PREPARATIONS AND REACTIONS OF CRESOL DIANIONS AND DIMETHYLPHENOL TRIANIONS (ANISOLE, ALKYL PHENOL, CYCLOPHANE).

Persistent Link:
http://hdl.handle.net/10150/183846
Title:
PREPARATIONS AND REACTIONS OF CRESOL DIANIONS AND DIMETHYLPHENOL TRIANIONS (ANISOLE, ALKYL PHENOL, CYCLOPHANE).
Author:
SIAHAAN, TERUNA JAYA.
Issue Date:
1986
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:
With n-BuLi/t-BuOK (Lochmann's base), protons are removed from the hydroxyl and methyl groups of cresols to give cresol dianions in yields of 85% (o), 95% (m), and 40% (p). These dianions react with alkyl halides, MeSiCl, Bu₃Sn Cl, CO₂, and oxidizing agents at carbon only, and with dialkyl sulfates at both carbon and oxygen. Thus phenol derivatives bearing primary alkyl groups can be prepared from the corresponding methylphenol via cresol dianions. Dimethylphenol trianions were prepared with Lochmann's base from all six isomers of dimethylphenol. 3,5-Dimethylphenol trianion was prepared in the best yield (80%); 2,3-, 2,4-, 2,5-, 2,6-, and 3,4-dimethylphenol trianions were prepared in 19.5%, 19%, 52%, 36%, and 44% yields, respectively. The common side products were dianions and tetraanions (in the latter, the fourth proton was usually pulled from the ring ortho to oxygen). These trianions were reacted with dimethyl sulfate to give anisole derivatives. 3,5-Dimethoxytoluene monoanion was reacted with n-BuBr to give a mixture of O,O'-dimethylolivetol (40%) and 4-butyl-3,5-dimethoxytoluene (34%).
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Cresol.; Phenols.; Organic compounds.
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.titlePREPARATIONS AND REACTIONS OF CRESOL DIANIONS AND DIMETHYLPHENOL TRIANIONS (ANISOLE, ALKYL PHENOL, CYCLOPHANE).en_US
dc.creatorSIAHAAN, TERUNA JAYA.en_US
dc.contributor.authorSIAHAAN, TERUNA JAYA.en_US
dc.date.issued1986en_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.abstractWith n-BuLi/t-BuOK (Lochmann's base), protons are removed from the hydroxyl and methyl groups of cresols to give cresol dianions in yields of 85% (o), 95% (m), and 40% (p). These dianions react with alkyl halides, MeSiCl, Bu₃Sn Cl, CO₂, and oxidizing agents at carbon only, and with dialkyl sulfates at both carbon and oxygen. Thus phenol derivatives bearing primary alkyl groups can be prepared from the corresponding methylphenol via cresol dianions. Dimethylphenol trianions were prepared with Lochmann's base from all six isomers of dimethylphenol. 3,5-Dimethylphenol trianion was prepared in the best yield (80%); 2,3-, 2,4-, 2,5-, 2,6-, and 3,4-dimethylphenol trianions were prepared in 19.5%, 19%, 52%, 36%, and 44% yields, respectively. The common side products were dianions and tetraanions (in the latter, the fourth proton was usually pulled from the ring ortho to oxygen). These trianions were reacted with dimethyl sulfate to give anisole derivatives. 3,5-Dimethoxytoluene monoanion was reacted with n-BuBr to give a mixture of O,O'-dimethylolivetol (40%) and 4-butyl-3,5-dimethoxytoluene (34%).en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectCresol.en_US
dc.subjectPhenols.en_US
dc.subjectOrganic compounds.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.identifier.proquest8623834en_US
dc.identifier.oclc697635565en_US
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