16000-65-0

Usage

Synthesis Reference(s)

Tetrahedron Letters, 24, p. 765, 1983 DOI: 10.1016/S0040-4039(00)81521-X

InChI:InChI=1/C14H30O2/c1-3-5-7-9-11-13(15)14(16)12-10-8-6-4-2/h13-16H,3-12H2,1-2H3

Upstream product

• 111-71-7 heptanal 
• 74-88-4 methyl iodide 
• 64-19-7 acetic acid 
• 131543-46-9 Glyoxal 
• 3761-92-0 n-hexylmagnesium bromide 
• 1846-67-9 hept-2-ynal 
• 41446-63-3 (E)-7-tetradecene 
• 693-02-7 hex-1-yne 
• 18232-30-9 1,1-diethoxy-2-heptyne 
• 32359-01-6 hexenylmagnesium bromide 
• 16000-63-8 racem.-tetradeca-5,9-diyne-7,8-diol 
• 10374-74-0 tetradec-7-ene 
• 85721-27-3 2,3-dihexyloxirane 
• 7757-83-7 sodium sulfite 

Downstream Products

• 334-48-5 1-decanoic acid 

Relevant academic research and scientific papers

Facile pinacol coupling of aliphatic ketones by Brook rearrangement in the presence of samarium species

Herein we report a practical pinacol coupling reaction, in which ketones (aldehydes) react smoothly with Sm and TMSBr to afford the diol products with Sm(II) or (III) siliyl species generated in situ. This reported method affords poor yields for aromatic ketone substrates and good yields for aliphatic ketones. Therefore, it distinguishes from most reductive coupling approaches that are more effective for aromatic carbonyl compounds and provides a facile and robust approach for the pinacol coupling of aliphatic ketones. Mechanistic studies also indicated the pinacolization probably proceeded via an anionic instead of radical coupling pathway involving the Brook rearrangement in the presence of samarium (II or III) silyl species.

Secondary amides as hydrogen atom transfer promoters for reactions of samarium diiodide

Two secondary amides (N-methylacetamide and 2-pyrrolidinone) were used as additives with SmI2 in THF to estimate the extent of N-H bond weakening upon coordination. Mechanistic and synthetic studies demonstrate significant bond-weakening, providing a reagent system capable of reducing a range of substrates through formal hydrogen atom transfer.

Synthesis of Diester-Based Lubricants from Enzymatically-Directed Epoxides

The present invention is generally directed to methods of making diester-based lubricant compositions, wherein formation of diester species proceeds via esterification of epoxide intermediates, and wherein the epoxide intermediates are generated via an enzymatically-driven mechanism. In some embodiments, the methods for making such diester-based lubricants utilize a biomass precursor and/or low value (e.g., Fischer-Tropsch (FT) olefins and/or alcohols) so as to produce high value diester-based lubricants. In some embodiments, such diester-based lubricants are derived from FT olefins and fatty acids. The fatty acids can be from a bio-based source (i.e., biomass, renewable source) or can be derived from FT alcohols via oxidation.

ISOLATION AND SUBSEQUENT UTILIZATION OF SATURATED FATTY ACIDS AND A-OLEFINS IN THE PRODUCTION OF ESTER-BASED BIOLUBRICANTS

The present invention is generally directed to the synthesis and/or manufacture of ester-based lubricant compositions. The present invention is also directed to methods of making these and other similar lubricant compositions, and to systems for implementing such methods (processes). In some embodiments, the methods for making such ester-based lubricants utilize a biomass precursor (e.g., triglyceride-bearing vegetable oils) such that the lubricant compositions generated by the methods and systems of the present invention can be properly deemed biolubricants. In these or other embodiments, lubricant precursor species can also be sourced or derived from Fischer-Tropsch (FT) and/or long-chain paraffin pyrolysis reaction products. The ester component of the lubricant compositions, produced in accordance with the methods and systems of the present invention, comprises largely diester species.

SYNTHESIS OF DIESTER-BASED BIOLUBRICANTS FROM EPOXIDES

The present invention is generally directed to methods of making diester-based lubricant compositions, wherein formation of diester species proceeds via direct esterification of epoxide intermediates. In some embodiments, the methods for making such diester-based lubricants utilize a biomass precursor and/or low value (e.g., Fischer-Tropsch (FT) olefins and/or alcohols) so as to produce high value diester-based lubricants. In some embodiments, such diester-based lubricants are derived from FT olefins and tatty acids. The fatty acids can be from a bio-based source (i.e., biomass, renewable source) or can be derived from FT alcohols via oxidation.

Diester-Based Lubricants and Methods of Making Same

The present invention is generally directed to diester-based lubricant compositions. The present invention is also directed to methods of making these and other similar lubricant compositions. In some embodiments, the methods for making such diester-based lubricants utilize a biomass precursor and/or low value Fischer-Tropsch (FT) olefins and/or alcohols so as to produce high value diester-based lubricants. In some embodiments, such diester-based lubricants are derived from FT olefins and fatty acids. The fatty acids can be from a bio-based source (i.e., biomass, renewable source) or can be derived from FT alcohols via oxidation.

Reactions of Et3ZnLi with ketones: Electronic and steric effects

Toluene solutions of composition Et3ZnLi react rapidly with aldehydes and ketones to form addition products. Et3ZnNa and Et3ZnK solutions react readily with the same substrates although metalation, as well as addition, is significant with substrates having α-hydrogens. The Et3ZnM solutions react with 2-cyclohexenone to give mainly the 1,4-addition product. Relative rates of addition of Et3ZnLi to substituted acetophenones give a Hammett ρ of 2.78. Addition of Et3ZnLi to acetophenone is slowed significantly by α and ortho methyl substituents; relative rates of addition to acetophenone, o-methylacetophenone, and tert-butyl phenyl ketone are 1.00, 0.012, and 0.003.

Ruthenium Tetroxide Oxidation of Alkenes. A More Complete Picture

The ruthenium tetroxide oxidation of some linear and cyclic alkenes, representatives of five substitution patterns, has been performed in acetone-water (5:1) solution at -70 deg C using stoichiometric ammounts of the oxidant.The main reaction products are 1,2-diols and/or α-ketols depending on the nature of the substrate little amounts of scission products, aldehydes and/or carboxylic acids, are also obtained.Generally 1,2-diols predominate over α-ketols except in the oxidation of (-)-α-pinene that afforded the α-ketol in 51percent yield while no trace of the corresponding 1,2-diol was detected.All reactions prceeded through the formation of unstable brownish precipitates, presumably the intermediate ruthenium (VI) esters, which easily decomposed during the work-up step.Results from oxidation of trans-7-tetradecene and cis and trans-11-tetradecenyl acetate indicated that the reaction was syn stereospecific.In some cases, 1,3-dioxolane products, formed by condensation of the 1,2-diol and the aldehyde materials, were also obtained among the reaction products.Their possible origin is briefly discussed.

Carbon-Carbon Bond Formation by Reductive Coupling with Titanium(II) Chloride Bis(tetrahydrofuran)

Titanium(II) bis(tetrahydrofuran) 1, generated by the treatment of TiCl4 in THF with two equivalents of n-butyllithium at -78 deg C, has been found to form carbon-carbon bonds with a variety of organic substrates by reductive coupling.Diphenylacetylene is dimerized to exclusively (E,E)-1,2,3,4-tetraphenyl-1,3-butadiene; benzyl bromide and 9-bromofluorene give their coupled products, bibenzyl and 9,9'-bifluorenyl, as do benzal chloride and benzotrichloride yield the 1,2-dichloro-1,2-diphenylethanes and 1,1,2,2-tetrachloro-1,2-diphenylethane, respectively.Styrene oxide and cis-stilbene oxide undergo deoxygenation to styrene and trans-stilbene, while benzyl alcohol and benzopinacol are coupled to bibenzyl and to a mixture of tetraphenylethylene and 1,1,2,2-tetraphenylethane.Both aliphatic and aromatic ketones are smoothly reductively coupled to a mixture of pinacols and/or olefins in varying proportions.By a choice of experimental conditions either the pinacol of the olefin could be made the predominant product in certain cases.The reaction has been carried out with heptanal, cyclohexanone, benzonitrile, benzaldehyde, furfural, acetophenone, benzophenone and 9-fluorenone.In a remarkable, multiple reductive coupling, benzoyl chloride is converted into 2,3,4,5-tetraphenylfuran in almost 50percent yield.The stereochemical course of two such couplings, that of diphenylacetylene to yield exclusively (E,E)-1,2,3,4-tetraphenyl-1,3-butadiene and that of acetophenone to produce only racemic-2,3-diphenyl-2,3-butanediol, is interpreted to conclude that the couplings proceed via two electron transfer pathways (TET) involving titanium(IV) cyclic intermediates of the titanirene and the oxatitanacyclopropane type, respectively. - Keywords: Carbon-Carbon Bond Formation, Reductive Coupling, Titanium(II) Chloride, Oxidative Addition, Carbonyl and Benzylic Halide Substrates

Process for the preparation of vicinal diols and/or epoxides

The present invention provides a process for the preparation of vicinal diols and/or epoxides by the oxidation of olefinically-unsaturated compounds with the use of an inorganic heptavalent rhenium compound as catalyst and of hydrogen peroxide as oxidation agent, wherein the reaction is carried out in a solvent selected from the group consisting of organic phosphoric acid esters and ethers with a boiling point above 50° C. under atmospheric conditions.