The chlorine leaving group isotope effect has been measured for the base-promoted elimination reaction of 1-(2-chloro-2-propyl)indene (1-Cl) in methanol at 30 degrees C: k(35)/k(37) = 1.0086 +/- 0.0007 with methoxide as the base and k(35)/k(37) = 1.0101 +/- 0.0001 with triethylamine (TEA) as the base. These very large chlorine isotope effects combined with large kinetic deuterium isotope effects of 7.1 and 8.4, respectively, are consistent not with the irreversible E1cB mechanism proposed previously (J. Am. Chem. Soc. 1977, 99, 7926) but with the E2 mechanism with transition states having large amounts of hydron transfer and very extensive cleavage of the bond to chlorine.
Rate constants and heats of reaction for the aromatization of benzene oxide (1) and the acid-catalyzed aromatization of benzene hydrate (2) in highly aqueous solution giving phenol and benzene, respectively, have been measured by heat-flow microcalorimetry. The measured heat of reaction of benzene oxide, DeltaH = -57.0 kcal mol(-1), is much larger than that of benzene hydrate, DeltaH = -38.7 kcal mol(-1), despite an unusually low reactivity of benzene oxide, rate ratio 0.08. The measured enthalpies agree with those calculated using the B3LYP hybrid functional corrected with solvation energies derived from semiempirical AM1/SM2 calculations. Comparison with the measured enthalpies of the corresponding reactions of the structurally related 1,3-cyclohexadiene oxide (3) and 2-cyclohexenol (4) of DeltaH = -24.9 kcal mol(-1) (includes a small calculated correction of -1.2 kcal mol(-1)) and DeltaH approximately 0 kcal mol(-1), respectively, gives a smaller aromatization energy for the benzene oxide than for the benzene hydrate reaction (DeltaDeltaDeltaH = 6.6 kcal mol(-1)). This suggests that benzene oxide is unusually stabilized by a significant amount of homoaromatization as has been proposed previously (J. Am. Chem. Soc. 1993, 115, 5458). This unusual stability accounts for more than half of the approximately 10(7) times lower than expected reactivity of benzene oxide toward acid-catalyzed isomerization. The rest is suggested to originate from an unusually high energy of the carbocation-forming transition state.
The kinetics of the acid-catalyzed ring opening of naphthalene 1,2-oxide (5) in highly aqueous media to give naphthols has been measured by heat-flow microcalorimetry. The reaction enthalpy of this aromatization reaction was measured as DeltaH = -51.3 +/- 1.7 kcal mol(-)(1). The unexpectedly low reactivity of naphthalene oxide is suggested to be due to an unusually large thermodynamic stability. A crude estimate of the stabilization effect, approximately 1 kcal mol(-)(1)(not a significant stabilization), is obtained by using the measured reaction enthalpies of structurally related substrates as references. A larger value (2.7 kcal mol(-)(1)) was obtained by calculation using the B3LYP hybrid functional corrected with solvation energies derived from semiempirical AM1/SM2 calculations. The origin of this effect is discussed in terms of homoconjugative stabilization and homoaromaticity. There is a good linear correlation (with slope = 0.63) between the experimentally measured free energy of activation and the calculated enthalpy of carbocation formation in water.
The acid-catalyzed solvolysis of 2-methoxy-2-phenyl-3-butene (1-OMe) in 9.09 vol % acetonitrile in water provides 2-hydroxy-2-phenyl-3-butene (1-OH) as the predominant product under kinetic control along with the rearranged alcohol 1-hydroxy-3-phenyl-2-butene (2-OH) and a small amount of the rearranged ether 2-OMe. The more stable isomer 2-OH is the predominant product after long reaction time, K(eq) = [2-OH](eq)/[1-OH](eq) = 16. The ether 2-OMe reacts to give 2-OH and a trace of 1-OH. Solvolysis of 1-OMe in (18)O-labeled water/acetonitrile shows complete incorporation of (18)O in the product 1-OH, confirming that the reaction involves cleavage of the carbon-oxygen bond to the allylic carbon. A completely solvent-equilibrated allylic carbocation is not formed since the solvolysis of the corresponding chloride 1-chloro-3-phenyl-2-butene (2-Cl) yields a larger fraction of 1-OH. This may be attributed to a shielding effect from the chloride leaving group. Quantum chemical calculations of the geometry and charge distribution show that the cation should rather be described as a vinyl-substituted benzyl cation than as an allyl cation, which is in accord with its higher reactivity at the tertiary carbon.
The acid-catalysed solvolysis reaction of 9-methoxy-9-methyl-9,10-dihydroanthracene (2-OMe) in 50 vol% acetonitrile in water at 25 ЊC provides the substitution product 9-hydroxy-9-methyl-9,10-dihydroanthracene (2-OH) and the elimination product 9-methylanthracene (3). The rate-ratio of substitution-to-elimination was measured as k S /k E = 0.93. The alcohol also undergoes acid-catalysed aromatization to give the thermodynamically favoured product 3. The reaction enthalpy of this dehydration reaction was measured as ∆H = Ϫ10.2 ± 1.0 kcal mol Ϫ1 . The corresponding reaction of the secondary alcohol 9-hydroxy-9,10-dihydroanthracene (1-OH) has a reaction enthalpy of ∆H = Ϫ12.3 ± 0.8 kcal mol Ϫ1 . Addition of azide ion (0.25 M) gives rise to a large fraction of azide adduct 2-N 3 , which rapidly undergoes solvolysis. The "azide-clock" method yields rate constants for reaction of the carbocation to give alcohol and elimination product of k w = 2.2 × 10 8 s Ϫ1 and k e = 2.4 × 10 8 s Ϫ1 , respectively. The thermodynamic stability of the carbocation was estimated as pK R = Ϫ9.1. The alkene 9-methylene-9,10-dihydroanthracene (4) undergoes a slow acid-catalysed aromatization to give 3; no competing formation of 2-OH was observed.
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