1,8-Bis(dimethylamino)-2-(4-methoxyphenyl)naphthalene: An electrospray-active analogue for η6-coordinating ligands

Vikse, Krista L.; Kwok, Samantha; McDonald, Robert; Oliver, Allen G.; McIndoe, J. Scott

doi:10.1016/j.jorganchem.2012.07.009

Cited by 17 publications

(14 citation statements)

References 43 publications

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“…To the best of our knowledge, there is only one mention of the synthesis of a 2‐aryl derivative of the proton sponge. 1,8‐Bis(dimethylamino)‐2‐(4‐methoxyphenyl)naphthalene 11 e was synthesized in 41 % yield as an electrospray‐active analogue for η 6 ‐coordinating ligand, strarting from 2‐bromo‐1,8‐bis(dimethylamino)naphthalene and (4‐methoxyphenyl)boronic acid . To perform this the Pd(OAc) 2 /PPh 3 /NaHCO 3 /H 2 O/ n PrOH catalytic system (reflux, overnight) was used.…”

Section: Resultsmentioning

confidence: 99%

“…The good performance was noticed when the reaction was carried out with arylboronic acids bearing electron‐donating p ‐OMe and p ‐NMe 2 groups (Entries 4,5). It should be noted that authors did not report any by‐product(s) of the Suzuki coupling of 13 a with (4‐methoxyphenyl)boronic acid, though the target 2‐aryl derivative 11 e was isolated in a moderate yield. We reproduced the described procedure, while in addition to the target product 11 e (38 % yield), compound 14 was also isolated in 16 % yield.…”

Section: Resultsmentioning

confidence: 99%

“…We determined the basicity constants of compounds 11 , 12 and some other ortho ‐substituted derivatives of the proton sponge by the competitive method in DMSO‐d 6 (see Table ). Taking into account steric strain and associated destabilization of the 2‐phenyl 11 a and 2,7‐diphenyl DMANs 12 a as free bases, it would be logical to expect an increase in their basicity compared with the parent proton sponge.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of 2‐Aryl‐ and 2,7‐Diaryl‐1,8‐bis(dimethylamino)naphthalenes. Overview of the “Buttressing effect” in 2,7‐Disubstituted Proton Sponges

et al. 2020

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Suzuki arylation of 2‐halogeno and 2,7‐dihalogeno derivatives of 1,8‐bis(dimethylamino)naphthalene (proton sponge) was carried out. It was shown that the sterically hindered nature of the starting compounds in combination with the enhanced reactivity of their peri‐NMe2 groups allow to obtain the target 2‐aryl and 2,7‐diaryl derivatives in 20–34 % yields only. In most cases, a tandem Pd‐catalyzed hydrodehalogenation/N‐demethylation process was predominant. The latter, however, makes it possible to obtain yet unknown and synthetically valuable 2‐aryl‐N1,N1,N8‐trimethyl‐1,8‐diaminonaphthalenes (21–50 %), which can be easily converted into the corresponding proton sponges by conventional N‐methylation. Using the literature data on 2,7‐disubstituted derivatives of the proton sponge as a background together with the XRD and basicity measurements performed in this work, a comprehensive analysis of the so‐called “buttressing effect” in 2‐aryl‐ and 2,7‐diaryl‐1,8‐bis(dimethylamino)naphthalenes, along with previously unknown 2,6‐diphenyl‐N,N‐dimethyl‐p‐toluidine has been carried out for the first time.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthesis of 2‐Aryl‐ and 2,7‐Diaryl‐1,8‐bis(dimethylamino)naphthalenes. Overview of the “Buttressing effect” in 2,7‐Disubstituted Proton Sponges

et al. 2020

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“…There are several possible applications for proton sponges described in the literature: Farrer et al and Vikse et al used proton sponge analogon as electrospray-active ligands and tags for metal complexes but reported side reactions such as halide dissociation or oxidation of the electron-rich metal complex. 15,16 Hughes et al used proton sponges as hydride donors to transition metal complexes. 17 The classic proton sponge 1,8-bis(dimethylamino) naphthalene (DMAN) was successfully applied as a matrix for negative matrix assisted laser desorption ionisation (MALDI) for the analysis of biological samples by Shroff et al in 2009.…”

Section: Introductionmentioning

confidence: 99%

“…used proton sponge analogon as electrospray-active ligands and tags for metal complexes but reported side reactions such as halide dissociation or oxidation of the electron-rich metal complex. 15,16 Hughes et al. used proton sponges as hydride donors to transition metal complexes.…”

Section: Introductionmentioning

confidence: 99%

Using aromatic polyamines with high proton affinity as “proton sponge” dopants for electrospray ionisation mass spectrometry

Wirth

Rüger

Sklorz

et al. 2017

Eur J Mass Spectrom (Chichester)

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Proton sponges are polyamines with high proton affinity that enable gentle deprotonation of even mildly acidic compounds. In this study, the concept of proton sponges as signal enhancing dopants for electrospray ionisation is presented for the first time. 1,8-Bis(dimethylamino)naphthalene (DMAN) and 1,8-bis(tetramethylguanidino)naphthalene (TMGN) were chosen as dopants, using methanol and acetonitrile/methanol as solvents. Individual standard compounds, compound mixtures and a diesel fuel as a complex sample matrix were investigated. Both proton sponges enhanced signal intensities in electrospray ionisation negative mode, but TMGN decomposed rapidly in methanolic solution. Significantly higher signals were only achieved using the acetonitrile/methanol mixture. On average a more than 10-fold higher signal intensity was measured with 10mol l DMAN concentration. A stronger signal increase of alcohol functionalities was observed compared to acid functionalities. All compound classes which were detected in the diesel fuel (CH- and CHO-class) received roughly 100-fold higher signal intensities when using DMAN as a dopant. Furthermore, the number of detected compounds as well as the double bond equivalent of the detected compounds increased. The compound class distribution shifted when adding DMAN and the formerly dominant CHO-, CHO-, and CHO- classes received similar relative intensities as formerly less accessible classes. The findings depict DMAN as a promising additive for electrospray ionisation negative analysis of at least mildly acidic compounds, even within complex sample material.

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Current Electrospray Mass Spectrometry: An Overview. PartB. Analyte Charging

Verkerk

2015

Encyclopedia of Analytical Chemistry

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Electrospray ionization (ESI) is an atomization and ionization method through which a solution‐phase analyte can be transferred into the gas‐phase as an ion via minute charged droplets. The second part of this two‐part review on electrospray mass spectrometry reviews the final part of the charged droplet trajectory and covers transfer into the gas‐phase and ionization of the analyte. The now customary separation into the ion evaporation model (for small analytes) and the charged residue model (for large analytes) is followed and reviewed. These models yield insight into the charging process, but observations made with newer atomization techniques and quantitation limitations imposed by ionization suppression (matrix effect) indicate that a complete understanding is not available yet. Deviations from expected charged residue or ion evaporation behavior will be indicated. Chemical and charge‐driven surfactancy is discussed in relation to small analyte ionization and quantitation, whereas hydration and kinetic trapping of protein conformers are treated as part of the charged residue model.

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1,8-Bis(dimethylamino)-2-(4-methoxyphenyl)naphthalene: An electrospray-active analogue for η6-coordinating ligands

Cited by 17 publications

References 43 publications

Synthesis of 2‐Aryl‐ and 2,7‐Diaryl‐1,8‐bis(dimethylamino)naphthalenes. Overview of the “Buttressing effect” in 2,7‐Disubstituted Proton Sponges

Synthesis of 2‐Aryl‐ and 2,7‐Diaryl‐1,8‐bis(dimethylamino)naphthalenes. Overview of the “Buttressing effect” in 2,7‐Disubstituted Proton Sponges

Using aromatic polyamines with high proton affinity as “proton sponge” dopants for electrospray ionisation mass spectrometry

Current Electrospray Mass Spectrometry: An Overview. PartB. Analyte Charging

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