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There have been isolated and definitely identified from petroleum six naphthenic acids: 3,3,4-trimethylcyclopentaneacetic,3 cyclopentanecarboxylic,4 cyclopentaneacetic,4 3-methylcyclopentaneacetic,4 dl -1,2,2-trimethylcyclopentane-carboxylic5 and solid 4-methylcyclohexanecar-boxylic6 acids. Since this manuscript was prepared, however, Buchman and Sargent have been able to show that von Braun's acid is not 3,3,4trimethylcyclopentaneacetic acid.Results reported in this paper were obtained in a continuation of the petroleum acid research on a complex mixture of acids obtained from the sodium carbonate washing of Signal Hill, California, straight run gasoline.5,7Since Hancock was able to isolate camphonanic acid from the higher boiling acids through the fact that it is not esterified by treatment with methanol and dry hydrochloric acid, it seemed possible that other unesterifiable acids might be present in the acids containing eight to ten carbon atoms. Accordingly various fractions of acids boiling in the C § to Cjo range were carefully fractionated and then each fraction was separately heated for twenty-four hours with methanol and dry hydrogen chloride. These operations yielded a total of 800 g. of unesterified acids. By subjecting 22 liters of still higher boiling stored material to the same treatment another 2030 g. of unesterified material was obtained.Careful fractionation of these acids yielded 400 cc. of esters that had been dissolved in the acids, 700 cc. of liquid acids and 940 g. of acids that solidified in the receiver or in the condenser. Fractional liberation of these solid acids from their sodium salts yielded 280 g. of camphonanic acid, 500 g. of another solid acid melting 70-80°,(1) From theses submitted by Billie Shive, Joe Horeczy and George Wash in partial fulfillment of requirements for the Doctor of Philosophy degree, June, 1941.

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A CieH86N Base from California Petroleum 909 Esters could uot be made with chloroor bromoacetic acids. With phthalic anhydride at 130-1400 for one hour the bis-monophthalate, the sodium salt of which gave precipitates with salts of the heavy metals, was formed along with a heavy neutral oil which could not be purified, apparently the neutral ester. This predominates when the reaction temperature is higher, 150-160°, regardless of the proportion of the anhydride.Other Reactions.-Condensation took place when thiodiglycol was heated with dimethylaniline, raising the temperature gradually from 120 to 160 °in eighteen hours with the addition of zinc chloride in portions. The product was a heavy oil boiling at 204-210°(8 mm.), containing sulfur and dissolving in dilute acids.Mustard gas sulfoxide, (C1CH2CH2)2S0, was refluxed with potassium acetate in absolute alcohol and also in acetic acid but no reaction could be detected in either case.The sulfone, (C1CH2CH2)2S02, was refluxed with potassium acetate in acetic acid solution; a reaction took place.After filtering off the salt and volatilizing the acetic acid, a reddish viscous liquid remained for which no method of purification could be found. Potassium i-valerate gave a similar product. From the sulfone and sodium benzoate in absolute alcohol the calculated amount of sodium chloride was obtained along with benzoic acid. The benzoate of thiodiglycol has been oxidized to the corresponding sulfoxide and sulfone.1 Summary Thiodiglycol has been purified and its properties determined. Several esters have been made from it and their properties determined.(5) Fromm and Kohn, Ber., St, 321 (1921).

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