The Friedel-Crafts Acylation Reaction and its Application to Polycyclic Aromatic Hydrocarbons

Gore, P. H.

doi:10.1021/cr50002a001

Cited by 230 publications

(79 citation statements)

References 111 publications

(149 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…It had been reported that Friedel-Crafts acylation reaction is a reversible reaction and the elimination of by-produced HCl is necessary to move the equilibrium toward the product site [11]. We had reported that the replacement of the solvent to the fresh one accelerated the Friedel-Crafts acylation catalyzed by AlCl 3 and higher molecular weight PEK could be obtained [3].…”

Section: Mechanism Of Precipitation Polymerizationmentioning

confidence: 99%

Consideration of Solvent Effect on Precipitation Polymerization of Poly(ether-ketone)s via Friedel-Craft Acylation

et al. 2006

View full text Add to dashboard Cite

Precipitation polymerization of diphenyl ether and isophthaloyl chloride catalyzed by AlCl 3 via Friedel-Crafts acylation was examined in various solvents to clarify the polymerization behavior. Polymerizations were carried out in three categorized solvents based on the solubility to both catalyst and polymer, which were cyclohexane (CH), 1,2-dichloroethane (DCE) and DCE containing 2 wt% nitrobenzene (2%-NB). In DCE which was widely used, the oligomers were precipitated as a form of the complex with AlCl 3 at the early stage of polymerization. The precipitates of the oligomers were swollen by the solvent, in which any short-range regular structure did not exist. The further polymerization proceeded even in the precipitates with eliminating by-produced HCl, and high molecular weight poly(ether-ketone)s (PEK) were finally formed. Nevertheless the reaction in 2%-NB yielded the well-swollen precipitates, the high molecular weight PEK was not synthesized in the precipitates because the reaction was terminated by not only the inefficient elimination of HCl due to the higher solubility of HCl but also the deactivation of catalyst by coordination of NB to AlCl 3 . Although the precipitation occurred more readily in CH due to the lower solubility of oligomers, the polymer was not synthesized in the precipitates. The resulting precipitates comprised of the dimers were not swollen in this case, and thereby it was very difficult to react between dimers and eliminate HCl from the precipitates. The solvents having high miscibility to catalyst and the polymers, low solubility of HCl gas, and no basicity are necessary for making high molecular weight polymers via the precipitation polymerization.

show abstract

Section: Mechanism Of Precipitation Polymerizationmentioning

confidence: 99%

Consideration of Solvent Effect on Precipitation Polymerization of Poly(ether-ketone)s via Friedel-Craft Acylation

et al. 2006

View full text Add to dashboard Cite

show abstract

“…[7][8][9][10] does assist in the halogen migration as well as in the reductive removal of one of the halogen atoms, with the latter reaction depending upon the presence of an oxidizable substance. However, acidic solvents of lower polarity (and this includes phenolic products of the reaction to some extent) can accoinplish the same thing.…”

Section: Summary Re Factors Which Affect Halogen Ii4igration and Rmentioning

confidence: 99%

Halogen Migration and Elimination in the Claisen Rearrangement of Allyl 2,6-Dihalophenyl Ethers

Piers¹,

Brown²

1963

Can. J. Chem.

View full text Add to dashboard Cite

-4 study has been made of some factors affecting the migration or elimination of halogen in the Claisen rearrangement of allyl 2,6-dihalophenyl ethers.I n the thermal rearrangement of allyl 2,6-dichlorophenyl ether, carried out in a number of solvents of different dielectric constant, halogen ~liigratio~l proceeds somewhat better in highly polar solvents. However, a competitive reduction to the monohalogenated allylphenol occurs in the presence of oxidizable solvents and/or products. The reaction is also conlplicated by the catalytic effects of certain solvents and the phenolic products, which give results similar to those obtained with Lewis acids. Stannous chloride acts as a Lewis acid and catalyzes the rearrangement of allyl 2,6-dichlorophenyl ether with simultaneous halogen rearrangement. As well, a competitive reductive removal of the halogen takes place. Results from the rearrangenlent of allyl 2,6-dibromophenyl ether with zinc chloride and of ally1 2,G-dichlorophenyl ether with zi~lc bromide, as well as those from the stannous chloride reactions indicate -that the halogen mi,oration takes place not only by an allylic shift but also via a co~npetitive halogen substitution probably occurring by an Ss2' pathway possibly assisted by a zinc halide bridge mechanism and/or an ionic species such as ZnS?\i@.

show abstract

“…Under these conditions deacylations and acyl rearrangements become feasible [Buehler & Pearson, 1970;Pearson & Buehler, 1971;Gore, 1974]. The concept of reversibility in Friedel-Crafts acylations [Gore, 1955[Gore, , 1964 was put forward in 1955 by Gore, who proposed that "the Friedel-Crafts acylation reaction of reactive hydrocarbons is a reversible process" [Gore, 1955]. Gore concluded that "Reversibility is an important factor in acylation reactions" [Gore, 1955].…”

Section: Introductionmentioning

confidence: 99%

“…The concept of reversibility in Friedel-Crafts acylations [Gore, 1955[Gore, , 1964 was put forward in 1955 by Gore, who proposed that "the Friedel-Crafts acylation reaction of reactive hydrocarbons is a reversible process" [Gore, 1955]. Gore concluded that "Reversibility is an important factor in acylation reactions" [Gore, 1955]. The reversibility studies have been focused mainly on unusual aspects of selectivity, including deacylations, one-way rearrangements and kinetic versus thermodynamic control [Gore, 1974].…”

Section: Introductionmentioning

confidence: 99%

Polycyclic Aromatic Ketones – A Crystallographic and Theoretical Study of Acetyl Anthracenes

Pogodin¹,

Cohen²,

Mala’bi³

et al. 2011

Current Trends in X-Ray Crystallography

View full text Add to dashboard Cite

The Friedel-Crafts Acylation Reaction and its Application to Polycyclic Aromatic Hydrocarbons

Cited by 230 publications

References 111 publications

Consideration of Solvent Effect on Precipitation Polymerization of Poly(ether-ketone)s via Friedel-Craft Acylation

Consideration of Solvent Effect on Precipitation Polymerization of Poly(ether-ketone)s via Friedel-Craft Acylation

Halogen Migration and Elimination in the Claisen Rearrangement of Allyl 2,6-Dihalophenyl Ethers

Polycyclic Aromatic Ketones – A Crystallographic and Theoretical Study of Acetyl Anthracenes

Contact Info

Product

Resources

About