- Method for preparing formate-type compound
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The invention discloses a method for preparing a formate-type compound. The method comprises the following steps of: adopting an alcohol-type compound and 1,3-dihydroxyacetone as reaction raw materials, and under the existence of a composite catalyst and an oxidant, reacting for 2-48 hours in a reaction medium in a reactor at a reaction temperature of 25-100 DEG C so as to obtain the formate-typecompound. The method disclosed by the invention is simple, and is mild in reaction condition, and by the method, a target product can be obtained by low cost and high yield; the used catalyst has highcatalytic activity, and is easily separated from a reaction system to be repeatedly used; the whole process is environment-friendly, and the reaction raw material (1,3-dihydroxyacetone) is easily converted from a side product (glycerol) of biodiesel, so that the utilization of the glycerol is promoted.
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Paragraph 0039; 0047; 0048
(2018/07/30)
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- Purified mCPBA, a Useful Reagent for the Oxidation of Aldehydes
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Purified mCPBA is a useful reagent for the oxidation of several classes of aldehyde. Although linear unbranched aliphatic aldehydes are oxidized to the corresponding carboxylic acids, α-branched ones undergo Baeyer–Villiger oxidation to formates. α-Branched α,β-unsaturated aldehydes provide enolformates and/or epoxides, which can be saponified to α-hydroxy ketones with shortening of the carbon chain by 1 carbon. Unbranched α,β-unsaturated aldehydes undergo an interesting Baeyer–Villiger oxidation/epoxidation/formate migration/BV oxidation cascade, which results in formyl-protected hydrates with an overall loss of two carbon atoms.
- Horn, Alexander,Kazmaier, Uli
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p. 2531 - 2536
(2018/03/21)
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- Experimental and computational studies on solvent effects in reactions of peracid-aldehyde adducts
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Solvent effects on liquid phase oxidation of aldehydes by dioxygen and m-chloroperbenzoic acid were studied experimentally. The main products were the corresponding carboxylic acid and a formate ester formed by Baeyer-Villiger rearrangement. In alcohol solvents (particularly methanol) substantially higher acid to formate ratios were formed than in solvents not capable of forming hydrogen bonds. Formation of both main products can be rationalised via rearrangement reactions of two epimeric peracid-aldehyde adducts, of which the interactions with methanol were studied computationally employing DFT methods at the DNPP level with the Spartan program (v5.0). The calculations indicate that structures of the adducts rearranging to give two equivalents of acid resemble the transition state of the reaction more than structures of the epimeric adducts rearranging to the acid and formate ester in 1:1 ratio. Therefore, the enhanced favor of the formation of acid in the presence of methanol can be explained in the light of Hammond's postulate.
- Lehtinen, Christel,Nevalainen, Vesa,Brunow, G?sta
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p. 4741 - 4751
(2007/10/03)
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- Experimental and computational studies on substituent effects in reactions of peracid-aldehyde adducts
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Liquid phase oxidation of six branched and four linear aldehydes by dioxygen and m-chloroperbenzoic acid was studied experimentally. 2-Substituted (α-branched) aldehydes reacted to give formates (via Bayer-Villiger mechanism) whereas the related linear saturated aldehydes were converted to the corresponding carboxylic acids. Formation of both these products can be rationalized via rearrangement reactions of peracid-aldehyde adducts 1. Computational studies employing DFT methods at the DNPP level with the Spartan program (v5.0) were carried out in order to understand properties of those adducts. Conformational properties of the adducts 1 were found to shed light on the differences observed in the reactions of linear and branched adducts. (C) 2000 Elsevier Science Ltd.
- Lehtinen, Christel,Nevalainen, Vesa,Brunow, G?sta
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p. 9375 - 9382
(2007/10/03)
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