GB1008642A - Alkenyl sodium compounds and derivatives thereof - Google Patents

Abstract

In the process for preparing alkenyl sodium compounds by reacting at least one alkyl sodium compound with a non-terminal alkene containing at least 6 carbon atoms (see Division C2), any unmetalated excess of alkene, being a mixture of isomers of said alkene initially present, is recovered from the reaction mixture. The alkenyl sodium compounds so produced may be reacted with halobenzenes to produce alkylated benzenes. Specification 1,008,643 is referred to.ALSO:The invention comprises alkenyl sodium compounds, having the sodium substituent in the 1- or 3-position in the alkenyl chain, which are prepared by reacting at least one alkyl sodium compound with a non-terminal alkene containing at least six carbon atoms at a temperature below 30 DEG C., preferably between - 25 DEG C, and + 20 DEG C., to produce one or more sodium derivatives. The alkyl sodium compound may contain from 1 to 12 carbon atoms. The non-terminal alkene preferably contains less than 25 carbon atoms, e.g. 2-, and 3-hexene, 2-dodecene, 5-dodecene or 11-tricosene. The reaction may be carried out in batch, semi-continuous or continuous fashion, preferably in the presence of a saturated hydrocarbon medium. The alkene is preferably used in molar excess, preferably at least 2 : 1, of the alkyl sodium compound. The unmetallated excess of alkene, being a mixture of isomers of the alkene initially present, may be recovered from the reaction medium. The metallated derivatives can be contacted with electrophilic reagents to yield a mixture of 1-substituted and 3-substituted alkenyl derivatives. With CO2, the resulting carbonated mixture may be acidified to yield a mixture of 1- and 3-substituted monocarboxylic acids. The metallated derivatives can be subjected to other reactions with electrophilic reagents such as SO2 and SO3 to produce sulphinic and sulphonic acids respectively; with N-haloamines to produce amines; with epoxides to produce primary alcohols; with aldehydes to produce secondary alcohols; with ketones to produce tertiary alcohols; with a ,b -unsaturated esters to produce monomeric and polymeric condensation products. The amines may be oxidized to form amine oxides. Example (1) relates to the reaction between 2-dodecene and amyl sodium, to give dodecenyl-sodium-3 and 2-dodecenyl-sodium-1, which on carbonation give 3-tridecenoic acid and a -vinyl undecanoic acid. The alkenyl-sodium mixture was also reacted with acetaldehyde to give 2-hydroxy-3-vinyldodecane and 2-hydroxy-4-tetradecene. Reactions carried out as in Example (1) and the acids obtained using different alkenes are identified in Table II shown in Example (4). Specification 1,008,043 is referred to.