Quinones. Part 11. The reaction of o-aminothiophenol with o-benzo- and o-naphtho-quinones: a new route to 1H-phenothiazin-1-ones

Abstract

H-Phenothiazin-1 -ones can be obtained by the condensation of o-aminothiophenol with 3,5-di-tbutyl-and 3-t-butyl-5-phenyl-o-benzoquinones. In the absence of large blocking groups the phenothiazinones are unstable. A methyl group at C -4 leads via the quinone-methide tautomer, to formation of a spiro-dimer the crystal structure of which was determined by X-ray analysis. By further reaction with o-aminothiophenol, 1 N-phenothiazin-1 -ones yield triphenodithiazines (benzothiazinop henot h iazi nes) .

Advanced Routes in Synthesis and Reactions of Lawsone Molecules (2‐Hydroxynaphthalene‐1,4‐dione)

“…Oxidation of naphthalen‐1,2‐dione ( 19) with H 2 O 2 yielded compound 1 . While reaction of compound 19 with NaOH in MeOH, H 2 SO 4 and Ni in MeOH or CHCl 3 , concentrated calcium chloride (CaCl 2 ), HCl, sodium hypochlorite and potassium carbonate (K 2 CO 3 ) , HCl, H 2 SO 4 , dimethyl phenethylamine, dichromate (VI) and zinc(ш) chloride (ZnCl 3 ) , H 2 SO 4 in EtOH , or alkali disulfite in open air gave compound 1 . Treatment of 3,4‐dioxo‐3,4‐dihydronaphthalen‐1‐sulfonic acid ( 20) with H 2 SO 4 yielded 1 .…”

“…Treatment of 3,4‐dioxo‐3,4‐dihydronaphthalen‐1‐sulfonic acid ( 20) with H 2 SO 4 yielded 1 . Reaction of 3‐chloronaphthalen‐1,2‐dione ( 21 ) with H 2 SO 4 , then reduction with Ni in MeOH or EtOH gave compound 1 . Basic hydrolysis of 4‐(phenylthio)naphthalen‐1,2‐dione ( 22 ) by NaOH in EtOH or H 2 O at 2 min produced 1 in 80% yield .…”

“…Reaction of 3‐chloronaphthalen‐1,2‐dione ( 21 ) with H 2 SO 4 , then reduction with Ni in MeOH or EtOH gave compound 1 . Basic hydrolysis of 4‐(phenylthio)naphthalen‐1,2‐dione ( 22 ) by NaOH in EtOH or H 2 O at 2 min produced 1 in 80% yield . Hydrolysis of 1,1″‐binaphthyl‐3,3″,4,4″‐tetraone ( 23 ) in open air gave compound 1 .…”

“…Chemical treatment of N‐(3,4‐dioxo‐3,4‐dihydronaphthalen‐1‐yl)cyanamide ( 28 ) with HCl or H 2 SO 4 yielded 1 . Therefore, heating of 4‐(phenylamino)naphthalen‐1,2‐dione ( 29 ) in HCl, H 2 SO 4 , or acetic acid produced 1 . Treatment of 4‐aminonaphthalen‐1,2‐dione ( 30 ) in alkaline solution gave 1 .…”

“…The chemical reaction of 39 with HI in methylene chloride (CH 2 Cl 2 ) at 20°C , HCl and KI , H 2 SO 4 and Ni in MeOH or EtOH , or HCl in FeCl 3 in EtOH, hexane, or benzene yielded compound 1 . Moreover, oxidation of naphthalen‐1,4‐dione ( 40 ) in open air , reaction with HCl, d‐N,a‐dimethylphenethylamine, dichromate (VI), ZnCl 3 in EtOH , buffered aqueous solution at λ 360–440 μm or NaOH, boron trifluoride diethyl etherate afforded 1 .…”