No abstract

The intermediate compound, a-nitrosoanisyl chloride, was treated with hot sodium carbonate solution.Upon separating the product and recrystallizing it from alcohol it was identified as the di-(pmethoxypheny1)-furazane oxide by mixed melting point. Anisohydroxamyl chloride when treated in a similar way gave identical results.The material liquefied and then partially solidified. SummaryStereoisomeric anisohydroxamyl chlorides were not obtained by chlorinating the anisaldoximes either with chlorine gas or with nitrosyl chloride. In the latter reaction an unstable nitroso intermediate was isolated and studied. By chlorinating with an excess of chlorine, m-chloro and m,m'-dichloroanisohydroxamyl chlorides were prepared.In the preparation and cleavage of the hindered trihalomethyl ketones previously reported, the question has arisen as to whether the insolubility of these compounds in the aqueous solutions used might not have an important influence on the rates a t which the reactions proceed. The use of alcohol and pyridine as solvents has disclosed some evidence which supports this point of view.2 In order to subject this idea to a crucial test, 3,5-dimethyl-4-acetylbenzoic acid (V) has been synthesized and studied. Since this compound and the trihalomethylketonic acids derived from it are soluble in aqueous alkalies, the insolubility factor is eliminated.As the starting point for the synthesis of the ketonic acid, dimethylterephthalic acid (I)3 was used. Esterification with methanol gave the half ester (11), which was then converted into the corresponding acid chloride (111) by the action of thionyl chloride. Treatment with methylzinc iodide, followed by hydrolysis, transformed the acid chloride into the desired keto acid (V).3,5-Dimethyl-4-acetylbenzoic acid when dissolved in solutions of sodium hypochlorite and sodium hypobromite gave, respectively, 3,5-dimethyl-4-trichloroacetylbenzoic acid (VI) and 3,5-dimethyl-4-tribromoacetylbenzoic acid (VII). This synthesis of these trihalomethylketonic acids in alkaline solution demonstrates that they are moderately stable toward alkalies. Moreover, when dissolved in sodium hydroxide solutions a t 0' they could (1) Eighth paper on the haloforrn reaction. (2) Fuson, Lewis and Du Puis, i t i d . , 64, 1114 (1932). (3) Noyes, Am. Chem. J., '20, 809 (1898); Hufferd and Noyes, THIS JOURNAL, 48, 928 (1921). For references to previous articles see Fuson, Bertetti and Ross, THIS JOURNAL, 54, 4380 (1932).

Ethoxypropyl alcohol and 7-ethoxypropyl bromide were made essentially as described by Noyes.4 Forty grams of gthoxypropyl bromide was refluxed for three and one-half hours on a water-bath with 28 g. of potassium cyanide, 6 cc. of water and 40 cc. of alcohol. The liquid was then decanted from the precipitated salts, which were washed with ether. The combined solution was diluted with water and extracted several times with ether. After removal of the solvent from the dried ether extract, the product was fractionated under reduced pressure: wt., about 16 g.; b. p. (716 mm.) 175°. The reported b. p. (750 mm.) is 181.2-181.5°.5-Ethoxybuty lamine, EtOC4H8NH2.-Ten grams of ethoxybutyronitrile and 200 cc. of absolute methanol were placed in a flask under an efficient reflux condenser.Twenty-six grams of sodium, cut into small pieces, was added as rapidly as possible through the condenser.

Vol. 57 rotation and analysis was dried in vacuo over phosphorus pentoxide at 100°.This salt melted at 170-180°. Rotation. 0.5000 g. made up to 5 cc. in methyl alcohol gave an, 2.86°; l = 2; [a]26D 14.3°.