Synthesis and characterization of conjugate diacyl piperazine derivatives
Konjuge diaçil piperazin türevlerinin sentezi ve karakterizasyonu
Yazar: SEDA ÜNALAN
Danışman: DOÇ. DR. MEHMET YILMAZ
Kocaeli Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2018
Konu: Kimya = Chemistry

Özet:
Bu çalışma konjuge diaçil piperazin türevlerinin sentezini içermektedir. Ticari bir ürün olan dietilfosfonaasetat ile asetofenon (97a) , benzofenon (97b) , 1-(5-metilfuran-2-il)etanon (97c) , 1-(tiyofen-2-il)etanon (97d) bileşiklerinin ayrı ayrı reaksiyonlarından sırasıyla (E)-etil 3fenilbüt-2-enoat (98a) , etil 3,3-difenilakrilat (98b), (E)-etil 3-(5-metilfuran-2-il)büt-2-enoat (98c) ve (E)-etil 3-(tiyofen-2-il)büt-2-enoat (98d) sentezlendi. (Tablo 3.1) Sentezlenen esterlerin NaOH ile hidrolizinden sırasıyla (E)-3-fenilbüt-2-enoik asit (99e), 3,3-difenilakrilik asit (99f), (E)-3-(5-metilfuran-2-il)büt-2-enoik asit (99g), (E)-3-(tiyofen-2-il)büt-2-enoik asit (99h) sentezlendi. (Tablo 3.2) (99e-h) bileşiklerinin SOCl2 ile reaksiyonundan sırasıyla (E)-3fenilbüt-2-enoil klorür (100e) , 3,3-difenilakriloil klorür (100f) , (E)-3-(5-metilfuran-2-il)büt2-enoil klorür (100g), (E)-3-(tiyofen-2-il)büt-2-enoil klorür (100h) bileşikleri sentezlendi. (Tablo 3.3) Sinnamoil klorür (100i) bileşiği ise satın alındı.  
Piperazin'in metakrilik anhidrit ile reaksiyonundan 2-metil-1-(piperazin-1-il)prop-2-en-1-on (metakriloil piperazin)  (101a) sentezlendi. Bu bileşiklerin metakrilik anhidrit ve (100a-i) bileşikleri ile reaksiyonlarından diaçil piperazin türevleri olan, 1,1'-(piperazin-1,4-diil)bis(2metilprop-2-en-1-on) (102a), (2E,2'E)-1,1'-(piperazin-1,4-diil)bis(3-fenillprop-2-en-1-one) (102b), (E)-1-(4-sinnamoilpiperazin-1-il)-2-metillprop-2-en-1-on (102c), 1-(4metakriloilpiperazin-1-il)-3,3-difenilprop-2-en-1-on (102d), (E)-1-(4-metakriloilpiperazin-1il)-3-fenilbüt-2-en-1-on (102e), (E)-1-(4-metakriloilpiperazin-1-il)-3-(5-metilfuran-2-il)prop2-en-1-on (102f), (E)-1-(4-metakriloilpiperazin-1-il)-3-(5-metilfuran-2-il)büt-2-en-1-on (102g), (E)-1-(4-metakriloilpiperazin-1-il)-3-(tiyofen-2-il)prop-2-en-1-on (102h), (E)-1-(4metakriloilpiperazin-1-il)-3-(tiyofen-2-il)büt-2-en-1-on (102i), (2E,4E)-1-(4metakriloilpiperazin-1-il)hekza-2,4-dien-1-on (102j), (2E,4E)-1-(4- metakriloilpiperazin-1-il)5-fenilpenta-2,4-dien-1-on (102k), (E)-1-(4-sinnamilpiperazin-1-il)-2-metillprop-2-en-1-on (102l), bileşiklerinin sentezi gerçekleştirildi. Elde edilen ürünler kromatografik yöntemler kullanılarak saflaştırıldı. Tüm yeni bileşikerin yapıları spektroskopik (1H-NMR, 13C-NMR, IR) yöntemler ve HRMS kullanılarak aydınlatıldı.  
Anahtar Kelimeler: Diaçil Piperazin, Konjuge Ester, Konjuge Karboksilik Asit, Metakrilik Anhidrit.

Abstract:
This work involves the synthesis of conjugated diacyl piperazine derivatives. compounds (E) -ethyl 3-phenylbut-2-enoate (98a), ethyl 3,3-diphenylacrylate (98b) and (E) -ethyl 3- (5-methylfuran-2-yl) but-2-enoate (98c) were synthesized from individual reactions of the compounds diethylphosphonoasetate with acetophenone (97a), benzophenone (97b), 1- (5-methylfuran-2-yl) ethanone (97c), 1- (thiophen-2yl) ethanone (97d) respectively. (Table 3.1). (E) -3-phenylbut-2-enoic acid (99e), 3,3-diphenyl acrylic acid (99f), (E) -3- (5-methylfuran-2-yl) but-2-enoic acid (99g) and (E) -3- (thiophen-2-yl) but-2-enoic acid (99h) was synthesized from the hydrolysis of the synthesized esters with NaOH. (99e-h) compounds were synthesized (E)-3-phenylbut-2-enoyl chloride (100e), 3,3-diphenylacryloyl chloride (100f), (E)-3-(5-methylfuran-2-yl)but-2-enoyl chloride (100g) and (E)-3-(thiophen2-yl)but-2-enoyl chloride (100h).respectively from the reaction of SOCl2. (Table 3.3) Sinnamoyl chloride (100i) was purchased. 
Synthesized 2-methyl-1- (piperazin-1-yl) prop-2-en-1-one (methacryloyl piperazine) by reacting piperazine with methacrylic anhydride. These compounds were also reacted with methacrylic anhydride and (100a-i) compounds to synthesize 1,1 '- (piperazine-1,4-diyl) bis (2-methylprop-2-en-1-one) (102a), (2E, 2'E) -1,1'- (piperazine-1,4-diyl) bis (3-phenylprop-2-en-1-one) (102b), (E) -1- (4cinnamoylpiperazin-1-yl) -2-methylprop-2-en-1-one (102c),   1- (4methacryloylpiperazin-1-yl) -3,3-diphenylprop-2-en-1-one (102d), (E) -1- (4methacryloylpiperazin-1-yl) -3-phenylbut-2-en-1-one (102e), (E) -1- (4methacryloylpiperazin-1-yl) -3- (5-methylfuran-2-yl) prop-2-en-1-one (102f), (E) -1- (4-methacryloylpiperazin-1-yl) -3- (5-methylfuran-2-yl) but-2-en-1-one (102g), (E) 1- (4-methacryloylpiperazin-1-yl) -3- (thiophen-2-yl) prop-2-en-1-one (102h), (E) -1- (4-methacryloylpiperazin-1-yl) -3- (thiophen-2-yl) but-2-en-1-one (102i), (2E, 4E) 1- (4-methacryloylpiperazin-1-yl) hexa-2,4-dien-1-one (102j), (2E, 4E) -1- (4methacryloylpiperazin-1-yl) -5-phenylpentane-2,4-dien-1-one (102k), (E) -1- (4cinnamylpiperazin-1-yl)-2-methylprop-2-en-1-one (102l) compounds of the piperazine derivates in which diacyl piperazine derivates. The obtained products were purified using chromatographic methods. All new compound structures were clarified using spectroscopic (1H-NMR, 13C-NMR, IR, HRMS) methods. 
Keywords: Conjugated Carboxylic Acid, Conjugated Ester, Diacyl Piperazine, Methacrylic Anhydride.