772-46-3Relevant academic research and scientific papers
2,2,5,5-Tetramethyltetrahydrofuran (TMTHF): A non-polar, non-peroxide forming ether replacement for hazardous hydrocarbon solvents
Byrne, Fergal,Forier, Bart,Bossaert, Greet,Hoebers, Charly,Farmer, Thomas J.,Clark, James H.,Hunt, Andrew J.
, p. 3671 - 3678 (2017/08/15)
An inherently non-peroxide forming ether solvent, 2,2,5,5-tetramethyltetrahydrofuran (2,2,5,5-tetramethyloxolane), has been synthesized from readily available and potentially renewable feedstocks, and its solvation properties have been tested. Unlike traditional ethers, its absence of a proton at the alpha-position to the oxygen of the ether eliminates the potential to form hazardous peroxides. Additionally, this unusual structure leads to lower basicity compared with many traditional ethers, due to the concealment of the ethereal oxygen by four bulky methyl groups at the alpha-position. As such, this molecule exhibits similar solvent properties to common hydrocarbon solvents, particularly toluene. Its solvent properties have been proved by testing its performance in Fischer esterification, amidation and Grignard reactions. TMTHF's differences from traditional ethers is further demonstrated by its ability to produce high molecular weight radical-initiated polymers for use as pressure-sensitive adhesives.
Comparative performance evaluation and systematic screening of solvents in a range of Grignard reactions
Kadam, Asha,Nguyen, Mylinh,Kopach, Michael,Richardson, Paul,Gallou, Fabrice,Wan, Zhao-Kui,Zhang, Wei
, p. 1880 - 1888 (2013/09/24)
The solvent effect on the Grignard reaction of benzyl, aryl and heteroaromatic substrates has been systematically evaluated based on reaction efficiency, ease of subsequent work-up, safety and greenness. 2-Methyltetrahydrofuran (2-MeTHF), which can be derived from renewable resources, had at least an equal if not a superior overall process most notably in suppressing the Wurtz coupling by-product from the benzyl Grignard reactions. It is therefore a recommended alternative solvent to Et2O and THF for the preparation of most Grignard reagents and their subsequent reactions.
Ether-directed ortho-C-H olefination with a palladium(II)/monoprotected amino acid catalyst
Li, Gang,Leow, Dasheng,Wan, Li,Yu, Jin-Quan
supporting information, p. 1245 - 1247 (2013/03/13)
Weak coordination is powerful! A PdII-catalyzed olefination of ortho-C-H bonds of arenes directed by weakly coordinating ethers is developed by using monoprotected amino acid (MPAA) ligands. This finding provides a method for chemically modifying ethers, which are abundant in natural products and drug molecules. HFIP=hexafluoroisopropanol. Copyright
Friedel-Crafts alkylation of benzene with 1,2-diphenyl-2-propanol, 1-chloro-2,3-diphenylpropane and 2-methyl-1-phenyl-2-butanol
Khalaf, Ali A.,Awad, Ibrahim M.,El-Emary,El-Aal, H.A.K. Abd
experimental part, p. 595 - 600 (2011/08/21)
The alkylation of benzene with 1,2-diphenyl-2-propanol (1) using AlCl 3/CH3NO2 catalyst gave a mixture of 1,2,2- (4) and 1,1,2-triphenylpropane (5) as product alkylates. With 85% H 2SO4 catalyst, the product consisted of E-1,2-diphenylpropene (6) after 2 h of a mixture of 5 and 6 after 18 h. Similar alkylation of benzene with 1-chloro-2,3-diphenylpropane (2) using AlCl 3 catalyst gave a mixture consisting of 4, 5 and 6. Finally, alkylation of benzene with 2-methyl-1-phenyl-2-butanol (3) using AlCl 3/CH3NO2 gave 2-methyl-1,1-diphenylbutane (10) as sole product alkylate. The identities of the products were confirmed spectroscopically and by comparison with unequivocally prepared samples. Mechanisms are proposed to rationalise the observed results.
Iron(II) chloride-mediated addition of dialkylmagnesium to carbonyl compounds
Sada, Mutsumi,Matsubara, Seijiro
, p. 800 - 801 (2008/12/21)
Addition reactions to carbonyl compounds with a complex reagent, prepared from organomagnesium and iron(II) chloride, were examined. The reagent works as effective nucleophile to an easily enolizable ketone such as β-tetralone; it also added to keto ester chemoselectively. Copyright
Solvent applications of 2-methyltetrahydrofuran in organometallic and biphasic reactions
Aycock, David F.
, p. 156 - 159 (2012/12/26)
2-Methyltetrahydrofuran (MeTHF) is a commercially available solvent that is produced from renewable resources. The properties of MeTHF place it between tetrahydrofuran (THF) and diethyl ether in solvent polarity and Lewis base strength. In many cases, MeTHF can replace THF in organometallic reactions. The formation and reaction of Grignard reagents in MeTHF and THF are similar. MeTHF can be used as a solvent for low-temperature lithiation, for lithium aluminum hydride reductions, for the Reformatsky reaction, and for metal-catalyzed coupling reactions. MeTHF is also a good substitute for dichloromethane in biphasic reactions.
Preparation of alcohols from sulfones and trialkylboranes
Billaud, Célia,Goddard, Jean-Philippe,Le Gall, Thierry,Mioskowski, Charles
, p. 4451 - 4454 (2007/10/03)
The reaction of sulfone anions with trialkylboranes followed by thermal isomerization of the obtained boron compounds in the presence of excess borane-methyl sulfide complex and by alkaline hydroperoxide oxidation yields primary alcohols.
Highly enantioselective addition of primary alkyl Grignard reagents to carbocyclic and heterocyclic arylketones in the presence of magnesium TADDOLate preparative and mechanistic aspects
Weber, Beat,Seebach, Dieter
, p. 6117 - 6128 (2007/10/02)
In the presence of equimolar amounts of the Mg alkoxide from α,α,α',α'-tetraphenyl-2,2-dimethyl-1,3-dioxolan-4,5-dimethanol (a TADDOL) primary Grignard reagents (Et, Pr, Bu, Oct, 3-butenyl) add to carbo- and heteroaromatic methyl ketones in THF at -100°C to give tertiary alcohols of enantiomeric excesses reaching values above 98%. The scope and limitation of the method are investigated. The reaction, which occurs in a vigorously stirred heterogeneous mixture, give best results in the absence of steric hindrance of the reacting centers; Grignard reagents made from alkyl bromides are superior to those obtained from chlorides; there is a perfect linear relationship between the ee of the TADDOL and of the product 2-phenyl-2-decanol; those tertiary alcohols of which the absolute configuration is known, are formed by nucleophilic attack from the Re face of the keto carbonyl groups. Three tentative mechanistic models for the stereochemical course of the reaction are discussed.
ELECTROSYNTHESIS OF ALCOHOLS FROM ORGANIC HALIDES AND KETONES OR ALDEHYDES
Sibille, Soline,d'Incan, Esther,Leport, Louis,Perichon, Jacques
, p. 3129 - 3132 (2007/10/02)
The electrosynthesis of a wide range of alcohols from organic halides and ketones or aldehydes is achieved under simple and mild conditions in an undivided electrolytic cell using different sacrificial anodes.
THE ATE COMPLEXES OF ALUMINIUM. REACTIVITY AND STEREOSELECTIVITY WITH RESPECT TO EPOXIDES AND CARBONYL COMPOUNDS. CATALYTIC ACTIVATION BY SALTS OF TRANSITION METALS
Boireau, G.,Abenhaim, D.,Henry-Basch, E.
, p. 3061 - 3070 (2007/10/02)
When used in non-coordinating solvents (hydrocarbons) NaAlEt4 and LiAlnBu4 are good alkylation agents for epoxides.The presence of catalytic quantities of transition-metal salts, particularly NiCl2 or NiBr2, greatly accelerate the reactions, making them possible within a reasonable time in the case of disubstituted epoxides such as cyclohexene oxide, 2-3 epoxybutane, 1 phenyl-2,3-epoxybutane.In the case of aliphatic epoxides, dialkylmagnesium, NaAlEt4 and LiAlnBu4 lead mainly to alkylation of the least substituted carbon of the epoxide ring; while in the case of epoxides with C-O bond in the benzyl position, it is this carbon that is alkylated.The reaction always proceeds by total inversion of the configuration of the carbon in the epoxide ring, namely the site of the alkylation. NaAlEt4 is also good agent for alkylating carbonyl compounds when used in solvents of low basicity such as diethylether, or in totally non-coordinating solvents such as the hydrocarbons.The yields of the alcohol are greatly improved by using catalytic quantities of NiCl2.The behaviour of NaAlEt4 with 2-phenylpropanol is quite remarkable: in diethylether NaAl-Et4 gives predominantly the pair of enantiomers predicted by Cram's rule and with greater stereoselectivity than if EtMgBr was used, while in pentane the reaction is no longer stereoselective.Finally, with a cyclic ketone, 4-t-butylcyclohexanone, NaAlEt4 in diethylether and in hexane in the presence of NiCl2 gives predominantly the equatorial alcohol resulting from an axial attack, which is generally not favoured at all.
