Pentaklordienler ve Halonaftokinonların S- ve N- nükleofillerle yeni sübstitüe dien, trien ve kinon bileşiklerinin sentezi
Synthesis of novel diene, triene and quinone compounds from the reactions of Pentachlordienes and Halonaphthoquinones with –S and –N nucleophilles
Yazar: ELVIRA BABAYEVA
Danışman: PROF. DR. CEMİL İBİŞ
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Doktora, 2017
Konu: Kimya = Chemistry

Özet:
Bu çalışmanın ilk aşamasında etil alkol ve sodium karbonat varlığında 2,3-Dikloro-1,4-naftakinon 3-amino 1,2 propandiol ve 1- metil piperazin ile reaksiyonundan N-sübstitüe başlangıç maddelerden 2-(2,3-dihidroksipropilamino)-3-klor-1,4-naftakinon (2) ve 2-(4-metilpiperazinil)-3- klor 1,4-naftakinon (14) sentezlendi.  
2-(2,3-dihidroksipropilamino)-3-klor-1,4-naftakinon (2) bileşiği etanol ve sodyum karbonat ortamında 6-Merkapto-1-heksanol, 3-Merkapto-2-butanol, 2-merkaptofenol, 4-florotiyophenol, 1-merkapto-2-propanol, tert-dodesilmerkaptan, 2,2'-(etilendioksi)-bis(etilenamin), butil-3-merkapto propiyonat, 4-bromtiofenol, 2-merkaprobenzil alkol, metil 3-merkapto propiyonat ile bileşikleri ile oda sıcaklığında reaksiyona sokularak yeni N,S-, N,N-sübstitüe bileşikleri 2-(2,3-dihidroksipropilamino)-3-(6-merkapto 1-heksanol)- 1,4-naftakinon (3), 2-(2,3-dihidroksipropilamino)-3-(3-merkapto 2-butanol) -1,4-naftakinon (4), 2-(2,3-dihidroksipropilamino)-3-(2-merkaptofenol)1,4-naftakinon (5), 2-(2,3-dihidroksipropilamino)-3-(4-florotiyofenol) 1,4-naftakinon (6), 2-(2,3-dihidroksipropilamino)-3-(1-merkapto-2-propanol) 1,4-naftakinon (7), 2-(t-dodesillmerkaptan)-3-etanol 1,4-naftakinon (8), 2-(2,3-dihidroksi propilamino)-3-(butil-3-merkaptopropiyonat)1,4-naftakinon(9), 2-(2,3-dihidroksi propilamino)-3-(4-bromtiyofenol) 1,4-naftakinon (10), 2-(2,3-dihidroksipropilamino)-3-(2-merkaprobenzil alkol) 1,4-naftakinon (11), 2-(2,3-dihidroksipropilamino)-3-(metil-3-merkaptopropiyonat) 1,4-naftakinon (12), 2,3-(2,2'-(etilendioksi)- bis(etilenamin))-1,4-naftakinon (13) bileşikleri elde edildi. 
2-(4-metilpiperazinil)-3- klor 1,4-naftakinon (14) bileşiğini etanol ve sodyum karbonat ortamında  Butil-3-merkapto propiyonat,  metil-3-merkapto propiyonat, 6- merkapto-1-heksanol, 4-florotiyofenol, 4-bromotiyofenol, pentaflorotiyofenol ile reaksiyona sokarak yeni N,S-  2-(4-metilpiperazinil)-3- (butil-3- merkaptopropiyonat)- 1,4-naftakinon (15), 2-(4-metilpiperazinil)-3-( metil-3- merkaptopropiyonat) 1,4-naftakinon (16), 2-(4-metilpiperazinil)-3-(6-merkapto-1-heksanol) 1,4-naftakinon (17), 2-(4-metilpiperazinil)-3-(4-flor1otiyofenol) 1,4-naftakinon (18), 2-(4-metilpiperazinil)-3-(4-bromotiyofenol  ) 1,4-naftakinon (19),  2-(4-metilpiperazinil)-3-( pentaflorotiyofenol) 1,4-naftakinon (20) bileşiği senrezlendi. 
2,3-Diklor-1,4-Naftakinon'un, etil alkol ve sodyum hidroksil varlığında 5-merkapto-1-metil tetrazol, 4-t-oktilfenol, n-butil-4-hidroksibenzonat,  1-(4-klorobenzil)-piperazin ile oda sıcaklığındakı reaksiyonundan yeni  2-(5-merkapto- 1-metil tetrazol)-3-etoksi 1,4-naftakinon (21), 2-(4-tert oktilfenol)- 3-kloro 1,4-naftakinon (22), 2-( n-butil-4-hidroksibenzoat)- 3-kloro 1,4-naftakinon (23), 2-( 1-(4-klorobenzil)-piperazin)- 3-kloro 1,4-naftakinon (24), 2-( 2-flüoro-5-triflorometilfenol)- 3-kloro 1,4-naftakinon (25) bileşikleri elde edildi. 
Bu çalışmanın diğer başlangıç maddesi trikloretilenin dibenzilperoksit varlığında serbest radikaller üzerinden yürüyen dimerizasyonu sonucu 1,1,3,3,4,4-heksaklor-buten-1 (26) bileşiği sentez edildi. 1,1,3,3,4,4-heksaklor-buten-1'nin, farklı ortamlarda tert-nonil-merkaptan,  toluen-3,4 ditiyol, tert-dodesil-merkaptan, 2,3-dimerkapto-1-propanol, 7-merkapto-4-metil kumarin ile oda sıcaklığındaki reaksiyonundan yeni 1,1,4,4- (tert-nonyl-mercaptan)-3-klor- 1,3-butedien (27), 1,1,4- (tert-nonil-merkaptan)-3,4-diklor-1,3-butedien (28), 1,1- (2,3-dimerkapto-1-propanol)-3,4,4- triklor- 1,3-butedien (29), 1,1,4,4- (2,3-dimerkapto-1-propanol)-3-klor-1,3-butedien (30), 1 - (tert-dodesil-mercaptan)-1,3,4,4- tetraklor-1,3-butedien (31), 1,4- (tert-dodesil-mercaptan)-1,4- diklor -1-buten-3-in (32), 1,1,4,4- (tert-dodesil-mercaptan)-3-klor-1,3-butedien (33), 1- (toluen-3,4 ditiyol)-1,3,4,4- tetraklor-1,3-butedien (34), 1,4,4- (toluen-3,4 ditiyol)-1,3-diklor-1,3-butedien (35), 1,1,3,4,4- (7-merkapto-4-metil kumarin)- 1,3-butedien (36), 1,1,4,4- (7-merkapto-4-metil kumarin)-3-klor-1,3-butedien (37), 1,1,4,4-(tert-nonyl-mercaptan)- 12,3-butatrien (38), 1,1,2,4-(tert-nonyl-mercaptan)-1-buten-3-in (39)   bileşikleri elde edildi.
Sentezlenen yeni bileşikler kolon kromatografisi ile ayrılıp saflaştırıldıktan sonra yapıları mikroanaliz,  NMR (1H-NMR, 13C-NMR), FT-IR, MS spektroskopik yöntemleri ile aydınlatıldı. 
Bu çalışma İstanbul Üniversitesi Bilimsel Araştırma Projeleri Koordinasyon Birimi tarafından desteklenmiştir. Proje numarası: 42390

Abstract:
In the first phase of this study, N-substitution starting materials 2- (2,3-dihydroxypropylaminyl) -3-chloro-1,4-naphthoquinone (2) and 2- (1-methylpiperazinyl) -3-chloro 1,4-naphthoquinone (14) were synthesized from the reactions  of 2,3-dichloro-1,4-naphthoquinone (1) with 3-amino 1,2-propanediol and 1-methyl piperazine in the presence of ethyl alcohol and sodium carbonate.
Unknown new N, S-, N, N-substituted compounds 2- (2,3-dihydroxypropylamino) -3- (6-mercapto 1-hexanol) -1,4-naphthoquinone (3), 2- (2,3-dihydroxypropylamino) -3- (3-mercapto 2-butanol) -1,4-naphthoquinone (4), 2- (2,3-dihydroxypropylamino) -3- (2-mercaptophenol) 1,4-naphthacinone (5), 2- (2,3-dihydroxypropylamino) -3- (4-fluorothiophenol) 1,4-naphthoquinone (6), 2- (2,3-dihydroxypropylamino) -3- (1-mercapto-2-propanol) 1,4-naphthoquinone (7), 2- (tert-dodecylmercaptan) -3-ethanol 1,4-naphthacinone (8), 2- (2,3-dihydroxypropylamino) -3- (butyl-3-mercapto propionate) 1,4-naphthoquinone (9), 2- (2,3-dihydroxypropylamino) -3- (4-bromothiophenol) 1,4-naphthoquinone (10), 2- (2,3-dihydroxypropylamino) -3- (2-mercaptobenzyl alcohol) 1,4-naphthoquinone (11),  2- (2,3-dihydroxypropylamino) -3- (methyl 3-mercapto propionate) 1,4-naphthoquinone (12), 2,3- (2,2 '- (ethylenedioxy) -bis (ethyleneamine)) - 1,4-naphthoquinone (13), were synthesized from the reactions of starting material 2- (2,3-dihydroxypropylamino) -3-chloro-1,4-naphthoquinone (2) with 6-mercapto-1-hexanol, 3-mercapto-2-butanol, 2-mercaptophenol, 4-fluorothiophenol, 1-mercapto-2-propanol, tert-dodecylmercaptan, 2,2'-(ethylenedioxy)-bis(ethyleneamine), Butyl-3-mercapto propionate, 4-bromtiophenol, 2-mercaptobenzyl alcohol, methyl 3-mercapto propionate in the presence of ethyl alcohol and sodium carbonate  at room temperature.
 New N, S- substituted compounds 2- (4-methylpiperazinyl) -3- (butyl-3-mercapto propionate) -1,4-naphthoquinone (15), 2- (4-methylpiperazinyl) -3- (methyl-3-mercapto propionate) -1,4-naphthoquinone (16), 2- (4-methylpiperazinyl) -3- (6-mercapto-1-hexanol) -1,4-naphthoquinone (17), 2- (4-methylpiperazinyl) -3- (4-fluorothiophenol) -1,4-naphthoquinone (18), 2- (4-methylpiperazinyl) -3- (4-bromothiophenol) -1,4-naphthoquinone (19), 2- (4-methylpiperazinyl) -3- (pentafluorothiophenol) 1,4-naphthoquinone (20) were synthesized from the reactions of starting material 2- (4-methylpiperazinyl) -3-chloro-1,4-naphthoquinone (14) with Butyl-3-mercapto propionate, Methyl-3-mercapto propionate,  6-mercapto-1-hexanol, 4-fluorothiophenol, 4-bromothiophenol, pentaflortiofenol in the presence of ethyl alcohol and sodium carbonate  at room temperature.
New compounds 2- (5-mercapto-1-methyl tetrazole) -3-ethoxy 1,4-naphthoquinone (21), 2- (4-tert-octylphenol) -3-chloro 1,4-naphthoquinone (22), 2- (n-butyl-4-hydroxybenzonate) -3-chloro 1,4-naphthoquinone (23),  2- (1- (4-chlorobenzyl) -piperazine) -3-chloro 1,4-naphthoquinone (24) were synthesized  from the reactions  of 2,3-Dichloro-1,4-naphthoquinone (1) with 5-mercapto-1-methyl tetrazole, 4-tert-octylphenol, N-butyl-4-hydroxybenzonate, 1- (4-chlorobenzyl) -piperazine in the presence of ethyl alcohol and Sodium hydroxide at room temperature.
In this work, other firstly compound 1,1,3,3,4,4-hexachloro-1-butene (20) was synthesized from the trichloroetylene's free radical dimerization with dibenzoylperoxide. 1,1,4,4- (tert-nonyl-mercaptan) -3-chloro-1,3-butadiene (27), 1,1,4- (tert-nonyl-mercaptan) -3,4-dichloro-1,3-butadiene (28), 1,1- (2,3-dimercapto-1-propanol) -3,4,4-trichloro- 1,3 -butadiene (29), 1,1,4,4- (2,3-dimercapto-1-propanol) -3-chloro-1,3-butadiene (30), 1 - (tert-dodecyl-mercaptan) -1,3,4,4-tetrachlor-1,3-butadiene (31),  1,4- (tert-dodecyl-mercaptan) -1,4-dichloro-1-buten-3-yne (32), 1,1,4,4- (tert-dodecyl-mercaptan) -3-chloro-1,3-butadiene (33), 1- (toluene-3,4 dithiol) -1,3,4,4-tetrachlor-1,3-butene (34), 1,4,4- (toluene-3,4 dithiol) -1,3-dichloro-1,3-butene (35), 1,1,3,4,4- (7-mercapto-4-methylcarbamoyl) -1-buten-3-one (36), 1,1,4,4- (7-mercapto-4-methylcarbamoyl) -3-chloro-1,3-butadiene (37), 1,1,4,4- (tert-nonyl-mercaptan) -12,3-butatriene (38), 1,1,2,4- (tert-nonyl-mercaptan) -1 -buten-3-yne (39)  were synthesized from the reaction of starting compound 1,1,3,3,4,4-hexachloro-1-butene (26) with Tert-nonylmercaptan, toluene-3,4 dithiol, tert-dodecylmercaptan, 2,3-dimercapto-1-propanol, 7-mercapto-4-methyl coumarin in the presence of in different situations.
The strucures of these newly synthesized compounds were charecterized by using microanalyses, IR, 1H NMR, 13C NMR and MS spectroscopy.
This work was supported by Scientific Research Projects Coordination Unit of Istanbul University. Project number: 42390