80717-21-1Relevant academic research and scientific papers
Cyclopentadienyl and pentamethylcyclopentadienyl ruthenium complexes as catalysts for the total deoxygenation of 1,2-hexanediol and glycerol
Thibault, Michelle E.,Dimondo, Domenico V.,Jennings, Michael,Abdelnur, Patricia Verardi,Eberlin, Marcos N.,Schlaf, Marcel
supporting information; experimental part, p. 357 - 366 (2011/04/18)
The ruthenium aqua complexes [cp*Ru(OH2)(N-N)](OTf) (cp* = η5-pentamethylcyclopentadienyl, N-N = 2,2′-bipyridine, phen = 1,10-phenanthroline, OTf- = trifluoromethanesulfonate) and the acetonitrile complex [cpRu(CH 3CN)(bipy)](OTf) (cp = η5-cyclopentadienyl) are water-, acid-, and thermally stable (>200°C) catalysts for the hydrogenation of aldehydes and ketones in sulfolane solution. In the presence of HOTf as a co-catalyst, they effect the deoxygenation of 1,2-hexanediol to 1-hexanol and hexane. Glycerol is deoxygenated to 1-propanol in up to 18% yield and under more forcing conditions completely deoxygenated to propene. The structure of the acetonitrile pro-catalyst [cpRu(CH3CN)(bipy)](OTf) has been determined by X-ray crystallography (space group P1 (a = 9.3778(10) A; b = 10.7852(10) A; c = 11.1818(13) A; α = 101.718(5)°; β = 114.717(4)°; γ = 102.712(5)°; R = 3.95%).
Oxymetallation. Part 15. Oxidation of Hex-1-ene by Thallium(III) Trifluoroacetate in Methanol
Bloodworth, A. J.,Lapham, David J.
, p. 3265 - 3271 (2007/10/02)
Hex-1-ene reacts with thallium(III) acetate in methanol to afford 2-methoxyhexylthallium diacetate which undergoes no appreciable decomposition when kept in methanol at room temperature for one week, but which, upon treatment with solid potassium bromide and a catalytic amount of 2,6-dimethyl-18-crown-6, cleanly affords a high yield of 1-bromo-2-methoxyhexane (1).By contrast, the methoxythalliation adduct obtained with thallium(III) trifluoroacetate undergoes oxidative dethalliation fairly rapidly (ca. 85percent dethalliation after 2 h) to give 1,2-dimethoxyethane (2) and 2-methoxyhexanol (3) as major products.It is suggested that compounds (2) and (3) arise by facile ligand exchange followed by transfer of methoxy- or hydroxy-groups from thallium to C-1 in an SNi process.If the methoxythalliation is carried out with thallium(III) trifluoroacetate in dichloromethane with methanol (2 equiv.) the oxidative dethalliation is complete after only 1 h, but 1-methoxyhexan-2-ol (4) and 2-methoxy-1-trifluoroacetoxyhexane (5) are obtained as additional products.It is suggested that ligand exchange is not effective under these conditions and that dethalliation via an oxonium ion, which leads to compounds (2) - (4), competes with the SNi process which affords compounds (5).Only small amounts (10percent) of hexan-2-one are obtained in the oxidations.
