Reaction of Iodobiphenyls and Iodonaphthalenes with Concentrated Sulfuric Acid. Attempted Extension of the Jacobsen Reaction to Polycyclic Systems

Suzuki, Hitomi; Yamamoto, Naotaka

doi:10.1246/bcsj.45.289

Cited by 4 publications

(1 citation statement)

References 6 publications

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“…Indeed, 1,8-diiodonaphthelene 1 was reported to possess a distorted structure by Bock et al 7 To evaluate the reactivity, we focused on the Jacobsen rearrangement. 8 While this reaction is an originally sulfuric acid induced migration or replacement reaction of alkyl groups in alkylbenzenes, Suzuki et al found that the iodo group in iodobenzenes also rearranges under similar conditions, which proceeds through intermolecular electrophilic substitution via a cationic intermediate. 9 Despite the inherent potential, this reaction has not been used practically because of low efficiency and the requirement of harsh reaction conditions.…”

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confidence: 99%

Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups

Iwai,

Nishiguchi,

Nishiwaki

2023

J. Org. Chem.

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The naphthalene ring is distorted due to steric repulsion between iodo groups at the peri-positions. Due to the distortion, 1,8-diiodonaphthalene underwent a halo-Jacobsen rearrangement when treated with trifluoromethanesulfonic acid, producing 1,5-diiodonaphthalene and 1,4-diiodonaphthalene. In this reaction, acid-induced dehalogenative homocoupling also proceeded to form 4,4′-diiodo-1,1′-binaphthyl. The reaction selectivity could be controlled by varying the reaction temperature. DFT calculations and some control experiments revealed that these compounds were formed by different pathways.

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confidence: 99%

Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups

Iwai,

Nishiguchi,

Nishiwaki

2023

J. Org. Chem.

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Jacobsen Rearrangement

2010

Comprehensive Organic Name Reactions and Reagents

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The polysubstituted aromatics conversion into corresponding sulfonated aromatics with the migration of substituents in contact with concentrated sulfuric acid and under these conditions, the halogenated polyalkylaromatics undergo disproportionation of halogen atoms. Hence, this reaction is generally referred to as the Jacobsen rearrangement or Jacobsen reaction. In addition, the study finds that among the polyalkyl benzenes, only the tetraalkyl or pentaalkyl benzenes undergo this reaction. On the other hand, hexaalkyl benzenes, are more stable toward concentrated sulfuric acid, even if they are in contact with it for several months. This reaction is always followed by the evolution of sulfur dioxide, together with the production of amorphous tarry byproducts. More over, this rearrangement is worked for polyalkyl as well as halogenated aromatics and the fluorinated aromatics are the exceptions. For the case of halogenated aromatic compounds, halogen atoms often migrate to give disproportionated products. This reaction has been used to prepare multisubstituted alkyl aromatics with substituents in the vicinal position.

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ChemInform Abstract: RK. VON JODBIPHENYLEN UND JODNAPHTHALINEN MIT KONZENTRIERTER SCHWEFELSAEURE, VERSUCH EINER AUSDEHNUNG DER JACOBSEN‐RK. AUF POLYCYCLISCHE SYSTEME

Suzuki¹,

Yamamoto²

1972

Chemischer Informationsdienst

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Reaction of Iodobiphenyls and Iodonaphthalenes with Concentrated Sulfuric Acid. Attempted Extension of the Jacobsen Reaction to Polycyclic Systems

Cited by 4 publications

References 6 publications

Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups

Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups

Jacobsen Rearrangement

ChemInform Abstract: RK. VON JODBIPHENYLEN UND JODNAPHTHALINEN MIT KONZENTRIERTER SCHWEFELSAEURE, VERSUCH EINER AUSDEHNUNG DER JACOBSEN‐RK. AUF POLYCYCLISCHE SYSTEME

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