Selective synthesis of 2-ethyl-1-hexanol from n-butanol through the Guerbet reaction by using bifunctional catalysts based on copper or palladium precursors and sodium butoxide

Catalytic Upgrading of Ethanol to n‐Butanol: Progress in Catalyst Development

“…[9] However,t his reaction was carried out in pure alcohol to avoid the detrimental effecto fw ater. [10] As ubsequent reports howedt hat an [Ir(OAc) 3 ]c atalyst with a ligand (bathophenanthroline disulfonic acid disodium salt) exhibited 26 %s electivity to n-butanol at 52 %e thanol conversion in water,b ut iridium precipitates could be observed. [11] The upgrading of ethanol to n-butanol in this homogeneous reactions ystem is proposed to proceed through the Guerbet reaction( Scheme 1b): the preciousm etal (Ir) was responsible for alcohol dehydrogenationa nd subsequent unsaturated aldehydeh ydrogenation to higher alcohol, whereas the strong inorganic base (e.g.,N aOH, EtONa)w as responsible for the aldol coupling step.…”

Synthesis of Biomass‐Derived Ethers for Use as Fuels and Lubricants

“…[80,81] The carbon number of linear alcohols can be furtheri ncreased via the Guerbet pathway,w hich affords branched alcohols such as 2ethyl-1-hexanol, 2-hexyl-1-decanol, and 2-decyl-1-tetradecanol. [82] Olefinsd erived from biomassa re also useful synthons for producing ethers. For example, isobutene can be selectively formed from acetone or ethanol over zinc oxide dispersed on zirconia in the presence of water, [83,84] or through fermentation of biomass-derived sugars.…”

Effect of Alcohol Structure on the Kinetics of Etherification and Dehydration over Tungstated Zirconia

“…Symmetrical branched ethers (1E) are only formed in small amounts from the coupling of small Guerbet alcohols (2-ethyl-1-hexanol and 2-butyl-1-octanol), and are not formed from the coupling of bulkier alcohols (> C 16 ). The pathways for these reactions are shown in Scheme2,a nd the resultsa re summarized in Ta ble 4.…”

“…[6] Longer chain branched ethers in the C 28 -C 32 range have low pour points ande xcellent lubricant properties, [7][8][9] and could replace poly-alpha-olefin lubricants,which are produced fromf ossil reserves. [16] Some generalapproaches to producing linear and branched alcoholsf rom biomass-derived platform molecules are summarized in Scheme 1. Ethanol and butanol can be obtained in high yields through fermentation processes such as ABE (acetone-butanol-ethanol) fermentation.…”