Scope and mechanism of the rearrangement of alkoxybenzyl anions to alkylphenoxide ions; cyclophanes from 2,6-dimethylanisole.

Persistent Link:
http://hdl.handle.net/10150/184679
Title:
Scope and mechanism of the rearrangement of alkoxybenzyl anions to alkylphenoxide ions; cyclophanes from 2,6-dimethylanisole.
Author:
Suvannachut, Kessara.
Issue Date:
1989
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
Alkoxy alkyl groups migrate to benzylic carbon when alkyl alkylphenyl ethers are treated with n-butyllithium and potassium t-butoxide. For alkyl 2,6-dialkylphenyl ethers, yields of the rearrangement products range from 45-70%. Rearrangement products are obtained in 10-30% yield from other dimethylanisoles and methylanisoles. The reactions appear to proceed by homolytic cleavage of the alkoxy alkyl group of alkoxybenzyl anions followed by recombination of the resulting radical pair in a different way. The reaction is useful for preparing 2,6-dialkylphenols and their corresponding ethers. The rearrangement can be avoided by using methyl ethers and working at or below room temperature. This was shown by reacting the dianion from methyl 2,6-dimathylanisole with dialkyl sulfates to give methyl 2,6-dialkylanisoles, with a,ω-dihalides to give methoxy[n]metacyclophanes (n = 8-15), dimethoxy[n.n]metacyclophanes (n = 5-10) and trimethoxy[S.S.S]metacyclophane, and with oxidizing agents to yield dimethoxy[2.2]metacyclophane.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Phenols -- Synthesis.; Rearrangements (Chemistry); Organic compounds -- Synthesis.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Bates, Robert B.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleScope and mechanism of the rearrangement of alkoxybenzyl anions to alkylphenoxide ions; cyclophanes from 2,6-dimethylanisole.en_US
dc.creatorSuvannachut, Kessara.en_US
dc.contributor.authorSuvannachut, Kessara.en_US
dc.date.issued1989en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractAlkoxy alkyl groups migrate to benzylic carbon when alkyl alkylphenyl ethers are treated with n-butyllithium and potassium t-butoxide. For alkyl 2,6-dialkylphenyl ethers, yields of the rearrangement products range from 45-70%. Rearrangement products are obtained in 10-30% yield from other dimethylanisoles and methylanisoles. The reactions appear to proceed by homolytic cleavage of the alkoxy alkyl group of alkoxybenzyl anions followed by recombination of the resulting radical pair in a different way. The reaction is useful for preparing 2,6-dialkylphenols and their corresponding ethers. The rearrangement can be avoided by using methyl ethers and working at or below room temperature. This was shown by reacting the dianion from methyl 2,6-dimathylanisole with dialkyl sulfates to give methyl 2,6-dialkylanisoles, with a,ω-dihalides to give methoxy[n]metacyclophanes (n = 8-15), dimethoxy[n.n]metacyclophanes (n = 5-10) and trimethoxy[S.S.S]metacyclophane, and with oxidizing agents to yield dimethoxy[2.2]metacyclophane.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectPhenols -- Synthesis.en_US
dc.subjectRearrangements (Chemistry)en_US
dc.subjectOrganic compounds -- Synthesis.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorBates, Robert B.en_US
dc.contributor.committeememberSteelink, Corneliusen_US
dc.contributor.committeememberKeller, Philip C.en_US
dc.contributor.committeememberMulvaney, James E.en_US
dc.contributor.committeememberRund, John V.en_US
dc.identifier.proquest8915987en_US
dc.identifier.oclc702371728en_US
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