exo Vicinal Hydride Shift in the 3-endo-Methyl-2-norbornyl Cation<sup>1</sup>

“…bp 67°(0.4 mm); n2L5D 1.5286; ir 3040, 2940, 2860, 1640, 1470, 1450, 1440, 1430, 1350, 1330, 1260, 1210, 1040, 960, 850, 680, 670 cm"1; NMR 1.2-2.83 (complex m, 14), 5.83 (d, 1, J = 7.0 Hz, C1C=CH); mass spectrum m/e (rel intensity) 184 (11), 183 (4), 182 (31), 147 (20), 115 (35), 114 (47), 113 (100), 112 (96), 94 (14), 91 (21), 79 (57), 78 (12), 77 (43), 69 (27), 67 (26), 41 (18).…”

Section: Methodsmentioning

confidence: 99%

Large enhancement of apparent isomerization rates in endo vs. exo precursors for trifluoromethanesulfonic acid catalyzed tricycloundecane rearrangements

Takaishi¹,

Inamoto²,

Aigami³

et al. 1975

J. Org. Chem.

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“…One of the more intriguing results of this type is the reported rearrangement of 2-endo-phenyl-2-ea:o-borneol (4) and 1-phenylcamphene (5) to produce 4-phenylisoborneol (6).2 Obviously a gross structural reorganization has taken place, although the final product is again derived from a secondary norbornyl cation.…”

mentioning

confidence: 99%

Acid-catalyzed addition of acetic acid to 2-arylbornenes and 2-arylapobornenes

Kuehl¹,

Caple²

1973

J. Org. Chem.

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Huyser, Bredeweg, and Van Scoy4•5 in explaining increased decomposition rates of di-iert-butyl peroxide in primary and secondary alcohols and amines.Figure 1.-First-order plot for the decomposition of di-terti-butyl peroxide (DTBP) in benzene with 0.043 mmol of L3RhCl, 600 psig Hz, 20 mg of Ph3P, 120°. Experimental SectionMaterials.-Except for the metal systems, commercial materials were used in this work: benzene, triphenylphosphine, tetralin, phenol, m-cresol, and Ionol. The following metal complexes were prepared as previously described: (Ph3P)3RhCl,6•7 (Ph3P)3RhBr,7 (Ph3P)2CORhCl,7 (Ph3P)"RhH,8 9and (Ph3P)3-RuClz.8Decomposition of Di-iert-butyl Peroxide.-A solution of 0.79 g (5.4 mmol) of di-iert-butyl peroxide, 0.020 g (0.076 mmol) of Ph3P, and 30 ml of benzene was charged in a nitrogen atmosphere to an 80-ml Inconel magnetically stirred autoclave (total free space including system, 126 ml). A pressure of 600 psig hydrogen was charged to the vessel. The temperature (120°) was maintained ±1% by a thermostatically controlled heating mantle. In experiments using metal catalysts, 0.043 mmol of catalyst was also added to the reaction solution. In experiments in which (Ph3P)3RhCl concentrations were varied, 0.021, 0.06, and 0.09 mmol of catalyst were employed. The reaction mixture was analyzed by standard glc techniques for di-iert-butyl peroxide, iert-butyl alcohol, and acetone.Decomposition of Di-iert-butyl Peroxide with Additives.-The above procedure and amounts of reactants were used and 0.5or 1.0-g amounts of tetralin, phenol, m-cresol, or Ionol were also added. Glc analysis showed no loss of m-cresol in m-cresol experiments.Registry No. -fert-Butyl alcohol, 75-65-0; ¿erf-butyl peroxide, 110-05-4.

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exo Vicinal Hydride Shift in the 3-endo-Methyl-2-norbornyl Cation¹

Cited by 7 publications

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The Preparation and Properties of Trimethylenecyclopropane

The Preparation and Properties of Trimethylenecyclopropane

Large enhancement of apparent isomerization rates in endo vs. exo precursors for trifluoromethanesulfonic acid catalyzed tricycloundecane rearrangements

Acid-catalyzed addition of acetic acid to 2-arylbornenes and 2-arylapobornenes

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exo Vicinal Hydride Shift in the 3-endo-Methyl-2-norbornyl Cation1

Cited by 7 publications

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The Preparation and Properties of Trimethylenecyclopropane

The Preparation and Properties of Trimethylenecyclopropane

Large enhancement of apparent isomerization rates in endo vs. exo precursors for trifluoromethanesulfonic acid catalyzed tricycloundecane rearrangements

Acid-catalyzed addition of acetic acid to 2-arylbornenes and 2-arylapobornenes

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exo Vicinal Hydride Shift in the 3-endo-Methyl-2-norbornyl Cation¹