Chemistry of methylnorbornyl cations.  II.  Sources and identification of sixteen of the methylnorbornanols

Berson, Jerome A.; McRowe, Arthur W.; Bergman, Robert G.; Houston, Donald.

doi:10.1021/ja00987a013

Cited by 10 publications

(7 citation statements)

References 4 publications

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“…Epicamphor. This was prepared by the hydroboration of bornylene (Berson, McRowe, Bergman & Houston, 1967). The mixture of borneol and epiborneol so obtained was oxidized with Jones reagent to yield a mixture of camphor and epicamphor, separation of which was achieved through the rate of semicarbazone formation (Huckel & Fechtig, 1962).…”

Section: Methodsmentioning

confidence: 99%

Metabolism of camphors and related compounds

Robertson

Hussain

1969

Biochemical Journal

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1. The metabolism of (+/-)-norcamphor, (+)-camphor, (-)-camphor, (+)-epicamphor, (+/-)-camphorquinone, (+/-)-camphane-2,5-dione and camphane was investigated in rabbits. All the compounds except camphane-2,5-dione increased the content of glucuronide in the urine. 2. (+/-)-Norcamphor was reduced to endo-norborneol; (+)-camphor, contrary to expectation, was reduced to (+)-borneol, as well as being hydroxylated to (+)-5-endo-hydroxycamphor and (+)-3-endo-hydroxycamphor, 5-endo-hydroxycamphor being the predominant product. (+)-Epicamphor was reduced mainly to (+)-epiborneol; (+/-)-camphorquinone gave 3-endo-hydroxycamphor and 2-endo-hydroxyepicamphor, the former being the major metabolite. (+/-)-Camphane-2,5-dione was reduced to 5-endo-hydroxycamphor. Camphane was hydroxylated to borneol and epiborneol, the latter predominating. 3. An explanation of these findings is given in terms of steric hindrance and thermodynamic stability. 4. The possibility was investigated that NADH was involved in the reductions.

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Section: Methodsmentioning

confidence: 99%

Metabolism of camphors and related compounds

Robertson

Hussain

1969

Biochemical Journal

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“…3-, 5-, 6-and 7-Methylnorbornane-2-diazonium ions were generated as exolendo mixtures by photolysis of the corresponding methyl-2-norbornanone tosylhydrazones (3,5,23,27,32,34,45,47) in aqueous sodium hydroxide. The composition of the meth>l-2-exo-norbornanols indicated virtually complete Wagner-Meerwein equilibration of the cationic intermediates.…”

Section: Decomposition Of Methylnorbornane-zdiazonium Ionsmentioning

confidence: 99%

“…

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unclassified

Desaminierungsreaktionen, 36¹⁾ Zerfall von Methylnorbornan‐2‐diazonium‐Ionen

1981

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Eingegangen am 1. Oktober 1980 3-, 5-, 6-und 7-Methylnorbornan-2-diazonium-lonen wurden als exolendo-Gemische durch Photolyse der entsprechenden Methyl-2-norbornanon-tosylhydrazone (3, 5, 23, 27, 32, 34,45, 47) in wanriger Natronlauge erzeugt. Die Zusammensetzung der Methyl-2-exo-norbornanole zeigte vollstandige Wagner-Meerwein-Aquilibrierung der kationischen Zwischenstufen. 6.2-H-Verschiebungen zwischen sekundaren Kationen waren unter diesen Bedingungen relativ langsam, doch war die Bildung des tertiaren Kations 54 eine Hauptreaktion der 6-Methyl-2-norbornan-diazoniumlonen. 3,2-H-Verschiebungen zwischen sekundaren Kationen wurden nicht beobachtet; aus 3-Methyl-2-norbornan-diazonium-Ionen erhielt man weniger als 240 tertiaren Alkohol. Methyl-2-endo-norbornanole mit der Konstitution des Ausgangsmaterials wurden ebenfalls gefunden. Die Desaminierung der stereoisomeren 3-Methyl-2-norbornylamine (59, 60, 67, 70) in wanriger Perchlorsaure zeigte, dan endo-Alkohole nur aus endo-Diazonium-lonen entstanden. Die Stellung der 3-Methylgruppe hatte einen starken Einflun auf die Ausbeute an endo-Alkohol (58% aus 59 gegen 7% aus 70). Ein neuer Reaktionsweg zu den endo-Alkoholen wird vorgeschlagen. Deamination Reactions, 36 1)Decomposition of Methylnorbornane-Zdiazonium Ions .3-, 5-, 6-and 7-Methylnorbornane-2-diazonium ions were generated as exolendo mixtures by photolysis of the corresponding methyl-2-norbornanone tosylhydrazones (3,5,23,27,32,34,45, 47) in aqueous sodium hydroxide. The composition of the meth>l-2-exo-norbornanols indicated virtually complete Wagner-Meerwein equilibration of the cationic intermediates. 6,2-H shifts between secondary cations were rather slow under these conditions, but formation of the tertiary cation 54 was a major reaction of &methyl-2-norbornanediazonium ions. 3.2-H shifts between secondary cations were not observed and less than 2% of tertiary alcohol was produced from 3-methyl-2-norbornanediazonium ions. Methyl-2-endo-norbornanols of retained constitution were also found. Deamination of the stereoisomeric 3-methyl-2-norbornylamines (59,60,67, 70) in aqueous perchloric acid revealed that endo alcohols arose from endo diazonium ions only. The position of the 3-methyl group strongly affected the yield of endo alcohol (58% from 59 vs. 7% from 70). A novel reaction path to the endo alcohols is suggested.Die Solvolyse von 2-exo-und -endo-Norbornylbrosylat ergibt ausschliefllich 2-exoNorbornanol bzw. dessen Ester2). Dagegen erhalt man bei der Desaminierung der 2-Norbornylarnine auch e n d o -P r o d~k t e~*~) .Das abweichende Verhalten von Sulfonsaureestern und Diazonium-Ionen kornpliziert die Diskussion uber offene oder verChem. Ber. 114(1981)

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“…in eq. 2, which it can undergo at any one stage and (ii) there has been an enormous amount of solvolysis and acid-catalysis work (which can be used for comparison purposes) carried out on methyl-substituted 2-norbornyl systems, including all of the monomethyl analogs (2) and a great many di-(3) and trimethyl (4) systems. Many of the di-and trimethyl systems studied (like a-fenchol) are terpenes or rearrangement products derived from these.…”

Section: Introductionmentioning

confidence: 99%

Predicting the Most Favored Path and the Overall Rate of Multistep: 2-Norbornyl Cation Rearrangements. The Assignment of a Trial Activation Energy for Each Unique Step

Haseltine¹,

Huang²,

Ranganayakulu³

et al. 1975

Can. J. Chem.

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Observable 2-norbornyl cations undergo at least five different rearrangement reactions, all of which are known from previous work on this system. In this paper, these rearrangement categories have been subdivided to reflect secondary-tertiary energy and rate differences and a trial set of activation free energies AG* is derived for each subdivided step. The most important of these parameters is the energy difference between secondary and tertiary (methyl) systems which was estimated as 5.5 kcal/mol. These parameters allow one, for the first time, to make a rational assessment of the overall reaction course of multistep rearrangement reactions in this system, for example, those observed in a number of bicyclo[2.2.1]heptyl(norbornyl) terpene systems.R. HASELTINE, E. HUANG, K. RANAGNAYAKULU, T. S. SORENSEN et N. WONG. Can. J. Chem. 53,1876Chem. 53, (1975

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Chemistry of methylnorbornyl cations. II. Sources and identification of sixteen of the methylnorbornanols

Cited by 10 publications

References 4 publications

Metabolism of camphors and related compounds

Metabolism of camphors and related compounds

Desaminierungsreaktionen, 36¹⁾ Zerfall von Methylnorbornan‐2‐diazonium‐Ionen

Predicting the Most Favored Path and the Overall Rate of Multistep: 2-Norbornyl Cation Rearrangements. The Assignment of a Trial Activation Energy for Each Unique Step

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Chemistry of methylnorbornyl cations. II. Sources and identification of sixteen of the methylnorbornanols

Cited by 10 publications

References 4 publications

Metabolism of camphors and related compounds

Metabolism of camphors and related compounds

Desaminierungsreaktionen, 361) Zerfall von Methylnorbornan‐2‐diazonium‐Ionen

Predicting the Most Favored Path and the Overall Rate of Multistep: 2-Norbornyl Cation Rearrangements. The Assignment of a Trial Activation Energy for Each Unique Step

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Desaminierungsreaktionen, 36¹⁾ Zerfall von Methylnorbornan‐2‐diazonium‐Ionen