2-nitrohalobuta-1,3-dien'in merkaptokumarin ile reaksiyonundan S- ve N, S-sübstitüe bileşiklerin sentezi
The synthesis of S-and N,S-substituted compounds from the reactions of 2-nitrohalobuta-1,3-diene with mercapto coumarin
Yazar: FİLİZ AVCI
Danışman: DOÇ. DR. F. GÜLAY KIRBAŞLAR ; PROF. DR. CEMİL İBİŞ
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2008
Konu: Kimya = Chemistry

Özet:
Bu çalışmaya trikloroetilen'in radikalik dimerleşmesi ile hazırlanan polihalojenli organik bileşiğin sentezlenmesi ve çeşitli reaksiyonları ile elde edilen 4-bromo-1,1,3,4-tetrakloro-2-nitro-1,3-butadien bileşiğinin (1) sentezlenmesi ile başlandı.Çalışmanın sonraki aşamasında (1) bileşiğinin tiyol ile olan reaksiyonu incelendi. Çalışmaya 4-bromo-1,1,3,4-tetrakloro-2-nitro-1,3-butadien (1) bileşiğinin 7-merkapto-4-metilkumarin (5) ile reaksiyonundan 4-bromo-1,3,4-trikloro-2-nitro-1-(7-kumarintiyo-4-metil)-1,3-butadien (2) ve 4-bromo-3,4-dikloro-2-nitro-1,1-bis(7-kumarintiyo-4-metil)-1,3-butadien (3) bileşikleri sentezlenerek devam edildi.Çalışmanın son aşamasında ise elde edilen mono(tiyo)sübstitüe nitrodien bileşiğinin bazı piperazin ,piperidin türevleri ve 1,4-diokso-8-azaspiro[4,5] dekan ile reaksiyonları incelendi.4-Bromo-1,3,4-trikloro-2-nitro-1-(7-kumarintiyo-4-metil)-1,3-butadien (2) bileşiği, sırasıyla N-( 4-fluorofenil)-piperazin (6), N-fenil piperazin (7), N-(2-metoksifenil) -piperazin (8), N-etoksikarbonil piperazin (9), N-formil piperazin (10), N-(2-florofenil) piperazin (11), N-(4-metil) piperidin (12), N-(4-benzil) piperidin (13), 1,4-diokso-8-azaspiro[4,5] dekan (14) ile reaksiyona sokuldu.Reaksiyonlar sonucunda sırasıyla N-[1-(7-kumarintiyo-4-metil)-4-bromo-3,4-dikloro-2-nitro-1,3-butadienil)]-N'-[4-fluorofenil]-piperazin (2a) ,N-[1-(7-kumarintiyo-4-metil)-4-bromo-3,4-dikloro-2-nitro-1,3-butadienil)]-N'-fenilpiperazin(2b),N-[1(7kumarintiyo-4-metil)-4-bromo-3,4-dikloro-2-nitro-1,3-butadienil)]-NI--[1-(2- metoksifenil)] piperazin (2c), N-[1-(7-kumarintiyo-4-metil)-4-bromo-3,4-dikloro-2-nitro-1,3-butadienil)]-NI-etoksikarbonil piperazin (2d), N-[1-(7-kumarintiyo-4-metil)-4-bromo-3,4-dikloro-2-nitro-1,3-butadienil)]-N'-[formil]-piperazin (2e), N-[1-(7-kumarintiyo-4-metil)-4-bromo-3,4-dikloro-2-nitro-1,3-butadienil)]-N'-[2-fluorofenil]-piperazin (2f), 4-bromo-3,4-dikloro-2-nitro-1-(7-kumarintiyo-4-metil)-1-(4-metil piperidinil)-1,3-butadien (2g), 4-bromo-3,4-dikloro-2-nitro-1-(7-kumarintiyo-4-metil)-1-(4-benzilpiperidinil)-1,3-butadien(2h),4-bromo-3,4-dikloro-2-nitro-1-(7-kumarintiyo-4-metil)-1-(1,4-dioksoazaspiril)-1,3-butadien(4) bileşikleri sentezlendi.Ürünler kristallendirme veya kolon kromatografisi yöntemlerinden biriyle saflaştırılmıştır. Bu yeni ürünlerin yapıları mikroanaliz ve spektroskopik yöntemler (1H-NMR, APT, IR, MS, UV gibi) ile aydınlatılmıştır.

Abstract:
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-1,1,3,4-tetrachloro-2-nitro-1,3-butadiene (1).In the following step, reaction of thiol with the compound (1) were investigated. Therefore, 4-Bromo-1,3,4-trichloro-2-nitro-1-(7-coumarinthio-4-methyl)-1,3-butadiene (2), and 4-Bromo-3,4-dichloro-2-nitro-1,1-bis (7-coumarinthio-4-methyl)-1,3-butadiene (3) were synthesized from the reactions of 4-bromo-1,1,3,4-tetrachloro-2-nitro-1,3-butadiene (1) with 7-mercapto-4-methylcoumarin.In the last step, reactions of derivatives of piperazine, piperidine and 1,4-dioxoazospiro [4,5] decan with the mono(thio)substituted nitrodien compound were explored.To obtain N-[1-(7-coumarinthio-4-methyl)-4-bromo-3,4-dichloro-2-nitro-1,3-butadienyl)]-N'-[4-fluorophenyl]-piperazine (2a), N-[1-(7-coumarinthio-4-methyl)-4- bromo-3,4-dichloro-2-nitro-1,3-butadienyl)]-NI-phenyl piperazine (2b), N-[1-(7-coumarinthio-4-methyl)-4-bromo-3,4-dichloro-2-nitro-1,3-butadienyl)]-N'-[1-(2-methoxyphenyl)]-piperazine (2c), 4- N-[1-(7-coumarinthio-4-methyl)-4-bromo-3,4-dichloro-2-nitro-1,3-butadienyl)]-NI-ethoxycarbonyl piperazine (2d), N-[1-(7-coumarinthio-4-methyl)-4-bromo-3,4-dichloro-2-nitro-1,3-butadienyl)]-NI-[formyl]-piperazine (2e), N-[1-(7-coumarinthio-4-methyl)-4-bromo -3,4-dichloro-2-nitro-1,3-butadienyl)]-N'-[2-fluorophenyl]-piperazine (2f), 4-Bromo-3,4-dichloro-2-nitro-1-(7-coumarinthio-4-methyl)-1-(4-methyl piperidinyl)-1,3-butadiene (2g), 4-Bromo-3,4-dichloro-2-nitro-1-(7-coumarinthio-4-methyl)-1-(4-benzyl piperidinyl)-1,3-butadiene (2h) and 4-bromo-3,4-dichloro-2-nitro-1-(7-coumarinthio-4-methyl)-1-(1,4-dioxoazospiryl)-1,3-butadiene (5) the reactions of 4-bromo-1,3,4-trichloro-2-nitro-1-(7-coumarinthio-4-methyl)-1,3-butadiene (2) with N-( 4-fluorophenyl)- piperazine (6), N- phenyl piperazine (7), N-(2- methoxyphenyl)- piperazine (8), N- ethoxycarbonyl piperazine (9), N- formyl piperazine (10), N-(2-fluorophenyl) piperazine (11), N-(4-methyl piperidinyl) (12), N-(4-benzyl piperidinyl )(13), 1,4-dioxoazospiro [4,5] decan (14) were performed, respectively.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, APT , UV and MS).