Halodienlerden yeni tiyoeterlerin sentezi
The synthesis of new thioethers from halodienes
- Tez No: 178140
- Danışmanlar: PROF.DR. CEMİL İBİŞ, YRD. DOÇ. DR. GÖKŞİN AYDINLI
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Piperazin, Tiyoeterler, Tiyoller, Piperazine, Thioethers, Thiols
- Yıl: 2007
- Dil: Türkçe
- Üniversite: İstanbul Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Kimya Ana Bilim Dalı
- Bilim Dalı: Organik Kimya Bilim Dalı
- Sayfa Sayısı: Belirtilmemiş.
Özet
Bu çalımaya trikloroetilen'in radikalik dimerlemesi ile hazırlanan polihalojenli organik bileiin sentezlenmesi ve çeitli reaksiyonları ile elde edilen 4-bromo-2-nitro- 1,1,3,4-tetrakloro-buta-1,3-dien bileiinin (6) sentezlenmesi ile balandı. Çalımanın sonraki aamasında (6) bileiinin tiyollerle olan reaksiyonları incelendi. Çalımaya 4-bromo-2-nitro-1,1,3,4-tetrakloro-buta-1,3-dien (6) 1-dekantiyol ile reaksiyonundan 4-bromo-1-desiltiyo-2-nitro-1,3,4-trikloro-buta-1,3-dien (15) bileii ve p-bromotiyofenol ile reaksiyonundan 4-bromo-1-(4-bromofeniltiyo)-2-nitro-1,3,4- trikloro-buta-1,3-dien (17) bileii sentezlenerek devam edildi. Çalımanın son aamasında ise elde edilen mono(tiyo)sübstitüe nitrodien bileiklerinin morfolin ve bazı piperazin türevleri ile reaksiyonları incelendi. 4-bromo-1-desiltiyo-2-nitro-1,3,4-trikloro-buta-1,3-dien (15) bileii, sırasıyla N- (difenilmetil)-piperazin (18), N-(2-florofenil)-piperazin (20), morfolin (22), N-(2- metoksifenil)-piperazin (24), N-etoksikarbonil-piperazin (26), N-(4-florofenil)-piperazin (28) ve N-fenilpiperazin (30) ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 4-bromo-1-desiltiyo-1-[N-(difenilmetil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (19), 4-bromo-1-desiltiyo-1-[N-(2-florofenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3- dien (21), 4-bromo-1-desiltiyo-1-morfolin-2-nitro-3,4-dikloro-buta-1,3-dien (23), 4- bromo-1-desiltiyo-1-[N-(2-metoksifenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (25), 4-bromo-1-desiltiyo-1-[N-etoksikarbonil-piperazin]-2-nitro-3,4-dikloro-buta-1,3- dien (27), 4-bromo-1-desiltiyo-1-[N-(4-florofenil)-piperazin]-2-nitro-3,4-dikloro-buta- 1,3-dien (29) ve 4-bromo-1-desiltiyo-1-(N-fenilpiperazin)-2-nitro-3,4-dikloro-buta-1,3- dien (31) bileikleri sentezlendi. 4-bromo-1-(4-bromofeniltiyo)-2-nitro-1,3,4-trikloro-buta-1,3-dien (17) bileii, sırasıyla N-(difenilmetil)-piperazin (18), N-(2-florofenil)-piperazin (20), morfolin (22), N-(2-metoksifenil)-piperazin (24), N-etoksikarbonil-piperazin (26), N-(4-florofenil)- piperazin (28) ve N-fenilpiperazin (30) ile reaksiyona sokuldu. Reaksiyonlar sonucunda sırasıyla 4-bromo-1-(4-bromofeniltiyo)-1-[N-(difenilmetil)-piperazin]-2-nitro-3,4- dikloro-buta-1,3-dien (32), 4-bromo-1-(4-bromofeniltiyo)-1-[N-(2-florofenil)- piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (33), 4-bromo-1-(4-bromofeniltiyo)-1- morfolino-2-nitro-3,4-dikloro-buta-1,3-dien (34), 4-bromo-1-(4-bromofeniltiyo)-1-[N-(2- metoksifenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (35), 4-bromo-1-(4-bromofeniltiyo)- 1-[N-etoksikarbonilpiperazin]-2-nitro-3,4-dikloro-buta-1,3-dien (36), 4- bromo-1-(4-bromofeniltiyo)-1-[N-(4-florofenil)-piperazin]-2-nitro-3,4-dikloro-buta-1,3- dien (37) ve 4-bromo-1-(4-bromofeniltiyo)-1-(N-fenilpiperazin)-2-nitro-3,4-diklorobuta- 1,3-dien (38) bileikleri sentezlendi. Sentezlenen yeni 2 adet mono(tiyo)nitrobuta-1,3-dien bileikleri ve bu bileiklerin 14 adet piperazin türevi ürünleri orjinaldir. Oluan bu yeni ürünler kristallendirme veya kolon kromotografisi yöntemlerinden biriyle saflatırıldı. Yapıları mikroanaliz ve spektroskopik yöntemler (IR, 1H-NMR, 13C-NMR, UV ve MS) ile aydınlatıldı.
Özet (Çeviri)
Our investigations started with the synthesis of polyhalogenated butenes which is easily obtained from the radical dimerization of trichloroethylene and its subsequent reactions leading to the compound 4-bromo-2-nitro-1,1,3,4-tetrachloro-buta-1,3-dien (6). In the following step, reactions of thiols with the compound (6) were investigated. Therefore, 4-bromo-1-decylthio-2-nitro-1,3,4-trichloro-buta-1,3-dien (15) and 4-bromo- 1-(4-bromophenylthio)-2-nitro-1,3,4-trichloro-buta-1,3-dien (17) were synthesized from the reactions of 4-bromo-2-nitro-1,1,3,4-tetrachloro-buta-1,3-dien (6) with 1- decanethiol and p-bromothiophenol, respectively. In the last step, reactions of morpholine and derivatives of piperazine with the mono(thio)substituted nitrodien compounds were explored. To obtain 4-bromo-1-decylthio-1-[N-(diphenylmethyl)-piperazine]-2-nitro-3,4-dichlorobuta- 1,3-dien (19), 4-bromo-1-decylthio-1-[N-(2-fluorophenyl)-piperazine]-2-nitro-3,4- dichloro-buta-1,3-dien (21), 4-bromo-1-decylthio-1-morpholine-2-nitro-3,4-dichlorobuta- 1,3-dien (23), 4-bromo-1-decylthio-1-[N-(2-metoxyphenyl)-piperazine]-2-nitro- 3,4-dichloro-buta-1,3-dien (25), 4-bromo-1-decylthio-1-[N-etoxycarbonyl-piperazine]- 2-nitro-3,4-dichloro-buta-1,3-dien (27), 4-bromo-1-decylthio-1-[N-(4- fluorophenyl)- piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (29) and 4-bromo-1-decylthio-1-(Nphenylpiperazine)- 2-nitro-3,4-dichloro-buta-1,3-dien (31), the reactions of 4-bromo-1- decylthio-2-nitro-1,3,4-trichloro-buta-1,3-dien (15) with the N-(diphenylmethyl)- piperazine (18), N-(2-fluorophenyl)-piperazine (20), morpholine (22), N-(2- metoxyphenyl)-piperazine (24), N-etoxycarbonyl-piperazine (26), N-(4-fluorophenyl)- piperazine (28) ve N-phenylpiperazine (30) were performed, respectively. Analogously, 4-bromo-1-(4-bromophenylthio)-1-[N-(diphenylmethyl)-piperazine]-2- nitro-3,4-dichloro-buta-1,3-dien (32), 4-bromo-1-(4-bromophenylthio)-1-[N-(2- fluorophenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (33), 4-bromo-1-(4- bromophenylthio)-1-morpholine-2-nitro-3,4-dichloro-buta-1,3-dien (34), 4-bromo-1-(4- bromophenylthio)-1-[N-(2-metoxyphenyl)-piperazine]-2-nitro-3,4-dichloro-buta-1,3- dien (35), 4-bromo-1-(4-bromophenylthio)-1-[N-etoxycarbonyl-piperazine]-2-nitro-3,4- dichloro-buta-1,3-dien (36), 4-bromo-1-(4-bromophenylthio)-1-[N-(4- fluorophenyl)- piperazine]-2-nitro-3,4-dichloro-buta-1,3-dien (37) and 4-bromo-1-(4-bromophenylthio) -1-(N-phenylpiperazine)-2-nitro-3,4-dichloro-buta-1,3-dien (38) were synthesized by the interaction of 4-bromo-1-(4-bromophenylthio)-2-nitro-1,3,4-trichloro-buta-1,3-dien (17) with the N-(diphenylmethyl)-piperazine (18), N-(2-fluorophenyl)-piperazine (20), morpholine (22), N-(2-metoxyphenyl)-piperazine (24), N-etoxycarbonyl-piperazine (26), N-(4-fluorophenyl)-piperazine (28) ve N-phenylpiperazine (30), respectively. Synthesized two mono(thio)nitrobuta-1,3-dien compounds and their fourteen piperazine derivatives are original. The novel products were purified either crystallization or via column chromatography. Structure of these novel products were characterized by microanalysis, spectroscopic methods (IR, 1H-NMR, 13C-NMR, UV and MS).
