Browsing by Author "K. W. Bentley"

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    Novel Analgesics and Molecular Rearrangements in the Morphine-Thebaine Group. 11.' Alcohols Derived from 6,14-endo-Etheno- and 6,14-endo-Ethanotetrahydrothebaine
    (2012-11-20) K. W. Bentley; G. Hardy; B. Meek
    A series of secondary and tertiary alcohols have been prepared by the reduction and reaction with Grignard reagents of the aldehyde I (R = H), the ketones I (R = Me, Et, n-Pr, and Ph), and their 6,14-ethano analogs. The stereospecificity of the reactions is explained. In this way analgesics of very high potency, up to 500 times that of morphine, have been obtained
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    Novel Analgesics and Molecular Rearrangements in the Morphine-Thebaine Group. 11.' Alcohols Derived from 6,14-endo-Etheno- and 6,14-endo-Ethanotetrahydrothebaine
    (2012-11-14) K. W. Bentley; D. G. Hardy; B. Meek
    A series of secondary and tertiary alcohols have been prepared by the reduction and reaction with Grignard reagents of the aldehyde I (R = H), the ketones I (R = Me, Et, n-Pr, and Ph), and their 6,14-ethano analogs. The stereospecificity of the reactions is explained. In this way analgesics of very high potency, up to 500 times that of morphine, have been obtained
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    Novel Analgesics and Molecular Rearrangements in the Morphine-Thebaine Group. 111.’ Alcohols of the 6,14-endo-EthenotetrahydrooripavinSee ries and Derived Analogs of N- Allylnormorphine and -norcodeine
    (2012-11-14) K. W. Bentley; D. G. Hardy
    Secondary and tertiary alcohols of general structures IV and V have been prepared by the demethylation of the corresponding bases I and I1 described in part I1 of this series. The phenols so obtained are analgesics of extremely high potency, up to an unprecedented 12,000 times that of morphine. The bases of this and earlier series have been converted into analogs of N-allylnormorphine and N-allylnorcodeine of general structures XI and XI1 via the N-cyanonor compounds and via novel N,N’-methylenebis compounds XI11 resulting from the reaction of the bases I and I1 with methyl azodicarboxylate. Some bases of the series XI1 are morphine antagonists of unprecedented potency, up to 150 times that of N-allylnormorphine
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    Novel Analgesics and Molecular Rearrangements in the Morphine-Thebaine Group. 111.’ Alcohols of the 6,14-endo-EthenotetrahydrooripavinSee ries and Derived Analogs of N- Allylnormorphine and -norcodeine
    (2012-11-14) K. W. Bentley; D. G. Hardy
    Secondary and tertiary alcohols of general structures IV and V have been prepared by the demethylation of the corresponding bases I and I1 described in part I1 of this series. The phenols so obtained are analgesics of extremely high potency, up to an unprecedented 12,000 times that of morphine. The bases of this and earlier series have been converted into analogs of N-allylnormorphine and N-allylnorcodeine of general structures XI and XI1 via the N-cyanonor compounds and via novel N,N’-methylenebis compounds XI11 resulting from the reaction of the bases I and I1 with methyl azodicarboxylate. Some bases of the series XI1 are morphine antagonists of unprecedented potency, up to 150 times that of N-allylnormorphine
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    Novel Analgesics and Molecular Rearrangements in the Morphine-Thebaine Group. I. Ketones Derived from 6,14-endo-Ethenotetrahydrothebaine
    (2012-11-14) K. W. Bentley; D. G. Hardy
    Several ketones I1 derived from 6,14-endo-ethenotetrahydrothebaine have been prepared by the Diels- Alder addition of certain a,P-unsaturated ketones to thebaine, by the action of cadmium alkyls on the corresponding acid chloride I1 (R = Cl), and, in some cases, by the action of Grignard reagents on the corresponding ester I1 (R =OEt) which is the adduct of thebaine and ethyl acrylate. Both 7a and 70 forms of the ketone I1 (R = Me), the ester I1 (R = OEt), and the nitrile 111 have been isolated. Attempts to convert the 7a ketone TI (R = Me) into the 7/3 isomer have resulted only in the formation of a keto1 X (R = H). Many of the bases prepared in this work are potent analgesics. The reaction product obtained from thebaine methiodide and p-benzoquinone has been shown to be a charge-transfer complex and not a true Diels-Alder adduct.
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    Novel Analgesics and Molecular Rearrangements in the Morphine-Thebaine Group. I. Ketones Derived from 6,14-endo-Ethenotetrahydrothebaine
    (2012-11-14) K. W. Bentley; G. Hardy
    Several ketones I1 derived from 6,14-endo-ethenotetrahydrothebaine have been prepared by the Diels- Alder addition of certain a,P-unsaturated ketones to thebaine, by the action of cadmium alkyls on the corresponding acid chloride I1 (R = Cl), and, in some cases, by the action of Grignard reagents on the corresponding ester I1 (R =OEt) which is the adduct of thebaine and ethyl acrylate. Both 7a and 70 forms of the ketone I1 (R = Me), the ester I1 (R = OEt), and the nitrile 111 have been isolated. Attempts to convert the 7a ketone TI (R = Me) into the 7/3 isomer have resulted only in the formation of a keto1 X (R = H). Many of the bases prepared in this work are potent analgesics. The reaction product obtained from thebaine methiodide and p-benzoquinone has been shown to be a charge-transfer complex and not a true Diels-Alder adduct