The Nitrogen Compounds in Petroleum Distillates. XXIII. The Structure of a C₁₆H₂₅N Base from California Petroleum¹

Abstract

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).

Petroleum Acids and Bases

“…The other alpha carbon was known to carry a methyl group, as was the gamma carbon; consequently, the structure of the base was known to be 2,4-dimethyl-6-(2,2,6trimethylcyclohexyl)pyridine. Since the acid obtained on ozonolysis had been found to be one of the most highly hindered acids known, it is not surprising that this base should also be protected by this unit (30,38),…”