Fluoranthen und seine Derivate. IV

Braun, Julius v.; Manz, Gottfried

doi:10.1002/jlac.19324960110

Cited by 17 publications

(9 citation statements)

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“…Although the bromination of fluoranthene in carbon bisulfide leads primarily to the 3 isomer, small but unspecified amounts of the 8 isomer have been reported. 22 No 8-bromofluoranthene, although small amounts of the 3,8-dibromo compound, could be detected in the present study, but the preparative bromination was conducted in the presence of PBr3, which may well have made the bromine a less selective reagent.…”

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confidence: 67%

Rates of Bromination of Polynuclear Aromatic Hydrocarbons¹

Altschuler¹,

Berliner²

1966

J. Am. Chem. Soc.

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bromination of pmethoxybenzyl alcohol3 by the hydrogen bromide method,'Q followed by methanolysis with sodium methoxide. Benzyl alkyl ethers were obtained by the treatment of benzyl chloride with sodium alkoxide at the reflux temperature for 3-4 hr. The ethers were all purified by rectification under vacuum ( Table VIII).The other materials were the same with those described pre- viously. 3 (4 : 6 vol. %). The homogeneous reaction mixture was allowed to stand in a flask with a loosely held glass stopper without stirring; no difference in rates was observed between reactions with and without stirring. Aliquots were taken out at appropriate intervals of time, and the produced aldehyde was estimated by means of ultraviolet spectrophotometry after extracting with chloroform as reported previously. 3Materials. Substituted benzyl methyl ethers except the p methoxy derivative were prepared by way of the side-chain bromination of corresponding toluenes, followed by treatment with sodium methoxide. p-Methoxybenzyl ether was synthesized by the (19) R.Abstract: Rate constants for the bromination of several polynuclear aromatic hydrocarbons by molecular bromine were determined in aqueous acetic acid at 25 O. Partial rate factors were obtained from the rates and the major reaction products. The partial rate factors, and some obtained previously, were correlated with MO reactivity parameters and with the rates of other electrophilic substitution reactions. Addition accompanies substitution in the bromination of phenanthrene and anthracene.lthough interest in the reactivities of polynuclear A aromatic systems has increased as a result of the availability of various MO reactivity parameters with which the experimental reactivities can be compared, there are only very few reactions series in which these reactivities have been assessed in direct electrophilic substitution reactions. The studies that cover the largest number of compounds are those on n i t r a t i~n ,~ deuterio depr~tonation,~ the basicity toward hydrogen fluoride,6 and, to a lesser extent, chlorination.' To these we now add bromination. ResultsReactions were carried out in aqueous acetic acid. In acetic acid, as well as in other solvents of low dielectric constant, the kinetics of bromination is complicated by the intervention of terms which are of high order in bromine, and by the complexing of unreacted bromine with bromide ion which is formed as the reaction proceeds.* It is for this reason that investigations that did employ bromination for a comparison of relative rates have often relied on a comparison of time intervals required to reach a definite per cent of reaction, and rate constants were not determined. For instance, (1) Relative Reactivities of Polynuclear Aromatic Systems. (2) Taken from the Ph.D. thesis of L. Altschuler, Bryn Mawr Col-(3) To whom inquiries should be addressed. (4) M.in an earlier study of bromination, Mason compared the times for 5 and 10% bromination of hydrocarbons in 80% acetic acid.g Under these conditions, the bromination ...

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confidence: 67%

Rates of Bromination of Polynuclear Aromatic Hydrocarbons¹

Altschuler¹,

Berliner²

1966

J. Am. Chem. Soc.

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“…1-Hydroxyfluoranthene was prepared via the sulfonate and alkali fusion according to the method of Braun and Manz. 20 Multiple recrystallizations from chlorobenzene gave a material of melting point 188-189°( lit.20 mp 190°).…”

Section: Methodsmentioning

confidence: 99%

Inhibition of Free-Radical Reactions. II.¹ Kinetic Study of the Reaction of Peroxy Radicals with Hydroquinones and Hindered Phenols

Mahoney¹

1966

J. Am. Chem. Soc.

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The rate of dissociation of 2,2,3,34etraphenylbutane (TPB) in solution at 60.0' has been measured by the oxygen scavenging-antioxidant technique. The first-order rate constant is independent of oxygen pressure (above 200 mm) in chlorobenzene and has the value of 2.0 i 0.1 X sec-1 in the three solvents chlorobenzene, nitrobenzene, and isopropylbenzene. In the three solvents the efficiency of radical production is essentially unity.Solutions of 9,lO-dihydroanthracene (0.050 to 1.580 M> in chlorobenzene containing TPB absorb oxygen at a rate which is accurately first order in hydrocarbon and one-half order in TPB, indicating a lack of solvent effects due to variations in hydrocarbon concentration in the region examined. A series of hydroquinones and hindered phenols were then employed as inhibitors for the 9,lO-dihydroanthracene-TPB system. Rate measurements conducted in the presence and in the absence of added hydroperoxide are consistent with the view that chain transfer reactions of the radicals derived from the inhibitor with hydrocarbon and with hydroperoxide are very inefficient processes for these compounds. Although the relative reactivities of these inhibitors vary among themselves by a factor of 2000, the results of this portion of the study also demonstrate that peroxy radicals derived from TPB and from the hydrocarbon are indistinguishable in their rates of reaction with each inhibitor. ow concentrations of phenols and hydroquinones (1963), is considered paper I in this series.Chemists," John Wiley and Sons, Inc., New York, N. Y., 1961, p 192.

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“…Gerty (79), repeating Goldschmiedt's work, isolated a tetrachlorofluoranthene. Much later von Braun and Manz (18,19), while investigating the orientation of substituents in fluoranthene, found that under suitable conditions dibromination may be avoided and two monobromofluoranthenes formed.…”

Section: Reduction Of Fluoranthenementioning

confidence: 99%

“…The product is useful as a coupling component for azo dyes (98). D. SUBSTITUTION BY THE FRIEDEL-CRAFTS REACTION von Braun and Manz (19) deduced from the results of their experiments that benzoyl chloride in the presence of aluminum chloride and carbon disulfide gave a mixture of 8-benzoyl-and 3-benzoylfluoranthenes, the former being the main product. This is in direct contrast to the effects of bromination, nitration, and sulfonation.…”

Section: Orientation Of Substitutionmentioning

confidence: 99%

“…Under similar conditions, substitution in the 8-position with phthalic anhydride and with oxalyl chloride was obtained. Substitution in the secondary products occurs in the same position with both benzoyl chloride and phthalic anhydride, since the oximes, by Beckmann transformation, hydrolysis, and Curtius degradation, yielded the known 3aminofluoranthene (19) (see page 496).…”

Section: Orientation Of Substitutionmentioning

confidence: 99%

See 1 more Smart Citation

The Chemistry of Fluoranthene.

Tucker¹,

Whalley²

1952

Chem. Rev.

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Fluoranthen und seine Derivate. IV

Cited by 17 publications

References 5 publications

Rates of Bromination of Polynuclear Aromatic Hydrocarbons¹

Rates of Bromination of Polynuclear Aromatic Hydrocarbons¹

Inhibition of Free-Radical Reactions. II.¹ Kinetic Study of the Reaction of Peroxy Radicals with Hydroquinones and Hindered Phenols

The Chemistry of Fluoranthene.

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Fluoranthen und seine Derivate. IV

Cited by 17 publications

References 5 publications

Rates of Bromination of Polynuclear Aromatic Hydrocarbons1

Rates of Bromination of Polynuclear Aromatic Hydrocarbons1

Inhibition of Free-Radical Reactions. II.1 Kinetic Study of the Reaction of Peroxy Radicals with Hydroquinones and Hindered Phenols

The Chemistry of Fluoranthene.

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Rates of Bromination of Polynuclear Aromatic Hydrocarbons¹

Rates of Bromination of Polynuclear Aromatic Hydrocarbons¹

Inhibition of Free-Radical Reactions. II.¹ Kinetic Study of the Reaction of Peroxy Radicals with Hydroquinones and Hindered Phenols