Epichlorohydrin, with boron trifluoride

Electrolytic reduction, apparatus, 52, 23 Enol acetates, acylation of, 52,1 Enol esters, preparation, 52, 39 Epichlorohydrin, with boron trifluoride diethyl therate and dimethyl ether to give trimethyloxonium tetra-fluoroborate, 51,142 ESTERIFICATION OF HINDERED ALCOHOLS f-BUTYL p-TOLUATE,... 

Eqn. (a) shows the interaction of epichlorohydrin with boron trifluoride etherate in the presence of absolute methylene-chloride (CHgClg) to yield triethyl oxonium borontrifluoride (I). 

Polyepichlorohydrin and dimethylamine Polymerisation of epichlorohydrin in carbon tetrachloride with boron trifluoride/ether catalyst, then reaction with dimethylamine. Applied to cotton by exhaust method or pad-dry. Scheme 10.65 Good yields with direct dyes using only 2 g/l salt. Excellent build-up with most reactive dyes only 10% of normal salt usage needed for low-reactivity dyes and none for highly reactive types. Washing fastness very good but light fastness impaired. 

Epichlorohydrin, 54, 20 with boron trifluoride diethyl etherate and dimethyl ether to give trimethylox-onium tetrafluoroborate, 51, 142... 

Epichlorohydrin, 46, 24 reaction with boron trifluoride ether to form triethyloxonium fluo-borate, 46,113... 

Chloro-2-hydroxypropyl derivatives of such polysaccharides as cellulose and cross-linked dextran (Sephadex) may be prepared by treatment with epichlorohydrin in boron trifluoride etherate. These 3-chloro-2-hydroxypropylated polysaccharides may, in turn, react with ammonia, or primary, secondary, or tertiary amines, and the resultant derivatives of cellulose and Sephadex LH-20, particularly an 0-[3-(di-butylamino)-2-hydroxypropyl] derivative of the latter, are useful anion-exchangers. In the amination procedure, between 50 and 100% of the chlorine atoms are utilized, except in the reaction with tertiary... 

Boron trifluoride, with dimethyl ether and epichlorohydrin to give tri-methyloxonium tetrafluorobo-rate, 51,142... 

Epichlorohydrin (140 g) is added, with stirring and exclusion of moisture, to a solution of boron trifluoride-ether (285 g, 2 moles) in ether (500 ml) at such a rate that the ether remains boiling vigorously. The oily product that separates at first solidifies towards the end of the addition of the epichlorohydrin. Stirring is continued for a further 2 h, the mixture is left overnight, then the triethyloxonium fluoroborate is filtered off, washed thoroughly with ether, and dried in a vacuum. The yield is 269 g. The material is stable almost indefinitely under ether. 

When halogen atoms are present in the epoxide such as in epichlorohydrin, 3,3,3-trichloropropylene oxide (TCPO) or 4,4,4-trichloro-l,2-butylene oxide (TCBO), or in the initiator, acid catalysts, e.g. boron trifluor-ide etherate, may be used (13-18). Vogt cind Davis (16) found that, if the concentration of catalyst/ini-tiator (polyol) complex is decreased with respect to TCPO in order to obtain higher molecular weight products, side reactions such as cyclization reactions become increasingly important. Boron trifluoride also promotes dimerization of alkylene oxides to dioxane or alkyl derivatives of dioxane as described by Fife and Roberts ( ). The use of acid catalysts, e.g. Lewis acids, promotes formation of a greater amount of terminal primary alcohol groups when compared to base catalysis of epoxides. 

Friedel-Crafts reaction catalysts like anhydrous aluminum chloride are readily soluble in the nitroalkanes. Solutions containing up to 50% aluminum chloride are easily prepared in nitroalkane solvents. These catalytically active complexes, AICI3-RNO2, can be isolated and used in solvents other than the nitroalkane. The reactants in the Friedel-Crafts reaction are often soluble in the nitroalkane reaction medium. Other catalysts like boron trifluoride (BF3), titanium tetrachloride (TiC ), and stannic tetrachloride (SnClj) are also soluble in the nitroalkane solvents. Reaction types which use nitroparaffins as solvents include alkylation of aromatics, acetylation of aromatics, halogenations, nitrations, and the reaction of olefins and hydrogen sulfide to yield mercaptans. Nitroparaffins are used with catalysts such as alkyl-metal (e.g., triethylaluminum, vanadium, or titanium) salts in the polymerization reactions of alkylene oxides, epichlorohydrin, propylene, butylene, vinyl chloride, and vinyl ethers. The nitroparaffin acts as an activator for the catalyst or can serve as the reaction solvent. 

Dioxolanes are also prepared by KlO-catalyzed reaction of l-chloro-2,3-epoxypropane (Epichlorohydrin) with aldehydes or ketones, in carbon tetrachloride at reflux (eq 3). In the reaction of acetone with the epichlorohydrin, the efficiency of catalysts varies in the order K10 (70%) > Tin(IV) Chloride (65%) > Boron Trifluoride (60%) = Hydrochloric Acid (60%) >Phosphorus(V) Oxide (57%). 

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