- Steric effects and mechanism in the formation of hemi-acetals from aliphatic aldehydes
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Some physical properties (pKa, log POW, boiling points) of hexanoic acid 1 (X = COOH) and its seven isomers 2, 3, 4, 5, 6, 7, 8 (X = COOH) are reported. Hexanal 1 (X = CHO) and its seven isomeric aldehydes 2, 3, 4, 5, 6, 7, 8 (X = CHO) are shown to equilibrate, in methanol solution, with their hemi-acetals. Logarithms of equilibrium constants correlate with values of Es for the isomeric C5H11 substituents, and with logs of relative rates for saponification of the corresponding methyl esters with ρ = 0.52, reflecting the reduced steric demand of hydrogen compared to oxygen in the quaternization of ester and aldehydic carbonyl groups. Rates of equilibration have also been measured in buffered methanol. For hexanal, with a 2:1 Et3N:AcOH buffer, the buffer-independent contribution is dominated by the methoxide catalysed pathway. Rates in this medium have been determined for isomers 1, 2, 3, 4, 5, 6, 7, 8 (X = CHO), and their logarithms do not correlate with logarithms of equilibrium constants for hemi-acetal formation or with substituent steric parameters derived from ester formation or saponification, indicating that the steric changes associated with full quaternization of the carbonyl group are not mirrored in the transition structures for hemi-acetal formation. It is suggested that transition states for hemi-acetal formation are relatively early so that steric interactions are effectively those between the nucleophile and ground state conformations of the aldehydes. A comparison of the entropies of hemi-acetal formation with entropies of activation has provided a basis for a suggested transition structure. Comparisons with acid chloride hydrolyses are made. Copyright 2013 John Wiley & Sons, Ltd. Logarithms of equilibrium constants for formation hemi-acetals of hexanal and its seven isomeric aldehydes correlate well with values of Es for the isomeric C5H11 substituents, and with logs of relative rates for saponification of the corresponding methyl esters. Logarithms of rate constants for hemi-acetal formation do not, indicating that the steric changes associated with full quaternization of the carbonyl group are not mirrored in the transition structures for hemi-acetal formation. The reasons for this are discussed. Copyright
- Daw, Graham,Regan, Andrew C.,Watt, C. Ian F.,Wood, Evan
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p. 1048 - 1057
(2014/01/06)
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- METHOD FOR HYDROGENATING METHYLOL ALKANALS
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Disclosed is a method for the catalytic hydrogenation of methylol alkanals of general formula (I), wherein R1 and R2 independently represent an additional methylol group or an alkyl group with 1 to 22 C atoms, or an alkyl group with 1 to 22 C atoms, or an aryl group or aralkyl group with 6 to 33 C atoms, in the liquid phase on a hydrogenation catalyst. The inventive method is characterized in that a pH value ranging between 6.3 and 7.8 is adjusted in the hydrogenation feed by adding at least one tertiary amine.
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- Alkane Functionalization on a Preparative Scale by Mercury-Photosensitized Cross-Dehydrodimerization
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Alkanes can be functionalized with high conversions and in high chemical and quantum yields on a multigram scale by mercury-photosensitized reaction between an alkane and alcohols, ethers, or silanes to give homodimers and cross-dehydrodimers.The separation of the product mixtures is often particulary easy because of a great difference in polarity of the homodimers and cross-dimers.It is also possible to bias the product composition when the ratio of the components in the vapor phase is adjusted by altering the liquid composition.This is useful either to maximize chemical yield or to ease separation by favoring the formation of the most easily separated pair of compounds.The mechanistic basis of the reaction is discussed and a number of specific types of syntheses, for example of 2,2-disubstituted carbinols, are described in detail.The selectivity of cross-dimerization is shown to exceed that for homodimerization and reasons are discussed.Relative reactivities of different compounds and classes of compound are MeOHp-dioxanecyclohexane1,3,5-trioxacyclohexaneethanolisobutaneTHFEt3SiH.The observed selectivities generally parallel those for homodimerization, reported in the preceding paper, but certain differences are noted, and reasons for the differences are proposed.The bond-dissociation energy of Et3SiH is estimated from the reactivity data to be 90 kcal/mol.Eleven new carbinols are synthesized.
- Brown, Stephen H.,Crabtree, Robert H.
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p. 2946 - 2953
(2007/10/02)
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- Shape Selective Alkane Hydroxylation by Metalloporphyrin Catalysts
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A series of manganese and iron porphyrins with sterically protected pockets are shown to be shape selective alkane hydroxylation catalysts.With iodosobenzene as oxidant, good regioselectivity is observed for hydroxylation of alkanes at the least hindered methyl group by using the very sterically hindered (5,10,15,20-tetrakis(2',4',6'-triphenylphenyl)porphyrinato)manganese(III) acetate (MnTTPPP(OAc)) as catalyst; The moderately hindered (5,10,15,20-tetrakis(2',4',6'-trimethoxyphenyl)porphyrinato)manganese(III) acetate shows little selectivity toward terminal CH3 hydroxylation but does show enhancement for the adjacent, ω - 1, CH2 site.Primary selectivity is dependent on the size and shape of the alkane substrate, with more bulky substituents giving greater primary selectivity.Substituting pentafluoroiodosobenzene or m-chloroperbenzoic acid as oxidants yields similar selectivity, thus conclusively demonstrating metal based oxidation via a common intermediate for these three systems.In contrast, tert-butyl hydroperoxide or 2,2,2-trifluoroethanol solubilized pentafluoroiodosobenzene show no primary carbon selectivity, and reaction product ratios are independent of the metalloporphyrin catalyst; this demonstrates that the site of oxidation with these oxidants is not metal based.The iron porphyrin derivatives also show good primary selectivity, although to a lesser degree than with the Mn derivatives, proving that these oxidations too are metal based.The regioselectivities for alkane hydroxilation shown by TTPPP derivatives are comparable to or better than those found for some isozymes of cytochrome P-450 which are responsible for primary alcohol biosynthesis from steroids, fatty acids, and alkanes.
- Cook, Bruce R.,Reinert, Thomas J.,Suslick, Kenneth S.
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p. 7281 - 7286
(2007/10/02)
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- Shape-selective Alkane Hydroxylation
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A series of sterically hindered manganese porphyrins have been used to catalyse shape-selective alkane hydroxylation, increasing the production of primary alcohols.
- Suslick, Kenneth,Cook, Bruce,Fox, Mary
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p. 580 - 582
(2007/10/02)
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