The synthesis and characterization of quinone derivatives with heteroccyclic ring

In this master's thesis study, new N- and S-substituted-1,4-naphthacinone derivatives with potential biological activity were synthesized by Michael addition reactions of some quinone compounds with amine nucleophiles. 2,3-Dichloro-1,4-naphthacinone (1), 2-Methyl-1,4-naphthacinone (8), 2,3-Dibromo-1,4-naphthacinone (11) and chloranil (20) were used as starting materials in the experiments. Reactions with thiol and amine derivatives as nucleophiles were studied. As a result of different reactions of quinone compounds with nitrogen (N) and Sulfur (S) hetereatoms containing nucleophiles, new substituted quinone compounds were synthesized. The reaction of 2,3-Dichloro-1,4,-naphthoquinone NQ (1) with 1-(2-pyrimidyl)piperazine (2) in Na2CO3/Ethanol gave the new compound 3-chloro-2-(1-(2-pyrimidyl)piperazine)-1,4,- naphthoquinone (3). The reaction of NQ (1) with 1-(2-methoxyphenyl)piperazine (4) in Na2CO3/Ethanol gave the new compound 3-chloro-2-(-1-(2-methoxyphenyl)piperazine)-1,4-naphthoquinone (5). The reaction of 2,3-Dichloro-1,4-naphthoquinone (1) with 1,4-benzodioxane-6-amine (6) in Na2CO3/Ethanol medium led to the new compound 2-chloro-3-(2,3-dihydro-1,4-benzodioxine-6-ylamino)1,4-naphthoquinone (7). The reaction of NQ (1) with 4,4-Diaminodiphenyl sulfide (14) in Na2CO3/Ethanol to the new compound 2-chloro-3-(4,4'-thioanilinyl)-1,4- naphthoquinone (15). The reaction of 2,3-Dichloro-1,4- naphthoquinone (1) with 4-(Methylthio)aniline (16) in Na2CO3/Ethanol gave the known compound 2-chloro-3-(4-(Methylthio)aniline)-1,4- naphthoquinone (17). The reaction of 2,3-Dichloro-1,4- naphthoquinone (1) and 4-Fluorothiophenol (18) compounds in Na2CO3/Ethanol according to the synthesis method yielded the new compound 3-Ethoxy-2-(4-Fluorothiophenol)-1,4- naphthoquinone (19). The reaction of NQ (1) with 2,4-dibromoaniline (27) in Na2CO3/Ethanol gave the known compound 2-chloro-3(2,4-dibromoaniline)-1,4- naphthoquinone (28). The reaction of 2-Methyl-1,4-naphthoquinone (8) with 1-(2-pyrimidyl)piperazine (2) in Na2CO3/Ethanol gave the new compounds 2-methyl-3-(1-(2-pyrimidyl)piperazine)-1,4- naphthoquinone (9) and 2-ethoxy-3-(1-(2-pyrimidyl)piperazine)-1,4- naphthoquinone (10). The reaction of 2,3-Dibromo-1,4- naphthoquinone (11) with 2,2-(Ethylenedioxy)diethanethiol (12) in Na2CO3/Ethanol gave the known compound 2,3-(Ethylenedioxy)diethanethiol-1,4- naphthoquinone (13). The reaction of p-Chloranil (20) with compound (14) in Na2CO3/Ethanol gave the new compound (21) 2-(2-(4-[4-aminophenyl]sulfanyl)phenyl amino)-5,6-dichloro-3-ethoxy benzoquinone (22) 2,5 bis([4-(4-aminophenyl)sulfanyl]phenyl)amino-6 chloro-3 ethoxy benzoquinone. The reaction of p-Chloranil (20) with 2,3-difluoroaniline (23) in Na2CO3/Ethanol medium yielded the new 2-ethoxy-3,5,6-tri(2,3-difluoroaniline) chloranil (24), 2-chloro-3,6-diethoxy-5-(2,3-difluoroaniline) chloranil (25) and 2-chloro-5-ethoxy-di(2,3-difluoroaniline) chloranil (26) were obtained. The structures of all the substances were elucidated by various analysis methods (Elemental analysis, FT-IR, 1H-NMR, 13C-NMR, MS, HRMS). Keywords: Quinone, Naphthoquinone, Amine, Thiol, Michael Addition, Organic Synthes