Cumulative Influence of Dimethylamino Groups on the π-System Properties of Aromatic Hydrocarbons

Zweig, Arnold; Lancaster, John; Neglia, Maria T.; Jura, Walter H.

doi:10.1021/ja01073a044

Cited by 66 publications

(25 citation statements)

References 1 publication

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“…A more palatable explanation is that the N-methyl groups interfere sterically with attack on the positions ortho to the amine group and thus deter polymer formation. This is consistent with the fact that little ortho-para or ortho-ortho benzidine is formed when N,N-dimethylaniline is oxidized electrolytically (3) even though MO calculations indicate only slight differences between the electron densities at the ortho and para positions in dimethylaniline (1).…”

Section: Fig 4 Supposed Polymer Unitsupporting

confidence: 77%

Electrode Filming in Ring Substituted Anilines

Prater

1973

J. Electrochem. Soc.

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The study of the electrode filming behavior of a series of ring substituted anilines has indicated that filming occurs only in those compounds containing several doubly activated ring positions. This leads to the conclusion that the films arise due to multiple ring-ring coupling.Electrode filming is one of the banes of the electrochemist's existence. All too often, an interesting compound is electrolyzed and found to yield an insoluble material which rapidly coats the electrode and renders it nonconducting. Such filming makes obtaining electrochemical data difficult at best, and usually necessitates the use of very rapid transient methods in which the data are (hopefully) collected before significant filming has occurred. More often, however, the compound is simply set aside and some more well-behaved compound is studied.It is generally assumed that these films are polymeric materials, but, to the author's knowledge, no one has considered the problem of why some compounds form such films and others do not. This paper reports the results of a survey of the filming properties of a series of ring substituted anilines and suggests that these results are understandable on the basis of the effects of the substituents on the activities of various ring positions. Experimental All solutions were prepared from acetonitrile which had been stored over Call2 and then triply distilled from P4010. The solutions were 0.1M in tetraethylammonium perchlorate. The ring substituted anilines were obtained from Eastman-Kodak and were used as received. The N,N-dimethylated anisidines were prepared from the corresponding anisidines by methylation with trimethylphosphate (1). Solutions were ca. 10-3M in the anilines. The working electrode was a platinum wire and the reference electrode was a silver wire. The potentiostat and voltage scanner were of standard design. Results and DiscussionThe results which were obtained for a series of ring substituted anilines are summarized in Table I. There was little difficulty in separating these compounds into the two categories shown in Table I on the basis of their cyclic voltammograms. Those compounds which were classed as nonfilming exhibited cyclics similar to that of o-anisidine as shown in Fig. 1. After stirring the solution, a second cyclic could be obtained which differed in peak height from the first by less than 2% and in peak potential by less than 30 inV.Those compounds which were classified as filming exhibited behavior similar to that of m-aminophenol shown in Fig. 2. The first cyclic on a clean electrode was characterized by a broad, rounded peak and a rapid decrease in current after switching the direction of potential scan. After stirring the solution, the second * Electrochemical Society Active Member. Table I. Filming behavior of ring substituted anilinescyclic yielded a peak height significantly smaller than before and the peak potential was shifted by several hundred millivolts. After wiping the electrode, a third cyclic was obtained. In general, the peak height for this third cy...

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Section: Fig 4 Supposed Polymer Unitsupporting

confidence: 77%

Electrode Filming in Ring Substituted Anilines

Prater

1973

J. Electrochem. Soc.

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“…Apart from the general low reactivity of substrates 1-3 and 8, to be likely imputed to their very negative reduction potentials, 9,17,18 the results obtained in this work indicate rather similar behaviors of anisidines 1-3 and 8 and of methoxy-substituted anisoles, both in the relative reactivity and in the regioselectivity of cleavage. As regards the relative reactivity, the following order can be drawn for anisidines: 8 > 1 > 2 >> 3; this order parallels quite well that found for anisoles (2,6-dimethoxy > o-methoxy ≥ m-methoxy > pmethoxy).…”

Section: Discussionsupporting

confidence: 50%

Electron-transfer-induced reductive dealkoxylation of alkyl aryl ethers. III. Reductive cleavage of methoxy-substituted N,N-dimethylanilines (N,N-dimethylanisidines)

Azzena¹,

Dessanti²,

Melloni³

et al. 2002

Arkivoc

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“…Within the assumption of a reasonably small value for the 'inner sphere' reorganization energy barrier for the present systems, the data are in agreement with a relatively large, nearly solvent-independent Coulomb term in the Rehm-Weller energy-balance equation. [24]. Naphthalene (Roth, scintillation grade) and MeCN (UV grade) were used without further purification.…”

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confidence: 99%

“…p-Xylene, mesitylene, anisole, aniline. 1,2,4-trimethoxybenzene (1,2,4-TMB), N-methylaniline, triethylamine, N,N-dimethylaniline (N,N-DMA), and NJ"diethylani1ine (N,N-DEA) were distilled using a Fischer column under Ar, 3,4-dimethoxy-N,N-dimethylaniline (3,4-DMDMA) and 2,4-dimethoxy-N,N-dimethylaniline (2,CDMDMA) were synthetized according lo [24]. Naphthalene (Roth, scintillation grade) and MeCN (UV grade) were used without further purification.…”

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confidence: 99%

Free‐Energy Dependence of the Ion Yield of Photo‐Induced Electron‐Transfer Reactions in Solution

Vauthey

Suppan

Haselbach

1988

Helvetica Chimica Acta

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A study of photo-induced electron-transfer reactions in MeCN with 9,IO-dicyanoanthracene as acceptor and 21 electron donors with transient photoconductivity measurements is reported. The free-ion yield and the rate constant of back electron transfer are determined. For exergonic reactions, the 'Marcus-inverted' region is observed. The fit with the theory is best, when a nearly solvent-independent Coulomb term is used in the calculation of the energy balance.

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Cumulative Influence of Dimethylamino Groups on the π-System Properties of Aromatic Hydrocarbons

Cited by 66 publications

References 1 publication

Electrode Filming in Ring Substituted Anilines

Electrode Filming in Ring Substituted Anilines

Electron-transfer-induced reductive dealkoxylation of alkyl aryl ethers. III. Reductive cleavage of methoxy-substituted N,N-dimethylanilines (N,N-dimethylanisidines)

Free‐Energy Dependence of the Ion Yield of Photo‐Induced Electron‐Transfer Reactions in Solution

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