Butyl bromide with sodium cyanide

In an extension of this work, the reuse of the polymeric catalyst was addressed and several new PE-poly(alkene) glycol copolymers were prepared [68]. Commercially available oxidized polyethylene (CO2H terminated, both high and low molecular weight) was converted to the acid chloride and reacted with Jeffamine D or Jeffamine EDR, and subsequently converted to the tributylammonium bromide salt with butyl bromide. These new quaternary salts were shown to catalyze the nucleophihc substitution of 1,6-dibromohexane with sodium cyanide or sodium iodide. While none of the polymeric quaternary salts catalyzed the reaction as well as tetrabutylammonium bromide, the temperature-dependent solubility of the polymers allowed removal of the polymer by simple filtration. 

Into a 1500 ml. round-bottomed flask place 97-5 g. of finely-powdered sodium cyanide (1), 125 ml. of water, and a few chips of porous porcelain. Attach a reflux condenser and warm on a water bath until all the sodium cyanide dissolves. Introduce a solution of 250 g. (196 ml.) of n-butyl bromide (Sections 111,35 and 111,37) in 290 ml. of pure methyl alcohol, and reflux gently on a water bath for 28-30 hours. Cool to room temperature and remove the sodium bromide which has separated by filtration through a sintered glass funnel at the pump wash the crystals with about 100 ml. of methyl alcohol. Transfer the filtrate and washings to From n caproamide by SOClj method. 

Reaction XXXVUI. (a) Action of Aqueous and Alcoholic Potassium or Sodium Cyanide on Aliphatic Halogen Compounds, and Hydrolysis of the Nitriles so formed. (B., 14, 1965 15, 2318.)—The preparation and hydrolysis of nitriles are dealt with on p. 151 and p. 239 respectively. In many cases, however, it is unnecessary to isolate the nitrile it can be directly hydrolysed to the corresponding acid on its formation. Among others, the following syntheses have been carried out in this way — i (i.) w-Valeric acid [jpentan acid] from w-butyl bromide (Am. Soc., 42, 310). 

The cyanoacetic acid obtained from monochloroacetic acid and sodium cyanide, is treated with hydrochloric acid and ethanol to yield the diethyl ester of malonic acid. The ester, in absolute ethanol, is reacted with the stoichiometric proportion of metallic sodium so as to replace only one active hydrogen of the methylene (CH2) group. Thereupon, a slight excess of the calculated amount of allyl bromide is added. The second replaceable hydrogen is abstracted with 1-methyl butyl bormide and the resulting product is made to react with a theoretical amount of thiourea to yield thiamylal. The free acid thus obtained is conveniently transformed into the official sodium salt by neutralization with a stoichiometric proportion of sodium hydroxide (1 1). 

The reaction of trispentailuorophenylmethane with sodium or lithium hydride under an argon atmosphere in hexamethylphosphoramide at 20— 25 °C gives a solution of the trispentafluorophenyl carbanion [(C F, C ] (c/ p. 392), the n.m.r. spectrum of which has been described. It seems probable that bispentafluorophenyl carbanions are involved in the formation of 1,1,2,2-tetrakispentafluorophenylethane from bispentafluorophenylmethyl bromide and cyanide ion, triphenylphosphine, or butyl-lithium, and their failure to carbonate during the last reaction at - 70 °C has been attributed to their relatively high stability. ... 

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