Metal solvent-based synthesis

A new approach for the synthesis of functionalized 4-alkylquinolines was developed utilizing electrogenerated carbanions <07SL1031>. The desired 4-alkylquinolines 83 were synthesized through a sequential alkylation/heterocyclization of p-(2-aminophenyl)-a,p-ynones 84 and the electrogenerated carbanions of nitroalkanes 85. This novel approach avoided metal and base catalysts and is performed under solvent free conditions. 

Phosphonium cation-based ILs, in some applications, offer superior properties as compared to nitrogen cation-based ILs such as their use as extraction solvents, chemical synthesis solvents, electrolytes in batteries and super-capacitors, in corrosion protection, etc. Phosphonium-based ILs have many industrial and pharmaceutical applications such as lubricants, entrainers, electrolytes, media for metal deposition, paramagnetic flnids, and extractants for sulfur-containing compounds. 

Mixed-metal catalysts based on 002(00)9 have proved effective In the synthesis of N acyl amlnoaclds, starting with either allylic alcohols, oxiranes (eqn.15) or trifluoropropene. The oxidative carbonylatlon of organomercury compounds Is subject to solvent effects. The Pd catalysed carbonylative cross-coupling of aryl Iodides with triIsobutylaluminium gives secondary benzyl alcohols a variety of functional groups are tolerated.Carbamate esters... 

Anouti M, Caftlon-Caravanier M, Diidi Y, Gahano H, Lemordant D (2008) Synthesis and characterization of new pyrroUdinium based protic ionic liquids. Good and superionic liquids. J Phys Chem B 112(42) 13335-13343. doi 10.1021/jp805992b Abbott AP, Capper G, Davies DL, McKenzie KJ, Obi SU (2006) Solubility of metal oxides in deep eutectic solvents based on choline chloride. J Chem Eng Data 51(4) 1280-1282. doi 10.1021/je060038c... 

The first reported synthesis of acrylonitrile [107-13-1] (qv) and polyacrylonitrile [25014-41-9] (PAN) was in 1894. The polymer received Htde attention for a number of years, until shortly before World War II, because there were no known solvents and the polymer decomposes before reaching its melting point. The first breakthrough in developing solvents for PAN occurred at I. G. Farbenindustrie where fibers made from the polymer were dissolved in aqueous solutions of quaternary ammonium compounds, such as ben2ylpyridinium chloride, or of metal salts, such as lithium bromide, sodium thiocyanate, and aluminum perchlorate. Early interest in acrylonitrile polymers (qv), however, was based primarily on its use in synthetic mbber (see Elastomers, synthetic). 

Nucleophilic Substitution Route. Commercial synthesis of poly(arylethersulfone)s is accompHshed almost exclusively via the nucleophilic substitution polycondensation route. This synthesis route, discovered at Union Carbide in the early 1960s (3,4), involves reaction of the bisphenol of choice with 4,4 -dichlorodiphenylsulfone in a dipolar aprotic solvent in the presence of an alkaUbase. Examples of dipolar aprotic solvents include A/-methyl-2-pyrrohdinone (NMP), dimethyl acetamide (DMAc), sulfolane, and dimethyl sulfoxide (DMSO). Examples of suitable bases are sodium hydroxide, potassium hydroxide, and potassium carbonate. In the case of polysulfone (PSE) synthesis, the reaction is a two-step process in which the dialkah metal salt of bisphenol A (1) is first formed in situ from bisphenol A [80-05-7] by reaction with the base (eg, two molar equivalents of NaOH),... 

A direct application of the ring-opening reaction of an epoxide by a metal enolate amide for the synthesis of a complex molecule can be found in the synthesis of the trisubstituted cyclopentane core of brefeldin A (Scheme 8.35) [68a]. For this purpose, treatment of epoxy amide 137 with excess KH in THF gave a smooth cyclization to amide 138, which was subsequently converted into the natural product. No base/solvent combination that would effect cyclization of the corresponding aldehyde or ester could be found. 

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