2011 YÜksek lisans tez özetleri

The Synthesis of New Thioethers From Halobutadienes and Thiols

In the first step of our study, 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) was synthesized to use as a starting compound.

In the second step of our study, the reactions of 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) and 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4), which are used as starting compounds, with various thiols were investigated.

The reaction of 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) with 2-aminothiophenol in the presence of NaOH in EtOH was carried out and new 1-(2-aminophenylthio)-1,2,3,4,4-pentachloro-1,3-butadiene (2) and 1,4-bis(2-aminophenylthio)-1,2,3,4-tetrachloro-1,3-butadiene (3) compounds were obtained. From the direct reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) with 4-(t-buthyl)benzylmercaptan, new 2-nitro-1-[4-(t-buthyl)benzylthio]-1,3,4,4-tetrachloro-1,3-butadiene (5) compound was obtained. The reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) with 4-(t-buthyl)benzylmercaptan in the presence of NaOH in EtOH was carried out and new 4,4-dichloro-2-nitro-1,1,3-tris[4-(t-buthyl)benzylthio]-1,3-butadiene (6) compound was obtained. From the direct reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene (4) with 2,3,5,6-tetrafluorothiophenol new 2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-1,3,4,4-tetrachloro-1,3-butadiene (7) compound was obtained.

In the third and last step of our study, the reactions of mono(thio)substituted-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene compounds which we obtained, with N-nucleophile compounds (morpholine, piperazine and their derivatives) were investigated and new N,S-disubstituted nitrodiene compounds were obtained.

From the reaction of 2-nitro-1-[4-(t-buthyl)benzylthio]-1,3,4,4-tetrachloro-1,3-butadiene (5) with morpholine, new 1-morpholino-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (8) compound was obtained. The new compounds N,N-bis[2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadienyl]-piperazine (9), 1-[(2-fluorophenyl)piperazinyl]-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (10), 1-[(4-fluorophenyl)piperazinyl]-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (11), N,N-bis[2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadienyl]-2,5-dimethylpiperazine (12) and 1-(N-methylpiperazinyl)-2-nitro-1-[4-(t-buthyl)benzylthio]-3,4,4-trichloro-1,3-butadiene (13) were synthesized from the reaction of 2-nitro-1-[4-(t-buthyl)benzylthio]-1,3,4,4-tetrachloro-1,3-butadiene (5) with piperazine, 1-(2-fluorophenyl)piperazine, 1-(4-fluorophenyl)piperazine, 2,5-dimethylpiperazine and N-methylpiperazine in turn. From the reaction of 2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-1,3,4,4-tetrachloro-1,3-butadiene (7) with morpholine, new 1-morpholino-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (14) compound was obtained. The new compounds 1-[(2-fluorophenyl)piperazinyl]-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (15), 1-[(4-fluorophenyl)piperazinyl]-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (16) and 1-(N-methylpiperazinyl)-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-butadiene (17) were synthesized from the reaction of 2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-1,3,4,4-tetrachloro-1,3-butadiene (7) with 1-(2-fluorophenyl)piperazine, 1-(4-fluorophenyl)piperazine and N-methylpiperazine in turn.

The novel products were purified either crystallization or via column chromatography. Structures of these novel products were characterized by microanalysis and spectroscopic methods (FTIR, ¹H-NMR, ¹³C-NMR and MS).