Bazı naftakinon ve benzokinon gruplu yeni eterlerin ve tiyoeterlerin sentezi.
The synthesis of new ethers and thioeters as the substituted of some naphthoquinone and benzoquinone.
Yazar: ŞENOL YAVUZ
Danışman: PROF. DR. CEMİL İBİŞ
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2012
Konu: Kimya = Chemistry
Dizin: P-benzokinon = P-benzoquinone

Özet:
Bu çalışmada başlangıç maddesi olarak 2,3-diklor-1,4-naftakinon (1), p-kloranil (2) ve p-floranil (3) bileşiklerinin alkoller ve tiyoller ile reaksiyonları incelendi. Bu reaksiyonlar sonucunda yeni kinon gruplu eter ve tiyoeter bileşikleri sentezlendi.2,3-diklor-1,4-naftakinon (1)'un dietilen glikol monometileter ile asetonitril varlığındaki reaksiyonundan bilinmeyen 2-(2-(2-metoksietoksi)etoksi)-3-klor-1,4-naftakinon (4) sentezlendi. 2,3-diklor-1,4-naftakinon (1)'un 2-(2-merkaptoetil)pirazin ile kloroform varlığındaki reaksiyonundan bilinmeyen 2-(2-(pirazin-2-il)etiltiyo)-3-klor-1,4-naftakinon (5) ve bilinmeyen 2-bis(2-(pirazin-2-il)etiltiyo)-1,4-naftakinon (6) sentezlendi.p-Kloranil (2)'in 2,3,4,5,6-pentaflorotiyofenol ile etanol varlığındaki reaksiyonundan bilinmeyen 2,3,5,6-tetrakis(pentaflorofeniltiyo)siklohekza-2,5-dien-1,4-dion (7) ve bilinmeyen 2-etoksi-3,5,6-tris(pentaflorofeniltiyo)siklohekza-2,5-dien-1,4-dion (8) sentezlendi. p-kloranil (2)' in 3-merkapto-1-hekzanol ile etanol varlığındaki reaksiyonundan bilinmeyen 7-kloro-8-etoksi-3,4-dihidro-4-propil-2H-benzo[b][1,4]oksatiepin-6,9-dion, 8-kloro-7-etoksi-3,4-dihidro-4-propil-2H-benzo[b][1,4]oksatiepin-6.9-dion izomer karışımı (9), bilinmeyen 4,8-dipropil-3,4,9,10-tetrahidrobenzo[1,2-b:5,4-b']bis([1,4]oksatiepin)-6,12(2H,8H)-dion (10) ve bilinmeyen 2,3,5,6-tetrakis(1-hidroksihekzan-3-iltiyo)siklohekza-2,5-dien-1,4-dion (11) sentezlendi. p-kloranil (2)'in 2-etil-1-hekzanol ile asetonitril varlığındaki reaksiyonundan bilinmeyen 2-(2-etilhekziloksi)-3,5-6-triklorosiklohekza-2,5-dien-1,4-dion (12) sentezlendi. p-kloranil (2)'in 2-(2-merkaptoetil)pirazin ile etanol varlığındaki reaksiyonundan bilinmeyen 2-(2-(pirazin-2-il)etiltiyo)-3-kloro-5,6-dietoksisiklohekza-2,5-dien-1,4-dion, 2-(2-(pirazin-2-il)etiltiyo)-6-kloro-3,5-dietoksisiklohekza-2,5-dien-1,4-dion (13) izomer karışımı, bilinmeyen 2,5-bis(2-(pirazin-2-il)etiltiyo)-3,6-dietoksisiklohekza-2,5-dien-1,4-dion (14) ve bilinmeyen 2,3,5-tris(2-(pirazin-2-il)etiltiyo)-6-etoksisiklohekza-2,5-dien-1,4-dion (15) sentezlendi.p-Floranil (3)'in 1,8-dihidroksi-3,6-ditiyooktan ile asetonitril varlığındaki reaksiyonundan bilinmeyen 12,13-difloro-2,3,5,6,8,9-hekzahidrobenzo[b][1,4,7,10]-diokzaditiyasiklododesin-11,14-dion (16) ve bilinmeyen 2,3,5-trifloro-6-(2-((2-((2-hidroksietil)tiyo)etil)tiyo)etoksi)siklohekza-2,5-dien-1,4-dion (17) sentezlendi. p-floranil (3)'in 1,6-hekzandiol ile asetonitril varlığındaki reaksiyonundan bilinmeyen 2,6-bis(6-hidroksihekziloksi)-3,5-diklorosiklohekza-2,5-dien-1,4-dion (18) sentezlendi.p-Kloranil (2)'in 2-(2-merkaptoetil)pirazin ile kloroform varlığındaki reaksiyonundan bilinmeyen 2,3,5-tris(2-(pirazin-2-il)etiltiyo)-6-klorosiklohekza-2,5-dien-1,4-dion (19) ve bilinmeyen 2,3,5,6-tetra(2-(pirazin-2-il)etiltiyo)siklohekza-2,5-dien-1,4-dion (20) sentezlendi. p-kloranil (2)'in 3-piridinol ile asetonitril varlığındaki reaksiyonundan bilinmeyen 2,3,5-trikloro-6-(piridin-3-iloksi)siklohekza-2,5-dien-1,4-dion (21) sentezlendi. p-kloranil (2)'in 3-merkapto-1,2,4-triazol ile asetonitril varlığındaki reaksiyonundan bilinmeyen 2-(1H-1,2,4-triazol-3-iltiyo)-3,5,6-triklorosiklohekza-2,5-dien-1,4-dion (22) sentezlendi.Elde edilen bütün bileşikler kromotografik yöntemlerle saflaştırıldı. Yapıları ise mikroanaliz ve spektroskopik metotlarla (IR, 1H-NMR, 13C-NMR, MS) tayin edilerek aydınlatıldı.

Abstract:
In this study, the reactions of as a starting materials 2,3-dichloro-1,4-naphthoquinone (1), p-chloranil (2) and p-fluoranil (3) compounds with acohols and thiols were examined. As a result of the reactions, ether and thioether compounds with new quinone group were synthesized.The unknown 2-(2-(2-methoxyethoxy)ethoxy)-3-chloro-1,4-naphthoquinone (4) was synthesized by the reaction of 2,3-dichloro-1,4-naphthoquinone (1) with diethylene glycol monomethylether in the presence of acetonitrile..The unknown 2-(-(pyrazin-2-yl)ethylthio)-3-chloro-1,4-naphthoquinone (5) and 2,3-bis(2-(pyrazin-2-yl)ethylthio)-1,4- naphthoquinone (6) were synthesized by the reaction of 2,3-dichloro-1,4-naphthoquinone (1) with 2-(2-mercaptoethyl)pyrazine in the presence of chloroform.The unknown 2,3,5,6-tetrakis(pentafluorophenylthio)cyclohexa-2,5-diene-1,4-dione (7) and 2-ethoxy-3,5,6-tris(pentafluorophenylthio)cyclohexa-2,5-diene-1,4-dione (8) were synthesized by the reaction of p-chloranil (2) with 2,3,4,5,6-pentafluorothiophenol in the presence of ethanol.The unknown a mixture of isomer compounds 7-chloro-8-ethoxy-3,4-dihydro-4-propyl-2H-benzo[b][1,4]oxathiepine-6,9-dione and 8-chloro-7-ethoxy-3,4-dihydro-4-propyl-2H-benzo[b][1,4]oxathiepine-6,9-dione (9) unknown 4,8-dipropyl-3,4,9,10-tetrahydrobenzo[1,2-b:5,4-b?]bis([1,4]oxathiepine)-6,12(2H,8H)-dione (10) and unknown 2,3,5,6-tetrakis(1-hydroxyhexan-3-ylthio)cyclohexa-2,5-diene-1,4-dione (11) were synthesized. by the reaction of p-chloranil (2) with 3-mercapto-1-hexanol in the presence of ethanol. The unknown 2-(2-ethylhexyloxy)-3,5,6-trichlorocyclohexa-2,5-diene-1,4-dione (12) was synthesized by reaction of p-chloranil (2) with 2-ethyl-1-hexanol. in the presence of acetonitrile. The unknown a mixture of isomer compounds 2-(2-(pyrazin-2-yl)ethylthio)-3-chloro-5,6-diethoxycyclohexa-2,5-diene-1,4-dione and 2-(2-(pyrazin-2-yl)ethylthio)-6-chloro-3,5-diethoxycyclohexa-2,5-diene-1,4-dione (13), unknown 2,5-bis(2-(pyrazin-2-yl)ethylthio)-3,6-diethoxycyclohexa-2,5-diene-1,4-dione (14) and 2,3,5-tris(2-(pyrazin-2-yl)ethylthio)-6-ethoxycyclohexa-2,5-diene-1,4-dione (15) were synthesized by the reactions of p-chloranil (2) with 2-(2-merkaptoetil)pirazin in presence of ethanol.The unknown 12,13-difluoro-2,3,5,6,8,9-hexahydrobenzo[b][1,4,7,10]dioxadithiacyclododecine-11,14-dione (16) and 2,3,5-trifluoro-6-(2-((2-((2-hydroxyethyl)thio)ethyl)thio)ethoxy)cyclohexa-2,5-diene-1,4-dione (17) were synthesized by the reactions of p-fluoranil (3) with 1,8-dihydroxy-3,6-dithiaoctane in the presence of acetonitrile. The unknown 2,6-bis(6-hydroxyhexyloxy)-3,5-difluorocyclohexa-2,5-diene-1,4-dione (18) was synthesized by reaction of p-fluoranil (3) with 1,6-hexandiol in the presence of acetonitrile.The unknown 2,3,5-tris(2-(pyrazin-2-yl)ethylthio)-6-chlorocyclohexa-2,5-diene-1,4-dione (19) and 2,3,5,6-tetrakis(2-(pyrazin-2-yl)ethylthio)cyclohexa-2,5-diene-1,4-dion (20) were synthesized by reactions of p-chloranil (2) with 2-(2-mercaptoethyl)pyrazine in the presence of chloroform.The unknown 2,3,5-trichloro-6-(pyridin-3-yloxy)cyclohexa-2,5-diene-1,4-dione (21) was synthesized by reaction of p-chloranil (2) with 3-pyridinol in the presence of acetonitrile. The unknown 2-(1H-1,2,4-triazol-3-ylthio)-3,5,6-trichlorocyclohexa-2,5-diene-1,4-dione (22) was synthesized by reaction of p-chloranil (2) with 3-mercapto-1,2,4-triazole in the presence of acetonitrile.The known and new products were purified by chromographic methods. The structured of compounds were determined by micro analysis and spectroscopic methods (IR, 1H-NMR, 13C-NMR, MS)