Presence Of Aluminum Halides Research Articles

Cascade reaction of 2,3-naphthalenediol with benzene in the presence of aluminum halides

2,3-Naphthalenediol on superelectrophilic activation with aluminium halides smoothly reacts with benzene to give 4-((3-phenyl-1H-inden-1-yl)methyl)benzene-1,2-diol, which in turn undergoes intramolecular cyclization to form 5,10-methano-5-phenyldibenzo[a,d]cycloheptane-2,3-diol. The mechanistic aspects of these unusual transformations are discussed.

Mechanistic investigation of superelectrophilic activation of 1,1'-bi-2-naphthols in the presence of aluminum halides.

7,7'-Dihydroxy-1,1'-bi-2-naphthol, as a result of superelectrophilic activation in the presence of an excess of aluminum halides, reacts with cyclohexane and benzene to yield 5,6,7,8,5',6',7',8'-octahydro-7,7'-dioxo-bi-2-naphthol and its 5,5'-diphenyl derivative, respectively. In contrast, isomeric 6,6'-dihydroxy-1,1'-bi-2-naphthol does not react at all under the same reaction conditions, while the parent 1,1'-bi-2-naphthol (BINOL) reveals an alternative mode of behavior. The mechanistic aspects of these intriguing results are discussed on the basis of experimental and theoretical (DFT) study of the protonation and complexation properties of the starting BINOLs.

Theory and Practice of the Preparation of Adamantylarenes

The adamantylation of diphenyl oxide and phenol with 1-chloro(bromo)adamantanes in a liquid phase has been studied. The reaction has been performed under kinetic control and under the conditions of reaching chemical equilibrium using the following catalysts: Amberlyst 36 Dry, in situ HBr, and AlCl3. The kinetics of isomerization of (1-adamantyl)- and (2-adamantyl)diphenyl oxides has been studied at 333 and 417 K in the presence of AlCl3 and Amberlyst 36 Dry, respectively. The equilibrium of the positional and structural “bridge–bridgehead” isomerization has been studied in the range of 333–523 K. It has been found that high selectivity of the adamantylation of diphenyl oxide or phenol can be achieved in the case of the use of sulfonated cation-exchange resins as a catalyst. In the presence of aluminum halides or HBr, the reaction mixture has been represented by all the possible isomers and adamantane.

Reactions of 2,3-naphthalenediol with cyclohexane in the presence of aluminum halides

2,3-Naphthalenediol (7) undergoes selective ionic hydrogenation with cyclohexane in the presence of excess AlCl3 or AlBr3 to afford 5,6,7,8-tetrahydro-2,3-naphthalenediol (8). Compound 8 can be further converted into 5,6,7,8-tetrahydro-1,2-naphthalenediol (9) and pyrocatechol (10). The discovered reactions represent new and efficient synthetic approaches to produce difficult to obtain derivatives of 7. The mechanistic aspects of the reactions, and the potential involvement of superelectrophilic dicationic intermediates, are discussed.

Electrophilic dimerization of naphthols in the presence of aluminum halides

Naphthols undergo dimerization in the presence of an excess of aluminum halides to give mixtures of isomeric hydroxynaphthyltetralones.

ChemInform Abstract: Alkylation of Aliphatic Compounds with Tetraorganosilanes in the Presence of Aluminum Halides

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactions of arylacetylenic compounds with arenes in the presence of aluminum halides

Conjugated arylacetylenic ketones and aldehydes, propargyl-type alcohols, and arylacetylenes reacted with arenes in the presence of AlBr3 or AlCl3 as catalyst to give substituted indenes. 3-Arylpropynoic acids under analogous conditions gave rise to 3,3-diarylindan-1-ones, while the corresponding methyl esters were converted into methyl 3,3-diarylprop-2-enoates. The key intermediates in the transformations of acetylenic ketones and aldehydes and propargyl-type alcohols into indene derivatives are resonance-stabilized propargyl—allenyl cations -C≡ C-C+ ↔ -C+=C=C which reacted with one of the resonance structures to give isomeric indenes, depending on the substituent nature.

Polycondensation of naphthalene and its alkyl derivatives

Polycondensation of naphthalene and its alkyl derivatives (stripping oil, 2,5-dimethylnaphthalene) in the presence of aluminum halides was performed. Under the action of an ultrasonic field on a benzene solution of naphthalene in the presence of the catalyst, intermolecular condensation and benzene addition are observed.

Superacidic Activation of Maleimide and Phthalimide and Their Reactions with Cyclohexane and Arenes

AbstractWhen activated in the CF3SO3H/SbF5 acid system maleimide (1) and phthalimide (2) undergo selective ionic hydrogenation with cyclohexane to give 1,5‐dihydropyrrol‐2‐one (3) and phthalimidine (11), respectively. When treated with aluminum halides, N‐phenylmaleimide (4) reacts with cyclohexane to give N‐phenylsuccinimide (5), whereas 2 still gives 11. Imide 1 also condenses with benzene in trifluoromethanesulfonic acid (CF3SO3H) to give 1,5‐dihydro‐5,5‐diphenylpyrrol‐2‐one (7) as the major product. However, in the presence of aluminum halides 1 reacts with benzene, toluene, and o‐dichlorobenzene to give 3‐arylsuccinimides 8–10, respectively. Imide 2 reacts with benzene under the influence of trifluoromethanesulfonic acid as well as aluminum halides to yield 3,3‐diphenylphthalimidine (12). The mechanism of these reactions, with potential involvement of superelectrophilic dicationic intermediates, is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Superacidic Activation of 1- and 3-Isoquinolinols and Their Electrophilic Reactions1

Isomeric 1- and 3-isoquinolinols (11 and 12) when activated in CF(3)SO(3)H-SbF(5) acid system undergo selective ionic hydrogenation with cyclohexane to give 5,6,7,8-tetrahydro-1(2H)- and 5,6,7,8-tetrahydro-3(2H)-isoquinolinones (22 and 27). Under the influence of aluminum chloride similar products were also obtained along with 3,4-dihydro-1(2H)- and 1,4-dihydro-3(2H)-isoquinolinones (23 and 28), respectively. Compounds 11 and 12 also condense with benzene in the presence of aluminum halides, under mild conditions, to give 3,4-dihydro-3-phenyl-1(2H)- and 1,4-dihydro-1-phenyl-3(2H)-isoquinolinones (24 and 29), respectively. Prolonged reaction time or catalysis under strongly acidic HBr-AlBr(3) provides an alternative reaction pathway to yield 5,6-dihydro-6,8-diphenyl-1(2H)- and 5,6,7,8-tetrahydro-6,8-diphenyl-3(2H)-isoquinolinones (25 and 30), respectively. Products 24 and 29 were also found to revert back to 11 and 12 in the presence of aluminum halides in o-dichlorobenzene. The mechanism of these intriguing reactions, which involves superelectrophilic dicationic intermediates, is discussed.

ChemInform Abstract: Ionic Hydrogenation of α,β‐Unsaturated Ketones with Cyclohexane in the Presence of Aluminum Halides.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactions of 5-, 6-, 7-, 8-hydroxyquinolines and 5-hydroxyisoquinoline with benzene and cyclohexane in superacids.

Isomeric 5-, 6-, 7-hydroxyquinolines (11-13) and 5-hydroxyisoquinoline (14) gave N,C-diprotonated dications in CF(3)SO(3)H-SbF(5) superacid medium. Compounds 11, 13, 14, and 8-hydroxyquinoline (5) underwent selective ionic hydrogenation with cyclohexane in the presence of aluminum chloride. Compounds 11 and 14 condense with benzene in the presence of aluminum halides. The detailed mechanism of reactions, which involves superelectrophilic dicationic intermediates, is discussed.

Ionic Hydrogenation of α,β-Unsaturated Ketones with Cyclohexane in the Presence of Aluminum Halides

4-Methyl-3-penten-2-one, 3-hepten-2-one, 3-methyl-1-phenyl-2-buten-1-one, 4-(2,4-dichlorophenyl)-, 4-(4-hydroxyphenyl)-, 4-(4-methoxyphenyl)-, 4-(2-hydroxyphenyl)-, and 4-(4-dimethylaminophenyl)-3-buten-2-ones, and 3-(4-methoxyphenyl)-1-phenyl-2-propenone react with cyclohexane in the presence of excess aluminum chloride or aluminum bromide in CH2Cl2 or CH2Br2, respectively, at room temperature to form the corresponding saturated ketones in high yields. Using 4-phenyl- and 4-(4-methoxyphenyl)-3-buten-2-ones as examples, it was shown that the reaction pattern does not change in going from the Lewis acids AlCl3 and AlBr3 to proton-donor acid system CF3SO3H-SbF5. The reactive intermediates are likely to be C-protonated complexes of α,β-unsaturated ketones with aluminum halides or their O,C-diprotonated analogs.

Trapping of protonated phenols (ethers) by aromatics in superacids

Condensation of phenols and their methyl ethers with aromatics is easily carried out in HF–SbF5 or in the presence of aluminum halides (AlCl3 or AlBr3). The postulated mechanism implies trapping of the diprotonated phenolic moiety by aromatics (benzene, naphthalene, tetrahydroquinoline) or through an intramolecular process.

ChemInform Abstract: Condensation of 1‐Naphthol with o‐Dichlorobenzene in the Presence of Aluminum Halides.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Novel Halogenation of Thiophenes with Benzeneseleninyl Chloride and Aluminum Halide.

AbstractIn the presence of aluminum halides, Ph‐SeO‐X is an efficient regioselective halogenating reagent for heterocyclic compounds such as (I).

New hydrogenating systems for ionic hydrogenation

Ethyldichlorosilane and alkylisopropylbenzenes in the presence of aluminum halides are hydride ion donors in the ionic hydrogenation of olefins, alkyl halides, and trifluoroacetate derivatives of alcohols.

Reduction of dimethyldichlorosilane with ethyldichlorosilane in presence of aluminum halides

Ethyldichlorosilane in the presence of 4 mole% AlBr3 or 12 mole % AlCl3 reduces dimethyldichloro-silane to dimethylchlorosilane (21% yield). Here a substantial amount of the ethyldichlorosilane is converted to ethylchlorosilane and ethylsilane. CH3SiHCl2 and CH3SiH2Cl were also detected in the reaction products, the formation of which is apparently due to the demethylating action of the aluminum halides on either (CH3)2SiCl2 or its reduction products.

Liquid-phase transformations of m-xylene in presence of metal halides

1. A study was made of the transformations of m-xylene in presence of aluminum halides and also in presence of Sn, Ti, Sb, and Zn chlorides and their equimolecular mixtures with aluminum chloride. 2. It was shown that in presence of AlCl3 or AlBr3 m-xylene undergoes isomerization with formation of 18–20% by weight of p-xylene. This yield is 75.6–85.2% of the equilibrium value. 3. It was found that addition of SbCl3 or SnC4 to aluminum chloride results in suppression of the drastic effects of aluminum chloride alone with almost complete elimination of side reactions of demethylation and methylation.

The Isomerization of Cyclohexane and Methylcyclopentane in the Presence of Aluminum Halides. I. The Nature of the Catalyst

The Isomerization of Cyclohexane and Methylcyclopentane in the Presence of Aluminum Halides. I. The Nature of the Catalyst