−, 9: X1=Cl, X=I−), dimethoxyphenethyl ([(MeO)2C6H3(CH2)2‐N+Me2‐C18H37][Br−], 11), acetamido ([H3C(O)NH‐(CH2)3‐N+Me2‐C18H37][Cl−], 12) cyano ([N≡C–CH2‐N+Me2‐C18H37][Cl−], 13), organocarbonylamino ([R‐C(O)2NH‐(CH2)3‐N+Me2‐C18H37][Br−], 14: R=t‐Bu‐, 15: R=PhCH2‐), phthalimido ([PhthN‐(CH2)3‐N+Me2‐C18H37][Br−], 16), amino ([H2N‐(CH2)3‐N+Me2‐C18H37][Br−] 17), acetylthio ([HC(O)S‐(CH2)3‐N+Me2‐C18H37][Cl−], 18), thiol ([HS‐(CH2)3‐N+Me2‐C18H37][Cl−] 19), disulfa ([‐S‐(CH2)2‐N+Me2‐C18H37]2[Br−]2, 20) C18 QACs prepared by thermal and or microwave driven Menshutkin reactions are detailed. All new compounds were characterized by NMR spectroscopy, HRMS spectrometry and in the case of 1 and 6 by X‐ray crystallography.

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Solvent Effects in the Menschutkin Reaction

Cited by 39 publications

References 0 publications

Robust UV-Curable Antimicrobial Polymeric Coatings for Medical Plastics Prepared by Controlled Radical Polymerization

Robust UV-Curable Antimicrobial Polymeric Coatings for Medical Plastics Prepared by Controlled Radical Polymerization

Strategies for the Synthesis of N-Arylammonium Salts

A C₁₈ Quaternary Ammonium Library

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Solvent Effects in the Menschutkin Reaction

Cited by 39 publications

References 0 publications

Robust UV-Curable Antimicrobial Polymeric Coatings for Medical Plastics Prepared by Controlled Radical Polymerization

Robust UV-Curable Antimicrobial Polymeric Coatings for Medical Plastics Prepared by Controlled Radical Polymerization

Strategies for the Synthesis of N-Arylammonium Salts

A C18 Quaternary Ammonium Library

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Product

Resources

About

A C₁₈ Quaternary Ammonium Library