- Understanding ketone hydrodeoxygenation for the production of fuels and feedstocks from biomass
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Although we can efficiently convert bioderived furans into linear alkanes, the most energy-intensive step in this approach is the hydrodeoxygenation of the intermediate polyketone. To fully understand this process, we have examined the hydrodeoxygenation of a model compound, 3-pentanone, which allows us to follow this process stepwise using Pd/C, H2 (200 psi), and La(OTf)3 in acetic acid to remove the oxygen atom at temperatures between 25 and 200 C. We have found that ketone reduction to an alcohol is followed by acetoxylation, which provides a more facile route to C-O bond cleavage relative to the parent alcohol. (Chemical Presented).
- King, Amanda E.,Brooks, Ty J.,Tian, Yong-Hui,Batista, Enrique R.,Sutton, Andrew D.
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p. 1223 - 1226
(2015/02/19)
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- Hydroacetoxylation of olefins with acetic acid genetated in situ from vinyl acetate in the presence of ruthenium complexes
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Ruthenium complexes catalyze the decomposition of vinyl acetate releasing the acetic acid and its subsequent addition to linear and cyclic olefins.
- Khusnutdinov,Shchadneva,Khisamova,Dzhemilev
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experimental part
p. 155 - 160
(2011/05/03)
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- Kinetics and mechanism of nucleophilic displacements with heterocycles as leaving groups. Part 23. Studies at the borderlines between reactions proceeding (i) via free carbocations, (ii) via rate-determining formation of ion-molecule pairs, and (iii) via rate-determining nucleophilic ...
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Evidenece is presented to demonstrate that at the borderline between first order reaction via the formation of free carbocations, both mechanism proceed independently, without merging.Similarly at the borderline between first-order (rate determining formation) and second-order (rate-determining nucleophilic attack) rections of intimate ion-molecule pairs, both reactions again proceed independently.
- Katritzky, Alan R.,Brycki, Bogumil
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p. 1161 - 1169
(2007/10/02)
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- THE REACTION OF LEAD TETRAACETATE WITH HYDROCARBONS
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The free radical reaction of lead tetraacetate with hydrocarbons has been investigated.The products of these reactions are the acetate esters.The hydrogen abstracting species from lead tetraacetate is found to have a primary to secondary to tertiary selectivity of 1:27:123 based upon relative reactivities.
- Mosher, Melvyn W.,Cox, Jeffery L.
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p. 3753 - 3756
(2007/10/02)
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- Classical Carbonium Ions. Part 13. Rearrangements from Secondary to Primary Alkyl Groups during Reactions involving Carbonium Ions
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The rearrangement of cyclohexylamine to cyclopentylmethyl derivatives, earlier reported in brief, is confirmed.A similar reaction with 4-trans-t-butylcyclohexylamine is shown to give trans-3-t-butylcyclopentylmethyl derivatives, defining the conformational requirements and stereochemical course of the rearrangement.In similar reactions 2-butylamine and 3-pentylamine give, in small yield, derivatives of primary alcohols.Cyclohexyl toluenesulphonate probably gives a very small yield of cyclopentylmethyl acetate.All these reactions involve the formation of products formally derived from carbonium ions much less stable than those initially generated, and yields, though small, are much larger than can be accounted for by classical descriptions.It is proposed that corner-protonated cyclopropanes ('non-classical carbonium ions') are 'intermediates' of very short lifetime in these reactions; the extent to which it is possible to regard species of very short lifetime as intermediates is discussed.
- Cooper, Catherine N.,Jenner, Peter J.,Perry, Nigel B.,Russel-King, Jonquil,Storesund, Hans J.,Whiting, Mark C.
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p. 605 - 612
(2007/10/02)
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