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Rate of dehydration for butan-2-ol and butane-2,3-diol
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Max Paluan
Rate of dehydration for butan-2-ol and butane-2,3-diol
For this question, given the lack of initial information, I'm making the following assumptions:
Butane-2,3-diol dehydrates to give butan-2-one
2-butanol dehydrates to give but-2-ene
Butane-2,3-diol dehydration is nicely described in this paper from Emerson1:
Aqueous 2,3-butanediol was shown to react in a pseudo-first-order reaction in the presence of sulfuric acid to form methyl ethyl ketone. The reaction could be described by a pinacol rearrangement mechanism and had an activation energy of 36 kcal/mol.
Finding the data for dehydration of 2-butanol proved more elusive. One study2 conducted dehydration rate experiments for secondary alcohols at 250 °C and 40 bar pressure and obtained a rate constant for 3-hexanol to be $k = \pu{(0.067 \pm 0.021) h^{-1}}$. Assuming this rate would be similar to 2-butanol, we can find the activation energy via the arrhenius equation, which comes out to be around 48 kJ/mol, which is around 11.52 kcal/mol. Another source3 conducted the same experiment over a copper-chromite catalyst, and obtained an activation energy of 13 kcal/mol. This means that 2-butanol will dehydrate faster than butane-2,3-diol.
From a conceptual standpoint, this makes sense: The pinacol rearrangement mechanism would require a hydride shift, which would be the RDS and would take more time and energy than a simple carbocation formation. However, if you're comparing absolute reaction rates, a large number of factors come into play, and given the right conditions, butane-2,3-diol can dehydrate faster than butan-2-ol.
References:
Emerson, Richard R., et al. “Kinetics of Dehydration of Aqueous 2,3-Butanediol to Methyl Ethyl Ketone.” Industrial & Engineering Chemistry Product Research and Development, vol. 21, no. 3, 1982, pp. 473–77. doi:10.1021/i300007a025
Bockisch, Christiana, et al. “Kinetics and Mechanisms of Dehydration of Secondary Alcohols Under Hydrothermal Conditions.” ACS Earth and Space Chemistry, vol. 2, no. 8, 2018, pp. 821–32. doi:10.1021/acsearthspacechem.8b00030.
Joseph Sires Cantrell, "Rate and activation energy of the first order dehydration of 2-butanol over a copper chromite catalyst", 1954, source
For this question, given the lack of initial information, I'm making the following assumptions:
Butane-2,3-diol dehydrates to give butan-2-one
2-butanol dehydrates to give but-2-ene
Butane-2,3-diol dehydration is nicely described in this paper from Emerson1:
Aqueous 2,3-butanediol was shown to react in a pseudo-first-order reaction in the presence of sulfuric acid to form methyl ethyl ketone. The reaction could be described by a pinacol rearrangement mechanism and had an activation energy of 36 kcal/mol.
Finding the data for dehydration of 2-butanol proved more elusive. One study2 conducted dehydration rate experiments for secondary alcohols at 250 °C and 40 bar pressure and obtained a rate constant for 3-hexanol to be $k = \pu{(0.067 \pm 0.021) h^{-1}}$. Assuming this rate would be similar to 2-butanol, we can find the activation energy via the arrhenius equation, which comes out to be around 48 kJ/mol, which is around 11.52 kcal/mol. Another source3 conducted the same experiment over a copper-chromite catalyst, and obtained an activation energy of 13 kcal/mol. This means that 2-butanol will dehydrate faster than butane-2,3-diol.
From a conceptual standpoint, this makes sense: The pinacol rearrangement mechanism would require a hydride shift, which would be the RDS and would take more time and energy than a simple carbocation formation. However, if you're comparing absolute reaction rates, a large number of factors come into play, and given the right conditions, butane-2,3-diol can dehydrate faster than butan-2-ol.
References:
Emerson, Richard R., et al. “Kinetics of Dehydration of Aqueous 2,3-Butanediol to Methyl Ethyl Ketone.” Industrial & Engineering Chemistry Product Research and Development, vol. 21, no. 3, 1982, pp. 473–77. doi:10.1021/i300007a025
Bockisch, Christiana, et al. “Kinetics and Mechanisms of Dehydration of Secondary Alcohols Under Hydrothermal Conditions.” ACS Earth and Space Chemistry, vol. 2, no. 8, 2018, pp. 821–32. doi:10.1021/acsearthspacechem.8b00030.
Joseph Sires Cantrell, "Rate and activation energy of the first order dehydration of 2-butanol over a copper chromite catalyst", 1954, source
I just looked up the Emerson reference that you cited, and it also says the departure of H2O is generally believed to be rate-limiting, although it may be concerted with and aided by the hydride shift. Certainly, the hydride shift alone is not the RDS and would not "take more time and energy than a simple carbocation formation". In fact, concerted hydride shift would lower the reaction barrier by assisting the H2O elimination and leading directly to a more stable carbocation.More
Why do you think hydride shift is RDS? All literature I have seen says it’s the cation formation that is rate-determining. It would be slower than 2-butanol because of electron withdrawing effect of second OH which destabilizes cation, apparently enough to overcome the statistical advantage of two OH groups.More
@Andrew: The mechanism is similar to neopentyl alcohol elimination. Primary carbocation formation is assisted by concomitant shift of methide group. Nevertheless, the reaction is slow.More
For this question, given the lack of initial information, I'm making the following assumptions:
Butane-2,3-diol dehydration is nicely described in this paper from Emerson1:
Finding the data for dehydration of 2-butanol proved more elusive. One study2 conducted dehydration rate experiments for secondary alcohols at 250 °C and 40 bar pressure and obtained a rate constant for 3-hexanol to be $k = \pu{(0.067 \pm 0.021) h^{-1}}$. Assuming this rate would be similar to 2-butanol, we can find the activation energy via the arrhenius equation, which comes out to be around 48 kJ/mol, which is around 11.52 kcal/mol. Another source3 conducted the same experiment over a copper-chromite catalyst, and obtained an activation energy of 13 kcal/mol. This means that 2-butanol will dehydrate faster than butane-2,3-diol.
From a conceptual standpoint, this makes sense: The pinacol rearrangement mechanism would require a hydride shift, which would be the RDS and would take more time and energy than a simple carbocation formation. However, if you're comparing absolute reaction rates, a large number of factors come into play, and given the right conditions, butane-2,3-diol can dehydrate faster than butan-2-ol.
References:
For this question, given the lack of initial information, I'm making the following assumptions:
Butane-2,3-diol dehydration is nicely described in this paper from Emerson1:
Finding the data for dehydration of 2-butanol proved more elusive. One study2 conducted dehydration rate experiments for secondary alcohols at 250 °C and 40 bar pressure and obtained a rate constant for 3-hexanol to be $k = \pu{(0.067 \pm 0.021) h^{-1}}$. Assuming this rate would be similar to 2-butanol, we can find the activation energy via the arrhenius equation, which comes out to be around 48 kJ/mol, which is around 11.52 kcal/mol. Another source3 conducted the same experiment over a copper-chromite catalyst, and obtained an activation energy of 13 kcal/mol. This means that 2-butanol will dehydrate faster than butane-2,3-diol.
From a conceptual standpoint, this makes sense: The pinacol rearrangement mechanism would require a hydride shift, which would be the RDS and would take more time and energy than a simple carbocation formation. However, if you're comparing absolute reaction rates, a large number of factors come into play, and given the right conditions, butane-2,3-diol can dehydrate faster than butan-2-ol.
References:
More
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