Method of carbon chain extension using novel aldol reaction

a technology of aldol and carbon chain, which is applied in the field of carbon chain extension using novel aldol reaction, can solve the problems of poor selectivity, process less suitable for large-scale industrial use, and zinc-proline catalysts have shown only to successfully catalyze, and achieves high specificity and increase the length of carbon chains

Inactive Publication Date: 2011-02-17
LOS ALAMOS NATIONAL SECURITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the reactions resulted in a range of carbon chain lengths, and thus exhibited poor selectivity.
All of these factors contribute to making the process less suitable for large-scale industrial use.
To date, however, zinc-proline catalysts have shown only to successfully catalyze reactions between ketones and aromatic aldehydes (for example, benzaldehydes) and not between ketones and reagents derived from biomass sources, such as HMF.

Method used

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  • Method of carbon chain extension using novel aldol reaction
  • Method of carbon chain extension using novel aldol reaction
  • Method of carbon chain extension using novel aldol reaction

Examples

Experimental program
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example 1

[0025]The reactions were performed in water without adjustment of pH. Piperidine was used in 5 mol %. HMF (0.631 g, 5.00 mmol) was charged in a small round bottom flask with a stirring bar, water (4.0 mL) was added. Acetone (0.290 g, 5.00 mmol (1 equivalent) or 0.25 mmol (0.5 equivalent) was then added. The mixture was then stirred while piperidine was added at room temperature. The reaction mixture was kept closed with a plastic cap and stirred for 20 hrs. The stirring bar was removed and silica gel was added. The mixture was dried with rotary evaporation. The residue was loaded on silica gel and eluted with 50% ethyl acetate in hexanes to provide mono-HMF adduct (0.191 g, 23%) as a light yellow solid. 1H NMR (CDCl3) δ 7.16 (d, J=16.0 Hz), 6.55 (d, J=3.45 Hz), 6.51 (d, J=16.0 Hz), 6.32 (d, J=3.40 Hz), 4.57 (s), 2.23 (s). 13C NMR (CDCl3) δ 198.6, 157.5, 150.6, 129.8, 123.9, 117.1, 110.5, 57.4, 27.9. And di-WAY adduct (0.469 g, 68%) as a dark reddish solid. 1H NMR (CDCl3) δ 7.43 (d, ...

example 2

[0026]In a 100 mL single-necked round bottom flask was placed HOBT (hydroxybenzotriazole) (1.95 g), L-Boc-proline (3.00 g), and 2-hydroxy-2-methyl-propyl-1-amine. To this was added 70 mL of anhydrous acetonitrile. This was stirred until homogenous and then chilled to 0° C. The EDC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide), (3.20 g) was added in one portion to this mixture. The mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed in vacuo. The remaining material was then taken up in 60 mL of methylene chloride and subsequently washed 4× with 10 mL of 5% citric acid. The suspension was filtered and dried over sodium sulfate. Filtration and removal of the solvent gave rise to the crude material. Purification by silica gel chromatography using 10% methanol / methylene chloride as eluent afforded 3.0336 g of an amide having the structure (IV), tert-butyl 2-(2-hydroxy-2-methylpropylcarbamoyl)pyrrolidine-1-carboxylate. 1H NMR (CDCl3) d 4.29 (J=...

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Abstract

Method of producing C8-C15 hydrocarbons comprising providing a ketone starting material; providing an aldol starting material comprising hydroxymethylfurfural; mixing the ketone starting material and the aldol starting material in a reaction in the presence of a proline-containing catalyst selected from the group consisting of Zn(Pro)2, Yb(Pro)2, and combinations thereof, or a catalyst having one of the structures (I), (H) or (III), and in the presence of a solvent, wherein the solvent comprises water and is substantially free of organic solvents, where (I), (II) and (III) respectively are:where R1 is a C1-C6 alkyl moiety, X═(OH) and n=2.In (III), X may be CH2, sulfur or selenium, M may be Zn, Mg, or a lanthanide, and R1 and R2 each independently may be a methyl, ethyl, phenyl moiety.

Description

STATEMENT OF FEDERAL RIGHTS[0001]The United States government has rights in this invention pursuant to Contract No. DE-AC52-06NA25396 between the United States Department of Energy and Los Alamos National Security, LLC for the operation of Los Alamos National Laboratory.FIELD OF THE INVENTION[0002]The present invention relates to methods of producing C8-C15 hydrocarbons from renewable feedstocks such as cellulosics, sugars and glycerin, by means of an organo-catalyzed aldol reaction.BACKGROUND OF THE INVENTION[0003]Development of sustainable methods of making transportation fuels and surfactants from renewable resources is becoming increasingly important, due to the desirability of decreasing dependence on petroleum resources. Carbohydrates obtained from biomass are renewable and readily available, and there has been much focus on producing fuel and other useful materials from biomass-derived starting materials. Other readily available starting materials include simple sugars, glyce...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07D307/46C07D407/06
CPCC07D207/16
Inventor SILKS, LOUIS A.GORDON, JOHN C.WU, RUILANHANSON, SUSAN KLOEK
Owner LOS ALAMOS NATIONAL SECURITY
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