Phenol, methylation nitration

DIMETHYL-0-(2-DIMETHYL-CARBAMOYL-l-METHYL-VINYL)PHOS-PHAT (German) (141-66-2) May react violently with antimony(V) pentafluoride. Incompatible with nitrates. Corrosive to cast iron, mild steel, brass, and stainless steel 304. Slow hydrolysis in water. Decomposes in storage at temperatures above 135°F/55°C. Incompatible with organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls, cresols, caprolactam solution, epichlorohydrin, ethylene dichloride, glycols, isocyanates, ketones, lead diacetate, magnesium, maleic anhydride, nitrates, nitromethane, phenols, silver nitrate, vinyl acetate. 

Chondrofoline, CgjHgjOjNj, 2H2O, crystallises from methyl alcohol in triangular plates, m.p. about 135°, [ajffg — 280-6° (dry base N/10. HCl). It is a phenolic base, contains three methoxyl groups, does not give a Millon reaction, but in methyl alcoholic solution gives a faint, pink-purple colour with ferric chloride. The nitrate forms needles m.p. 225° (dec.). 

Harmine, C13H12ON2, crystallises from methyl alcohol in colourless rhombic prisms, m.p, 266°, [a]D 0°. The hydrochloride, m.p. 269-5-270-5° (Chen ), nitrate, platinichloride, m.p. 264-6°, acid chromate and oxalate crystallise well. The salts show a deep blue fluorescence in dilute solution. Harmine behaves as a monoacidic base. It gives a methiodide, from which methylharmine, needles, m.p. 209°, may be prepared, and this in turn yields methylharmine methiodide. On demethylation harmine yields the phenolic base harmol, C12H10ON2, m.p. 321°.i ... 

The methyl ether was introduced after the Wittig reaction which used a protected carboxylic acid (ethyl ester). p-Nitrophenol is available and is one of the products of the nitration of phenol. 

Nitration of hydroxypropiophenone (7-1) followed by conversion of the phenol to its methyl ether by means of methyl iodide provides the intermediate (7-2) the nitro group is then reduced to the corresponding amine (7-3) by catalytic reduction. The newly introduced amine is then replaced by a nitrile group by successive conversion to the diazonium salt by means of nitrous acid followed by treatment with cuprous cyanide (7-4). Reaction with aluminum chloride removes the methyl ether to afford the ortho acylphenol (7-5). This is converted to the chromone (7-6) as above by reaction with benzoyl chloride and sodium benzoate. The nitrile is next hydrolyzed to the carboxylic acid (7-7) by means of sulfuric acid. The acid is then converted to its acid chloride by means of thionyl chloride and that treated with 2-(A -piperidyl)ethanol (7-8). There is thus obtained flavoxate (7-9) [8], a muscle relaxant whose name reflects its flavone nucleus. 

Dinitro-4-(tert-butyl)-phenol, crysts, mp 97-8°, is described in Beil 6, 525 [489] Butylphenol or Butylhydroxybenzene, Trinitro Derivative. c10HnN307 mw 285.21, N 14.73%. Only one isomer is described in the literature 3-(tert Butyl)-2,4,6 trinitrophenol. (CHg)3C.-C6H(0H)(N02)3 pale yel ndls(from ale), mp 172° was obtd by nitrating methyl ether of m-tert -butylphenol with mixed acid at 10-25°. Its expi props were not detd... 

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