Yüksek karbonlu bazı alifatik tiyoller ve aminlerden naftakinon türevlerinin sentezi
The synthesis of naphthoquinone derivatives from some high-carbon aliphatic thiols and amines
Yazar: SEMİH KURBAN
Danışman: DOÇ. DR. ÇİĞDEM SAYIL
İstanbul Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2011
Konu: Kimya = Chemistry

Özet:
Yapmış olduğumuz bu çalışmada, başlangıç maddesi olan 2,3-dikloro-1,4-naftakinon bileşiğinin alifatik tiyol ve amin bileşikleriyle olan reaksiyonları incelendi.S-, N-, S,N- nükleofilleri ile naftakinon bileşiklerinin çeşitli reaksiyonları sonucu bilinen ve bilinmeyen yeni sübstitüe naftakinon bileşikleri sentezlendi. Yeni naftakinon bileşiklerinin sentezlenmesinde; başlangıç maddesi olarak 2,3-dikloro-1,4-naftakinon bileşiği kullanıldı.Çalışmanın ilk aşamasında 2,3-dikloro-1,4-naftakinon bileşiği önce hekzadekantiyol ile reaksiyona sokuldu ve bilinmeyen yeni 2-(hekzadesiltiyo)-3-(kloro)naftalen-1,4-dion (2) ve literatürde bilinen 2,3-bis(hekzadesiltiyo)naftalen-1,4-dion (3) ve 2-etoksi-3-(hekzadesiltiyo)naftalen-1,4-dion (4) bileşikleri elde edildi. 2,3-dikloro-1,4-naftakinon bileşiği oktadekantiyol ile reaksiyona sokuldu ve literatürde bilinen 2-kloro-3-(oktadesiltiyo)naftalen-1,4-dion (5) 2,3-bis(oktadesiltiyo)naftalen-1,4-dion (6) ve 2-etoksi-3-(oktadesiltiyo)naftalen-1,4-dion (7) bileşikleri elde edildi. 2-Hekzadesiltiyo-3-(kloro)naftalen-1,4-dion (2) ve 2-kloro-3-(oktadesiltiyo)naftalen-1,4-dion (5) bileşiklerinin 4-(2-aminoetil)-morfolin ile reaksiyonundan, sırasıyla yeni 2-(hekzadesiltiyo)-3-((2-morfolinoetil)amino)naftalen-1,4-dion (8) ve 2-((2-morfolinoetil)amino)-3-(oktadesiltiyo)naftalen-1,4-dion (9) bileşikleri sentezlendi.Çalışmanın ikinci aşamasında, mono amin naftakinon bileşikleri sentezlendi ve bu bileşiklere yüksek karbonlu tiyoller eklendi.2,3-Dikloro-1,4-naftakinon (1) bileşiği anilin ile reaksiyona sokuldu ve literatürde bilinen 2- fenilamino -3-(kloro)naftalen-1,4-dion (10) bileşiği sentezlendi. 2- Fenilamino -3-(kloro)naftalen-1,4-dion (10) bileşiğinin hakzadekantiyol ve oktadekantiyol ile reaksiyonundan, sırasıyla yeni 2-fenilamino-3-(hekzadesiltiyo)naftalen-1,4-dion (11) ve 2-fenilamino-3-(oktadesiltiyo)naftalen-1,4-dion (12) bileşikleri sentezlendi. 2,3-Dikloro-1,4-naftakinon (1) bileşiği 4-floroanilin ile reaksiyona sokuldu ve literatürde bilinen 2-((4-florofenil)amino)-3-(kloro)naftalen-1,4-dion (13) bileşiği sentezlendi. 2-((4-Florofenil)amino)-3-(kloro)naftalen-1,4-dion (13) bileşiğinin hakzadekantiyol ve oktadekantiyol ile reaksiyonundan, sırasıyla yeni 2-((4-florofenil)amino)-3-(hekzadesiltiyo)naftalen-1,4-dion (14) ve 2-((4-florofenil)amino)-3-(oktadesiltiyo)naftalen-1,4-dion (15) bileşikleri sentezlendi. 2,3-Dikloro-1,4-naftakinon (1) bileşiği 4-florobenzilamin ile reaksiyona sokuldu ve literatürde bilinen 2-((4-florobenzil)amino)-3-(kloro)naftalen-1,4-dion (16) bileşiği sentezlendi. 2-((4-Florobenzil)amino)-3-(kloro)naftalen-1,4-dion (16) bileşiğinin hakzadekantiyol ve oktadekantiyol ile reaksiyonundan, sırasıyla yeni 2-((4-florobenzil)amino)-3-(hekzadesiltiyo)naftalen-1,4-dion (17) ve 2-((4-florobenzil)amino)-3-(oktadesiltiyo)naftalen-1,4-dion (18) bileşikleri sentezlendi. 2,3-Dikloro-1,4-naftakinon (1) bileşiği ß-naftilamin ile reaksiyona sokuldu ve literatürde bilinen 2-kloro-3-(naftalen-2-amino)naftalen-1,4-dion (19) bileşiği sentezlendi. 2-Kloro-3-(naftalen-2-amino)naftalen-1,4-dion (19) bileşiğinin hakzadekantiyol ve oktadekantiyol ile reaksiyonundan, sırasıyla yeni 2-(hekzadesiltiyo)-3-(naftalen-2-amino)naftalen-1,4-dion (20) ve 2-( naftalen-2-amino)-3-(oktadesiltiyo)naftalen-1,4-dion (21) bileşikleri sentezlendi. 2,3-Dikloro-1,4-naftakinon (1) bileşiği o-toluidin ile reaksiyona sokuldu ve literatürde bilinen 2-kloro-3-(o-tolilamino)naftalen-1,4-dion (22) bileşiği sentezlendi. 2-Kloro-3-(o-tolilamino)naftalen-1,4-dion (22) bileşiğinin hakzadekantiyol ve oktadekantiyol ile reaksiyonundan, sırasıyla yeni 2-(hekzadesiltiyo)-3-(o-tolilamino)naftalen-1,4-dion (23) ve 2-(oktadesiltiyo)-3-(o-tolilamino)naftalen-1,4-dion (24) bileşikleri sentezlendi. 2,3-Dikloro-1,4-naftakinon (1) bileşiği m-toluidin ile reaksiyona sokuldu ve literatürde bilinen 2-kloro-3-(m-tolilamino)naftalen-1,4-dion (25) bileşiği sentezlendi. 2-Kloro-3-(m-tolilamino)naftalen-1,4-dion (25) bileşiğinin hakzadekantiyol ve oktadekantiyol ile reaksiyonundan, sırasıyla yeni 2-(hekzadesiltiyo)-3-(m-tolilamino)naftalen-1,4-dion (26) ve 2-(oktadesiltiyo)-3-(m-tolilamino)naftalen-1,4-dion (27) bileşikleri sentezlendi.Sentezlenen yeni naftakinon bileşikleri kromatografik yöntemlerle saflaştırıldı. Bu bileşiklerin yapıları mikroanaliz ve spektroskopik yöntemler (IR, 1H-NMR, 13C-NMR, MS) kullanılarak aydınlatıldı.

Abstract:
That we have done in this study, reactions of aliphatic thiol and amine compounds with 2,3-dichloro-1,4-naphthoquinone as a starting compound, were investigated.The known and unknown new substituted-naphthoquinone compounds were synthesized by reactions of S-, N-, S,N- nucleophiles with naphthoquinones. 2,3-Dichloro-1,4-naphthoquinone was used as starting material to synthesis of new naphthoquinone compounds.In the first step of this study, firstly 2,3-dichloro-1,4-naphthoquinone (1) compound was reacted with hexadecanethiol and unknown novel 2-chloro-3-(hexadecylthio)naphthalene-1,4-dione (2) and 2,3-bis(hexadecylthio)naphthalene-1,4-dione (3) and 2-ethoxy-3-(hexadecylthio)naphthalene-1,4-dione (4) compounds that known in the literature, was obtained. 2,3-Dichloro-1,4-naphthoquinone (1) compound was reacted with octadecanethiol and 2-chloro-3-(octadecylthio)naphthalene-1,4-dione (5), 2,3-bis(octadecylthio)naphthalene-1,4-dione (6) and 2-ethoxy-3-(octadecylthio)naphthalene-1,4-dione (7) compounds that known in the literature, were obtained. The novel compounds 2-(hexadecylthio)-3-((2-morpholinoethyl)amino)naphthalene-1,4-dione (8) and 2-(octadecylthio)-3-((2-morpholinoethyl)amino)naphthalene-1,4-dione (9) were synthesized from the reactions of compounds 2-chloro-3-(hexadecylthio)naphthalene-1,4-dione (2) and 2-chloro-3-(octadecylthio)naphthalene-1,4-dione (5) with 4-(2-aminoethyl)-morpholin respectively.In the second step of this study, mono amine naphthoquinone compounds were synthesized and high-carbon thiols were added to this compounds.2,3-Dichloro-1,4-naphthoquinone (1) compound was reacted with aniline and 2-chloro-3-(phenylamino)naphthalene-1,4-dione (10) that known in the literature, was synthesized. The novel compounds 2-(hexzadecylthio)-3-(phenilamino)naphthalene-1,4-dione (11) and 2-(octadecylthio)-3-(phenilamino)naphthalene-1,4-dione (12) were synthesized from the reactions of compound 2-chloro-3-(phenylamino)naphthalene-1,4-dione (10) with hexadecanethiol and octadecanethiol respectively. 2,3-Dichloro-1,4-naphthoquinone (1) compound was reacted with 4-fluoroaniline and 2-(chloro)-3-((4-fluorophenyl)amino)naphthalene-1,4-dione (13) that known in the literature, was synthesized. The novel compounds 2-((4-fluorophenyl)amino)-3-(hexzadecylthio)naphthalene-1,4-dione (14) and 2-((4-fluorophenyl)amino)-3-(octadecylthio)naphthalene-1,4-dione (15) were synthesized from the reactions of compound 2-(chloro)-3-((4-fluorophenyl)amino)naphthalene-1,4-dione (13) with hexadecanethiol and octadecanethiol respectively. 2,3-Dichloro-1,4-naphthoquinone (1) compound was reacted with 4-fluorobenzylamine and 2-chloro-3-((4-fluorobenzyl)amino)naphthalene-1,4-dione (16) that known in the literature, was synthesized. The novel compounds 2-((4-fluorobenzyl)amino)-3-(hexadecylthio)naphthalene-1,4-dione (17) and 2-((4-fluorobenzyl)amino)-3-(octadecylthio)naphthalene-1,4-dione (18) were synthesized from the reactions of compound 2-chloro-3-((4-fluorobenzyl)amino)naphthalene-1,4-dione (16) with hexadecanethiol and octadecanethiol respectively. 2,3-Dichloro-1,4-naphthoquinone (1) compound was reacted with ß-naphthylamine and 2-chloro-3-(naphthalen-2-ylamino)naphthalene-1,4-dione (19) that known in the literature, was synthesized. The novel compounds 2-(hexadecylthio)-3-(naphthalen-2-ylamino)naphthalene-1,4-dione (20) and 2-(naphthalen-2-ylamino)-3-(octadecylthio)naphthalene-1,4-dione (21) were synthesized from the reactions of compound 2-chloro-3-(naphthalen-2-ylamino)naphthalene-1,4-dione (19) with hexadecanethiol and octadecanethiol respectively. 2,3-Dichloro-1,4-naphthoquinone (1) compound was reacted with o-toluidine and 2-chloro-3-(o-tolylamino)naphthalene-1,4-dione (22) that known in the literature, was synthesized. The novel compounds 2-(hexadecylthio)-3-(o-tolylamino)naphthalene-1,4-dione (23) and 2-(octadecylthio)-3-(o-tolylamino)naphthalene-1,4-dione (24) were synthesized from the reactions of compound 2-chloro-3-(o-tolylamino)naphthalene-1,4-dione (22) with hexadecanethiol and octadecanethiol respectively. 2,3-Dichloro-1,4-naphthoquinone (1) compound was reacted with m-toluidine and 2-chloro-3-(m-tolylamino)naphthalene-1,4-dione (25) that known in the literature, was synthesized. The novel compounds 2-(hexadecylthio)-3-(m-tolylamino)naphthalene-1,4-dione (26) and 2-(octadecylthio)-3-(m-tolylamino)naphthalene-1,4-dione (27) were synthesized from the reactions of compound 2-chloro-3-(m-tolylamino)naphthalene-1,4-dione (25) with hexadecanethiol and octadecanethiol respectively.The novel synthesized naphthoquinone compounds were purified by chromatographic methods. The structures of compounds were determined by using micro analysis and spectroscopic methods (IR, 1H-NMR, 13C-NMR, MS).