STUDIES ON THE POLYMETHYLBENZENES. I. A STUDY OF THE JACOBSEN REACTION WITH PENTAMETHYLBENZENE, AND THE PREPARATION OF PREHNITENE¹

Abstract

2994lbb mviN smith and album r. lux Vol. 51 dye) and the extremely soluble l-amino-4-phenol-sulfonic ester (0.46 mole per mole of dye). The yield ratio of the latter two products was identically the same as obtained in the cleavage of the unsulfonated dye.Cleavage of 4-Hydroxyazobenzene-4-sulfonic Acid at 140 to 145°.-The sodium salt of the dye and sodium sulfite solution of approximately 0.75 M concentration were heated in a steel autoclave at 140 to 145°. At the end of twenty hours cleavage was found complete. Analytical determinations yielded very nearly the same results: 3.6% of the consumed sulfite was changed to sulfate, a little more than was formed at the lower temperature. Summary 1. A new type reaction of monoazo dyes has been observed. They combine with two moles of a neutral sulfite, in solution, suffering cleavage into a primary amine and the salts of N-sulfonic and N-disulfonic acids.2. 4-Hydroxyazobenzene yielded approximately 0.78 mole of aniline, 0.22 mole of an N-sulfonic acid of aniline, 0.78 mole of an N-disulfonic and 0.22 mole of an N-monosulfonic acid of l-amino-4-phenol and no trace of unsulfonated aminophenol.3. 4'-Hydroxyazobenzene-4-sulfonic acid reacted similarly, sulfanilate being formed as a result of cleavage.4. Hydrolysis and rearrangement of free N-sulfonic acids resulted in complete recovery of the primary dye component in its original form; the secondary component yielded l-amino-4-phenol-5-sulfonic acid and an extremely soluble, stable l-amino-4-phenol-sulfonic ester, a compound not previously reported.5. An explanation of the cleavage reaction has been suggested, founded on an assumption of functional differences between the two nitrogen atoms of the azo group.

Separation, by distillation with acetic acid, of the aromatic hydrocarbons from the fraction of a midcontinent petroleum boiling between 154 and 162 C

“…BEHAVIOR WITH SYNTHETIC MIXTURES Acetic acid as an azeotropic agent to separate paraffinic and naphthenic hydrocarbons has been used by Schicktanz [23], who pointed out that it fulfills the requirements of an azeotropic agent in that it does not react with, nor polymerize, the hydrocarbons, is easily and quantitatively removable from the hydrocarbons (by washing with water), and is inexpensive and readily available. Although having a ' See White and Rose [8] (xylenes), Mair and Schicktanz [9] (trimethylbenzenes), Smith and coworkers [1O, 11,12] (tri· and tetramcthy Jbenzenes) , Clarke and Taylor [13] (xylenes), Armstrong and Miller [14] (goneral). low-boiling point (118.1° C), it forms azeotropes with petroleum hydrocarbons over a considerable range and may be used successfully with hydrocarbons boiling from 130° to 175° C [25].…”

“…Nitration of a sample of the original material (n~ 1.4314) yielded an unattacked oil, which, after distillation from sodium, had a refractive index of 1.4254. The change in refractive index would 11 A fraction which has a wide boiling range may include a uaphthene w hose b oiling point at 760 mm Hg is so much higher than tha t of some aromatic hydrocarbon present that there may be an overlapping of the boiling points of the corresponding azeotropes with a res ultant lack of separation . indicate a concentration of about 9 percent of aromatic hydrocarbons and agrees with the data from the acetic acid distillation.…”