Yeni aminonaftakinon bileşiklerinin mannich reakisyon ile sentezi, karaterizasyonu ve fotofiziksel/ elektrokimyasal özelliklerinin incelenmesi
Synthesis, characterization and investigation of the photophysical electroctemical properties of new aminonaphtaqui̇none compounds by mannich reaction
Yazar: GÜLHAN KÖKLÜ
Danışman: PROF. DR. AHMET TUTAR
Sakarya Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Organik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2023
Konu: Kimya = Chemistry

Özet:
Kinon ve türevi bileşikler biyolojik aktivitelerinden dolayı yaygın olarak araştırılmaktadırlar. Kınanın boyar maddesi olan hidroksinaftakinon ya da lawson saç, cilt, pamuk ve yün boyamasında eski çağlardan beri geleneksel olarak kullanılmaktadır. Naftakinonlar iki benzen halkasından oluşan kinon türevlerindendir. Naftakinon bileşiğinin türevleri antibakteriyel, antifungal, antiprotozoal , antikanser ve anti-inflamatuvar biyoaktif madde olup farmakolojide birçok kanser tedavisindeki ilaçlarda yaygın olarak kullanılmakta ve geliştirilmektedir.
2-hidroksi naftakinon bileşiği diğer adıyla lawson olarak bilinen bileşik kına yapraklarında bulunan kırmızı-turuncu renkli bir pigmenttir. Bazı naftakinon bileşikleri gibi lawson bileşiği de farklı kanser hücrelerinin büyümesini engellediği kanıtlanmıştır. Aminonaftakinon olarak bilinen 3-(aminometil)-2-hidroksi-1,4-naftakinon Mannich bazları ve metal kompleksleri önemli naftakinon türevlerinden biridir. Mannich reaksiyonu ilk olarak 1912'de Carl Ulrich Franz Mannich tarafından gerçekleştirilmiştir. Bu reaksiyon en az bir tane aktif hidrojen atomu içeren bileşikler ile aminler ve aldehitlerin kondezasyonuyla oluşur. Hem asidik ortamda hem de bazik ortamda reaksiyon vermektedirler. Biyolojik aktivite özelliği gösteren Mannich bazlar doğal bileşiklerde yaygın olarak bulunmaktadır. Tıbbi kimyada , amino asit, amino alkol ve nitrojen içeren mollekülerin yapılarında bu bileşikler yer almaktadır. Özellikle metal kompleksleri kanser hastalarının tedavisinde kullanılan kemoterapi ilaçlarının yapısında yer almaktadır.
Aminonaftakinon bileşikleri kolay sentezlenebilmesi, çeşitli fotofiziksel ve elektrokimyasal özellikleri nedeniyle günümüzde önemli bileşikler arasında yer almaktadır. Bu çalışmada farklı fonksiyonel gruplara sahip 8 tane benzaldehit bileşiği 2-hidroksi-1,4-aminonaftakinon bileşiği oktil amin ve bütil amin ile reaksiyona girerek 16 yeni aminonaftakinon bileşiği sentezlenmiştir. Sentezlenen bu moleküllerin kimyasal yapıları 1H NMR, FT-IR kullanılarak belirlenmiş, dönüşümlü voltametri, UV-vis ve floresans spektroskopisi ölçümleri yapılmış ve erime noktaları tayin edilmiştir.Sentezlenen naftakinonların erime noktaları 154oC ve 198oC arasındadır. 1×10-5 M derişimlerde hazırlanan çözeltilerde Uv-vis spektrumları incelendiğinde π→π* geçişine 365-504 nm arasında, σ→σ* geçişine ve n→σ* geçişine ait piklerin UV bölgede gözlenmiştir. Absorbsiyon katsayısı(Ɛ) 1400-3500 M-1.cm-1 olduğu görülmektedir. Mannich reaksiyonu sonucu elde edilen maddelerin verimlerinin de öngörüldüğü üzere yüksek çıkmış ve verimler karşılaştırılmıştır. Sentezlenin maddelerin verimleri % 64 ile %95 arasındadır.

Abstract:
Quinones are organic compounds that have been researched for many years and have a wide range of applications. These compounds are found in many areas such as the structure of fungi, bacteria and plants. Since they are colored compounds, they have been used as natural dyes. The first quinone synthesis took place in 1838. Quinone synthesis occurred by oxidation of quinic acid with MnO2 and sulfuric acid. In our daily life, quinones are mostly found in the structure of vitamins K1, K2, K3. The fact that quinone compounds show properties such as antibacterial, anti-inflammatory, anticancer, antitoxic, increases the importance of quinones. They also take part in redox reactions by showing good reduction and oxidation properties. Due to these reduction-oxidation properties, they are also used in energy storage. Vitamin K is a vitamin involved in blood clotting in the structure of foods such as almonds, prunes, pumpkin seeds, avocado, spinach. The most well-known of the quinone is p-benzoquinone. Quinones have two conjugated double bonds attached to the ring and the oxygens in their structure are usually located in the para or orto position.
Naphthaquinone are quinone structures consisting of two rings. They have been used in hair and skin dyeing for many years due to their color. Naphthaquinone derivatives can be obtained by many methods. Naphthaquinones are compounds used in dye-sensitized solar cells, cancer treatment and many pharmacological applications. Examples of naphthaquinones include structures such as lawson, juglon, alizarin.
Lawson is an orange-colored naphthaquinone with the formula C10H6O3, called 2-hydroxy-1,4-naphthaquinone. It forms the main component of henna. The Lawson compound can be used in fingerprint analysis, dye-sensitized solar cells and sunscreens.
Mannich reaction was first realized by Carl Ulrich Franz Mannich in 1912. This reaction occurs by condensation of amines and aldehydes with compounds containing at most one active hydrogen atom. Although there are reactions that take place in both basic and acidic media, those that take place in acidic media are more common. Mannich bases have many uses. In particular, metal complexes are included in the structure of chemotherapy drugs used in the treatment of cancer patients. Studies are continuing to develop the uses of these bases, which are widely used in the field of medicine.
Amine compounds are organic substances with nitrogen element in their structure. They are divided into 3 groups as primary, secondary and tertiary depending on the number of hydrogen in their structure. They can be aromatic or aliphatic. Aromatic amines are called anilines. Amines are lewis bases due to the unpaired electron pair on the nitrogen.In this thesis, 16 different aminonaphthaquinone molecules were synthesized. The chemical structures of these synthesized molecules were determined using 1H NMR, FT- IR, cyclic voltammetry, UV-vis and fluorescence spectroscopy and their melting points were determined. In this study, 16 new aminonaphthaquinone compounds were synthesized by reaction of 8 different benzaldehyde, butyl or octyl amine and 2-hydroxy-1,4-naphthoquinone. Ethanol was used as solvent. The melting points of the synthesized naphthaquinone are between 154oC and 198oC. In the UV-vis spectra of the solutions prepared at 1×10-5 M concentrations, λabs values between 365-504 nm belong to the π→π* transition, while the values between 200-350 nm belong to the σ→σ* transition and n→σ* transition. The absorption coefficient (Ɛ) is 1400-3500 M-1.cm-1. The yields of the substances obtained as a result of the Mannich reaction were also high as predicted and the yields were compared. The yields of the synthesized substances are between 64% and 95%.In the results of 1H NMR analysis, it is seen that the peaks of resonant hydrogens in aromatic structures are between 6-8 ppm, aliphatic hydrogens in amine groups are between 0-3 ppm and bridge hydrogen, which is a specific hydrogen of the compounds we synthesized, is between 4-6 ppm.
The synthesized compounds are as follows;
(1)2-((butylamino)(4-methoxyphenyl)methyl)-3-hydroxynaphthalene-1,4-dione. molecular formula C22H24NO4, melting point of the compound with 71% yield was calculated as 189oC.(2) 2-((butylamino)(p-tolyl)methyl)-3-hydroxynaphthalene-1,4-dione. The molecular formula of the orange colored solid formed in 90% yield is C22H24NO3 and the melting point is calculated as 198oC.(3) 2-((butylamino)(4-nitrophenyl)methyl)-3-hydroxynaphthalene-1,4-dione. The molecular formula of the yellow solid formed in 71% yield was C21H21N2O5, melting point 183oC.(4) 2-((4-bromophenyl)(butylamino)methyl)-3-hydroxynaphthalene-1,4-dione. The molecular formula of the yellow solid formed in 64% yield was C21H21BrNO3, melting point 190oC. (5)2-((butylamino)(4-chlorophenyl)methyl)-3-hydroxynaphthalene-1,4-dione. The molecular formula of the orange solid formed in 91% yield is C21H21ClNO3, melting point 192oC.(6)2-((4-(tert-butyl)phenyl)(butylamino)methyl)-3-hydroxynaphthalene-1,4-dione. The red solid formed in 85% yield has a molecular formula of C25H30NO3 and a melting point of 164°C. (7)2-((butylamino)(phenyl)methyl)-3-hydroxynaphthalene-1,4-dione. The molecular formula of the yellow solid formed in 91% yield is C21H22NO3, melting point 184oC. (8)2-hydroxy-3-((4-methoxyphenyl)(octylamino)methyl)naphthalene-1,4-dione. The molecular formula of the compound formed in 90% yield is C26H32NO4, melting point 184oC.(9) 2-hydroxy-3-((octylamino)(p-tolyl)methyl)naphthalene-1,4-dione was synthesized. The molecular formula of the yellow solid formed in 92% yield is C26H32NO3, melting point 166oC. (10)2-hydroxy-3-((4-nitrophenyl)(octylamino)methyl)naphthalene-1,4-dione was synthesized. The molecular formula of the yellow solid formed in 82% yield was C25H29N2O5 and the melting point was 160oC.(11) 2-((4-bromophenyl)(octilamino)methyl)-3-hydroxynaphthalene-1,4-dione was synthesized. The molecular formula of the yellow solid formed in 87% yield is C25H29BrNO3, melting point 162oC.(12) 2-((4-chlorophenyl)(octylamino)methyl)-3-hydroxynaphthalene-1,4-dione was synthesized. The molecular formula of the yellow solid formed in 95% yield is C25H29ClNO3, melting point 163oC.(13)2-((4-(tert-butyl)phenyl)(octylamino)methyl)-3-hydroxynaphthalene-1,4-dione was synthesized. The molecular formula of the orange solid formed in 93% yield is C29H38NO3, melting point183oC. (14)2-((heptilamino)(phenyl)methyl)-3-hydroxynaphthalene-1,4-dione was synthesized.The molecular formula of the dark yellow solid formed in 89% yield is C25H30NO3, melting point 170oC.(15)2-((butylamino)(3,5-dimethoxyphenyl)methyl)-3-hydroxynaphthalene-1,4-dione was synthesized. The molecular formula of the brick colored solid formed with 87% yield is C23H26NO5, melting point 180oC. (16)2-((3,5-dimethoxyphenyl)(octylamino)methyl)-3-hydroxynaphthalene-1,4-dione was synthesized. The melting point of the orange solid formed in 93% yield is C27H34NO5 , melting point 154oC.