SOME NEW SUBSTITUTED BENZYL ESTERS<sup>1</sup>

Barkenbus, Charles; Holtzclaw, John B.

doi:10.1021/ja01685a019

Cited by 9 publications

(2 citation statements)

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“…Received June 19,1980 The mechanism of the photobromination reactions of a series of 10-substituted 9-methylanthracenes with bromotrichloromethane was reexamined. It was shown, contrary to the previous report, that the reaction proceeded by a mixed chain involving abstraction by both the bromine atom and the trichloromethyl radical.…”

mentioning

confidence: 99%

Polar radicals. 15. Interpretation of substituent effects on the mechanism of electrolytic reduction of the carbon-halogen bond in series of substituted benzyl halides

Tanner¹,

Plambeck²,

Reed³

et al. 1980

J. Org. Chem.

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The electrochemical polarographic reduction of a series of substituted benzyl chlorides and benzyl bromides showed half-wave potentials which gave excellent Hammett linear free-energy correlations for each series. These correlations were obtained using " substituent constants. The correlation with ' suggests that the potential-determining electrochemical process involves carbon-halogen bond breaking or, alternatively, radical anion intermediate formation. The Hammett p values for each correlation were calculated; their magnitudes, Cl > Br, were in the inverse order of their reactivity toward chemical reduction. As in the case of trialkyltin hydride reduction, both p values were positive. The results of the polarographic electroreduction of benzyl iodide and benzylmercuric iodide confirmed the previously reported mechanism for reduction; namely, that the iodide underwent reaction with mercury to form benzylmercuric iodide, which was subsequently reduced, as was benzylmercuric iodide itself, by a process having two distinct polarographic waves. The half-wave potentials for the second wave (the wave at the most negative potential) for series of substituted benzyl iodides and benzylmercuric iodides were both found to give excellent Hammett correlation, having positive p values. The correlations were both obtained by using ' substituent constants. The success of the use of these substituent constants was taken as a confirmation of the suggestion, previously made, that the second step in the electroreduction was the reduction of the benzylmercuryl radical, and suggests that the process is concerted with carbon-mercury bond rupture.

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confidence: 99%

Polar radicals. 15. Interpretation of substituent effects on the mechanism of electrolytic reduction of the carbon-halogen bond in series of substituted benzyl halides

Tanner¹,

Plambeck²,

Reed³

et al. 1980

J. Org. Chem.

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“…1,4-Dimethoxynaphthalene (DMNH), 22 and 4-cyanobenzyl chloride 23 The other reactions were similarly carried out and the product yields obtained are detailed in Table 1. The following products were isolated and characterised.…”

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confidence: 99%

Photoinduced benzylation of 1,4-dimethoxynaphthalene by benzyl halides

Albini¹,

Siviero²,

Mella³

et al. 1995

J. Chem. Soc., Perkin Trans. 2

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Irradiation of 1,4-dimethoxynaphthalene (DMNH) in the presence of 4-substituted benzyl chlorides (X-C 6 H 4 CH 2 Cl, X = H, Cl, CN, or NO 2 ) in either acetonitrile or benzene solution results in benzylation of DMNH, predominantly at position 2 and to a lesser extent on the unsubstituted ring. Steady state and flash photolysis studies show that charge transfer between singlet excited DMNH and the chlorides is involved. The reaction occurs predominantly in-cage via concerted electron transfer and carbon-chlorine bond cleavage with X = H or Cl , while with X = NO 2 fragmentation of the benzyl chloride radical anion occurs out-of-cage, but the process in this case is much less efficient due to competing back electron transfer.--

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Über die Oxydationsprodukte von Thiocarbonsäureamiden, VI. Methylierung von Thiocarbonsäureamid‐S‐oxyden mit Diazomethan

Walter

Voß

Curts

et al. 1962

Justus Liebigs Ann. Chem.

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Im Gegensatz zu offenkettigen Thioamiden lassen sich Thioamid-S-oxyde rnit Diazomethan methylieren. Die Methylierung erfolgt am Stickstoff der Thioamidgruppe. Aus Thiobenzanilid-und Thiobenz-p-toluidid-S-oxyd konnten kristalline Methylierungsprodukte erhalten werden. In den anderen Fallen wurden die Methylierungsprodukte durch Papier-und Diinnschichtchromatographie identifiziert. Der Methylierungsverlauf wird unter Berucksichtigung einer beim N-Methyl-thiobenzamid-S-oxyd auftretenden Besonderheit diskutiert.Offenkettige Thioamid-S-oxyde zeichnen sich vor den entsprechenden Thioamiden dadurch aus, daB sie rnit Diazomethan in Methanol oder in Athanol methyliert werden, wie zuerst am Thioacetamid-S-oxydz) beobachtet wurde. Die den Beginn der Reaktion anzeigende lebhafte Stickstoffentwicklung klingt nach einiger Zeit ab.In diesem Stadium der Reaktion laBt sich papierchromatographisch mit Jod/Azid bzw.FeCI3 nur ein Fleck rnit dem R,-Wert * ) des Ausgangsmaterials nachweisen. Erst nach mehrmaligem Zusatz von Diazomethan-Losung zeigen sich zwei neue, nur mit dem Jod-Azid-Reagenz nachweisbare Flecke rnit R,= 1 . I 1 (Me-1) und 1.22 (Me-2) in Pyridin/Garungsamylalkohol/Wasser (35 : 35 : 30).* ) RT = RF bez. auf Thioacetamid.

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SOME NEW SUBSTITUTED BENZYL ESTERS¹

Cited by 9 publications

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Polar radicals. 15. Interpretation of substituent effects on the mechanism of electrolytic reduction of the carbon-halogen bond in series of substituted benzyl halides

Polar radicals. 15. Interpretation of substituent effects on the mechanism of electrolytic reduction of the carbon-halogen bond in series of substituted benzyl halides

Photoinduced benzylation of 1,4-dimethoxynaphthalene by benzyl halides

Über die Oxydationsprodukte von Thiocarbonsäureamiden, VI. Methylierung von Thiocarbonsäureamid‐S‐oxyden mit Diazomethan

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SOME NEW SUBSTITUTED BENZYL ESTERS1

Cited by 9 publications

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Polar radicals. 15. Interpretation of substituent effects on the mechanism of electrolytic reduction of the carbon-halogen bond in series of substituted benzyl halides

Polar radicals. 15. Interpretation of substituent effects on the mechanism of electrolytic reduction of the carbon-halogen bond in series of substituted benzyl halides

Photoinduced benzylation of 1,4-dimethoxynaphthalene by benzyl halides

Über die Oxydationsprodukte von Thiocarbonsäureamiden, VI. Methylierung von Thiocarbonsäureamid‐S‐oxyden mit Diazomethan

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SOME NEW SUBSTITUTED BENZYL ESTERS¹