THE NITROSULFONIC ACIDS OF p-XYLENE.

Abstract

I. Introduction. Nolting and Kolinl record the preparation of an aminosulfonic acid of p-xylene to which they ascribe the formula : 1,4 6 2 CsHz (CH3) z"zS0s.H This acid was prepared by reducing with ammonium sulfide, or with tin and hydrochloric acid, the solution resulting from the treatment of p-xylenesulfonic acid with red, fuming nitric acid. The nitro-acid was not isolated, nor were any of its derivatives prepared. Guy G. Frary2 describes a nitrosulfonic acid of p-xylene which he prepared by nitrating p-xylenesulfonic acid with nitric acid (sp. gr. 1.60) in the cold. The potassium, sodium, calcium, barium, strontium, magnesium, copper, and zinc salts were prepared and of these the potassium, barkm, copper, and zinc salts were analyzed. Most of these were prepared from the crude acid solution and were purified with difficulty.

Zur Synthese sulfonierter Derivate von 2‐Amino‐p‐xylol

“…The 2-amino-p-xylene-6-sulfonic acid (3) was prepared via three routes: (1) sulfonation of 2-amino-5-chloro-p-xylene (19) to 5-amino-2-chloro-p-xylene-3-sulfonic acid (20) followed by hydrogenolysis ; (2) sulfur dioxide treatment of the diazonium salt derived from 2-amino-6-nitro-p-xylene (21) to 2-nitro-p-xylene-6-sulfonyl chloride (1 1) followed by hydrolysis to 2-nitro-p-xylene-6-sulfonic acid (4) and Bichamp reduction ; (3) Be'champ reduction of 2-chloro-3-nitro-p-xylene-5-sulfonic acid (13) to 3-amino-2-chloro-p-xylene-5-sulfonic acid (16) and subsequent hydrogenolysis. Catalytic reduction of 13 in aqueous sodium carbonate solution gave mixtures of 3 and 16.2-Aminop-xylene-3-sulfonic acid (27) was synthesized via two routes: (1) reaction of 19 with sulfamic acid to 2-amino-5-chloro-p-xylene-3-sulfonic acid (26) followed by hydrogenolysis; (2) sulfur dioxide treatment of the diazonium salt derived from 2-amino-3-nitro-p-xylene (28) to 2-nitro-p-xylene-3-sulfonyl chloride (12), hydrolysis to 2-nitrop-xylene-3-sulfonic acid (7) and Be'champ reduction.…”

“…Die fur die Synthese von 2-Amino-p-xylol-6-sulfonsaure (3) als Zwischenstufe vorstellbare 2-Nitro-p-xylol-6-sulfonsaure (4) war gemass Literaturangaben nicht isomerenfrei durch Sulfonieren von 2-Nitro-p-xylol ( 5 ) [4] [5] oder durch Nitrieren von p-Xylol-2-sulfonsaure (6) [4] [6] (vgl. auch [I]) herstellbar.…”

“…x \ Anders gestaltete sich die Isomerenverteilung nach der Nitrierung des entweder durch Reaktion von p-Xylol(l0) mit Chlorsulfonsaure [7] oder von 6 mit Phosphorpentachlorid [4] [8] herstellbaren p-Xylol-2-sulfonylchlorids (9). Behandlung mit Nitriersaure bei max.…”

“…Behandlung mit Nitriersaure bei max. 35" ergab ein bei 49"-50" schmelzendes Rohprodukt; fur die drei Nitro-p-xylol-sulfonylchloride sind in [4] die Schmelzpunkte 60", 75" bzw. 109,5" angegeben.…”

“…Nitrierung von p-Xylol-2-sulfonsuure (6). 45 g (0,2 mol) Kaliumsalz von 6 [4] werden bei -5" in 150 ml 100proz. Schwefelsaure durch starkes Ruhren fein suspendiert.…”