Preparation of Ketone Acetals from Linear Ketones and Alcohols

Lorette, N. B.; Howard, William Lee; Brown, Jay H.

doi:10.1021/jo01093a028

Cited by 62 publications

(22 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Petroleum ether with a boiling range of 35 -65 °C was used; THF was distilled from sodium benzophenone ketyl immediately before use. The following reagents were prepared according to literature procedures: 4-methoxybenzaldehyde dimethylacetal [21], 3,3-dimethoxypentane [22].…”

Section: Methodsmentioning

confidence: 99%

An aldol approach to a building block corresponding to the C21-C26-part of FK506

Namyslo

Schäfer

Maier³

1999

J. prakt. Chem.

View full text Add to dashboard Cite

Section: Methodsmentioning

confidence: 99%

An aldol approach to a building block corresponding to the C21-C26-part of FK506

Namyslo

Schäfer

Maier³

1999

J. prakt. Chem.

View full text Add to dashboard Cite

“…Thus, to obtain the maximum ketal yields lower temperatures are preferred. At the same time, the thermodynamic stability of the cyclic ketal products depends on the molecular structure of the precursor diols and carbonyl compounds, what is supported by the different equilibrium yields obtained either within the reactions of the diol with the different carbonyl compounds [48][49][50] or in transacetalization (transketalization) reactions [51]. In order to determine the thermodynamic equilibrium for the reactions of interest (yielding the corresponding cyclic acetals from 1,2-PD and 2,3-BD) and to evaluate the relation between the reactants molecular structure and the reaction thermodynamic, experimental measurements of the equilibrium constant temperature dependence were conducted.…”

Section: The Ketalization Of 12-pd and 23-bd With Acetone And Mekmentioning

confidence: 97%

Bio-Based Solvents and Gasoline Components from Renewable 2,3-Butanediol and 1,2-Propanediol: Synthesis and Characterization

Samoilov

Goncharova

et al. 2020

Molecules

View full text Add to dashboard Cite

In this study approaches for chemical conversions of the renewable compounds 1,2-propanediol (1,2-PD) and 2,3-butanediol (2,3-BD) that yield the corresponding cyclic ketals and glycol ethers have been investigated experimentally. The characterization of the obtained products as potential green solvents and gasoline components is discussed. Cyclic ketals have been obtained by the direct reaction of the diols with lower aliphatic ketones (1,2-PD + acetone → 2,2,4-trimethyl-1,3-dioxolane (TMD) and 2,3-BD + butanone-2 → 2-ethyl-2,4,5-trimethyl-1,3-dioxolane (ETMD)), for which the ΔH0r, ΔS0r and ΔG0r values have been estimated experimentally. The monoethers of diols could be obtained through either hydrogenolysis of the pure ketals or from the ketone and the diol via reductive alkylation. In the both reactions, the cyclic ketals (TMD and ETMD) have been hydrogenated in nearly quantitative yields to the corresponding isopropoxypropanols (IPP) and 3-sec-butoxy-2-butanol (SBB) under mild conditions (T = 120–140 °C, p(H2) = 40 bar) with high selectivity (>93%). Four products (TMD, ETMD, IPP and SBB) have been characterized as far as their physical properties are concerned (density, melting/boiling points, viscosity, calorific value, evaporation rate, Antoine equation coefficients), as well as their solvent ones (Kamlet-Taft solvatochromic parameters, miscibility, and polymer solubilization). In the investigation of gasoline blending properties, TMD, ETMD, IPP and SBB have shown remarkable antiknock performance with blending antiknock indices of 95.2, 92.7, 99.2 and 99.7 points, respectively.

show abstract

“…Acetalization is known to be an exothermic reaction, [38,39] therefore acceleration of the reaction by the temperature increase leads to lower values of equilibrium yields. In the case of transacetalization of solketal by 2-EHA, the increase in temperature resulted in the increase in reaction rate with no significant influence on the equilibrium conversion (was around (Table 1): the equilibrium conversion has not been influenced by temperature change.…”

Section: Comparison Between Direct Reaction and Transacetalizationmentioning

confidence: 99%

Transacetalization of Solketal: A Greener Route to Bioglycerol‐Based Speciality Chemicals

Samoilov

Maximov

2018

ChemistrySelect

View full text Add to dashboard Cite

In the present study the potential of solketal transacetalization reaction has been demonstrated as an effective method of synthesis of acetals of glycerol and lipophilic carbonyl compounds (2‐ethylhexanal, n‐decanal, cyclopentanone, cyclohexanone). In solketal transacetalization with 2‐ethylhexanal reaction rate was significantly higher than of direct acetalization of glycerol both with and without a solvent because on the contrary to glycerol solketal is freely miscible with lipophilic compounds. Unlike the direct acetalization, reaction rate increased along with the temperature with no losses in equilibrium conversion. Furthermore, by stripping of by‐product acetone from the reaction zone we have succeeded in increasing the product yield in one‐pot synthesis to 97–98%, so that no further purification is needed. Finally, transacetalization was shown to be catalyzed with solid acids much more efficiently than the direct reaction (the cheap and eco‐friendly montmorillonite K‐10 catalyst was found to be the most active). Based on the regulations revealed, a green atom‐efficient synthetic protocol to obtain higher glycerol acetals and ketals has been proposed.

show abstract

Preparation of Ketone Acetals from Linear Ketones and Alcohols

Cited by 62 publications

References 4 publications

An aldol approach to a building block corresponding to the C21-C26-part of FK506

An aldol approach to a building block corresponding to the C21-C26-part of FK506

Bio-Based Solvents and Gasoline Components from Renewable 2,3-Butanediol and 1,2-Propanediol: Synthesis and Characterization

Transacetalization of Solketal: A Greener Route to Bioglycerol‐Based Speciality Chemicals

Contact Info

Product

Resources

About